CA1234733A - Pourable fluid detergent compositions - Google Patents

Abstract

ABSTRACT
Pourable, fluid, non sedimenting, laundry detergent composition, comprising water, surfactant, builder, a surfactant desolubilising electrolyte and, optionally, the usual minor ingredients, consist essentially of : at least one predominantly aqueous liquid phase which is separable into a distinct layer by centrifuging the composition at 800 times normal earth gravity at 25°C for 17 hours, and which contains at least part of the electrolyte and one or more other phases which together contain at least part of the builder as solid particles dispersed in the composition and at least part of the surfactant.

Description

:~3~3~

PARBOIL FLUID DETERGENT COMPOST ITCHINESS
_ The present invention relates to novel, a~ueous-based, parboil, fluid detergent compositions containing effective quantities of detergent builder This application is a dive-soon of cop ending Canadian patent application Serial no.
421,409 filed February 11, 1983.
DEFINITIONS

The term "builder" is sometimes used loosely in the detergent art to include any non-surfactant whose presence in a detergent formulation enhances the cleaning effect of the formulation. More usually, however, the term is restricted to those typical "builders", which are primarily useful as a means of preventing or ameliorating the adverse effects on washing of calcium and magnesium ions e.g. by chelation, sequestering, precipitation or absorption of the ions, and secondarily as a source of alkalinity and buffering.
The term "Builder" is used herein in the latter sense, and refers to additives which ameliorate the aforesaid adverse effects to a substantial extent. It includes sodium or potassium tripolyphosphate and other phosphate and condensed phosphate salts such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates, amino iris ethylene phosphonates and ethylenediamine tetramethylene phosphonates. It also includes alkali metal carbonates, zealots and such organic sequestrants as salts of nitrilotriacetic acid, citric acid and ethylene Damon tetracetic acid, polymeric polycarboxylic acids such as polyacrylates and malefic android based copolymers.

For the avoidance of doubt "Builder" is used herein to include water soluble alkali metal silicates such as sodium silicate, but excludes additives such as carboxymethyl cellulose, or polyvinyl pyrrolidone whose function is primarily that of soil suspending or ~n~i-redeposi~i3n agent "Electrolyte" is used herein in relation to a component of a liquid detergent composition to denote those non-surface active, ~:3~733 water soluble, ionic compounds which dissociate at least partially in aqueous solution to provide ions, and which tend to lower the sailboat or muzzler concentration in the composition of the surfactants present by a "salting out" effect. It includes water soluble dissociable~ inorganic salts such do, for example alkali metal or ammonium, chlorides, nitrates, phosphates, carbonates, silicates and polyphosphates, and also certain water soluble non-surface active organic salts which disyllables or "salt out" those surfactants which are present in the composition. It does not include salts of cations which form water insoluble precipitates with the surfactants present, or salts which, at the concentrations used, tend to give unacceptable crystallization when the composition is stored.

"Hydrotrope" is used herein in relation to a component of a liquid detergent composition to denote any water soluble compound which tends to increase the volubility in the composition of the surfactants present. Typical Hydrotropes include urea and the alkali metal or ammonium salts of the lower alkyd Bunsen sulphonic acids such as sodium Tulane sulphonate and sodium zillion sulphonate.
Whether a given compound is an Electrolyte or a Hydrotrope may in some cases depend upon which surfactants are present in the particular liquid detergent composition.

As used herein "Soap" means an at least sparingly 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 Cog 22 natural and synthetic fatty acids, including Starkey, palmitic, oleic, linoleic, ricinoleic, bunk and dodecanoic acids, resin acids and branched chain ~onocarboxylic acids.

The "Usual Minor Ingredients" includes those ingredients other than Water, Active Ingredients builders and Electrolytes which may be included in laundry detergent compositions, typical lye in proportions up to I and which are compatible in the relevant Formulation with a parboil, chemically stable Non-sedimenting composition. The term includes anti redeposition agents, perfumes, dyes, optical brightening agents, Hydrotropes, solvents, buffers bleaches, corrosion inhibitors, antioxidant, preservatives, scale inhibitors, humectants, enzymes and their stabilizers, bleach activators, and the like.
As used herein "Functional Ingredients" means ingredients which are required to provide a beneficial effect in the wash liquor and includes ingredients which contribute to the washing effectiveness of the composition e.g. surfactants, Builders, bleaches, optical brighteners, buffers, enzymes and anti-redeposition agents, and also anti-corrosives but excludes water, solvents, dyes, perfume, Hydrotropes, sodium chloride, sodium sulfite, solubilisers and stabilizers whose sole function is to impart stability, fluidity or other desirable characteristics to a concentrated formulation.

"Payload", means the percentage of Functional Ingredients based on the total weight of the composition.

"Asset Ingredients", means surface active materials.

All references herein to "Centrifuging", unless stated to the contrary are to be construed as referring to centrifuging at 25C
for 17 hours at 800 times normal gravitational force.

The expression "Separable Phase" is used herein to denote phases which are each separable from the mixture to form a distinct layer upon Centrifuging. A single Separable Phase may comprise two or more thermodynanncally distinct phases, which are not separable from each other on Centrifuging as in, for example, a stable emulsion.

"Dispersed" is used herein to describe a phase which is discontinuously distributed as discrete particles or droplets in at least one other phase. "Co-continuous" describes two or more interpenetrating phases each of huh yes csn~inuously through a common volume, or else is formed of discreet elements which interact to form a continuous matrix tending to maintain the position and orientation of each element in relation to the matrix when the ~:3~33 system is at rest. "Interspersed" describes two or more phases which are either Co-continuous or of which one or more is Dispersed in the other or others.
References to solid phases are to substances actually present in the composition in the solid state at ambient temperature, and including any water of crystallization or hydration unless the context requires otherwise. A "Solid Layer" is a solid, pasty or nonoperable gelatinous layer formed on Centrifuging.

"Total Water" refers to waxer present as liquid waxer in a predominantly aqueous phase, together with any other water in the composition, e.g. water of crystallization or hydration or water dissolved or otherwise present in any predominantly non-aqueous phase. "Dry Weight" refers to residual weight after removal of Total Water and also of any solvent which has a boiling point below 110C.

The term "Fo~lulation" is used to describe the combination of ingredients which make up the Dry Weigh of a composition. Thus the same Formulation may be exemplified by a number of compositions, differing in their Percentage Dry Weight.

All references herein to "viscosities" unless otherwise stated are to the viscosity as measured on a cup and bob viscometer at 25C after two minutes running using a 20 mm internal diameter flat bottomed cup, 92 mm long, and a 13.7 mm diameter bob, 44 mm long, with conical ends having a 45 horizontal angle, and 4mm diameter spindle, rotating at 350 rum. The tip of the bob was 23mm from the base of the cup. This corresponds to Contrives "Roommate 30"
viscometer using measuring system C at speed setting 30. These conditions are unsuitable for measuring Viscosities greater than 12 Pascal Seconds at which partial loss of contact between the bob and the sample may a n so.

"Parboil" as used herein means having d Viscosity of less than 11.5 Pascal Seconds.

7~3 "Lo" phase denotes a fluid, isotropic, micelldr solution of surfactdnt in water, which occurs at concentrations between the critical muzzler concentration and the first lyotropic mesophase, wherein the surfactant molecules aggregate to form spherical or rod shaped muzzles.

"G" phase refers to a liquid crystal phase of the type, also known in the literature as "neat phase" or "lamellar phase" in which the surfactant molecules are arranged in parallel layers of indefinite extent separated by layers of water or an aqueous solution. The layers may be bowlers or interdigited layers of surfactant. the "G" phase for any given surfactant or surfactant mixture normally exists in a narrow range of concentrations. Pure lug" phases can normally be identified by examination of a sample under a polarizing microscope, between crossed polarizer.
Characteristic textures are observed in accordance with the classic paper by Receiver, JOCKS Vol. 31 P628 ~1954~ or in Jo Killed and Interracial Science, Vol. 30 No. 4, SUE (1969).

"Yield Points" whenever referred to herein are as measured on an RML Series II "DEER" RUM Remoter at 25C.

All percentages, unless otherwise stated, are by weight, based upon the total weight of the composition.

References herein to "sedimentation" include references to upward as well as downward separation of solid particles. "Non-sedimenting" means not undergoing significant visible separation of phases after three months a room temperature under normal earth gravity. Separation of up to go of the volume of the composition Jo form a clear aqueous phase external thereto, or up to I by volume of a Solid Layer is not considered significant for the purposes of this invention.

~;~3~7~33 TECHNICAL BACKGROUND

Liquid detergents have hitherto been used mainly for light duty applications such as dish washing. The market for heavy duty detergents e.g. laundry detergents, has been dominated by powders, due to the difficulty of getting an effective amount of surfac~an~
and in particular of builder into a stable liquid formulation. Such liquids should in theory be cheaper than powder detergents since they would avoid the need to dry and would in many instances replace the sulfite filler conventionally used in powder detergents with water. They also offer the possibilities of greater convenience and more rapid dissolution in wash water than powder. Attempts to provide solutions of the Functional Ingredients have been relatively unsuccessful commercially. One reason for this lack of success has been that the most commonly used and cost effective Functional Ingredients, e.g. sodium tripolyphosphate and sodium Dadaist Bunsen sulphonate, are insufficiently soluble in aqueous compositions.
Potassium pyrophosph~te and amine salts of the Active Ingredients which are more soluble Hyde been tried as alternatives but have not been found cost effective.

Unbolt liquid detergents containing high levels of surfac~ant have been marketed for laundry use, but are unsuitable for hard water areas and have enjoyed only limited success.

A different approach is to attempt to suspend the excess Builder as a solid in the liquid solution of surfactant. The problem however has been to stabilize the system to maintain the Builder in suspension and prevent sedimentation. This has in the assay r~q~ir~d I y s~phis~ir~ed f~rmula~i~ns, DreYrn~ina realization of the potential cost saving, and relatively low concentrations of solid Builder, giving limited washing effectiveness. This approach has been conditioned by certain ~L234~733 assumptions: that the detergent should as far as possible be in solution; that the amount of suspended solid should be minimized to avoid difficulties in stabilizing the suspension against sedimentation; and that special thickeners or stabilizers were essential to prevent sedimentation.

The products hitherto introduced commercially have suffered from certain serious drawbacks. In particular, the individual compositions have been proved highly sensitive to relatively small variations in Formulation and manufacturing procedure. Departure from a particular composition, optimized within fairly narrow limits, generally results in instability and diminished shelf life.
The formulator has therefore been restricted to particular ingredients and proportions, which have not included many of the most effective combinations of surfactants and Builder for laundry purposes.

Because no general adequate theoretical explanation for the stability of such systems has been proposed, it has not proved possible to predict which compositions will be stable and which unstable, or hew to set about stabilizing any given surfactant Builder combination which may be desired for reasons of washing effectiveness or cost. Each composition has had to be discovered by trial and error, and little flexibility has existed for adapting the individual compositions to special requirements.

Moreover in general, the Payload has been undesirably low. In addition the proportion of Builder to Active Ingredient has generally been less than is preferred for optimum washing, and expensive ingredients, not usually required in powder Formulations, haze often been nPedPd Jo increase the amount of Fun at Ingredient in solution, and to inhibit sedimentation of the suspended solid.

t733 INTRODUCTION To THE INVENTION

We have now discovered that by observing certain conditions it is possible to formulate Non-sedimenting, Parboil, fluid, aqueous based detergent compositions which have novel structural features and which can employ as surfactant virtually any surfactant or surfactant combination which is useful in laundry applications, in desired optimum proportions with any of the commonly used detergent Builders. In general, compositions of our invention can be obtained, which contain substantially higher Payloads at effective Builder to surfactant ratio than have hitherto been attainable.

Preferred embodiments of our invention exhibit at least some of the following advantages compared with products marketed hitherto: Higher Payload; increased Builder to surfactant ratio;
improved stability; lower cost due to use of cheaper ingredients and ease of production; satisfactory mobility; improved washing performance; "non-drip" characteristics, permitting the compositions to be added to the compartments of washing machines designed to operate with powders 9 Wit trout premature release; a consistency suitable for automatic dispensing; and the flexibility to select optimum ~urfactant combinations for the requirements of any particular market We have found that in general, contrary to what had been assumed in the art, the higher the amount of undissolved material the more stable the composition. We have discovered, in particular, that the lower the proportion of the Active Ingredients dissolved in the liquid aqueous phase, and the higher the proportion present as an Interspersed structure of solid or lamellar phase, the more readily can a Non-sedimenting, Parboil product be obtained at high Payloads. We have further discovered thaw most surfactants commonly used in powder detergents can have a stabilizing effect on aqueous suspensions of Functional Ingredients, when present in certain novel structured states in the composition, which Jay, at high Payloads, be sufficient to stabilize the composition without the presence of 3~f33 special stabilizers, not otherwise required for the Formulation. We have also discovered that surfactants can be constrained to form an open three dimensional structure conferring stability on aqueous suspensions, by the presence of Electrolytes and by controlling the conditions of mixing We have discovered that by applying the above principles it is possible to formulate laundry detergents as thixotropic gels which may contain suspended particles of solid Builder, which have particular advantages over conventional detergent suspensions.

THE PROP Art The prior art on liquid detergents is extremely voluminous.
However, for the purpose of this invention the numerous references to light duty liquids and to unbolt or built clear liquid laundry detergents in which all ingredients are present in solution may be disregarded. The Builder level in each case is substantially less than desirable.

Recent general Seymour ryes of the current state of the art include JOCKS April 1981) POW - "Heavy Duty Laundry Detergents"
which includes a review of the typical commercially available liquid formulations, and "Recent Changes in Laundry Detergents" by Rutkowski, published in 1981 by Marcel Decker Inc. in the Surfactan~
Science Series.

The bow principle avenues of approach to the problem of formulating fully built liquid detergents, have been to emulsify a surfactant in an aqueous solution of Builder or to suspend a solid Builder in an aqueous solution or emulsion of surfactant.

The former approach is exemplified by U.S.P.3235505, U.S.P.3346503, U.S.P.33~1557, U.S.P.35090S9, U.S.P.3574122, U.S.P.3323309 and Canadian Patent 917031. In each of these patents an aqueous solution of a water soluble Builder is sufficiently concentrated to salt out the surfactant (usually a liquid non-;onic ~;~3~733 type) and the latter is dispersed in the aqueous medium as colloidal droplets, with the aid of various emulsifiers. In each case the system is d clear emulsion, which generally, contains relatively low levels of Builder, and which is undesirably expensive due to the cost of using soluble Builders.

The alternative approach is exemplified by BY 855893, B.P.948617, B.P.943271, B.P.2028365. E.P.38101, Australian P.522983, US 4018720 U.S.P.3232878, U.S.P.3075922 and U.S.P.2920045. The formulations described in these patents separate, on Centrifuging, into a Solid Layer comprising the majority of the sparingly soluble Builder and an aqueous layer containing at least the majority of the Active Ingredients. Commercial products corresponding to the example of Australian patent No. 522983 have been marketed recently in Australia. The stability of these compositions is generally highly sensitive to minor variations in Formulation. Most require expensive additives which are not Functional Ingredients.

A different approach is to suspend solid builder in an an hydrous liquid non-ionic surfactant e.g. BY 1600981. Such systems are costly, restrictive with regard to choice of surfactant and give unsatisfactory rinsing properties.

~'~3~733 Several patents describe emulsions in which the Builder is in the dispersed phase of an emulsion rather than in suspension.
U.S.P.4057506 describes the preparation of clear emulsions of sodium tripolyphosphate, and U.S.P.4107067 describes inverse emulsions in which an aqueous solution of Builder is dispersed in a liquid crystal surfactant system.

Reference may also be made to the numerous patents relating to hard surface cleaners, in which an abrasive is suspended usually in an aqueous solution of surfactant, e.g. B.P.2031455, U.S.P.3281367 and U.S.P.3813349. U.S.P.3956158 describes suspensions of abrasive in a gel system of interlocking fires oil e.g. asbestos or soap.
However, the low levels of surfactant, absence of Builder and presence of high concentrations of abrasive, generally preclude these patents from being of any assistance in the formulating of laundry detergents.

Powder detergents are normally prepared by spray drying aqueous slurries, which may superficially resemble liquid detergent formulations, but which are not required to be stable to storage, and which, are prepared and handled at elevated temperatures. Such slurries are generally not Parboil at ambient temperature. Patents describing the preparation and spray drying of such slurry intermediates include U.S.P.3639288 and W. Gunman OWLS 1567656.

Other publications of possible interest are:

Australian patent 507431, which describes suspensions of Builder in aqueous surfactant, stabilized with sodium carboxymethyl cellulose or clay as a thickening agent. However, the levels of Functional Ingredients, an in particular of builder, in the formulations exemplified, are not sufficient for a fully acceptable commercial product;

U.S.P.3039971 describes a detergent paste containing the Builder in solution;

3 ~17 3 Fry Patent 2283951 describes suspensions of zealot Builders in non ionic surfactant systems; the compositions are, however, stiff pastes rather than Parboil fluids;

BY 1506427 and BY 1468181 describe suspensions of Builder in aqueous surfactant, which are generally insufficiently stable for commercial purposes AWAKES. Symposium series No. 194 "Silicates in Detergents"
describes the effect of silicates on liquid detergents.

It will be understood that each of the foregoing patent references was selected from the very extensive prior art, and relevant aspects highlighted with the aid of hindsight using our knowledge of the invention as a guide to such selection and highlighting. The ordinary man skilled in the art at the time of our first claimed priority, and without foreknowledge of the applicant's invention, would not necessarily have selected those patents as being particularly significant or those aspects as being of special interest or relevance.

The foregoing summary does not therefore represent the overall picture of the art possessed by the ordinary skilled man. We believe that the latter has generally held the view, either that fully built liquid detergents containing sparingly soluble Builders were unattainable, or what progress towards such formulations would be by suspending the Builder in aqueous solutions of the surfactant, earlier, alternative approaches having failed.

THE INVENTION
, _ According to one embodiment the invention provides d Non-sedimenting, Parboil, fluid detergent composition comprising at least one predominantly aqueous liquid Separable Phase, containing sufficient dissolved Electrolyte to provide from 2 to 4~5 gram ions per lithe of said phase total of alkali metal cations; at least I by weight of the composition of surfactant; and suspended solid I

I

Builder. The composition has a Payload between the minimum concentration to provide a Non-sedimenting composition and the maximum concentration to provide a Parboil composition. Preferably the Electrolyte is selected from alkali metal chlorides, phosphates, condensed phosphates, phosphonates, citrates, nitrilotriacetates, ethylene immune tetracetates, carbonates, silicates, and mixtures thereof.

According to a second embodiment, the invention provides a parboil, fluid, non-sedimenting, aqueous bused detergent composition, comprising water, surfactant, particles of solid Builder suspended in the composition, and dissolved surfactant-desolubilising Electrolyte, the proportion of dissolved Electrolyte being above the minimum concentration a which the composition exhibits increased viscosity and/or increased stability on recovery after exposure to a shear stress and the Pay Load is above the minimum at which the formulation provides a Non-sedimenting composition but below the maximum at which it is Parboil.

According to a third embodiment, our invention pro-vises a Non-sedimenting, Parboil, fluid detergent compost-lion having a Payload of greater than 25% which, on Centric fusing, is separable into a single liquid layer containing sufficient dissolved Electrolyte to provide from 2 to 4.5 gram ions per lithe of said layer of the sodium ion present therein and a Solid Layer containing surfactant and Builder.

According to a fourth embodiment our invention come proses a Non-sedimenting, Parboil, fluid, detergent come position containing surfactant, which comprises substantially linear alkyl-benzene sulphonate, said composition having a Payload of at least 25~ by weight and being separable on Centrifuging into a predominantly aqueous liquid layer con-twining sufficient dissolved Electrolyte to provide from 2 to 4.5 gym ions per lithe of alkali metal to said layer and at least one other layer, said at least one other layer compare-sing solid Builder and at least part of said surfactant.

According to a fifth embodiment our invention comprises a Non-sedimen~ing, Parboil, fluid detergent composition having a Payload of at least 259i and comprising surfactant, dissolved Electrolyte and suspended solid Builder, which separates on Centrifuging into a predominantly aqueous layer containing sufficient ox said dissolved Electrolyte to provide from 2 to 4.5 gym ions alkali metal per lithe of said aqueous layer, and at least one other layer cannoning solid Builder and at least part of said surfactant, the weight ratio of the total Builder to the total surfactant being greater than 1.2:1.
According to one preferred embodiment, there is pro-voided a Parboil, Non-sedimenting, fluid detergent compost-lion consisting essentially of water and: (A) from 10 to 20%
based on the weight of the composition of surfactants compare-sing a substantially linear sodium alkyd Bunsen sulphonate having from 10 to 20 aliphatic carbon atoms and optionally an alkyd ethics sulfite having an alkyd group with from 10 to 20 carbon atoms, and/or a minor proportion of a non-ionic sun-fact ant and/or of a soap; (B) at least 15% of Builder partly present as solid and selected from condensed phosphates, car-donates, zealots, citrates, nitrilotriacetates, ethylenedia-mine tetracetates, orthophosphates, silicates and mixtures thereof, wherein at least 50~ by weight of said Builder is sodium tripolyphosphate and said Builder further comprises sufficient sodium carbonate to provide a shear stable come position; (C) optionally minor proportions of ingredients selected from carboxymethylcellulose, optical brightening agent, enzymes, bleaches, anti foams, cat ionic fabric softeners, smectite clays, fragrances, dyes and sodium chloride.

According to another preferred embodiment, there is pro-voided a Parboil, Non-Sedimenting, fluid, liquid detergent composition consisting essentially of water and: (A) from 10 to 20~ based on the weight of the composition of a mixture of substantially linear Cl0-l8 alkyd Bunsen sulphonate and C10_20 alkyd 1-10 mole ethics sulfite; (B) at least 15% by ~3~733 weight of thy composition of total Builder partly present as suspended solid, comprising sodium tripolyphosphate, zealot, sodium carbonate, and/or sodium silicate; (C) an aqueous Separable Phase containing sufficient dissolved Electrolyte selected from sodium tripolyphosphate, sodium carbonate, sodium silicate and mixtures thereof to provide from 2 to 4.5 gym mole per lottery of sodium ion in said phase; and (D) optionally any of the Usual Minor Ingredients; the Payload of said composition being above the minimum at which the compost-lion is Non~sedimenting but below the maximum at which it is Parboil.

According to a further embodiment, our invention pro-vises, in a liquid detergent composition of the type which comprises: an aqueous phase containing a mixture of dissolved Electrolytes comprising dissolved sodium tripolyphosphate, together with sodium carbonate and/or sodium silicate, at least I based on the weight of the composition of anionic surfactants selected from sodium linear alkyd Bunsen sulfa-notes, sodium alkyd ethics sulfites and mixtures thereof, solid sodium tripolyphosphate suspended in said aqueous phase, and any of the Usual Minor Ingredients; the improvement which consists in providing sufficient of said Electrolyte to con-tribute from 2 to 4.5 gym ions ox dissolved sodium ion per lithe in said aqueous phase.

According to a further embodiment our invention provide sin a liquid detergent composition of the type which exhibits at least one aqueous phase and suspended solid Builder and comprises about 12% by weigh of sodium alkyd Bunsen sulphonate, about I by weight of a sodium C12_1s primary alcohol ethics sulfite, about 15% by weight of sodium tripolyphosphate, about 2.5~ by weight of sodium carbonate, about 0.5~ by weight of optical brightener, and effective quantities of carboxymethyl cellulose, perfume, color or substantive bluing agents and the balance water; the improvement which consists in increasing the carbonate content to at least the minimum level a which the composition is shear thickening.

fly According to d further ernbodiment,our invention provides an aqueous, fluid detergent medium, capable of suspending solid particulate Builders to form Parboil, Non-Sedimenting suspensions, and comprising water, surfactants and dissolved Electrolyte, wherein said dissolved Electrolyte is sufficient to provide from 2 to 4.5 gym ions of alkali metal per lithe in said medium and said sun-fact ants are sufficient to Norm, on the presence of said Electrolyte, a vesicular and/or lamellar surfac~ant structure capable of supporting said Builder.

According to a further embodiment our invention provides an aqueous, fluid detergent medium capable of suspending solid particulate Builders to form Parboil, Non-Sedimenting suspensions, and comprising water, sufficient dissolved Electrolyte to provide from 2 to 405 gym ions sodium per lithe of said medium and from 7 to 35~ by weight of said medium of surfactants.

Preferably the compositions of our invention contain at least 4.7%, more preferably at least 5X, e.g. at least 5.6~, by weight of sodium carbonate.

In Gore detail, our invention provides Non-Sedimenting, Parboil, fluid detergent compositions comprising Active Ingredients and Dispersed solid Builder said compositions comprising at least one predominantly aqueous liquid phase and one or more other phases separable from said predominantly Allis liquid phase by Centrifuging and containing Active Ingredient present in at least one of said one or more other phases, and a Builder, present in at least one of said one or more other phases, said one or more other phases being Interspersed with the predominantly aqueous phase, all of which compositions exhibit at least some, but not necessarily all, of the fulling characteristics: They are ~hixotropic; they are gels; they comprise a continuous, at least predominantly aqueous Separable Phase, containing dissolved Electrolyte, a Separable Phase containing a substantial proportion of the Active Ingredient as ~3~733 spheroids or vehicles Interspersed with said at least predominantly aqueous phase, and a Dispersed solid phase consisting at least predominantly of Builder; said one or more other phases are at least predominantly non-aqueous; the compositions have a high Payload of Functional Ingredients, typically greater than 20~ by weight, e.g.
25 to 75%, more usually at least 30~ preferably at least OX most preferably at least 40~ by weight; they contain a high ratio of Builder to Active Ingredient e.g. greater than 1:1 preferably 1.2:1-to 4:1; they contain more than 5 and preferably more than 8X by weight of Active Ingredients; the predominantly aqueous phase contains a concentration of less than 15~, preferably less than I
e.g. less than I typically, in the case of non ionic surfactan~ or alkyd Bunsen sulphonates, less than 0.5X by weight dissolved Active Ingredients; the proportion by weight of Active Ingredient in the predNminant7y aqueous phase to total Active Ingredient in the composition is less than 1:1.5 preferably less than 1:2 e.g. less than 1:4; the at least one predominantly aqueous liquid phase contains sufficient Electrolyte to provide a concentration of at least 0.8, typically at least 1.2, preferably 2.0 to 4.5 gram ions per lithe of total alkali metal and/or ammonium cations; the compositions contain a least 15~ by weight, preferably more than 20X by weight of Builder; the Builder is at least predominantly sodium tripolyphospha~e; the Builder comprises z minor proportion of alkali metal silicate, preferably sodium silicate; the bulk Viscosity of the composition is between 0.1 and 10 Pascal seconds, preferably between 0.5 and 5 Pascal seconds; the composition has a Yield Point preferably of at least 0.2 e.g. at least 0.5, preferably less than 20 e.g. 1 to 15 Newtons/sq.m; a phase containing Builder comprises solid particles having a maximum particle size below the limit at which the particles tend to sediment; the particles have, adsorbed on their surfaces at least one crystal growth inhibitor sufficient to maintain the solid particles below the limit at which the particles tend to sediment; the composition contains an agglomeration inhibitor sufficient to prevent flocculation or coagulation of the solid particles.

CLASSIFICATION BY CENTRIFUGING
,, _ Aqueous based liquid laundry detergents containing suspended solid builder can, in general, conveniently be classified by Centrifuging as herein before defined.

Three principal types of laundry liquid having a continuous aqueous phase and dispersed solid are distinguishable, which will be hereinafter referred to as Group I, Group II and Group III
suspensions.

The firs Group of laundry suspensions is characteristic of the prior art discussed above which relates to suspensions of solid Builder in aqueous solutions or emulsions of surfactant. On Centrifuging as defined herein, Group I compositions separate into a Solid Layer consisting essentially of Builder, and a viscous liquid layer comprising water and surfactant. Formulation factors tending to form Group 1 compositions include the use of the more water soluble surfactants, such as alkyd ether sulfites, the presence of solubilising agents such as Hydrotropes and water miscible organic solvents, relatively low levels of Electrolyte and relatively low Payloads. Group 1 compositions Connally display at least some of the following typical properties. The bulk viscosity of the composition is determined by, and is similar to, the viscosity of the aqueous liquid layer. The aqueous layer typically has a viscosity of from 0.1-1.0 Pascal seconds. Viscosities of the compositions are generally also under 1 Pascal second, e.g. 0.3 to 0.6 Pascal seconds. The compositions usually have yield points of less than 0.4~ often less than 0.1, Newton my This implies a relatively unstructured composition. This is confirmed by neutron scattering and x-ray diffraction studies and by electron microscopy Subjection to high shear rate renders Group I compositions unstable.

Group II is essentially distinguished from Group I in that at least a substantial proportion of the surfactant is present in a Separable Phase, which is distinct from the predominantly aqueous liquid phase containing the Electrolyte. This Group is ~3~33 distinguished from Group III in what at least the major portion of the separable surfactant separates on Centrifuging as a liquid or liquid crystal layer Group II compositions typically show a three layer separation on Centrifuging, giving a non-viscous liquid aqueous layer (e.g.
less than 0.1 Pascal seconds, usually less than 0.02 Pascal seconds), which contains Electrolyte but little or no surfactant, a viscous liquid layer which contains a major proportion of the Active Ingredients and a Solid Layer consisting predominantly of Builder.

Group II compositions have, typically a very low Yield Point on being first prepared but become more gel like on aging. The Viscosity of the composition is usually between 1 and 1.5 Pascal seconds. The compositions of this type show evidence of lamellar structure in X-ray and neutron diffraction experiments and by electron microscopy.

Most Centrifuged Group If compositions have the liquid or liquid crystal surfactant layer uppermost, but we do not exclude compositions in which the aqueous Electrolyte layer is uppermost or in which there are two or more Solid Layers distinguishable from each other, at least one of which may sediment upwardly, in relation to either or both liquid layers on Centrifuging.
One distinction of Group III from the other Groups is that at least a substantial proportion of the surfactant Centrifuges into a Solid Layer.

Group III compositions may Centrifuge into more than one Solid Layer. Normally both surfactant and Builder sediment downwardly on Centrifuging and the bow phases are intermixed However some Group III compositions may provide an upwardly sedimentary surfactant phase or more than one surfactant phase at least one of which may sediment upwardly. It is also possible for some or all of the Builder to sediment upwardly.

~3~733 The third Group of laundry liquids is typical of those compositions of the present invention prepared from those surfactants which are more sparingly soluble in the aqueous phase, especially anionic surfactants such as sodium alkyd Bunsen sulphonates, as well as mixtures of such sur~actants with minor proportions of non-ionic surfactant. Group III compositions typically separate on Centrifuging into bow layers. The first of which is an aqueous layer containing dissolved Electrolyte and the second is a Solid Layer comprising Builder and surfactant.

The theological properties ox Group III, typically, show the strongest evidence for structure. The Viscosity of the suspension is substantially greater than that of the aqueous layer, e.g. typically 1.2 to 2 Pascal seconds The compositions generally have a fairly high Yield Point, e.g. greater than 1 Newton my On recovery after subjection to high shear stresses Group III compositions exhibit equal or greater stability and, often, increased viscosity.

There is a gradual ?rogr~,siGn rum soup I lo G,vup III with some compositions having some properties characteristic of one group and some characteristic of another. Soap based compositions of our invention, for example, may show, ion addition to a liquid layer and a Solid Layer, a small amount of a third layer which is liquid on Centrifuging, but have theological properties characteristic of Group IT

Compositions at the borderline of Groups I and II are sometimes shear unstable but may be converted into more shear stable Group III compositions of the invention by addition of sufficient Electrolyte and/or by increasing Pay Load. Most Group I
compositions may be converted into either Group II or III if sufficient Electrolyte is added. Conversely, Group II and Group III
can generally be converted Jo Group I, by addition of Hydrotrope.

~;~3~33 CLASSIFICATION BY Diffraction AND MICROSCOPY

Compositions of our invention and of the prior art, have been examined by x-ray and neutron diffraction and by electron microscopy.

Samples for neutron diffraction studies were prepared using deuterium oxide in plate of water. Water was kept to a minimum, although some ingredients, normally added as aqueous solutions (e.g.
sodium silicate), or as hydrates, were not available in a darted phoneme .

Deuterium oxide based compositions were examined on the Harley small angle Neutron Scattering Spectrometer. Both deuterium oxide based and aqueous samples were also examined using a small angle x-ray diffractometer. Aqueous samples were freeze fracture etched, coated with gold or gold/paladium and studied under the nester Noah m w Temperature anemone Electron Mi~r~r~p~.
Competitive commercial compositions which are not, of course, available in a deuterated form, could not be examined by neutron scattering.

As in the case of Centrifuging, the three techniques described above all provide an indication of three broad categories of liquid detergent suspension, which appear to correspond generally to the Group I, Group II and Group III compositions, described under "Classification by Centrifuging".

The first category of composition which included, generally those compositions belonging typically to Group I, was characterized under both neutron and x-ray analysis by high levels of small angle scattering and an absence of discrete peaks, corresponding to regular repeating, st~ctural features. Some compositions showed broad indistinct shoulders or humps, others a smooth con~inwum.

Small angle scattering is scattering very close to the fine of the incident beam and is usually dominated by scattering from dilute dispersions of in homogeneities in the composition. The shoulders ~L~3~33 or humps observed with some Group I compositions additionally show a form and angular displacement typical of concentrated muzzler solutions of surfactant (Lo phase).

Under the electron microscope typicd1 Group 1 compositions gave d largely featureless granular texture with crystals of Builder distributed apparently at random. These results were consistent with the hypothesis based on their theological properties that typical Group I compositions are relatively unstructured and lacking delectable Lamar features. However some members of Group I
showed evidence under the electron microscope of spherical structures of approximately 5 microns diameter.

A different type of pattern Weds obtained from typical Group II
met ho ho I ivy low vowels of ~rdl~
scattering near the incident beam, a peak typical of concentrated muzzler solution (Lo phase) and a sharply defined peak or peaks corresponding to a well defined lamellar structure. The positions of the latter peaks were in d simple numerical ratio, with first, second and, sometimes, third order peaks usually distinguishable.
The peaks were evidence of relatively broadly spaced lamely ~36-60 Angstrom). Under the electron microscope lamellar structures were visible.

Some Group III compositions gave relatively narrow and intense small angle scattering, together with distinct peaks indicative of a lamellar structure. The peaks were broader than in the case of typical Group II compositions, and second and third order peaks were not always separately distinguishable. In general the displacement of the peaks indicated a lamellar structure with the lamely more closely spaced than in the case of typical Group II compositions (erg. 26-36 Angstrom). Lamellar structures were clearly visible under the electron microscope. In other instances spheroidal structures could be observed.

PROPOSED STRUCTURE

We believe that the foregoing properties can most readily be explained by the hypothesis what our invention embodies a structure . . .

~;~3~33 of matter in which solid builder is suspended in a structured arrangement of solid surfactant hydrate, and/or of "G" phase surfactant in association with an Lo phase muzzler solution and/or of vehicles.

Certain embodiments of our invention are believed to comprise parboil gel systems in which there may be two or more Co-continuous or Interspersed phases. The properties of such compositions can be explained on the basis that they are thixo~ropic gels comprising a relatively weak three dimensional network of solid surfactant hydrate Interspersed with a relatively non viscous aqueous phase which contains dissolved Electrolyte, buy little or no surfactant. The network prevents sedimentation of the network-forming solids, and any suspended discrete particles. The nub forming solids may be present as platelets, sheets of indefinite extent, or fires or alternatively as asymmetric particles joined into or interacting to provide, a random mesh, which is Interspersed with the liquid The structure is sufficiently stable to inhibit or prevent precipitation on storage and will also limit the extent of spreading of the gel on a horizontal surface, however the structure is weak enough to permit the compositions to be poured or pumped. The solid structure is composed at least predominantly of surfactant hydrate e.g. sodium alkyd Bunsen sulphonate or alkyd sulfite. Thus no other stabilizing agent is required over that required in the end-use of the composition. Such gels may, in particular, exhibit a clay-like structure, sometimes referred to as a "house of cards" structure, with a matrix of plate shaped crystals orientated at random and enclosing substantial interstices, which accommodate the particles of builder. The solid surfactant may, in sore instances be associated with, or at least partially replaced by "G" phase surfactant.

Alternatively, the Builder is suspended in a system which may comprise spheroids or vehicles which may have an onion like structure, or outer shell, formed from successive layers of surfactant and which may contain at least one of the predominantly aqueous phases, e.g. an Electrolyte solution, or an "Lo" cellar ~3'~733 - 24 _ solution. At least one of the predominantly aqueous phases is the continuous phase. Evidence for the presence of vehicles is provided by microscopy in the case of the compositions containing olefin and paraffin sulphonates.

SURFACTANTS

The compositions of our invention preferably contain at least I by weight of surfactants. Preferably the surfac~ant constitutes from 7 to 35X by weight of the ccmposition9 e.g. 10 to I by weight.

The surfactant may for example consist substantially of an at least sparingly water-soluble, salt of sulphonic or moo esterified sulfuric acids e.g. an alkylbenzene sulphonate, alkyd sulfite, alkyd ether sulfite, olefin sulphonate, Al Kane sulphonate, alkylphenol sulfite, alkylphenol ether sulfite, alkylethanolamide sulfite, alkylethanolamide ether sulfite, or alpha sulfa fatty acid or its esters each having at least one alkyd or alkenyl group with from 8 to 22, more usually 10 to 20, alpha tic carbon atoms.
Said alkyd or alkenyl groups are preferably straight chain primary groups but may optionally be secorldary, or branched chain groups.
The expression "ether" hereinbeFore refers Jo polyoxyethylene, polyoxypropylene, glycerol and mixed polyoxyethylene-oxy propylene or mixed glossily oxYethylene or glyceryl-oxy propylene groups, typically containing from 1 to 20 oxyalkylene groups. For example, the sulphonated or sulfated surfactant may be sodium dodecyl Bunsen sulphonate9 potassium hexadecyl Bunsen sulphonate, sodium dodecyl dim ethyl Bunsen cellophane, sodium laurel sulfite, sodium tallow sulfite, potassium oilily sulfite, ammonium laurel monoethoxy sulfite, or monoethanolamine Seattle 10 mole ethoxylate sulfite Other anionic surfactants useful according to the present invention include fatty alkyd sulphosuccinates, fatty alkyd ether sulphosuccinates, fatty alkyd sulphosuccinamdtes, fatty alkyd ether sulphosuccinamates, azalea sarcosinates~ Allah towards, isethisnates, Soaps such as struts, palpitates, resonates, owlets, linoleates, and alkyd ether carboxylates. Anionic phosphate esters nay also be used. In each case the anionic surfactant typically 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 glycerol and/or from 1 to 20 ethyleneoxy and or propyleneoxy groups.

Certain anionic surfactants, such as olefin sulphonates and paraffin sulphondtes are commercially available only in a form which contains some disulphonates formed as by-products of the normal methods of industrial manufacture. The latter tend to syllables the surfactant in the manner of a Hydrotope. However the olefin and paraffin sulphona~es readily form stable compositions which, on Centrifuging, contain a minor portion of the total surfactant in the aqueous phase, and which show evidence of spheroidal structures.
These compositions are valuable, novel laundry detergents and which accordingly constitute a particular aspect of the present invention.

Preferred anionic surfactants art sodium salts. Other salts of commercial interest include those of potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine and alkyd amine containing up to seven aliphatic carbon atoms.

The surfactant may optionally contain or consist of non ionic surfactants. The non ionic surfac~ant may be e.g. a C10-22 alkanolamide of a moo or dip lower alkanolamine, such as coconut monoethanolamide. Other non ionic surfactants which may optionally be present, include ethoxylated alcohols, ethoxylated carboxylic so hD~yla$~d muons ~hDxyld~ed ~lkylol~mid~s, exulted alkylphenols9 ethoxylated glycerol esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and the propoxylated or ethoxylated and propoxylated analogies of 211 the aforesaid ethoxylated nonionics, all having a C~_2z alkyd or alkenyl group and up to 20 ethyleneoxy and/or propyleneoxy groups, or any other 3~7~3~
_ I _ non ionic surfactant which has hitherto been incorporated in powder or liquid detergent compositions e.g. amine oxides. The latter typically have at least one Cg_22, preferably C10_20 alkyd or alkenyl group and up to two lower (e.g. Clue, preferably Of 2) alkyd groups.

The preferred nonionics for our invention are for example those having an HUB range of 7~18 e.g. 12-15.

Certain of our detergents may contain cat ionic surfactants, and especially cat ionic fabric softeners usually as a minor proportion of the total active material. Cat ionic fabric softeners of value in the invention include qua ternary amine having two long go C12_22 typically C16 O) alkyd or alkeQyl groups and either two short chain (e.g. Of I atkyl groups, or one short chain and one bouncily group. They also include imidazoline and quaternised imidazolines having two 10ng chain alkyd or alkenyl groups, and amino amine and quaternised amino amine hazing two long chain alkyd or alkenyl groups. The quaternised softeners are all usually salts of anions which impart a measure of water volubility such as format, acetate, lactate, tart rate chloride, nethosulphate, ethosulphate, sulfite or nitrate. Compositions of our invention having fabric softener character may contain smectite clays.

Compositions of our invention may also contain amphoteric surfactant, which may be included typically in surfactants having cat ionic fabric softener, but may also be included, usually as a minor component of the Active Ingredients, in any of the other detergent types discussed above.

Amphoteric surfactants include buttons, sulphobetaines and phosphobetains formed by reacting a suitable tertiary nitrogen compound having a long chain alkyd or alkenyl group with the appropriate reagent such as chloroacetic acid or propane sultan.
Examples of suitable tertiary nitrogen containing compounds include:

_ I _ tertiary amine having one or two long chain alkyd or alkenyl groups, and optionally d bouncily group, any other substituent being a short chain alkyd group; imidazolines having one or bow long chain alkyd or alkenyl groups and amidoamines having one or two long chain alkyd or a1kenyl groups Those skilled in the detergent art will appreciate that the specific surfactant types described above are only exemplary of the commoner surfactan~s suitable for use according to the invention.
Any surfactant capable of performing a useful function in the wash liquor may be included. A fuller description of the principal types of surfactant which are commercially available is given in "Surface Active Agents and Detergents" by Schwartz Perry and Bench.

BUILDERS

The Builder, in preferred compositions of our invention is believed to be normally present, at least partially, as discrete solid crystallizes suspended in the composition. The cryostats typically have a size of up to 60 en 5 to 50 microns.

We have found that Formulations containing sodium tripolyphosphate as Builder, or at least a major proportion of sodium tripolyphosphate in admixture with other Builders, exhibit stability and mobility over a wider range of Dry Weight than corresponding Formulations with other Builders. Such Formulations are therefore preferred. Our invention, however, also provides compositions comprising other Builders such as potassium tripolyphosphate, carbonates, zealots, neutral rheostats, citrates, metaphosphates, pyrophosphates, phosphonates, ETA and/or polycarbDxylates~ ~p~iDnally but ~r~ferably~ in admixture with tripo1yphosphate. Orthophosphates may be present, preferably as minor components in admixture with tripolyphosphate, as may alkali metal silicates.

to The last mentioned are particularly preferred and constitute a feature of our preferred embodiments since they perform several valuable functions. They provide the free alkalinity desirable to saponify fats in the soil, they inhibit corrosion of aluminum surfaces in washing machines and they have an effect as Builders. In addition, they are effective as ~leotrolytes to "salt out" Active Ingredients from the predominantly aqueous liquid phase thereby reducing the proportion of Active Ingredient in solution and improve no the stability and fluidity of the compost n on.
Accordingly, we prefer that compositions of our invention should contain at least I and up to 12.3~ by weight of the composition preferably at least 2Z and up to 10X, most preferably morn than 3 and up to 6.5X e.g. 3.5 to So of alkali metal silicate, preferably s~d~u~ silicate measured do Sue based on the total weight of composition.

Typically, the silicate used to prepare the above compositions has an Noah: Sue ratio of from I to lo or 1:1.5 to 1:1.8. It will however be appreciated that any ratio of Noah (or other base) to Sue, or even silicic acid could be used to provide the silicate in the composition, and any necessary additional alkalinity provided by addition of another bass such as sodium carbonate or hydroxide.
Formulations not intended for use in washing machines do not require silicates provided that there is an alternative source of alkalinity.

The Builder normally constitutes at least 15Z by weight of the compositions, preferably at least 20~. We prefer that the ratio of Builder to surfactant is greater Han Al preferably 1.2:1 to 5:1.

ELEC~ROLYTr The concentration of dissolved organic material and more particularly of Active Ingredients in the predominantly aqueous, liquid phase is preferably maintained at a low level. This may be achieved by selecting, so far as possible, surfactants which are . 1~3'~'733 sparinSl~ soluble in the predominantly aqueous phase, and keeping to c minimum the amount of any more soluble surfactant which it desired for the particular end use. For a given surfactant system and Payload, we have found that it is generally possible to stabilize the system in accordance with an embodiment of our invention by including in the at lest one predominantly aqueous phase 2 sufficient quantity ox Electrolyte.

An effect of the Electrolyte is to limit the volubility of Active Ingredient in the at least one predominantly aqueous phase, thereby increasing the proportion of surfactant available to provide a solid, liquid crystal, or vesicular matrix which stabilizes the compositions of our invention.

Preferably, the proportion of Electrolyte dissolved in the a least one predominantly aqueous phase is sufficient to provide a concentration of 2.0 to 4.5 tram moles per lithe of alkali metal alkaline earth metal and/or ammonium cations. The stability ox the system ma be further improved by ensuring so far as possible that tune anions required in the composition are provided by salts which have a common cation, preferably sodium Thus, for example. thy preferred Builder is sodium tripolyphosphate the preferred anionic su-factants are sodium salts of sulphaSed or sulphonated anionic surfac~ants and any ~nti-redeposition agent, e.g. carboxymethyl cellulose. or alkali, e.g. silicate or carbonate are also preferably present as the sodium salts Sodium Sherwood, or other solely inorganic sodium salts may be added to increase the Electrolyte concentration and minimize the concentration of Active Insredientc in tune predominantly aqueous liquid phase The preferred electrolytes, however! are sodium carbonate and sodium silicate ~3~733 Alkaline earth metals are only normally present when the Active Ingredients comprise surfactants, such as olefin sulphonates or non-ionics which are tolerant of their presence. Sodium sulfite in concentrations greater than about 3% tends to give unacceptable crystallization when the composition is stored.
It is possible, alternatively, but less preferably to choose salts of potassium, ammonium, lower amine, alkanolamines or even mixed cations.
STABILIZING SUSPENDED SOLID
The particle size of any solid phase should be less than that which would give rise to sedimentation. The critical maximum limit to particle size will vary according to the density of the particles and the density of the continuous phase and the Yield Point of the composition.
Compositions of our invention preferably contain a particle growth inhibitor. The particle growth inhibitor is believed to function by adsorption onto the faces of suspended crystallizes of sparingly soluble solids preventing deposition of further solid thereon from the saturated solution in the predominantly aqueous liquid phase. Typical particle growth inhibitors include sulphonated aromatic compounds. Thus for example, a sodium alkyd Bunsen sulphonate such as sodium dodecyl Bunsen sulphonate when present as a surfactant is itself a particle growth inhibitor and may be sufficient to maintain particles of, for example, Builder in the desired size range without additional stabilizers.
Similarly, lower alkyd Bunsen sulphonate salts such as sodium zillion sulphonate or sodium Tulane sulphonate have stabilizing activity, as well as being conventionally added to liquid detergents as Hydrotropes. In our invention, however, the presence of the lower alkyd Bunsen sulphonates is less preferred.
Sulphonated naphthalenes especially methyl naphthalene sulphonates are effective crystal growth inhibitors.
They are not, however, normal ingredients of detergent compositions and therefore on cost grounds they are not preferred. Other particle growth inhibitors include f 7~3 water soluble polysaccharide derivatives such as sodium carboxymethyl cellulose, which is frequently included in detergent compositions as a soil anti-redeposition agent. We, therefore prefer that it should be present in minor amounts in compositions according to our invention, sufficient to perform its normal functions in detergent compositions and to assist in stabilizing the suspension, but preferably not sufficient to increase so substantially the viscosity of the predominantly aqueous liquid phase as to impair the pour ability of the composition.
Another group of particle growth inhibitors which may optionally be included in compositions according to our invention are the sulphonated aromatic dyes, especially the sulphonated aromatic optical brightening agents, which are sometimes included in powder Formulations.
Typical examples include Boyce (phenol-triazol-2-yl-2,2'-stilbene disulphonate salts and 4,4'-diphenylvinylene-2,2'-biphenyl disulphonate salts.
Such particle growth inhibitors may be included instead of, or more usually in addition to, for example, a sulphonated sur~actant.
Other effective particle growth inhibitors include lignosulphonates and C6_18 alone sulphonate surfactants, which latter compounds may also be present as part of the surfactant content of the composition.
The presence of an agglomeration inhibitor is also preferred. The agglomeration inhibitor for use according to our invention may also conveniently be sodium carboxymethyl cellulose. It is preferred that the composition should include an effective agglomeration inhibitor which is chemically distinct from the 3~33 - 32 _ particle growth inhibitor, despite the fact that, for example, sodium carboxymethyl cellulose, is capable of performing either function. It is sometimes preferred when preparing the detergent composition to add the crystal growth inhibitor to the composition prior to the agglomeration inhibitor, and to add the agglomeration inhibitor subsequent to the solid phase, so that the crystal growth inhibitor is first adsorbed onto the solid particles to inhibit growth thereof and the agglomeration inhibitor is subsequently introduced to inhibit agglomeration of the coated particles.

Other agglomeration inhibitors which may less preferably be used include polyacrylates and other polycarboxylates, polyvinyl pyrrolidone, car boxy methyl starch and lignosulphonates.

The concentration of the crystal growth inhibitor and agglomeration inhibitor can be widely varied according to the proportion of solid particles and the nature of the dispersed solid as well as the nature of the compound used as the inhibitor and whether that compound is fulfilling an additional function in the composition. For example, the preferred proportions of alkyd Bunsen sulphonate are as set out herein before in considering the proportion of surfactant. one preferred proportions of sodium car boxy methyl cellulose are up to 2.5b by weight of the composition preferably 0.5 to I by weight e.g. 1 to I although substantially higher proportions up to 3 or even I are not excluded provided they are consistent in the particular Formulation with a parboil composition. The sulphonated optical brighteners may typically be present in proportions of 0.05 to I by wow e.g. 0.1 to 0.3~
although higher proportions e.g. up to I may less preferably be present in suitable compositions.

~23~733 ALKALINITY
The compositions of our invention are preferably alkaline, being desirably buffered with an alkaline buffer adapted to provide a pi above 8 erg above 9 most preferably above 10 in a wash liquor containing the composition diluted to 0.5% Dry Weight. They preferably have sufficient free alkalinity to require from 0.4 to 12 mls. preferably 3 to 10 mls of N/10 Hal to reduce the pi of 100 mls. of a dilute solution of the composition, containing 0.5% Dry Weight, to 9, although compositions having higher alkalinity may also be commercially acceptable. In general lower alkalinities are less acceptable in commercial practice, although not excluded from the scope of our invention.
The alkaline buffer is preferably sodium tripolyphosphate and the alkalinity preferably provided at least in part by sodium carbonate or sodium silicate.
SOLUBILISERS
Hitherto, liquid detergent compositions have commonly contained substantial concentrations of Hydrotropes and/or organic water miscible hydroxylic solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol.
Such additives are often necessary to stabilize Group I
compositions. However, in Group II and III compositions of the present invention, they may have a destabilizing effect which often requires the addition of extra amounts of Electrolyte to maintain stability. They are, moreover, costly and not Functional Ingredients. They may, however, in certain circumstances, promote Pour ability. We do not therefore totally exclude them from all compositions of our invention, but we prefer that their presence be limited to the minimum required to ensure adequate Pour ability. If not so required we prefer that they be absent.

~;~3~3~
- 34 _ PAYLOAD

Selection of the appropriate Payload is generally important to obtain desired stability and Pourab;lity. Optimum Payload may vary considerably from one type of Formulation to another. Generally speaking it has not been found possible to guarantee Non-sedimenting compositions below about 35~ by weight Payload, although some types of Formulation can be obtained in a Non-sedimenting form below 30~
Payload and sometimes as low as 25~ Payload. In particular we have obtained Soap based Formulations at concentrations below US Pay Load erg 24~. WE do not exclude the possibility of making such Formulations at Payloads down to 20~.

Prior art references to stable compositions at low Payloads have either been limited to particular Formulations using special stabilizers, or have not provided sufficiently stable suspensions to satisfy normal commercial criteria.

For a given Formulation according to our invention a range of Pods can be identified within which the composition is both stable and Parboil. Generally below this range, sedimentation occurs and above the range the Formulation is too viscous. The acceptable range may be routinely determined for any given Formulation by preparing the suspension using the minimum water required to maintain a storable composition, dilutions a number of samples to progressively higher dilutions> and observing the samples for signs of sedimentation over a suitable period. For some Formulations the acceptable range of Payloads may extend from 30~, or 35~ to 60, or 70~, or even YO-YO by weight for others it may be much narrower, e.g. 40 to 45~ by weight.

If no stable Parboil range can be determined by the above methods, the Formulation should be modified according to the teaching herein ens. by the addition of more sodium silicate solution or other Electrolyte.

~3'~733 Typically Group IT Formulations show an increase in field Point with increasing Payload. The minimum stable Payload for such typical Group IT Formulations usually corresponds to a Yield Point of about 1-1.2 Newtons/m2.

PREPARATION

Compositions of our invention can, in many instances be readily prepared by normal stirring together of the ingredients.
However, some Formulations according to the invention are not fully stable unless the composition is subjected to more prolonged or vigorous mixing. In some extreme cases the solid content of product may require comminution in the presence of the liquid phase. The use of a killed mill for the latter is not excluded, but is not generally necessary. In some instances mixing under high shear rate provides products of high viscosity.

The order and conditions of mixing the ingredients are often important in preparing a stable structured mixture according to our invention. Thus a system comprising: water, sodium dodecylbenzene sulphonate, coconut monoethanolamide, sodium tripolyphosphate, sodium silicate, sodium carboxymethyl cellulose and optical brightener at I Dry Weight was unstable when the compounds were mixed in the order described above, but when mixed with the coconut monoethanolamide and sodium tripolyphospha~e added as the last of the Functional Ingredients, a stable composition was formed.

A method of preparation that we have found generally suitable for preparing stable mixtures from those Formulations which are capable of providing them is to mix the Active Ingredients or their hydrates, in a concentrated phoneme with concentrated (e.g. 30 to 60~, preferably 4~-50~ aqueous silicate solution, or alternatively, a concentrated solution of any other non-surfactan~ Electrolyte required in the Formulation. Other ingredients are then added including any anti-redeposition agents, optical brightening agents and foaming agents. The Builder when not required Jo provide the .

~;~3~733 initial Electrolyte solution, may be added last. During mixing, just sufficient water is added at each addition to maintain the composition fluid and homogeneous. When all the Functional Ingredients are present, the mixture is diluted to provide the required Pay Load. Typically, mixing is carried out at ambient temperature where consistent with adequate dispersion. Certain ingredients, e.g. non-ionic surfactants such as coconut monoethanolamide require gentle warming e.g. 40 for adequate dispersion. This degree of warming may generally be achieved by the heat of hydration of sodium tripolyphosphate. To ensure sufficient warming we prefer to add the tripolyphosphate in the an hydrous form containing a sufficiently high proportion of the high temperature rise modification commonly called "Phase I".
The foregoing procedure is only one of several methods that may be satisfactorily used for all or most of the compositions of our invention. Some Formulations are more sensitive to the order and temperature of mixing than others.
FORMULATION TYPES
Typically, our Formulations may most conveniently be an anionic type (Type "A") in which the Active Ingredient preferably consists at least predominantly of sulfated or sulphonated anionic surfactant, optionally with a minor proportion of other surfactants such as non ionic surfactan~.
Considering type "A" Formulations according to our invention in more detail, we particularly distinguish high foaming sulfite or sulphonate Formulations and low foaming Formulations.
High foaming Formulations may typically be based on sodium Clue straight or branched chain alkyd Bunsen sulphonate, alone or in admixture with a Clo_l8 alkyd sulfite and/or C10_20 alkyd l-10 mole ether sulfite.
Small amounts (ego up to 1% of the weight of the compositions) of Soap may be present to aid rinsing of the fabric. Non ionic foam boosters and stabilizers, such as C12-18 azalea (e-g- coconut) monoethanolamide or diethanolamide or their ~23'~733 ethoxylates, ethoxylated alkyd phenol, fatty alcohols or their ethoxylates may optionally be present as foam boosters or stabilizers, usually in proportions up to about I of the Dry Weight of the composition.

The sodium alkyd Bunsen sulphonate may be totally or partially replaced, in the above Formulations by other sulphonated surfactants including fatty alkyd zillion or Tulane sulphonates, or by erg. alkyd ether sulfites (preferably) or alkyd sulfites, paraffin sulphonates and olefin su1phonates, sulphocarboxylates, and their esters and asides, including sulphosuccinates and sulphosuccinamates, alkyd phenol ether sulfites, fatty azalea monoethanolamide ether sulfites or mixtures thereof.

Preferably the sulfated or sulphonated anionic surfac~ant consists substantially of alkyd Bunsen sulphonate preferably sodium alkyd Bunsen sulphonate, e.g. Coo 14 alkyd Bunsen sulphonate.
The proportion of alkyd Bunsen sulphonate in the absence of foam boosters it preferably From 20 to 60X e.g. 30 to 55~ of the Dry Weight of the composition.

Alternatively, the anionic surfactant may comprise a mixture of alkyd Bunsen sulphonate, and alkyd sulfite and/or alkyd ether sulfite and/or alkyd phenol ether sulfite in weight proportions of e.g. from 1:5 to 5:1 typically 1:2 to 2:1 preferably 1:1.5 to 1.5:1 e.g. 1:1. In the latter case the total anionic surfactant is preferably from 15 to 50% e.g. 20 Jo 40~ of the Dry Weight of the compositions, in the absence of foam booster.

7~3 The alkyd sulfite, and/or alkyd ether sulfite for use in admixture with the alkyd Bunsen sulphonate typically has an average of from 0 Jo 5 ethyleneoxy groups per sulfite group e.g. 1 to 2 groups .

According to a preferred specific embodiment our invention provides a Parboil, Non-sediment;ng, fluid detergent composition consisting essentially of water and: (A from 10 to 20~ based on the weigh of the composition of Active Ingredients comprising a substantially linear sodium alkyd Bunsen sulphonate having from 10 id 20 a1iphatic carbon atoms and optionally an alkyd ethics sulfite having an alkyd group with from 10 to 20 carbon atoms, and/or a minor proportion of a non-ionic surfactant and/or of a soap; (B) a least 15~ of Builder partly present as solid and selected from condensed phosphates, zealots, citrates, ni~rilotriacetates, ethylenediamine tetracetates, orthophosphates and silicates, wherein at least 50X by weight of said builder is sodium tripolyphosphate and said Builder further comprises at least sufficient sodium carbonate to provide a shear stable composition; and (C) optionally minor proportions of ingredients selected from carboxymethylcellulose, optical brightening agent, enzymes, bleaches, anti foams, smectite clays, fragrances, cat ionic fabric softeners, yes and sodium chloride.

According Jo a second preferred specific embodiment our invention provides a Parboil Non-Sedimenting, fluid, liquid detergent composition consisting essentially of water and from 10 to 20X based on the weight of the composition of a mixture of a substantially linear Clue alkyd Bunsen sulphonate and C10_20 alkyd 1-10 mole ethics sulfite; (B) at least 15~ by weight of the composition of total builder partly present as suspended solid, selected from sodium tripolyphosphate, elite, sodium carbonate, sodium silicate and mixtures whereof; [C3 an aqueous Separable Phase containing sufficient dissolved Electrolyte ~3~733 selected from sodium tripolyphosphate, sodium carbonate, sodium silicate and mixtures thereof to provide from 2 to 4.5 gym ions per lithe sodium in said phase; and (D) optionally any of the Usual Minor Ingredients; the Payload of said composition being above the minimum at which the composition it Non-sedimenting but below the maximum at which it is Parboil.
In an alternative Formulation the anionic surfactant consists substantially of alkyd sulfite and/or, alkyd ether sulfite. The total concentration of active Ingredients in the absence of foam booster is preferably from 15 to 50% of the Dry Weight of the composition. Typically the Active Ingredients comprise an average of from 0 to 5 e.g. 0.5 to 3 ethyleneoxy groups per molecule of sulfated surfactant. Ike fatty alkyd chain length is preferably from 10 to 20C, higher chain lengths being preferred with higher ethylene-oxy content.
Roy foregoing types may be varied by substituting for all or part of the anionic active content, any of the sulfated or sulphonated anionic surfactant classes herein before specified.
Soap may be added to any of the foregoing detergent Formulations as an aid to rinsing the fabric. Soap is preferably present for this purpose in concentrations of from 0 to 6% preferably 0.1 to 4% e.g. 0.5 to 2% by Dry Weight of the composition. The amount of Soap is preferably less than 25% of the total sulfated and sulphonated surfactant, to avoid foam suppression;
typically less than 10%.
Foam boosters and/or stabilizers may be incorporated in any of the foregoing types of high foam anionic detergent. The foam boosters or stabilizers are typically Clue alkyd non ionic or surfactants such as coconut monoethanolamide or diethanolamide or their ethoxylates, alkyd phenol ethoxylates, fatty alcohols or their ethoxylatPs or fatty acid ethoxylates. The foam booster and/or stabilizer is added typically in proportions up to 20% of the Dry I I

Weight of the composition e.g. 0.1 to I preferably 0.5 to 4X. The presence of form booster and/or stabilizer may permit a reduction of total concentration of Active Ingredients in d high foam product.
Typically, compositions comprising alkyd Bunsen sulphonate wit a foam booster and/or stabilizer will contain from 15 to 40X so alkyd Bunsen sulphatP based on the weight of the composition preferably 20 to 36X e.g. 25X with from 2 to I e.g. 4X of non ionic surfactant, the lower proportions of anionic surfactant being preferred with higher proportions of non ionic surfactant and vice versa. The other sulfated or sulphonated anionic surfa.~ant Formulations discussed above may be similarly reduced in active concentration by inclusion of foam boosters and/or stabilizers.

The Builder is preferably sodium tripolyphosphate, optionally but preferably with a minor proportion of soluble silicate although the alternative Builders herein before described may be employed instead as ma mixed Builders. The proportion of Builder in type "A" Formulations is usually at least 30% of the Dry Weight of the composition, preferably from 35X to 85X e.g. 40 to 80Z. Builder proportions in the range 50 to 70X of Dry Weight are particularly preferred. The Builder to Active Ingredients ratio should desirably be greater than 1:1 preferably from 1.2:1 to 4:1 e.g. from 1.5:1 to 3:1.

Low foaming Formulations are generally dependent upon the presence of lower proportions of sulfated or sulphonated anionic surfactant than in the high foam types together with higher, but still minor, proportions of Soap, and/or the addition of non-ionic, silicone, or phosphate ester foam depressants.

Our invention therefore provides. according to a further specific embodiment, a Non-sedimen~ing Parboil fluid, aqueous based detergent composition, comprising an at least predominantly aqueous phase containing Electrolyte in solution and suspended particles of Builder, said composition comprising iron 15 Jo 50~ based on Dry Weight of Active Ingredient , a least 30X of Builder based on wry Weigh, a ratio of Builder to Active Ingredient greater than 1:1, 7~3~

and optionally the Usual Minor Ingredients, wherein the surfactant comprises from 15 to 50X based on the Dry weight of the composition of sulfated and/or sulphonated anionic surfactant and an effective amount of at least one foam depressant Preferably, the foam depressant is selected from Soap, in a proportion ox from 20 to 60~ based on the weight of sulfated or sulphonated anionic surfactant, C16 I ~lkyl non ionic foam depressant in a proportion of up to 10~ of the Dry Weight of the composition, C16 20 alkyd phosphate ester in a proportion of up to 1nX ox the Dry Weight of the composition and silicone anti foams.
.

The function of Soap as a foam depressant is dependent on the proportion of Soap to sulfated or sulphonated anionic surfactant.
Proportions of 10~ or less are not effective as foam depressants but are useful as rinse aids in high foaming detergent compositions.
Foam depressant action requires a minimum proportion of about 20X of soap based on the sulfated and/or sulphonated surfactant. If the proportion of soap to sulphated/sulphonated surfactant in a type AYE'`
detergent is above about 60~ by weight, the foam depressant action us reduced. Preferably, the proportion of Soap is iron 25 to 50 eye. 30 to 45X of the weight of sulphated/sulphonat~d surfactant.

law foaming deterrents may contain, in addition to, or instead of soap, a non ionic foam depressant. This may, for example, be a C16 22 azalea monoethanolamide e.g. rape monoethanolamide, a C16 22 alkyd phenol ethoxylate, C16 22 alcohol ethoxylate or C16 22 fatty acid ethoxylate. Alternatively, or additionally, the composition may contain an alkali metal moo and/or do C16 alkyd phosphate ester. The non ionic or phosphate ester foam depressant is typically present in the ~onmu~ation in a proportion of up to 10%, preferably 2 to I e.g. 3 to 4X based on Dry Weight.

Silicone anti foams may also be used, as or as part of, the foam depressant. The effective concentration of these last in the Formulation is generally substantially lower than in the case of the other foam depressants discussed above. Typically, it is less than ., ~3~733 I preferably less than 0.1~, usually 0.01 to 0.05~ e.g. 0.02~ of the Dry Weight of the Formulation.

Our Formulations preferably contain the Usual Minor Ingredients. Certain fabric softeners, such as clays, may be included, however cat ionic fabric softeners are not nonmotile effective in anionic based Formula ail owns, but may sometimes be included in specially formulated systems.

The type "B" Fonmu1ations of our invention comprise Soap as the principal active component They may additionally contain minor amounts of non ionic or other anionic surfactants.

The typical percentage Dry Weight of type "B" Formulations may be rather lower than type "A", e.g. I to 60~, preferably 29 to 45~.
The total proportion of Active Ingredients is usually between 10 and I preferably lo to 40X e.g. 20 to 30X of the Dry Weight of the composition. Builder proportions are typically 20 to 80~ of Dry Weight. In general the mobility of type "B" Formulations can be improved by including sufficient water soluble inorganic Electrolyte, especially sodium silicate, in the Formulation.

High foam Soap Formulations may typically contain Active Ingredient consisting substantially of Soap, optionally with a minor proportion of a non ionic foam booster and/or stabilizer as described in relation to type "A" Formulations, Andre with sulfated anionic booster such as alkyd ether sulfite or alkyd ether su1phosuccinate.

Low foam type B Formulations may contain a lower concentration of Soap together with minor proportions of sulfated and or su~phon~tea anionic sur~actan~, nonlonlc or phosphate ester foam depressants and/or silicone anti foams.

The relationship between sulfated and/or sulphonated anionic surfactants and Soap in a type "B" low foam Formulation is the converse of what in a type "A" low foam Formulation. In a type "B"
Formulation, the sulfated and/or sulphonated anionic surfactan~

3 :~23~7~3 acts do foam suppressant when preset in a proportion of from about 20 to about 60~ of the weight of the Soap.

The non ionic, phosphate ester and silicone foam depressants are, conveniently, substantially as described in relation to type "I" detergents.

"Type "B" detergents may contain any of the Usual Minor Ingredients. As in the case of type "A" Formulations, kink fabric softeners are not normally included but other fabric softeners may be present.

Non-ionic based detergents (type I represent a further aspect of the present invention There has been a trend toward the use of non-ionic surfactants in laundry detergents because of the increasing proportion of man-made fire in the average wash. Non-tonics are particularly suitable for cleaning man-made fires.
However, no commercially acceptable, fully built, non-ionic liquid detergent has yet been marketed.

Even in the detergent powder field, the choice and level of non-ionic surfactant has been restricted. Many of the detergent Formulations of our invention herein before described have been designed to give stable, Parboil, fluid detergent compositions having a washing performance equivalent to existing types of powder Formulation, or to compositions which could readily be formulated as powders. However, it has not hitherto been possible to formulate certain types of potentially desirable non ionic based detergents satisfactorily, even as powders. This is because "solid"
compositions containing sufficiently high proportions of the desired non ionic surfactani often form sticky powers which do not flow freely and may give rise to packaging and storage problems. Such surfactants have therefore had to be restricted to below optimum proportions of detergent powders, or Jo low Pay Load, dilute, or light duty, liquid compositions.

1 2~3 ~733 Any of the non ionic surfactants herein before described or any mixture thereof may be used according to this embodiment of the invention. Preferably, the surfactant comprises a C12_18 alkyd group, usually straight chain, although branched chain and/or unsaturated hydrocarbon groups are not excluded.
Preferably, the non ionic surfactants present have an average HUB of 12 to 15.
The preferred non ionic surfactant in Type C
Formulations is fatty alcohol ethoxylate.
For high foam type "C" Formulations, we prefer Cl2_l8 alkyd nonionics having 8 to 20 ethylenoxy groups, alkyd phenol ethoxylate having 6-12 aliphatic carbon atoms and 8 to 20 ethyleneoxy groups together optionally with a minor proportion e.g. 0 to 20% of the Dry Weight of the composition of anionic surfactant preferably sulfated and/or sulphonated anionic e.g. alkyd Bunsen sulphonate, alkyd sulfite, alkyd ether sulfite, paraffin sulphonate, olefin sulphonate or any of the other sulfated or sulphonated surfactants described above, but not including substantial amounts of any foam depressant. The Formulation may however include a non ionic foam booster and/or sta~iliser such as Clue azalea monoethanolamide typically in proportions as described above in relation to type "A" Formulations.
Preferably the non-ionic Active Ingredients together have an HUB of 12-15.
Low foam non ionic compositions according to our invention are especially preferred. They preferably comprise 10 to 40% based on Dry Weight of the composition of C12 18 alkyd 5 to 20 mole ethyleneoxy, non ionic surfactants such as fatty alcohol ethoxylates, fatty acid ethoxylates or alkyd phenol ethoxylates, having a preferred HUB of 12 to 15. They optionally contain a minor proportion, e.g. up to 10~ by wright of the composition of any of the anionic sulfated and/or sulphonated surfactants herein before ~3'~73;3 .., described in relation to type "A" detergents, and they contain a foam depressant such as a moo, dip or trialkyl phosphate ester or silicone foam depressant, as discussed herein before in the context of low foaming type "A" detergents.

Type "C" Formulations may contain any of the Usual Minor Ingredients.

In particular, non ionic based detergents of our invention my incorporate cat ionic fabric softeners. The cat ionic fabric softeners may be added to type "C" Formulations in a weigh proportion based on the non ionic surfactan~ of from 1:1.5 to 1:4 preferably 1:2 to 1:3. The cat ionic fabric softeners are cat ionic surfactants having two long chain alkyd or alkenyl groups, typically two C16 20 alkyd or alkenyl groups, preferably two tallowyl groups. Examples include do C12_20 alkyd do (lower, ego C
3, alkyd) ammonium salts, e.g. do tallowyl dim ethyl ammonium chloride) dl(C16 20 alkyd) benzalkonium salts e.g. ditalluwyl methyl bouncily am~onium chloride, do C16_20 a y imidazolines and do C 6 20 azalea amino amine or quaternised amino amine, e.g. bus (tallow amino ethyl) ammonium salts.

Formulations containing cat ionic fabric softeners preferably do not contain sulfated or sulphonated anionic surfactants or soaps. They may however count in minor proportions ox anionic phosphate ester surfactants e.g. up to I by weigh of the composition preferably up to I They may additionally or alternatively contain minor proportions (e.g. up to 3X, preferably 1 to I by weight of ampho~eric surfactants such as buoyancy and sulphobetaines. They may also contain smectite clays, and the Usual or I~g~di~nt,.

My nor I n~redi ens Compositions of the invention may contain the Usual Minor Ingredients. Principal of these are anti redeposition agents, optical brightening agents and bleaches.

The most commonly used anti redeposition agent in make no deterrents is sodium carboxymethyl cellulose (SAC), and we prefer what this be present in compositions of this invention, e.g. in conventional amounts, e.g. greater than 0.1 but less than SO, and more usually between 0.2 and 4X, especially 0.5 to I preferably 0.7 to 1.5X. Generally speaking SCMC is effective at concentrations of about I and we prefer not to exceed the normal effective concentrations very substantially, since SCMC in greater amounts can raise the viscosity of a liquid composition very considerably. At the higher limits discussed above e.g. OX of SCMC, many Formulations cannot be obtained in a Parboil form at high Pay Loads.

Alternative anti redeposition and/or soil releasing agents include methyl cellulose, polyvinylpyrrolidone, carboxymethy7 starch and similar posy electrolytes, all of which may be used in place of SCMC, as may other water soluble silts of carboxymethyl cellulose.

Optical Brighteners (QBA's~ are optional, but preferred ingredients of the compositions of our invention. Unlike Rome prior art formulations, our compositions are not dependent on Oboes for stability and we are therefore free to select any convenient and cost effective OVA, or to omit them altogether. We have found that any of the fluorescent dyes hitherto recommended for use as Oboes in liquid detergents may be employed, as may many dyes normally suitable for use in powder detergents. The OVA may be present in conventional amounts However we have found thaw Oboes in some liquid detergent (e.g. type "C" formulations) tend to be slightly less efficient than in powder deterrents and therefore may prefer to add them in slightly higher concentrations relative to the Formulation Han is normal with powders. Typically concentrations 73~

of OVA between OOZE and OOZE are sufficient e.g. 0.075 to 0.3~
typo kelly 0.1 to 0.2~. Lower concentration could be used but are unlikely to be effective, while higher concentrations, while we do not exclude them are unlikely to prove cost effective and may, in some instances give rise to problems of Camped it ability.

Typical examples of Oboes which may be used in the present invention include : ethoxylated 1, 2-(benzimidazolyl~ ethylene; 2-s~y~ylnaphbh~1,2d-]oxazole; Boyce' methyl-2-benzoxazolyl) ethylene;d~sodium-~,4'-bis(6-methylethanolamine-3-anilino-11,3,5-triazin-2"-yl)-2,2'-stilbene sulphonate; N-(2-hydroxyethyl-4,4'-bis (benzimidazolyl)sti1bene; tetrasodium Boyce Boyce"-hydroxymethyl)-amino-6"(3"-sulphophenyl) amino-l", 3", treason"
ye amino]-2,2'-stilbenedisulphonate; disodium-4-(6"-sulphonaphtho~l',2'-d]triazo1-2-yl)-2-stilbenesulpfount; disodium Boyce~4"-(2"'-hydroxyethoxy)-6"-amino-1",3",5"-triazin--yule amino~_2,2'-stilbenedisulphonate; 4-methyl-7-dimethyl aminocoumarin;
and alkoxylated 4,4'-bis-(benzimidazolyl) stilbene.

Bleaches may optionally be incorporated in liquid detergent compositions of our invention subject to chemical stability and compatibility. Encapsulated bleaches may form part of the suspended solid.

The action of proxy bleaches in compositions of our invention may be enhanced by the presence of bleach activators such as twitter acutely ethylenediamine, in effective amounts.

Photoactive bleaches such as zinc or aluminum sulphonated phthalocyanin, may be present.

Perfumes and colorings are conventionally present in laundry detergents in amounts up to 1 or I and may similarly he present in compositions of our invention. Provided normal care is used in selecting additives which are compatible with the formulation, they do not affect the performance of the present invention.

3'~33 Proteoly~ic and amylolitic enzymes may optionally be present in conventional amounts, together optionally with enzyme stabilizers and carriers Encapsulated enzymes may be suspended.

Other Minor Ingredients include germicides such as formaldehyde , pacifiers such as viny latex emulsion and anticorrosives such as benzotri~zole.

Compositions of our invention are, in general suitable for laundry use and our invention provides a method of washing clothes or other soiled fabric by contacting and, preferably, agitating them in an aqueous wash liquor containing any composition of the i mention as described herein. Low foam compositions herein described are in particular of use in automatic washing machines.
The compositions may also be used on the washing of dishes, or the cleaning of hard surfaces, the low foam products being particularly suitable for use in dish washing machines. These uses constitute a further aspect of the invention.

Compositions of our invention may, generally, be used for washing clothes in boiling water, or for washing at medium or cool temperatures, eye. 50 to 80C, especially 55 to 68C, or 20 to 50C especially 30 to 40C, respectively. Typically the compositions may be added to the wash water at concentrations of between 0.0~ and I Dry Weight based on the wash water preferably 0.1 to I more usually 0.3 to lo ego 0.4 to 0.8~.

The invention will be il1ustra~ed by the following examples:
wherein aye figures relate to by wt. based on total composition, unless otherwise stated.

I ~2~73~

qg Compositions of the various Feed stocks Materials _.,..._ _, . . _. _ . _ 1.

For all formulations the alkyd Bunsen sulphonate used Weds the sodium salt of the largely para-sulphonated "Do bane" JO maternal.
(Do bane is a Registered Trade Mark), The composition is as follows:-Coo Of 1 C12 C13 C14 C15 13.0 27.0 27.0 19.0 11.0 1~0 This composition refers only to the alkyd chain length.

I Coconut Monoethanol am de Has the lot fowl no compost lion: -RC0 (NHCH2CH20H where R is as follows:-Us OOZE
C7 6.5g Cog ~-~
Oil I
C13 lg.5Z
C15 8.5 Starkey ~17 2 jog Olin C17 6.0 Linoleic C17 1.5~

3. Sodium alpha olefin sulphonate This material is the sodium salt of sulphonated C16/C1g olefin having the following approximate composition.

55,0~ C16 Terminal olefin 45.0~ C18 Terminal olefin r 1~3~7'33 4. Clue 1g Alcohol 8 moles Ethylene Oxide This material is an average 8 mole ethylene oxide condensate of an alcohol of the following composition:-Coo 3.0 C12 57.0 C14 20~0 C16 9.0 Clue 11.0~

5. Sodium Clue 17 n-Alkane Cellophane This material was prepared by neutralizing sulphonated C14-C17 neural paraffins with sodium hydroxide and contained 10X
disulphonates based on total Active Ingredients.

6. sodium C

This refers to the sodium salt of a sulfated fatty alcohol having the following composition:-Coo 3.0 C12 57.0X
C14 2~.0 C16 9.0 C18 11.0~

7. Sodium Tripolyphosphate This material was added as an hydrous NasP301o continuing Phase I.

8. Sodium Silicate _ This material is added Jo Formulations as a viscous aqueous solution containing 47~ solids wit a Nash ratio of 1:1.6.

3~33 9. Optical brightener The optical brightening agent for Examples 51 to 66 was the disodium salt of 4;4'- rdi(styryl-2-sulphonic acid)] biphenyl which is marketed under the trademark "TIN OPAL CBS-X ". The optical brightener for Examples 1 to wise a mixture of the aforesaid Optical brightener with the sodium salt of 4;4'- [Dow-chlorostyryl-3-sulphonic acid)] biphenyl which mixture is marketed under the trademark "TIN OPAL ATS-X".

Note All alcohols and their ethylene oxide adduces referred to are straight chained and primary.

All the examples were prepared by adding the surfactant, usually as hydrated solid, to a 47X solution of the silicate. The other ingredients were then added in the order shown in the tables reading from top to bottom, except that the principal Builder was added last. At etch stage, a small addition of water was made, whenever it was required in order to maintain a fluid homogeneous system. Finally, the composition was diluted to the desired percentage Dry Weigh The entire preparation was carried out as close as possible to ambient temperature consistent with adequate dispersion of the ingredients. In the case of examples 20,21,22 and 23, a concentrated aqueous solution of the electrolyte (i.e.
sodium chloride, sodium carbonate and potassium carbonate respectively) was used in place of the solution of silicate in the above procedure. In some instances, especially with relatively high melting non-ionic surfactants, such as coconut monoethanolamide, gentle warming e.g. to about 40C was required to ensure complete dispersion In all the Examples in which sodium tripolyphosphate was used in substantial amounts this temperature was achieved by the heat of hydration without external heating.

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Jo ~Z3'~33 Of the Examples, 1 and represent a basic type A Formulation, 3 and 4 a type A formulation with SCMC and optical brightener, I, (b) and (c) represent a type A Formulation at three different Pay Loads, 6 and 7 demonstrate that neither SCMC nor optical brightener is essential to obtain a Non-sedimentin~ Formulation: 8 contains anticorrosive and perfume; 9 (a) and (b) illustrate a high Builder to Active ratio Fonnulation (3:1~ at two Pay Loads lo and (b) illustrate a relatively lo Builder to Active Formulation do two Pay Loads; 11 oDrresponds to a Non-sedimenting Formulation obtained by centrifuging the Formulation of Example 9 at low Payload for only three hours and decanting the supernatent liquor; 12 illustrates the effect of relatively high SCMC levels; 13 to 19 illustrate Type A
Formulations with various anionic surfactants; 20 to 23 111ustrate various Electrolytes, and 24 is a Formulation in which sodium tripolyphosphate is the sole Electrolyte; 25 to 30 illustrate various Builders and mixtures thereof; 31 is a high Builder to Active Formulation; 32 is an enzyme Formulation; 33 contains Hydrotrope; 34 has a triethanolamine salt of the surfactant; I to 37 illustrate olefin sulphonate and 38 to 41 paraffin s~lphonate Formulations, in each case with successively increased Electrolyte; 42 to 45 illustrate type B formulations, 42 at three Pay Loads and I to 45 with increasing Electrolyte; 46 corresponds to Type B Formulation obtained after centrifuging 42 at low Pay Load for only three hours;
47 and 48 illustrate low foam Type A and C Formulations respectively;
49 to 53 illustrate various Type C Formulations; I is a Type C Form-elation with cat ionic fabric softener; I illustrates a branched chain alkyd Bunsen sulphonate9 56 coconut diethanolamide and 57 a non ionic free formulation; I and 59 illustrate the use of phosphsnate builders; 60 to 61 relate Jo formulations particularly adapted Jo die rent parts ox the North American market, being respectively phosphate free and high phosphate 62 Jo 65 are formulations adapted Jo the needs of certain Asian markets.

~3~733 The comparative example represents d commercial Fonmulationcurrently being marketed in Australia, which corresponds to Australian Patent 522983. The comparative example was the material as purchased, except for the neutron scattering results which were carried out on samples prepared in accordance with the example of the patent to match the commercial Formulation as analyzed and using deuterium oxide instead of water. The composition, by analysis was:

Sodium 010-14 linear alkylbenzene sulphonate 12 Sodium salt of three mole ethoxylate of 3 C12-15 alcohol sulfite Sodium tripolyphosphate 15 Sodium carbonate 2.5 Optical brightener (Tin opal LAMS) 0.5 Sodium carboxymethyl cellulose 1.0 Water to 100 The above composition corresponded to that specified in the example of the Australian patent, except that the latter specifies the sodium carboxymethyl cellulose, together with perfume, coloring and substantive blown agents as being "us".
-3~7~3~

3. Example Test Results The foregoing examples were subjected to various tests, the results of which are tabulated:

Note The Phases separated from the centrifuge test are numbered from the bottom (i.e. the densest layer) upwards.

~3~733 .

En lies 1 2 at ,, , - 1 Ce7~ifiuqe Test Results . _ i. No. of Phases Separated 1 2 1 2 _ . . . _ ii. Description Opaque clear Opaque clear solidVpaste thin so1id/paste thin Luke d Lockwood it Jo Al 80.9 19.1_ _ ~0.1 ..
(%) .
___ It _ 0.01

2. Classification (Group) III III
I

3. Yis~osity (Pays)

4. Yield Points (New~cnstn 2 x 10) _

5. Neutron Diffract Results l i _ char squatting _ _ Ida Jo of other peats _ b Dayton -c StnK~lral repeat distance (A) . .
lit Suggested Structure

6 X- Diffraction Results ray _ . _ i. Muzzler Scattering _ Ida No. of other perks _.
_ b Depone _ . _ c S fat Roy__ distance (A) _ iii. Sug$sted Structure r ..
L _ _ . _ .
_ . _ _ .. ._ . _ ._ _ . _:
Dun .
8. Mbbili~y Parboil Parboil __ . . , _ 9. Stability No sedimentation over No sedimentation 12 n~r~ths at ~rbie~Tt per 12 months at laboratory purrers aTbie~t lab~ratDry ~eratllre 73~

Else 3 I So 1.
i. _ 1 2_ 1 2 1 2 i i . Opaque clear Opaque clear Opaque clear solid/paste yin solid/pdste thin solid/paste thin _ liquid _ liquid it. is '.~ ' 77 3 vi. _, , , . 0.01 2. III _ III III
3 _ _ 1.70 ., , . __ 4. _ _ 1 12 5, Present- Newark . _ _ Ida _ _ 1 our b _ . nary c _ . _ 33.4 A
iii. ¦ Lowlier twitted solid 6.

b _ L_ __ . _ iii.

7.
i. _ ii. I .

8. Parable PQIrable ¦ Readily parboil ,,,, . _

9. No sedimentation aver No sedinerT~tion No sedimentation won 12 no at art t per 12 Il~lTthS at 12 runs at ~rbient 1 aborter rpera~res ant I ~perab~re up.

3 Lo 7 3 3 E lies I I 6 .. . . __ ...
_ l 2 1 ? 1 i i. Opaque clear Opaque clear Opaque clear solid/paste thin solid/paste thin solidlpaste thin Lydia liquid liquid Jo _ ___ _ _ .
iii. 81.7 18.3 45 ivy I
I, ho __ n 0~01 I III III
3 2 60 4.86 4.58 _ . _ __ 4 _ 36 178 Present-narn~
_ __ _ . .
Ida .. . __ b Norway, broad . .... __ c 34.9 A, 26.7 A
. ... I__.
iii. 2 Discrete lamellar squires _ 6.
Present ... _ _ __ .
Ida _ . _. e ___ . .. __ b Nan - . . ____ _ . . .
lit on ajar lime Jo lam~llar I
I _ i. ,,, ,, ,_ , i i. Laurel far Features .... _..... I, 8. Parable Viscous but Parable ¦ Curable 1, 9. No semi Te~tation Nor No sedimentation No sedimerttation per 12 rorrths at ambient also over 12 ninths at 12 ninths at ambient 3 ninths at and awoke arboreta t0~4. up.

3~733 Ex~rpl en 7 8 I
1. 1 i. 1_ 2 ! 1 2 1 2 i i. Opaque clear Opaque clear Opaque clear solid/paste thin solid/paste thin soli~/paste thin Lydia liquid liquid , I_ , --- - --' 'I
2. It _ III
3 3.04 2.84 1 4.00 . _ 5.
i. ._ .
ii pa c _ _ . . ___ I _ .. _ jig.
_ _ ....... __ I
6.
i. . . __ .~_ Ida b c , .. - .. .....
iii.
. . .

7.
...
ii. I

8. Parable ¦ Parable Parboil ., 9. No sedi~ntation o'er No sedimentation No sedimentation o'er 12 ninths at Aruba won 12 ninths at 12 nuns at ambient top ambient To up.

3'~33 Examples I aye) lo 1.
i. 1 2 1 2 1 2 i i. Opaque clear Opaque clear Opaque clear solid/paste thin solid/paste thin solid/paste thin l iaJid l I'm d l squid . , . .

_ vi-.
. , . _ ._ _ __ __ .
III III III

I- . ,.. ___~
_ .
Ida _ ¦
_ b I _ _ c . , .
iii.

6. __ _ _ i., .
Ida b .
c , , I_ _ iii.
I.
7.
... .. , , . . .
8. Viscous but parable Curable ¦ Yiscals Tut parable _, _ _ , ....... . - __ 9. No sedimentation aver No se~inentation No sedinelltaticn aver 12 r~rrths at ambient won 12 no at lo TDn~hs at Abbott up. Bennett up. up.

3~7~33 Exalpl en 11 12` _ 13 1.
i. 1 _ 2 1 2 1 2 i i . Opaque clear Opaque clear Opaque clear solid/pdste yin solid/paste thin solid/paste thin I liquid Luke iii._ _ it _ , .
Vi . To ' __ , , 2. III _ i LO
3 e 2 48 O 913 I ___ 1 _- f~8 c _ I_ __ iii.
Jo 6. 1 i. __ Ida I -b . _ . _ . .
iii.
1. ~_~ _ i. or- _ -ii.

I Parable Readily parboil Viscous it Parable Jo 9. No sedimentation aver No ~dinertation No sedimentation over 12 run at ambient over 12 rows at 12 Tenths at aTbierft I- aTbi~ p. I-~23~33 - 74- .

Eel en 14 ___ _15 16 1.
i. 1 2 1 _ 2 1 2 _ 3 ii. Opaque clear Opaque clear Opaque clear solid so1id/paste thin 501idlpaste yin solid/pasSe yin 1 idea 1 squid 1 idea _ . . _ __ .... .. .. _ ._ _ 72 (Yol/vol) 12 16 iv I 0.3 _ _ v ~0.7% 76.3 _ vi 0.01 z, I l III _ III
3. l.g5 3.00 2.97 r -- - _ _ _ _ _ _ _ _ _ .
i .____ _ _ . _ __ Ida _ b __ _ . _ __ -- . . _ iii.

6.
i. ..... _ _ Ida , ._ , _.
c . . . .
iii.
- . . _ __ _ .
7.
i _, , ..
ii.
.. . . I, , 8. Curable Visuals kit parboil Curable 9. No sedillentation over No sedine~tat~on ajar No sediner~ation over 12 ninths at arbierlt 6 nuns at ambient 6 nuns a ambient up. up. tat.

~3~7~33 Examples 17 18' 19 1.
i._ 1 2 _ 1 2 1 2 i it Opaque clear Opus clear Opaque clear solid/paste girl solid/paste viscous solid/paste thin livid 1 squid liquid _ .
Y , (volt?) 10 Jo.
iv 7.9 7 vow _ 1 < 0.01 I , _ , . =.
2. III __ III III
3. 5.15 _ 6.46 _ 2.20 4 4 36_ 5.
Present us peak one _ b very wrier c _ _ 6 A _ i i i . Mice far + 'I" Phase .
6.
Ye broad ._. .
Ida Jo -- O
b nearer at I, broad at 26 .
c _ 50 A = __ __ .
7.
ii.
_ _ _ _ _ , _ , _ _ , 8. Viscous but parboil Yiscslls but parable Curable _ g. No Swede renta~ion over No sedimentation over No sedimer~ation over

10 norms at orbit 6 nones at arbieTt 6 months at aTbieTt up. I-EX~TP1~ 20 21 1.
_ 2 1 2 i i. Opaque clear Opaque clear solidVpaste thin solid/paste yin 1 icky d 1 iqJid . _ 78 22 75 25 TV. , 0.1 v 79.6 79.1 _ . .
vi 0.01 0.01 , To .
___ 4.2B 2.48_ 4. __ ....
5.
i . _ Pi ,, Ida __ or b _ __ ___ sharp c _~_ 33.4 A
iii. La char hydrated solid 6.
Press .
. Ida _ one b she __ 32 A _ . _ i ii. Lowlier Hydrated solid I_ ,.. , _ . _ 7.
,, ,__ ii. .
__ __ - - . .
8. viscous kit parable Parable 9. No semi Tenta~ion over No semi rentation over 12 ninths at ambient 12 ninths at anbie~t top also 3 nuns at up. also 3 ~Dnths at O end 37C~ O end 37C

~Z3~7~3 _77 Examples 22 23 (a) 23-tb) _ . . , . . .
1.
i. 1 2 1 2 _ 1 2 i i. Opaque clear Opaque clear Opaque clear solid/paste twin solid/paste thin solid/paste thin liquid liquid liquid ill.
_ _ iv. 0.1 _ 0.1 ,_0.1 __ I I 82.9 _ _ Vi. 0.01 0.01 0.01 2. III III III
.. . . _ 3 ~.21 0.88 1.87 I, _. . .
5. ` - :

Ida b _ _ .
___ , _--iii.
_ ___ _ __ _ ii pa b _ ..
_ iii.

7 .
i.
- . . .
ii.
.
8. Pcur~12 ¦ Readily Curable ¦ Curable 9, No citation over No secnrertat~on aver No sex notation over 12 depths at arboreta 3 ~nths at ambient 12 ninths a Anita top. also 3 Tenths at up. To O art awoke ~3~733 _ 78_ 1 . c3(c) 24 ;. 1 2 1 1 2 1 1 2 I__.
ii. Opaque clear Opaque clear Opaque clear solid/paste twin solidJpaste thin solid/paste thin 1 squid _ 1 ibid I iqu;d iii Volvo I_ __ 0.1 v. __ ~4-6_ ! -owl _ ' _ _ _ _ . _ Allah III _ III
3._ _ 2.38 aye _ 1.99 _ . _ .
5.
i. _ Present - Norway . _ . .
Ida _ on _ b _ sham _ .
O
c _ 34.5 iii. lamellar yawed solid _ .
6.
i. Pus _ __ .
Ida _ _ one b Sham c _ 33 A --iii. L~rellar hydrated solid ._ . ._ _ . _ 7. 1 l _

11. _ B. Lowe Parboil ¦ Readily parboil _, . _ _ _ _ _ g. No sedimentation over No sedimentation over No sed~n~ntation over

12 IrDr~s at ambient 9 TorTths at aTbier~t 6 TDn~hs at Betty tern. Jo - up 3~733 Examples _ 26 27 _ 28 1.
i. 1 2 1 2 3 1 2 ii. Opaque clear Opaque clear solid Opaque clear solid/paste thinsolid/paste thin solid/paste thin I'd liquid liquid iii. (~l/vol) 35 _ I 1 74 _ _ 26 _ 0 8 _____ vi. _ _ _ .. , 2. _ I II _ _ III

. I ..
.
_ _ _ Ida . _ _ _ b . _ _ _ __.
iii. .
_ _ 6.
j. __ _ _ _ _ Ida __ _ _ _ .
b _ _ . _ iii.
_ _ _ _ I_ 7.

ii.
.. . . _ 8. Readily Curable Visors jut oriole Discs us pCllt~bl2 _ , .
9. No sedimentation o'er No se~irrentdt~cn per No s2dinerrtation over 2 no at ambient 9 months at aTbi~ 3 nD~ths at Bennett up. To ~9Tp.

Exiles__ _ 29 I 31 i. 1 2 3 1 _ 2 1 1 2 ii. Opaque clear solid Opaque clear Opaque clear solid past yin solidVpaste thin solid/paste thin l idea liquid ___ iii Volvo I ~37 13 ___ _ , _ O 1 , 0.01 . . _ 3 3.11 0.33 6.50 . .
4. . . _ 5.
_ _ .
if Ox , _ ..
c _ . , .
iii.

6.
i _ Ida _ _ c ___ ., _ _ _ _.
iii.
. .
7.
I_ _ !_ _ ii. .
_ 8. Pcur2ble Readily Pcurzble Visors jut pyre _ _ 9. No se~irentation over No sed7rrerrtation over No sed~n~rrtation over 1 rronths at into 2 7Dntt6 at irrupt 12 n~rrths at ancient . I, up. To ~3~33 _ I

Ex~Tples 32 _ 33 34 2 _ 1 _ 2 1 2 i i. Qpaqu~ clear Opaque cloy` Opaque clear solid past yin solid/pas~ yin solid/paste yin liquid liquid Lydia __~__ _ iii 72 I
_ I_ ....
. . . . I _ Al _ 0.3 _ ---_ 2 a __ MU _ 1.10 _ _ _ _ I.
_ _ . _ _ _ ii pa _ _ _ _ b . _ _ ._ C ___ Jo _ lit ' _ _ _ 6.
. , ii pa _ c iii.
- , _ .

11.
I_ " _ 8. Parable Vi saws pcur~le Really pcur2i)~e . ._ . _ _ _ _ _ 9. No sechnEntation over No sedilrerrtation over No sed~m~rrtat~on over 12 ninths at art 9 ~nths at ~rbient 4 ninths at Aryan up. To tarp.

. _ .

ii. Opaque clay Opaque clue Opaque clear viscaJs solid/paste visuals solid/paste visuals solid/paste thin liquid liquid liquid livid . . _ _ ~Stvol/Yol ) 15 15.0 _ . _ _ ~9.3 _ vow 0.5 . .
2. IIIIII _ _ _ I
3.7 4 Tao 1 0.5t~2 Tao _ 5. very bred with super-........................ . _ _ _ .
Ida one .
b name _ _ c 61 A _ _ iii. nuzzler phase 'I" Phase _ .
6.
_. Present Ida _ _ b sharp, sharp c 57, 38 A ___ I_ ._ _ _ . ._ i ii . mice far phi hose . _ _ _ 7.
_,__._. . . .
i i. Lapel far pharisee sane¦

. Visuals but curable Viscous pourab7eP~raDle , _ .
90 No sedimentation over ho sedirrertat~on over No irritation over 6 ninths at ambient 9 months at ~rbierTt 9 nDnt~s at attenuate up. pi I

!

Examples 38 39 _ UP
-- .

i 1 2 ! 1 2 1 2 3 ii. Opaque clear Opaque clear ` Opaque Opaque so1idVpas~e viscous solidlpaste viscous solid/paste jelled liquid liquid liquid solid _ _ . _ _ _ 23, _ .

68 61 58.1 . . _ . _ , vi. 0.15 _ 0.15 .
._~ _................... . .. _ L _ L lo I I I
3. 3.10 2.87 3.21 OHS 0.5 5.
by . _ . _ I_ Ida one _ _ _ _ _ b broad : --c 31 A
iii. McElroy 'I" Phase _. .
6.
i. Present very broad _ __ _ - -Ida one _ .
b sharp _ . _. . .
c ~3.5 A _ _ .
iii. McElroy + 'I" Phase _ . _ _ _ _ _ _ 7.
i, _ , _ _ _. .
ii. . Lonelier and Spheroidal features __ . _, _.
8. Curable I Curable Curable 9. No ~hnentation caner No nineteen over No cementation aver 12 ninths at ambient 9 months at ancient 6 months at ambient up. up. pi "

Examples 41 pa 4? (b) 1. 1 1 j. 1 2 3 1 1 2 ! 1 2 ii. Opaque thin Opaque Opaque viscous Opaque clear solid/paste liquid celled solidlpaste Lear solid/paste thin sol i d l issue d l icky d iii. _ I 0 42.0 ___ __ _ _ iv. _ 3.0 ___ V. _ _ 91.4 I I . ..
2 III III _ III
__ . .
3. 4.10 _ 0.73 1 _ 0.97 4. 4 s.
i.
_ Ida b _ _ I =
c _ 1 1 iii. I I .
. _ _ _ 6.
_ _ _ _ Ida - I -_ I__ iii. _ 7. I l i _ _ ! . . I
ii. I I

___ _ 8. Viscous ho. parable I Discs hut curable I YjSCQIS kit parable 9. No sedin~ntation Corey No seJin~nta~ion over No sedi~errtation over 4 months at ambient 12 rronths at Betty l? rDnt~ts at irrupt top. rip up.

~3~733 Examples 42(c~ 43 I

i. 1 2_ 11 2 I 1 2_ 3 Jo. Opaque clear ¦ Opaque clear Clear I Opaque clear clear solid/paste visuals I solid/paste thin viscaJs I solid/paste yin viscous _ _ liquid id livid ! liquid liquid iii.
i v.

vi 3. 1.72 1 1.19_ 1 2.74 _ 4.__ . . . _ _ 5. .
i. _ Ida _ _ by C - Jo iii. I I
_ .
- 6.
i-Ida I I _ b c iii. I . I

7. 1 l ii. I I
I I
.. . . _ . _ _ _ 8. Viscous it pctrable ¦ Yls~ous to ruble ¦ VjSCQ~S kit parable 9. No sedinE~ntat~on 1 No Sydney Aetna aver ¦ No sedim~lTtation o'er o'er 12 ~rDrrths at , 9 rowers at ambient ! 9 us at a~ttie~rt AT bit rip up. it.

~3~33 _ 86_ .

i. l 2 3 2 . I 1 2 i i . Opaql;eclear clear Okay clear Opaque clear solid/thin viscous soli~/paste viscous solid/paste thin paste liquid liquid _ lucid id iiiO qO(v/v)~3) 10 I _ -_ 1 78.0 22 iv. ! I owl v. ! 1 - --vi. I 1 0.91 2. II ¦ III I III
. .
3 2.4~ 1 11.0 ! 1.5~3 4.
I

pa _ __ _ _ _ .
b _ _ _ I _ _ _ c _ _ , _ iiio I

6.
_ _ Ida b __ _ _, iii. I, .

7 ; - -- -1.
__ _ _ ii. ,.

_ 8. ViscQls Tut pcur2ble Viscous but curable ¦ Readily pci~r~le __ i 9. No sedin~rtation Norway No sedir~ation per I No sedi~ntation over 9 n~rTths at aTbie~t 4 ninths at ~rbient 1 6 ninths at irrupttarp. top. . up.

Expels 47 by 47 I 48 1. i. 1 ___ , i i. Opaque clear Opaquely clear Opaque clear solid/paste thin solid past thin solid/paste thin solid livid liquid liquid _ , iii. En ED I 82 I 31.9(Y/v) Z3.4 44,7 __ iv 0~1 1 0.1 I 2~.6 v. _79 I 76.6 1 ~1.1 0.2 2. III I III I III
I __ 2~31i 3~6~i 1 5~9 I
s i _ _ _ b c 6.
_ .
Ida b c . _ . _ . _ _ iii.
. _ _ . .
. _ _ ii. _ !

8. Curable , Parable ¦ Viscous jut preboil , _ . _ _ . .
9. No sedi~ntation over lo Sydney Asian over No semi To anion over 12 n~rTths at ~rbient 12 ninths at ambient 12 us at aTbien~

~3'~33 Exasr~les aye . 49tb) 49 (c) 1.
i. 1 2 1 2 1 2 _ . . .
i i. Opaque clear Opaque clear Opaque clear solid/paste ruin solid/paste thin solid/paste yin liquid _ likelihood_ liquid _ __ iii. 76 I 77.5 22.5 iv. I 0.1 0.1 . . .
I it 7 . I
vi. 0.01 0.01 Owl 2. III III III
. .. . _ , _ , , 3. 0.~8 I 3.89 __ _ . _ . . , , .
i . Very Noel _____ ..
Ida __ __ one _ _ b very Norway c 65 A
. . _ , iii. Mice far 'I" Phase ('I" Pea _ _ 6.
_ _ very Hall_ .
Ida to __- O
b Nary at I & 28~
O--c Y. A
. _ iii. 'I," Phase + sat muzzler ' 7.
i.

, 8. Readily parable ¦ Curable ¦ Sisals kit Fireball , _ -9. No sex rotation over No sedation aver Jo sed~n~ntation over 12 nDrths at aTblerrt 12 nuns a aTbi~ 12 Tracy at abrupt to. up. up.

- 8 9 _ Exan~les 50 51 52 i. 1 2 3 1 1 2 3 1 1 2 3 i i. Opaque clear clear . OpaqtJe clear clay Opal clear solid thin oily solid thin ~risaJs solid thin solid vast liquid iii 59(v/v) 3g 2 45(v/v) 19 36 36(v/v) Jo 34 ___ _~_~
Iv. _ 0.1 31.5 v 72 48. I
___ vi 0.01 1.0 , 0.01 Jo 2. _ _ If III
3 11.~0 4.42 1.42 ,_ , , , . . .

,. _ ............... .

narr~/str~g Newark Ida I one one b broad Norway .
c 54.2 A 56.1 A
, .... ,..,.........
iii. . Muzzler 'I" Phase 'I" Phase ye . _ _ 6.
i. _ Norway Ida b Nan at AYE & 26 . ... .... ... O ---------- - __ . _ c 51 A
.... . .
iii. muzzler 'I" Phase -- . .. , .. ... __ __ ., ,,, .
7.
It ....... .
i i . . Lyle far fear _ 8. Yiscals but pctlrable Yiscals jut parboil ¦ Vlsca~s it parboil . _ . _ !
9. No sedimentation over No sechner~tion over No semi rotation won 12 rrorrths at arboreta o I ho at Bennett 4 wrier at orbit up. up. to.

~23 ~73~

zeros _ 53 _ 54 55 1. ;
i. 1 2 3 1 1 2 3 1 2 . _........... ... ... ....... ....... ... ... ... .... ....... ....... ........ ........ ._ i i . Opaque clear h3Xy Opaque clear my opaque clear solid/tnin solid solid/ thin solid solid/ -yin paste I paste liquid _ past liquid iii. 43(v/v) 19 38 VOW) 27 33 76 24 __ 1 iv. 0.1 32.9 C 0.2 0.05 . . . . .
v.71.6 51.5 82.2 vow 0.01 2. III III III
.. .. . _ 3. _ i 2.43 4. <0.5 _ .

__ _ ii. __ .. .. __ __ by _ . . _ c .
iii.

6.
i.
_ _ Ida b .. I.
._ . ___ . ... _ __ __ iii.

7. j ! . I
8. Pcur~le ¦ Parboil ¦ Pcura~le . No sedinentltion over No sedilrentation over No sedilren~tion over ninths at ambient 3 months do ardent 1 TDntil do ldt)ora~;)ry t91p. I Tbient tax.

~34733 Jo 9, ExanDles 56 57 58 Jo lo 1 2 1 1 2 - i 1 2 , . _____ _ ii. Opaque clear Opaque clear Opaquely clear solidVpaste thin solid past thin solidVpaste thin liquid liquid liquid . ! _ .. , . . - I. .
iii 82 5 17.5 64.9 35.1 1 77.0 23.0 , iv 0.02 0.3 0.4 . _.
Yip I
2. III ¦ III III
, , 3 1.8 2.1 2.9 4 _ 5.
i.
Ida b _ .
c . _, . ,, . _ . _ . ....... _ _ iii. . .

6. - .

Ida b . .
c , _ I
iii. l I

I , .
7.
... , .
ii. I I

8. Pow fable Parboil ¦ Curable .
9. No s~menta~ion over no ~hmentation over ¦ Jo s mentaticn over 1 month at labcrato~y 1 nonage at laboratory I 1 ninth at laboratory ambient stud. ambient Err I aTbien~ 'usTp.

lies 59 60 61 1. j 1.

. . _ _ _ ii. Opaque clear Opaque clear Opaque Okay clear solid/ thin solid thin solid solid,' ViscQls lo liquid Date liquid paste paste liquid was iii. 73.0 27.0 1 5(v/v) 45 ED I 95.0 5.0 iv. 0~1 1 0~05 26.2 Yip 2. III _ I_ III I III
3. __ 2.2 1 8.1_ 1 6.0 5.
ii a 1 c '- -' ! ' I
.

_ 6.

lo pa _ b _ ! _ . I _ c , ! _ , I
iii. I I

, 8. Parable ¦ Viscous it parboil ¦ V;SCQ~S jut curable I Jo s~i~errtation o'er ¦ lo sedirrentatlor7 per owe sedimentation over 1 non at Libra 1 Torrth at Libra 1 Roth at libretto irrupt top. l it top. ambient to.

~23~733 Jo _ 93 Ex~rples 62 I 64 ii. Opaque clcuqy Okay Claus Opaque clear Solid/
solid vi SKYE solid/ viscous solid/ thin paste paste liquid paste 1icuid paste liquid lit. 8 __~7.2 !~.~ 49.0_ll0(v~v) 40 _ I_ iv 21.3 1 so ! oily v.
vi.
2. _ III I III I III
3 _ 3.26 1 EYE 1 0.7 I I

_ .
Ida 'I
b !
c ! - -- !...... -----iii. ! I

6.
j, , Ida , c iii.

7.
i. !
.. _ 8. Parable ¦ Curable ¦ Readily pcllrable , 9. No sed~ne~dtion per I No sedimentation over lo sedimentation 1 Troth at laboratory ! 1 Roth at laboratory over 1 ninth at ~rbient try. ¦ æTbient tarp. liberator inn top.
, ~;~3~733 Exempt e 65 1.
iiOpaque solid paste Clear thin liquid iv _ I

MY i , .. _ 2. III
3. 0.5 ii a b c i a b c iii 7 .
i I
8 . Read lye Parboil e_ 9. No sedimentation over 1 month a laboratory 3~7~33 I
Comport Ye Exempt e A
1 .
. 1 2 i i puke Opaque - -solid viscous paste 1 i qua i d iii. __ ~Z4 7b iv. 17.3 v. Us vi . U. Z6 I .
0~3 . very brood --wit to i. _ superimposed peaks ii. a None __ i i i . con. _ my cellar dispersion 6 .
.. _ very wide it a one b _ spa n c QUA
iii. gone. muzzler dispersion ,.
i.
ii. Spheroidal lectures B. Readily Parboil 9. No sedimentation over 12 months at ambient temperature ~3~3 Certain of the foregoing examples were tested for washing performance as follows:-Series 1 Representative high foaming formulations were each compared with a standard powder formulation in machine washing tests on two different standard soiled fabric samples.

Cotton Conduit owns 31 95Z 100X ) Temp. 50C
90X 70~ ) Water 300 Pam calcium carbonate 16 100~ 100X Time 30 miss.
33 95~ 110~ Cone. = Equivalent effective Wash Powder 100X 100X Solids Standard The term "Effective Wash solids" refers to the sum of the Active Ingredient and Builder. The powder standard was used at 6gm/l and the Examples adjusted to give the same X Effective Wash Solids in the wash Liquor.

Son Representative formulations of both high and low foaming types were tested against equal wt. dosage at three temperatures.

I

Cotton Polyester/Cotton X Effective 40 60 85 of 40 pa o 85 I_ -Wash Solids I (c) 93 75100 I 75 85 5G

50 I 93 110110 95 180 200 2~0 Powder 100 100100 100 100 100 130 Standard Conditions: Taipei 40, 60 and 85C~
Water 300 Pam hardness Time 30 miss.
Cone. 6 gmJl ( as Russ vied) , Series 3 In thus series low foaming non-ionic based examples were tested against the powder standard.

Example X Effective Cotton Polyester/
Wash Solids Cotton 52 70 110~100b Conditions 53 66 105~ 90~ Temp. 50C
54 61 115%120~ Water 300 Pam hardness Time 30 miss Cone.
powder 6 gel exempt en l l gel Powder 100 100~ 100 Standard , ., ~3~33 Series 4 Two low foam non-ionic formulations were tested on naturally soiled fabric (15 successive washes with natural soiling) Conditions: Temperature 50C
Water 300 Pam hardness (wash and rinse) Wash time 30 miss Fabric 65 : 35 white polyester cotton Concentration EQUAL WIG _ i.e. 6 gel Results:

Example 52 = 100% Sty ) Optical whitener efficiency 54 = 75% Sty 52 = 95-100~ ) Soil Removal and 54 = 95-100~ ) Deposition efficiency Examples 20 and 24(b) were also compared against the comparative example for washing performance, shear stability and sodium ion concentration due to Electrolyte.

Both examples of the invention had superior washing performance and shear stability compared to the commercial product.

.

73~

I

Sodium ion in the aqueous Phase (i) direct (ii) by Washing Shear analysis of subtraction Performance Stability Electrolyte Comparative Example 22 Shear unstable 1.73 1.78 Example I 30 Shear stable 3.24 3.44 Example 24(b) 34 Shear stable 4.05 4.10 The washing performance is the average of evaluations of soil removal using eight different test fabric/soil combinations.

Shear stability was tested by passing a sample through a straight 40mm. tube having an internal radius of 0.25mm. under a pressure of 500 prig The comparative example sediment Ed rapidly after a single pass. The two examples of the invention were stable, even after two passes. The practical effect of this on the stability of the composition during normal industrial handling was illustrated by mixing the composition for a short time in an "Ilado" laboratory disperser model X40/34, Mario shaft 47/T at setting Noah, rotating at 7800 RUM The commercial product sediment Ed very rapidly, sedimentation commencing immediately after mixing. The examples of the invention showed no evidence of instability.

Sodium ion was estimated by Centrifuging the sample and separating the upper aqueous layer. Residual traces of suspended solid were removed by centrifugation at 20,000 G for 2 hours, after which no suspended crystals were observable. The dissolved electrolytes, OBOE. and anionic surfactant content were determined.
Total sodium ion in the aqueous phase was determined spectroscopically. Sodium ion content due to dissolved Electrolyte was calculated from the Electrolyte concentrations and confirmed by subtracting calculated sodium ion contributed by OBOE. and anionic surfactant from total sodium ion determined by spectroscopy.

q.

Claims (84)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A Non-sedimenting, Pourable, fluid, detergent composition comprising: at least one predominantly aqueous, liquid Separ-able Phase containing sufficient dissolved Electrolyte to contribute from 2 to 4.5 gm ions per litre of said phase of alkali metal cations; at least 5% by weight of the composition of surfactant; and suspended solid Builder.

2. A Pourable, fluid, Non-sedimenting, aqueous based detergent composition comprising water, surfactant, particles of solid Builder suspended in the composition, and dissolved surfactant-desolubilising Electrolyte, the proportion of dissolved Electrolyte being above the minimum concentration at which the composition exhibits increased viscosity and/or increased stability on recovery after exposure to shear stress and the Pay Load is above the minimum at which the formulation provides a Non-sedimenting composition but below the maximum at which it is Pourable.

3. A Non-sedimenting, Pourable, fluid detergent composition having a Payload of greater than 25% which, on Centrifuging is separable into a single liquid layer containing sufficient dissolved Electrolyte to provide from 2 to 4.5 gm ions per litre of said layer of the sodium ion present therein and a Solid Layer containing surfactant and Builder.

4. A composition according to any of claims 1 to 3, wherein said Electrolyte consists essentially of alkali metal chlorides, phosphates, condensed phosphates, phosphonates, citrates, nitrilotriacetates, ethylenediamine tetracetates, carbonates and/or silicates.

5. A Non-sedimenting, Pourable, fluid, detergent composition containing surfactant, which comprise a substantially linear alkyl benzene sulphonate, said composition having a Payload of at least 25%
by weight and being separable on Centrifuging into a predominantly 2...
aqueous liquid layer containing sufficient dissolved Electrolyte to supply from 2 to 4.5 gm ions per litre of alkali metal to said layer and at least one other layer, said at least one other layer comprising solid Builder and at least part of said surfactant.

6. A Non-sedimenting, Pourable, fluid, detergent composition having a Payload of at least 25% and comprising surfactant, dissolved Electrolyte and suspended solid Builder, which separates on Centrifuging into a predominantly aqueous layer containing sufficient of said dissolved Electrolyte to provide from 2 to 4.5 gm ions alkali metal per litre of said aqueous layer, and at least one other layer containing solid Builder and at least part of said surfactant, the weight ratio of the total Builder to the total surfactant being greater than 1.2:1.

7. A composition according to claim 6 having a Payload of at least 35% by weight.

8. A composition according to claim 7 having a Yield Point of at least 1 Newton per m2.

9. A composition according to claim 8 having a weight ratio of Builder to surfactant of from 1.2 : 1 to 4 : 1.

10. A composition according to claim 9 wherein the Builder comprises sodium tripolyphosphate.

11. A composition according to claim 10 containing at least 15% by weight thereof of Builder.

12. A composition according to claim 11 containing at least 20% by weight thereof of Builder.

13. A composition according to claim 12 containing more than 8% by weight thereof of surfactant.

14. A composition according to claim 13 having a pH

3...

greater than 8 when dissolved in a wash liquor at a concentration of 0.5% Dry Weight.

15. A composition according to claim 14 having a pH greater than 10 when dissolved in a wash liquor at a concentration of 0.5% Dry Weight.

16. A composition according to claim 15 having suf-ficient free alkalinity to require 0.4 to 12 mls one-tenth Normal hydrochloric acid to reduce the pH of 100 mls of diluted composition at 0.5% Dry Weight to 9.

17. A composition according to claim 16 having sufficient free alkalinity to require from 3 to 10 mls. one-tenth normal hydrochloric acid to reduce the pH of 100 mls. of diluted composition at 0.5% Dry Weight to 9.

18. A composition according to claim 17, wherein the surfactants comprise at least a major proportion of a sulphated and/or sulphonated anionic surfactant.

19. A composition according to claim 3,wherein said solid Builder comprises a condensed phosphate, phosphonate, carbonate, zeolite and/or orthophosphate.

20. A composition according to claim 19, wherein said dissolved electrolyte consists essentially of sodium carbonate, together with an alkali metal condensed phosphate, orthophosphate, citrate, nitrilotriacetate, chloride and/or ethylenediamine tetracetate.

21. A composition according to any of claims 3, 19 and 20, wherein the total Builder comprises a major proportion by weight thereof, of sodium tripolyphosphate.

22. A composition according to claim 18 wherein the surfactants constitute from 10 to 20% of the weight of said composition.

4...

23. A composition according to claim 3, wherein said solid builder comprises a condensed phosphate, phosphonate, car-bonate, zeolite and/or orthophosphate, said dissolved electrolyte consists essentially of sodium carbonate, to-gether with an alkali metal condensed phosphate, ortho-phosphate, citrate, nitrilotriacetate, chloride and/or ethylenediamine tetracetate, said total Builder comprises a major proportion by wieght thereof, of sodium tripoly-phosphate, and the surfactants constitute from 10 to 20% of the weight of said composition.

24. A composition according to any of claims 18, 19 and 23, wherein said sulphated and/or sulphonated anionic surfactant comprises a mixture of a substantially linear C10-14 alkyl benzene sulphonate and a C10-20 alkyl 1 to 10 mole ethylen-eoxy sulphate.

25. A composition according to claim 22 containing an effective amount of an antiredeposition agent.

26. A composition according to claim 25 wherein the antiredeposition agent is a carboxymethylcellulose.

27. A composition according to claim 26 containing from 0.5 to 2%
by weight of said composition of alkali metal or ammonium carboxymethyl cellulose.

28. A composition according to claim 27 containing an effective amount of an optical brightening agent.

29. A Pourable, Non-sedimenting, fluid detergent composition consisting essentially of water and: (A) from 10 to 20% based on the weight of the composition of surfactants comprising a substantially linear sodium alkyl benzene sulphonate having from 10 to 20 aliphatic carbon atoms and optionally an alkyl ethoxy sulphate having an alkyl group with from 10 to 20 carbon atoms, and/or a minor proportion of a non-ionic surfactant and/or of a soap; (B) at 5...
least 15% of Builder partly present as solid and selected from condensed phosphates, carbonates, zeolites, citrates, nitrilotriacetates, ethylenediamine tetracetates, orthophosphates, silicates and mixtures thereof, wherein at least 50% by weight of said Builder is sodium tripolyphosphate and said Builder further comprises sufficient sodium carbonate to provide a shear stable composition; (C) optionally minor proportions of ingredients selected from carboxymethylcellulose, optical brightening agent, enzymes, bleaches, antifoams, cationic fabric softeners, smectite clays, fragrances, dyes and sodium chloride.

30. A Pourable, Non-Sedimenting, fluid, liquid detergent composition consisting essentially of water and: (A) from 10 to 20% based on the weight of the composition of a mix-ture of substantially linear C10-18 alkyl benzene sulphonate and C10-20 alkyl 1-10 mole ethoxy sulphate; (B) at least 15%
by weight of the composition of total Builder partly present as suspended solid, comprising sodium tripolyphosphate, zeo-lite, sodium carbonate, and/or sodium silicate; (C) an aqueous Separable Phase containing sufficient dissolved Electrolyte selected from sodium tripolyphosphate, sodium carbonate, sodium silicate and mixtures thereof to provide from 2 to 4.5 gm mole per litre of sodium ion in said phase; and (D) optionally any of the Usual Minor Ingredients; the Payload of said composition being above the minimum at which the composition is Non-sedimenting but below the maximum at which it is Pourable.

31. A composition according to any of claims 18, 19 and 23, wherein said sulphated and/or sulphonated anionic surfactant comprises a mixture of a substantially linear C10-14 alkyl benzene sulphonate and a C10-20 alkyl 1 to 10 mole ethy-leneoxy sulphate, and the weight ratio of said alkyl benzene sulphonate to said alkyl ether sulphate is between 5:1 and 1:5.

32. A composition according to claim 29, wherein the weight ratio of said alkyl benzene sulphonate to said alkyl ether sulphate is between 5:1 and 1:5.

6...

33. A composition according to claim 30, wherein the weight ratio of said alkyl benzene sulphonate to said alkyl ether sulphate is between 5:1 and 1:5.

34. A composition according to any one of claims 1, 2 and 3 which, on recovery after exposure to high shear stress, ex-hibits increased viscosity.

35. A composition according to any one of claims 5, 6 and 29 which, on recovery after exposure to high shear stress, ex-hibits increased viscosity.

36. A composition according to claim 30 which, on recovery after exposure to high shear stress, exhibits increased vis-cosity.

37. A composition according to claim 36 containing more than 5.6% by weight of the composition of sodium carbonate.

38. A composition according to claim 37, wherein the Electrolyte and Builder consist essentially of sodium tri-polyphosphate and sodium carbonate.

39. A composition according to claim 38, wherein the pro-portion of soduim tripolyphosphate is from 14 to 32.7% of the weight of the composition.

40. A composition according to claim 39, wherein the pro-portion of sodium tripolyphosphate is greater than 15.8%
by weight.

41. A composition according to claim 40 containing from 2.1 to 18% by weight of substantially linear sodium alkyl benzene sulphonate.

7...

42. A composition according to claim 41 containing at least 9.0% by weight of sodium alkyl benzene sulphonate.

43. A composition according to claim 42 containing at least 9.9% by weight of sodium alkyl benzene sulphonate.

44. A composition according to claim 43 containing at least 11.2% by weight of sodium alkyl benzene sulphonate.

45. A composition according to claim 44 containing at least 12% by weight of alkyl benzene sulphonate.

46. A composition according to claim 45 containing at least 12.6% by weight alkyl benzene sulphonate.

47. A composition according to claim 46 containing up to 9.6% by weight of sodium alkyl ether sulphate.

48. A composition according to any one of claims 1, 2 and 3, wherein said Electrolyte consists essentially of sodium car-bonate and/or sodium silicate, and/or sodium tripolyphosphate.

49. A composition according to claims 5 or 6, wherein said Electrolyte consists essentially of sodium carbonate and/or sodium silicate, and/or sodium tripolyphosphate.

50. A composition according to any one of claims 1, 2 and 3, wherein the surfactants comprise a minor proportion of a non-ionic surfactant.

51. A composition according to any one of claims 5, 6 and 29, wherein the surfactants comprise a minor proportion of a non-ionic surfactant.

52. A composition according to claim 30, wherein the sur-factants comprise a minor proportion of a non-ionic surfac-tant.

8...

53. A composition according to any one of claims 1, 2 and 3, wherein the Electrolyte comprises a nitrate.

54. A composition according to any one of claims 5, 6 and 29, wherein the Electrolyte comprises a nitrate.

55. A composition according to claim 30, wherein the Electrolyte comprises a nitrate.

56. A composition according to claim 52, wherein the Electrolyte comprises a nitrate.

57. A method of washing clothes or other soiled fabric which comprises agitating them in an aqueous wash liquor containing a composition according to any one of claims 1, 2 and 3.

58. A method of washing clothes or other soiled fabric which comprises agitating them in an aqueous wash liquor containing a composition according to any one of claims 5, 6 and 29.

59. A method of washing clothes or other soiled fabric which comprises agitating them in an aqueous wash liquor containing a composition according to claim 30.

60. In a liquid detergent composition of the type which comprises: an aqueous phase containing a mixture of dissolved Electrolytes comprising dissolved sodium tripolyphosphate, together with sodium carbonate and/or sodium silicate, at least 5% based on the weight of the composition of anionic surfactants selected from sodium linear alkyl benzene sul-phonates, sodium alkyl ethoxy sulphates and mixtures thereof;
solid sodium tripolyphosphate, suspended in said aqueous phase, and any of the Usual Minor Ingredients; the improve-ment which consists in providing sufficient of said Electro-lyte to contribute from 2 to 4.5 gm ions of dissolved sodium 9...

ion per litre in said aqueous phase.

61. In a liquid detergent composition of the type which exhibits at least one aqueous phase and suspended solid Builder and comprises about 12% by weight of sodium alkyl benzene sulphonate, about 3% by weight of sodium C12-15 pri-mary alcohol ethoxy sulphate, about 15% by weight sodium tripolyphosphate, about 2.5% by weight of sodium carbonate, about 0.5% by weight of optical brightener, and effective quantities of sodium carboxymethyl cellulose, perfume, colour and/or substantive blueing agents and the balance water, the improvement which consists in increasing the sodium carbonate content to at least the minimum level at which the composition is shear thickening.

62. An improved composition according to either of claims 61 and 62, wherein the proportion of sodium carbonate is at least 5.6% by weight of the composition.

63. An aqueous, fluid detergent medium, capable of suspend-ing solid particulate Builders to form Pourable, Non-Sedi-menting suspensions, and comprising water, surfactants and dissolved Electrolyte, wherein said dissolved Electrolyte is sufficient to provide from 2 to 4.5 gm ions of alkali metal per litre in said medium and said surfactants are sufficient to form, in the presence of said Electrolyte, a vesicular and/or lamellar surfactant structure capable of supporting said Builder.

64. An aqueous, fluid detergent medium capable of sus-pending solid particulate Builders to form Pourable, Non-Sedimenting suspensions, and comprising water, sufficient dissolved Electrolyte to provide from 2 to 4.5 gm ions sodium per litre of said medium and from 7 to 35% by weight of said medium of surfactants.

65. A composition according to either of claims 63 and 64, wherein said dissolved Electrolyte consists substantially 10 . . .

of Builders.

66. A composition according to either of claims 63 and 64, wherein said Electrolyte consists substantially of Builders selected from sodium carbonate, sodium silicate, sodium citrate, sodium nitrilotriacetate, sodium phosphate, sodium pyrophosphate, a sodium polyphosphate, a sodium phosphonate and a mixture of any of the aforesaid Electrolytes.

67. A composition according to either of claims 63 and 64, wherein said surfactants consist substantially of sodium linear alkyl benzene sulphonate or a mixture thereof with sodium alkyl ether sulphate, sodium alkyl sulphate, sodium paraffin sulphonate, sodium olefin sulphonate, non-ionic surfactants and/or Soap.

68. A composition according to either of claims 63 and 64, wherein said Electrolyte consists substantially of Builders selected from sodium carbonate, sodium silicate, sodium citrate, sodium nitrilotriacetate, sodium phosphate, sodium pyrophosphate, a sodium polyphosphate, a sodium phosphonate and a mixture of any of the aforesaid Electrolytes, and said surfactants consist substantially of sodium linear alkyl benzene sulphonate or a mixture thereof with sodium alkyl ether sulphate, sodium alkyl sulphate, sodium paraffin sulphonate, sodium olefin sulphonate, non-ionic surfactants and/or Soap.

69. A composition according to any one of claims 1, 2 and 3 having a Viscosity less than 10 Pascal seconds.

70. A composition according to any one of claims 5, 6 and 29 having a Viscosity less than 10 Pascal seconds.

71. A composition according to any one of claims 30, 60 and 61 having a Viscosity less than 10 Pascal seconds.

11...

72. A composition according to either of claims 63 and 64 having a Viscosity less than 10 Pascal seconds.

73. A composition according to any one of claims 1, 2 and 3 having a Viscosity less than 5 Pascal seconds.

74. A composition according to any one of claims 5, 6 and 29 having a Viscosity less than 5 Pascal seconds.

75. A composition according to any one of claims 30, 60 and 61 having a Viscosity less than 5 Pascal seconds.

76. A composition according to either of claims 63 and 64 having a Viscosity less than 5 Pascal seconds.

77. A composition according to any one of claims 1, 2 and 3 having a Viscosity greater than 0,1 Pascal seconds.

78. A composition according to any one of claims 5, 6 and 29 having a Viscosity greater than 0.1 Pascal seconds.

79. A composition according to any one of claims 30, 60 and 61 having a Viscosity greater than 0.1 Pascal seconds.

80. A composition according to either of claims 63 and 64 having a Viscosity greater than 0.1 Pascal seconds.

81. A composition according to any one of claims 1, 2 and 3 having a Viscosity greater than 0.5 Pascal seconds.

82. A composition according to any one of claims 5, 6 and 29 having a Viscosity greater than 0.5 Pascal seconds.

83. A composition according to any one of claims 30, 60 and 61 having a Viscosity greater than 0.5 Pascal seconds.

84. A composition according to either of claims 63 and 64 having a Viscosity greater than 0.5 Pascal seconds.