PT79744B - Liquid detergent compositions - Google Patents

Abstract

Liquid detergent compositions suitable for laundry use consist essentially of water, Electrolyte, Active Ingredient and preferably a Builder. They comprise a space-filling, floc-like aggregate of surfactant containing spherulites, substantially cocontinuous with an aqueous liquid micellar solution. They are shear thinning, mobile, stable to shear stress, storage under extreme climatic conditions and high pH.

Description

DESCRIPTION OF THE INVENTION

The present invention relates to the process for the preparation of mobile, preferably flowable, aqueous based detergent compositions containing effective amounts of detergent additive.

Except where otherwise stated, or the context otherwise excludes, the terms that are in parentheses, wherever used in this specification and claims, shall have the meanings hereinafter assigned to them in this Defention Section.

The term "additive" is often poorly used in the art of detergents to include any surface active agents whose presence in a detergent formulation increases the wipe effect of the formulation. More usually, however, the term "limited" is typical of "additives" which are mainly useful with a means of preventing or ameliorating the unfavorable effects of washing calcium and magnesium ions, for example chelation, efflorescence, precipitation or absorption of the ions, and secondary as a source of alkalinity and buffer effect. The term "additive" is used here in the narrowest sense, and refers to additives which improve the effects of calcium in substantial amplitude. It also contains sodium or potassium tripolyphosphate and other phosphate and condensed phosphate salts such as orthophosphates, sodium or potassium pyrophosphates, metaphosphates or tetraphosphates, as well as phosphoates such as acetodiphosphonates, amino tris-methylene phosphonates and ethylenediamide tetramethylene phosphonates, also includes alkali metal carbonates, zeelites and sequestrants such as salts of nitrilotriacetic acid, citric acid and ethylenediamine diamine, polycarboxylic polymeric acids such as polyacrylate and copolymers based on maleic anhydride

For the avoidance of doubt the "additive" is used herein to include alkali metal silicates soluble in water, but excludes adi. such as carboxymethylcellulose or polyvinylpyrrolidone whose function is essentially that of soil-suspending agent or anti-deposit

" electrolyte " is used herein to mean those ionic compounds, which have a water solubility of

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.W

- less than 5 wt.%, Expressed as wt.% Water soluble anhydrous compound which at least partially dissociates in aqueous solution to provide ions, and which at the present concentrations have a tendency to lower the total solubility (including the micellar concentration) of surfactant soluble inorganic salts such as, for example, alkali metal or ammonium chlorides, nitrates, phosphates, carbonates, silicates, perborates and polyphosphates, and the like. also include certain soluble organic salts which desolubilize or "decrease the solubility" of the surfactants. They should not include salts of cations which form insoluble precipitates in the water with the surfactants present or which are only poorly soluble in the composition, such as calcium chloride or sodium sulphate.

References herein to the electrolyte content or concentration refer to the total dissolved electrolyte, including any dissolved additive, whether such an additive is also an electrolyte, but excludes any suspended solid.

"hydrotrope" denotes any water soluble compound which has a tendency to increase the solubility of surfactants in aqueous solution. Typical hydrotropes comprise urea and the alkali metal or ammonium salts of lower alkyl benzene acids such as toluene sulfonate and sodium sulfonate and xylene.

Whether a particular compound is an electrolyte or a hydrotrope can often depend on the active ingredients present. Sodium chloride is generally considered a typical electrolyte, but in relation to sultaines behaves as a hydrotrope. The "electrolyte" and the "hydrotrope", as used herein, must therefore be constructed in the context of the particular active ingredients.

When used herein "soap" means at least one sparingly water-soluble salt of an aliphatic monocarboxylic acid

natural or synthetic, the salt of which has surfactant properties. The term includes sodium, potassium, lithium,

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-4-Ânaphthalenamine of the natural and synthetic fatty acids which comprise the stearic, palmitic, oleic, linoleic, ricinoleic, beanic and dodecanoic acids, branched chain monocarboxylic acids and resins acids.

The "customary secondary ingredients" comprise those different water ingredients, active ingredients, additives and electrolytes which may be included in detergent laundry compositions, typically in up to 5% ratios, and which are compatible in the relevant formulation with the chemically stable, pourable composition non-sedimentation. The term comprises full-length dispersing agents, dispersants, antifoams, aromatics, colorants, brightness-producing optical agents, hydrotropes, solvents, buffers, deodorants, corrosion inhibitors, antioxidants, preservatives, scale inhibitors, humectants, enzymes and their stabilizers, activators of bleaching substances and the like. As used herein "functional ingredients" mean ingredients which are necessary to provide a beneficial effect on the washing liquor and include ingredients which contribute to the washing performance of the composition, for example, surface active agents, additives, bleaches, brightening agents alkaline buffers, enzymes and anti-deposit agents, and also anti-corrosive and antifoams, but excluding solvents, dyes, aromatics and stabilizers whose sole function is to impart stability, fluids other desirable characteristics to a formulation concentrated, "payload" means the percentage of functional ingredients based on the total weight of the compound, dog. "active ingredients" means surface active materials.

All references herein to "centrifugation", unless otherwise noted, are to be understood as referring to centrifugation at 25 ° C for 17 hours at 800 times the normal gravitational force.

All references to "high centrifugation G" means centrifugation at 20,000 G at 25 ° C. Unless otherwise noted, the high centrifugation G was performed for 5 minutes.

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The term "separable phase" is used herein to denote components or mixtures of components of a watertight composition, which are each separable from the composition to form a distinct layer after centrifugation. Unless the context otherwise requires all references to the composition of separable faeces are references to the compositions of the separate phases and references to the structure of a composition refers to the non-centrifuged composition. A single separable phase may comprise two or more thermodynamically distinct phases, which are not separable from each other by centrifugation, for example, of a stable emulsion or flake.

"dispersed" is used herein to describe a phase which is discontinuously distributed as distinct or small particles in at least one other phase, "co-continuous" describes two or more interpenetrating phases, each of which protrudes continuously or with a net continues through a common volume, or otherwise is formed of distinct or dissimilar elements which react to form a continuous matrix tending to maintain the position of each element relative to the matrix when the system is at rest, "interdispersed describes two or more phases which are co-continuous or one or more of which is dispersed in the other or other phases.

References to "solid phases" are the substances currently present in the composition in the solid state at room temperature, and including any water of crystallization or hydration unless the context otherwise requires. References to solids include references to microcrystalline solids to cryptocriatalins, i.e. solids whose crystals are not directly observed by optical microscope but whose presence can only be deduced. A "solid layer" and a non-pourable pasty solid gel layer formed by centrifugation.

" total water " refers to water present as liquid water in a predominant aqueous phase, together with any water or the composition, for example water of crystallization or hydration or water dissolved or otherwise present in any predominant non-aqueous phase , " dry weight " refers to residual weight after drying at constant weight at 14 ° C.

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The term "formulation" is used to disclose the combination of ingredients that constitute the dry weight of a composition.

Thus the same formulation can be exemplified by a number of compositions, differing in their dry weight percentages

"stable" means that no layer containing more than 2% of the total volume is separated from the batch of composition without 3 months at room temperature under normal gravity

The "shear test" means a test in which a sample 6 passed through a 40 mm straight tube with an inner radius of 0.25 mm radius under a pressure of 35.15 kg / cm2. The cut-off test was performed for all measurements described herein by aspirating a sample into a 500-ml pressure vessel through a large aperture tube, replacing the large aperture tube with the 0.25 mm ray and applying

O

a nitrogen pressure of 35.15 kg / cm2 in the pressure vessel until the latter is filled. The 0.25 mm tube was then replaced by the large aperture tube so that the cycle could be repeated. Typically, the foregoing process creates a shear rate of approximately 127,000 sec ^"1 ·

"stable to shear" means stable after 3 passes through the shear test, "unstable to shear" means unstable after exposure to 3 or fewer passes through the shear rate or at a lower shear rate, "unsatisfactory to cutting "is meant not to suffer loss of stability or a substantial increase in viscosity after moderate shear exposure. Cuttability was determined using a Convex" Rheomat 30 "viscometer and plate, measuring system 2, 252C, increasing the shear linearly from 0 to 280 sec- ¹ , for 1 minute (the "up") and decreasing it immediately and linearly to 0 sec- ¹ for 1 minute (the "descending").

A composition is considered non-shear sensitive ee APU cycle is stable and the viscosity at 150 sec ^"1 to" seed "is not higher than 10% ds more QUS in" ascending ".

"temperature stable" means that no layer containing more than 5% of the volume is separated from the batch of composition within 24 hours of being heated by immersion of a 20 gm sample in a water bath maintained at 90 ° C for 110 minutes, followed by immersion immediately in a water bath maintained at 100 ° C for 10 minutes.

Reference herein to the pH of the detergent compositions is

the pH when measured by a glass combined with Pye Unicam 401 /

/ calomel electrode ·

"conductivity" refers to the specific conductance measured at 25 ° C at a frequency of 50 KHertz. The results obtained were measured on a conductivity bridge "CDM 3 RADIOMETER * using a circulation and CDC 314 pipette cell.

The "first minimum conductivity" refers to the conductivity chart in relation to the increase in the concentration of dissolved electrolyte in a liquid detergent composition containing a fixed ratio of active ingredients to water,

I in which the conductivity, having usually risen initially

The term means the concentration of electrolyte corresponding to this minimum value or the lowest concentration of dissolved electrolyte corresponding to a plurality of such minimums.

All percentages, unless otherwise indicated, are by weight, based on the total weight of the composition

All references herein to "viscosity" except as otherwise mentioned are for the viscosity of the measurement in a beaker and pendulum viscosimeter at 25 ° C after two minutes of the test using a 20 mm flat bottom cup

} of the inner diameter, 92 mm in length, and a mass

with a diameter of 13.7 mm, 44 mm in length, with conical ends at an angle of 452 to the horizontal, and 4 mm in diameter of the spindle · The tip of the dough was 23 mm from the base of the bowl. This corresponds to the viscdtemftro Contravee "Rheomat 30" using the measuring system C.

"pourable" when used herein means having a viscosity of less than 2 seconds Pascal at a shear rate

"•1

136 sec.

"viscosity drop" means the difference between vis

the composition of a fine-cut composition measured at 21 ° C

viscosity measured at 136 sec ~

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"Elastic limits" when referred to herein as "

when measured on a Rheometer Deer RML Series II at 253C.

Phase "L" denotes a clear, fluid, isotropically fluid, isotropic solution of surfactant in water, which occurs at concentrations above the critical micelle concentration, and wherein the molecules of the surfactant are considered to be micelles spherical, flattened at the poles (disc) or alloyed in the direction of the poles (rod).

"bilayer" includes a thick surfactant layer of approximately two molecules, which is formed of two adjacent parallel layers, each comprising surfactant molecules which are arranged such that the hydrophobic moieties of the molecules are located in the inside the bilayer and the hydrophilic portions are located on their outer surfaces. The "bilayer" is also used herein to include interdigitated layers, which have less than two molecules in thickness. An interdigitated layer may be considered as a bilayer in which the two layers have penetrated there between leaving at least some degrees of overlap between the hydrophobic portions of the two layer molecules.

"spherolite" means a spherical and spheroidal body having dimensions of 0.1 to 30 microns. The spherolites can sometimes be deformed in rod, oblate, pear or baltere forms. "vesicle" means a spherole containing a liquid phase bounded by a bilayer. "multiple vesicle" means a vesicle containing one or more small vesicles.

"lamellar phase" means a hydrated solid or liquid crystal phase in which a plurality of dazzling pellets are arranged in a substantially parallel order, separated by layers of water or an aqueous solution and having a sufficiently regular shingle spacing of from 25 to 70 for are readily detectable by neutron diffraction when present as a substantial proportion of a composition. As used herein, the expression excludes multiple concentric vesicles.

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The phase "G" refers to a liquid crystal lamellar phase, of the type also known in the literature as the "clean" or "lamellar" phase. The "G" phase for any surfactant or mixture of surfactants, generally within a narrow range of concentrations. Pure "G" phases may generally be identified by examination of a sample under a polarizing microscope between cross polarizers. Observed textures characteristic of Roeevear's classic document, 3AOCS Vol. 31 P628 (1954) or 3. Colloid and In terfacial Science, Vol. 30 Nfl. 4, P.500 (1969).

"spherical phase G" means multiple vesicles formed from substantially concentric ticonioactive bilayer shells alternating with aqueous phase with a G-phase spacing. Typically the conventional G-phases may comprise a minor proportion of spherical G-phase.

"bleach" means an aqueous liquid phase containing electrolyte, which phase separates from or intercalates with a second liquid phase containing more active ingredient and less electrolyte than the bleach phase.

"lamellar composition" means a composition in which the majority of the surfactant is present as a lamellar phase, or in which a lamellar phase is the main sedimentation inhibition factor, "spherolytic composition" means a composition in which the highest part of the surfactant. vol is present as spherolites, or is mainly stabilized against sedimentation by means of a spherolytic surfactant phase.

Liquid detergents have hitherto been used primarily for light duty applications such as dishwashing. The market for heavy duty detergents, eg laundry detergents, has been dominated by powders because of the difficulty of obtaining an effective amount of surfactant and in particular of additive in a stable liquid formulation. Such liquids should in theory be lower than powder detergents since they should avoid the need for drying and should in many cases replace the filler

V

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♦ -10. sulfate conventionally used in powder detergents ccm

They also offer the possibilities of greater convenience and faster dissolution in wash water than at least the attempts to provide solutions for the functional ingredients have not been of good commercial success. A reason for this lack of success has been that the most generally used and cost-effective additives, for example sodium tripolyphosphate are insufficiently soluble in aqueous compositions. Furthermore, due to the effects of decreasing solubility, increasing the amount of additive there is a tendency to lower the amount of surfactant that can be dissolved and vice versa. Potassium pyrophosphate additives, together with amine salts of the more soluble active ingredients, have been tried as alternatives for sodium salts, but no efficient price has been found.

Liquid, non-additive detergents containing high levels of surfactant have been marketed for laundry use, but are inconvenient for hard water areas to which only limited success has been achieved, mainly restricted to markets where the use of effective additives is subject to legal constraints, and post competition to less severe corrsepondsntsmBnts

A different attempt is made to suspend the excess additive as a solid in a liquid micellar solution, or emulsion or surfactant. The problem however has been to stabilize the system to keep the additive in suspension and avoid sedimentation. The literature has proposed numerous relatively sophisticated formulations including the use of expensive potassium salts instead of the cheaper sodium salts of solubilizers such as hydrotropes, dispersants or solvents, all of which have prevented the realization of potential price savings. with such extraneous additives it has been found necessary to use relatively low concentrations of solid additive, which has limited wash efficiency. This attempt has been conditioned by certain conjectures: that the active ingredient

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- ¹¹ should as far as possible be in solution; that the amount of active ingredient should be relatively high; that the amount of suspended solid should be minimized to avoid difficulties in stabilizing the suspension against settling; that special stabilizers or stabilizers were essential to avoid sedimentation, and that the electrolytes which should de-lubricate the surfactant should be omitted or stored at very low levels

The greatest feature of art until now has been its empirical nature · No general theory, acceptable, has been

| proposed to interpret the stability of some compositions

and other instability. There is thus no way of predicting which compositions will be stable, and no general operative method for designating a new stable liquid detergent. The art generally does not contain applicable teachings, and even the specific examples of most patents liquid detergents, provides compositions that separate within a few weeks. The relatively few exceptions that have been discovered by chance and no extrapolation have been possible.

Products of this type were introduced commercially in Europe and Australia, but suffered certain serious drawbacks. The products were found to have weak relative potency due to the low ratio of additive to active ingredient to low alkalinity ·

They also gave evidence of undesirable sensitivity of mechanical and / or thermal stress eg in cutting or storage in extreme climatic temperature conditions.

While some compositions are separated in the cut, others become viscous viscous and most separate after storage at both 0 ° and 40 ° C. However, It is not yet known how to overcome the deficiencies cited above.

In addition to the compositions that have been commercially developed, many compositions have been proposed in the literature that

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These compositions are unstable, or insufficiently stable to withstand normal storage without sedimentation, or otherwise are too costly to manufacture in relation to their washing performance to be considered for commercial development

A set of compositions has recently been proposed wherein the active ingredients form a network of a lamellar phase, separable from the aqueous phase by centrifugation, which realizes a gel structure capable of supporting suspended solid additive particles. The gel structure is obtained by adding sufficient electrolyte to decrease the solubility of the active ingredient so as to form an aqueous bleach phase and a separable filler layer and by maintaining the solids content above a melamine for stability below ceiling for vertibility. The amount of electrolyte required depends on the hydrophilicity and melting point of the surfactant, and any solubilizing additives such as hydrotropes or solvents are present. The above gel compositions tend to be higher in payload and in the ratio of additive / active ingredient, and to have a higher effective price than the known commercial liquid compositions. In the art, the best of the foregoing lamellar gel compositions are higher priced effective elimination agents than the best laundry powders.

However, the lamellar compositions disclosed heretofore have a motility that is less than optimal for the same purposes.

We have now discovered a novel group of compositions comprising electrolyte, active ingredients and water which are capable of suspending solids such as additives to form stable compositions which combine improved washing ability with satisfactory mobility. The novel compositions are believed to owe their stability to a spherolytic structure previously not mentioned, and a general process of preparing stable β-mobile compositions with superior washability was discovered from a wide range of different in-

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and

-13gredientea assets ·

The embodiments of our invention have at least some of the following advantages compared to products marketed so far: high payload; elevates the additive to the surfactant ratio; stability; lower price due to the use of cheaper ingredients and ease of production; high mobility, improved washability; high pH and / or alkalinity; good stability at high or low storage temperatures; and satisfactory cutting behavior.

We have found that when active ingredients, dissolved electrolyte and mare are present in certain proportions depending on the particular active ingredients and electrolytes that are chosen, and a stable spherolytic composition is obtained which is capable of suspending solid particles as such. such compositions and to identify them by means of varieties of physical characteristics. We have further discovered how to optimize the proportions of active ingredients and electrolyte for obtaining compositions which are stable to shear stress and for temperature variations similar to those found in storage in a wide variety of climates and for high pH or alkalinity, and which will not highly mobile. Except for the compositions exemplified in the prior art in relation to lamellar compositions, our novel compositions appear to be stabilized by a surfactant present in a spherole phase rather than a lamellar phase.

The prior art on liquid detergents is extremely bulky. However, for the purpose of the present invention the numerous references to light-duty liquids and for making, or establishing, clear liquid laundry detergents in which all ingredients are present in solution can be neglected. The level of the additive is substantially lower than desirable.

Recent general summaries of the current state of the art include * 3A0CS (April 1981) P356A - Heavy Duty Laundry Detergent "

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^w -14que comprises an examination of typical liquid formulations and eat * cially available "Rscent Changes in Laundry detergent" by Rutkowski , published in 1981 by Marcel Dekker Inc. in the "Surfactant Science Series".

Three possibilities for approaching the problem of formulating the fully liquid detergents were to emulsify a disintegrant in an aqueous solution of an additive to suspend a solid additive in an aqueous emulsion or emulsion of surfactant and to suspend solid additive on a gel with a lamellar matrix of tenacious agent

I-active.

The first attempt is exemplified by PEU 3235505, PEU 3346153, PEU 3351557, PEU 3509059, PEU 3574122, PEU 3328309 and Canadian patent 917031. In each of these patents an aqueous solution of a water-soluble additive is sufficiently concentrated to reduce the solubility of the agent (usually a non-ionic type liquid) is also dispersed in the aqueous medium as epoxy droplets with the aid of various emulsifiers. In each case the system is a clear emulsion which generally contains relatively low levels of additive and is undesirably expensive due to the price of use of soluble additives.

| The second attempt is exemplified by GB 855893,

GB 948617, GB 943271, GB 1468181, GB 1506427, GB 2028365, PE 38101, P. Australian 522983, PEU 4018720, PEU 3232878, PEU 2920045. The compositions described in these patents are unstable, either unstable at temperature or stable to cut. Commercial products corresponding to examples of two of these patents have been commercially available in Australia and Europe. In particular a composition corresponding to the Australian Patent NS. 522983 made a certain commercial success, but bread was sensitive to cutting.

The third attempt is described in the

European Patent NS. 0086,614. The disclosed compositions have a matrix of lamellar glass surfactant

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Solid or liquid. Each composition may have higher viscosities than are desirable for certain uses.

A different approach is to suspend solid additive in a nonionic liquid anionic surfactant, for example BP 1600981. Such systems are expensive, restrictive of the choice of the surfactant and provide insatiably upward properties. The level of the additive is high compared to the total and low composition with respect to the active gradients and the cost efficiency is therefore very low. shah.

Various patents disclose emulsions wherein the additive is in the dispersed phase of an emulsion rather than in a suspension. US 4057506 discloses the preparation of clear emulsions of sodium tripolyphosphate, and U.S. Patent 4107067 discloses inverse emulsions in which an aqueous solution of additive is dispersed in a liquid crystalline surfactant system.

Reference may also be made to the numerous patents which refer to hard surface cleaners in which an abrasive is generally suspended in an aqueous solution of surfactant, for example, U.S. Patent 2031455, U.S. Patent No. 3281367, U.S. Patent 3813349, U.S. Patent 3,356,158 and U.S. Patent 4,302,347. However, the low levels of surfactant, absence of additive and the presence of high concentrations of abrasive generally prevent these patents from having any assistance in the formulation of laundry detergents.

Other publications of possible interest are: U.S. Patent 5,074,331, which describes suspensions of additive in aqueous surfactant stabilized with sodium carboxymethyl cellulose or clay as a thickening agent. However, the levels of the functional ingredients, and in particular of the additive, in the exemplified formulations are not sufficient for a fully acceptable commercial product and stability is inadequate to provide effective shelf life.

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US-3039971 discloses a detergent portion containing the additive in solution;

French Patent 2283951 describes suspensions of zolite additives in nonionic surfactant systems and the compositions are, however, thick pastes instead of mobile fluids.

U.S. Patent 3346504 and U.S. Patent 3346873 describe the solubilization of sultaines with hydrotropes, which are referred to herein as " electrolytes ".

The NQ symposium ACS. 194 "Detergent Silicates" describes the effect of silicates on liquid detergents.

It will be understood that each of the references of the foregoing patents has been chosen from the very extensive prior art, and important aspects highlighted with the aid of late development, using our knowledge of the present invention as a guide for such selection and enhancements. The person generally skilled in the art at the time of our first priority claimed, and without the applicant's invention, would not necessarily have chosen those patents as being particularly important or those aspects as being of particular interest or relevance.

The foregoing summary does not therefore represent the total description of the art possessed by the ordinarily specialized person.

According to a first embodiment, our invention provides a stable, pourable, fluid detergent composition consisting essentially of active ingredients, electrolyte and water and having solids suspension properties, wherein the ratio of electrolyte is sufficient to provide a stable temperature, non-cut sensitive, substantially non-lamellar composition.

According to a second embodiment, our in

provides a stable flowable detergent composition and

with suspending properties of solids and comprising

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The active ingredient and electrolyte, wherein the ratio of electrolyte is sufficient to provide a space-filled spherical filler which is stable at temperature and non-sensitive to shear.

According to a third embodiment, our invention provides a stable, pourable, fluid detergent composition having solids suspension properties and comprising water, active ingredients and electrolyte sufficient to form a dispersed stable phase which contains at least part of the ingredients which corresponds to a depression in the conductivity plot against electrolyte concentration which contains the first minimum conductivity, the ratio of said electrolyte being within the range at which the composition is temperature stable and non-sensitive to shear.

Preferably in each of the preceding embodiments the electrolyte concentration is sufficient to provide a stable shear composition.

Preferably the composition according to the preceding embodiments contains suspended solids, such as additives and / or abrasives. Suspended solids may be insoluble in the aqueous fluid medium, already present in amounts of saturation, or encapsulated in a material which prevents them from dissolving in the medium.

According to a fourth embodiment, our invention provides a stable and pourable fluid detergent composition containing water, active ingredients, suspended solids electrolytes, wherein the ratio of lectolith is sufficient to form a stable shear spherolytic composition with

-2

an elastic limit of 1 to 15 dynes cm ·

Preferably, the yield strength of the composition is greater than 1.5, more preferably greater than 2, even more preferably greater than 2.5, for example greater than 3 and preferably less than 10 dynes cm. 136 sec "" ¹ is less than 1.5, more preferably less than 1, for example 0.2 to 0.8 Pascal seconds,

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-18-

According to a fifth embodiment, the present invention provides a stable, flowable, stable and pourable detergent composition consisting essentially of water, from 5 to 25% based on the weight of the active ingredient composition, electrolyte and suspended solid additive, the preparation of the total weight of the additive for the active ingredient being from 1.4: 1 to 4: 1 and the electrolyte portion being sufficient to provide a stable, non-lamellar,

The composition may additionally contain the usual secondary in-gradients. The active ingredients are preferably present in a proportion of 10 to 20% more preferably 10 to 14% by weight and the total weight ratio of the active ingredient additive is from 1.5: 1 to 3: 1, for example 1 , 9: 1 to 2.5: 1.

According to a sixth embodiment, our invention provides a stable, pourable, fluid detergent composition comprising water, from 5 to 25% based on the weight of the active ingredient composition, electrolyte and suspended solid additive, and with an optional of at least 35% by weight, wherein the ratio of electrolyte is sufficient to provide a stable, spherical cut composition.

According to a seventh embodiment, our invention provides a water-containing detergent composition of 5 to 25% by weight of active ingredients, electrolyte and suspended solid additive, the total weight ratio of additive to active ingredients being 1, 5: 1 to 4: 1 and the proportion of electrolyte. to be sufficient to provide a stable spherolithic composition at 40Â ° C storage. Preferably the ratio of electrolyte is sufficient to render the composition stable at temperature

According to an eighth embodiment, our invention provides a stable, pourable, fluid detergent composition, composition comprising water, 5 to 20% by weight of active ingredients, electrolyte and suspended solid additive, peel ratio total active ingredient additive being from 1: 1 to 4: 1 and the ratio of electrolyte being sufficient to provide a temperature stable, non-sizable composition

2

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Which is centrifuged and separated into an aqueous layer containing more than 50% of the total weight of the active ingredients and a solid layer

According to a ninth embodiment, our invention provides a stable and pourable detergent composition consisting essentially of water, dissolved electrolyte and 8 to 14% by weight of the active ingredient composition together with suspended solid additive, optionally the usual secondary ingredients, the composition of which, by centrifuge

separated into a solid layer and a single liquid layer -2

| with a yield point greater than 1,5 cm ·

According to a twelfth embodiment, our invention provides a composition which consists substantially of water, active and electrolyte ingredients and solids suspending properties, wherein the active ingredients are capable of forming a stable composition in the first minimum conductivity , and the amount of pre-electrolyte is sufficient to provide a composition having a tensile strength

-2

cm 3 and a viscosity measured at 136 eq ^-1 , less than 0.25 second Pascal.

According to an eleventh embodiment, our invention provides a base detergent composition

| aqueous, pourable and stable substance consisting essentially of water,

active ingredients and additives comprising a predominantly aqueous first separable liquid phase containing at least part of the electrolyte in the solution and from 50 to 80% of the total weight of the active ingredients, at least one separable phase of dispersed solids comprising less the additive as a solid.

Preferably the predominantly aqueous separable phase comprises at least 40%, usually at least 50%, for example at least 60% of the total water.

According to a twelfth embodiment, the

our invention provides a base detergent composition

aqueous, stable and stable condition with a payload of more than 35% in

and a pH greater than 9 and comprising water, an electrolyte

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At least 5% by weight of active ingredients and at least 16% by the addition of an additive, electrolyte which is present in a proportion sufficient to render the composition stable to cutting but insufficient for the active ingredients to form a substantial proportion of a phase lamellar

According to a thirteenth embodiment, our invention provides an aqueous based liquid detergent composition comprising active ingredients sufficient to form a surfactant space filler flake containing spherolites intercalated with an aqueous fass and a

and the amount of the electrolyte is not less than that corresponding to the pri

minimum conductivity of the electrical conductivity plot as a function of the electrophyltol concentration, but below which corresponds to the formation of a lamellar phase, is sufficient to render the composition non-sensitive to the cut ·

According to a fourteenth embodiment, the nos. the invention provides a pourable and stable detergent composition comprising water, electrolyte, active ingredient and additive which is separated by centrifugation as herein defined in at least two layers containing: a predominantly aqueous layer containing dissolved electrolyte, at least 10% by weight . of total water, and from 80% to 50% by weight of the total active ingredient, and a solid layer containing at least one proportion

of the additive

According to another embodiment, our invention provides a stable spherolytic composition comprising active ingredients, electrolyte and water which does not have a clear, aqueous, clear phase after high G centrifugation at 20,000 G for 90 minutes.

As a further detail, our invention provides fluid, stable and pourable detergent compositions comprising water, active ingredients and electrolyte, all of which compositions have at least some, but not all, of the characteristic wafers: comprise a spherolytic phase interspersed with a bleach or phase and co-continuous with the bleach or L _x j phase are substantial

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-21 non-lamellar; comprise a flake system which is preferably space filler; comprise a floc system which is formed of particles comprising the active ingredients which are preferably surfactant-containing spherolites, typically with concentric shells of surfactant alternating with an aqueous phase, for example bleach

O

and with a repeat spacing of 60 to 100 A, preferably 70 to 90), often 75 to 85, for example 80 A; comprise spherolites of 0.5 to 5 microns, preferably 0.6 to 5 microns in diameter, which show a so-called "Malt Cross" texture when observed at suitable magnifications between cross polarizers; are subjected to shear thinning; have a viscosity drop of more than 0.35, usually greater than 0.4, often greater than 0.45 seconds Pascal, but preferably less than 2 seconds Pascal, for example 0.475 to 1.5, especially 0.48 to 1.1 seconds Pascal; have a high payload of functional ingredients, typically greater than 20% by weight, for example 25 to 75%, more usually at least 30%, preferably at least 35%, more preferably at least 40% by weight; contain a high ratio of additive to the active ingredient, for example greater than 1: 2: 1 to 4: 1, more preferably 1.4: 1 to 4: 1, most preferably 1.5: 1 to 3 , 5: 1; contain more than 5 and preferably more than 8% by weight of the active ingredient composition; contain less than 25%, preferably less than 20%, usually less than 15%, more preferably less than 14%, for example 10 to 13.5% by weight of the composition of active ingredients; form a single aqueous layer and a sulfid layer by centrifugation wherein the aqueous layer usually has a limit of the

elasticity of at least 1, preferably at least 1.5 g.

For example 2 to 10 dynes cm-2 and typically a viscosity of less than 1.5 seconds Pascal at 136 sec- ¹ ; the weight ratio of active ingredient in the predominantly aqueous layer formed after centrifugation based on the total active ingredient of the composition of greater than 50%, preferably greater than 55%, for example greater than 60% but less than 90%, preferably

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- less than 85%, for example less than 80%, such as 75 to 65%; no clear liquor layer is observed therein, for centrifugation G for 90 minutes; the pH of the composition is greater than 8.5, preferably 9 to 13, for example 9.5 to 12; the composition produces a wash liquor in dilution with 0.5% dry weight water having a pH greater than 9.7, preferably greater than 10, for example 10.9 to 11.1; the alkalinity is sufficient to require at least 0.8 ml of N / HCl HCl to reduce the pH of 100 ml of wash liquor at 0.5% dry weight to 9, preferably 1 roll for example 4.7 to 8 , 6 ml; the at least one predominantly aqueous liquid phase contains sufficient electrolyte to provide a concentration of at least 0.3, preferably at least 0.5, more preferably at least 1.2, for example 2.0 to 4.5 ions gram per liter of the total alkali metal and / or ammonium cations; the electrolyte concentration δ greater than that corresponding to the first conductivity minimum of the conductivity plot as a function of the electrolyte concentration; the conductivity is not more than 2 mS greater than the conductivity of the first minimum conductivity; the electrolyte concentration is below that which causes the formation of a substantial proportion of the lamellar phase; the electrolyte concentration is above the minimum which provides a composite. is preferably above the minimum which provides a shear stable composition; the non-cut sensitive composition 6; the composition is stable at temperature; the composition is stable at 40 ° C; the conductivity of the concentration is below 15 millisiemene per cm; the concentration is about 15% by weight, preferably more than 20% by weight of the additive; the additive - at least predominantly sodium tripolyphosphate; the additive comprises β-alkali metal silicate or carbonate, preferably β-sodium silicate or sodium carbonate; the viscosity of the composition at a rate of 136 ks cut "okay ¹ ejs sntrs 0.1 and 2 Pascal Seconds, preferably between 0.2 and DS 1 Pascal seconds eg 0.3 to 0.6 Pascal seconds, the composition TSM a limit of elasticity preferably at ms 1, more preferably at least 1.5, for example at least 2, preferably less than 30, for example less than 20, more preferably less than 15, usually less than 10,

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♦ -23nes / square cm, an additive-containing phase comprises solid particles having a particle size maximum below the range at which the particles tend to sediment; the composition is stable to cut; the active ingredients include eg. at least two components, one of which is a non-ethoxylated anionic surfactant and the other a surface active agent forming stable foams, such as an aryl sulfate, alkanol or amine oxide.

Interactions of Electrolyte and Tensioactive Agents

When the concentration of electrolyte dissolved in a suitable mixture of aqueous surfactants is progressively increased from zero, the composition typically passes through a series of readily recognizable steps as follows:

Step I

First the conductivity increases to a maximum, during which step the viscosity increases β the initially clear, optically isotropic phase begins to highlight the formation of spherolites. The latter are visible under the microscope, and show the so-called "Maltese cross" texture, generally associated with spherolitic phases "G" when examined between cross polarizers. However, the

| neutron diffraction, does not show any evidence of a

"G" or any other liquid crystal phase, and is compatible with a substantially micellar composition.

The compositions of Step I are generally clear and stable, but are not capable of suspending solid particles.

Step II

In the second stage the conductivity decreases with the

concentration of the electrolyte, and the composition becomes turbid. THE

high centrifugation G separates the composition into an aqueous phase

clear and in an opaque "emulsion phase", the volume ratio

of the last phase increasing with the increase of the concentration of the

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(i.e.

"Liquid Detergent Compositions"

*

In the microscope, it is observed that the spherulites are increasingly numerous and smaller in size, and to be added in loose flakes separated by optionally isotropic regions, flakes that become more compressed as the concentration increases of electrolyte.

Studies on neutron deflection are consistent with reduced micellar concentrations and a higher proportion of larger bodies, but not with the presence of any major portion of the "G" phase. The compositions of step II are turbid, and unstable and sediment rapidly.

Step III

The conductivity drops to a minimum θ then starts to rise. The spaces behind the spherolite flakes disappear and the spherolites form a space filling flake extending throughout the liquid phase. The high centrifugation G does not separate an aqueous phase, even when carried out for 90 minutes. A yield strength is observed, which increases to a maximum, and the composition becomes flowable to the cut with a marked drop in viscosity.

Neutron diffraction shows no evidence of any substantial proportions of the lamellar phase. Micellar magnetic resonance imaging does not similarly provide

| any substantial "G" phase content and indicates a low concentration

traction of micellar surfactant. The electron microscope indicates that at least some of the spherulites are multiple vesicles with a substantially concentric arrangement of partially overlapping shells or shells, possibly spaced wider than in a normal G phase.

The compositions of Step III are stable and capable of suspending solid particles to form a stable suspension. Such compositions of Step III constitute our invention.

Step IV

The addition of more dissolved electrolyte

reducing the size of the spherulites and enhancing the brightness of the texture in "Malta Cross". The spheroliths

they cease to be space fillers forming discontinuous flakes, separated by optically isotropic regions, the viscosity limit of the viscosity drop decreases and the conductivity increases to a maximum or begins to settle to a value. The diffraction of nsutrSas provides evidence of substantial "G" phases. The high centrifugation G separates a clear bleach phase from a cloudy layer. The composition is unstable, has a tendency to sediment and is incapable of suspending solid particles.

Step V

A lamellar composition δ formed by the type described in European Patent 0086614. The viscosity, when the water content is adjusted to the amplitude necessary to give a stable composition, is relatively high.

The foregoing sequence is typical of the β-β-triazole interactions with a wide variety of mixtures of the aqueous surfactants. If the composition already contains some dissolved electrolyte, such as in a detergent prepared containing suspended tripolyphosphate or in case the initial surfactant mixture is not completely soluble in water, the first step may not be observed. Likewise, if the solubility of the electrolyte is limited, such as, for example, in the case of sodium tripolyphosphate or sodium carbonate, addition of more electrolyte above its saturation limit should not admit the composition no longer in the sequence.

Preferred embodiments of the present invention are within the third step of the preceding sequence. Between the third stage the second and fourth stage, respectively, there are intermediary corapoaitions which are semi-stable. Such positions exhibit flakes of surfactant surfactants which are not completely space fillers as evidenced by the fact that the high centrifugation G carried out for 90 minutes results in the formation of an aqueous layer, either clear, or in which the spherolites are capable of being irrevocably destroyed. Such compositions, while stable at room temperature, are often unstable when exposed to various

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Such as high shear stress, high or low temperatures or changes in pH. Its ability to suspend solids from particles is often limited. A number of compositions proposed in the prior art are in these semi-stable areas.

We have found that, in general, the compositions within these semi-stable "boundary" areas may be mod. according to the teachings of this patent, by adjusting the electrolyte content to bring them closer to the action of the stable areas of Stage III ·

Usually, by centrifugation, the compositions of Step III of the present invention are separated into an aqueous layer containing the electrolyte and from 90 to 50% by weight of the total active ingredients substantially 80% -50%, more usually 75% to 55% for example 70% to 55% of the total active ingredients, and at least one other layer, said at least one further layer preferably containing from 15% to 80% by weight of the total active ingredient together with a substantial proportion of the additive The viscosities of our compositions at a shear rate of 136 sec- ¹ are typically between 0.1 and 2, preferably 0.2 and 1.5, for example 0.25 and 0.6 seconds Pascal, and viscosity drop is typically between 0.4 and 2, for example 0.45 to 1.5 seconds Pascal.

The compositions of Step III are non-shear sensitive and usually stable to shear. On the contrary, high shear forces tend to render the compositions semi-stable, unstable limits. The viscosity is often increased substantially even by moderate shear and may undergo rapid sedimentation. This may present practical difficulties during manufacture and bottling. The compositions of Step III of our invention are generally stable at high pH and for storage at temperatures around 402C or below 52C, except for many semi-stable compositions. They can be temperature stable, typically when heated to 100Â ° C.

The compositions of Step III typically do not show

any evidence of a lamellar phase in diffraction analysis

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-27-

but some compositions close to the limit with Step IV may show indication of minor amounts of the "G" phase.

Proposed structure

We are convinced that the foregoing behavior can be explained more easily with the assumption that the surfactant is progressively transferred from the micellar phase to the spherolytic phase with increasing electrolyte concentration. We are convinced that spherulites initially take the form of multiple vesicles in which a plurality of bi-layers are arranged substantially concentric, but with a longer and more irregular spacing than in a conventional "G" phase.

It is possible that there are two aqueous phases, one is a bleach phase, the latter phase of which may also be a phase containing less micelles and more electrolyte than the former. We have found that by increasing the electrolyte content and decreasing the proportion of active ingredient, the tendency is to obtain compositions which are less viscous for equivalent solid stability and payload. We believe this reduces the proportion of micellar surfactant without substantially reducing the amount of spheroliters. A lower micellar content reduces viscosity while the spherolytic phase remains sufficient to maintain stability.

We are convinced that in the preferred stable composition of our invention, that the spherulites are sufficiently heaped together and intimately to form an aggregate flake which is subs. tancialments of space, ie that it extends through the whole volume of the liquid. The spherolites probably influence each other to form a weak three-dimensional matrix, strong enough to withstand suspended particles, but fraught enough to break and flow easily under the influence of shear forces and to reform when exhausted. The size of the spherolites appears to be correlated with stability; compositions with large spherolites of 5 microns and more are less stable than those in which the highest surface active agent content is in the form of 0.5

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-28-

at 5 microns

As the electrolyte content increases the spheres will become smaller and possibly more compact, tending towards a tighter and more even spacing of a "G" spherical fae. As a consequence, the "G" phase spherolites no longer stay in time and the composition becomes ready for sedimentation.

Active Ingredients

The compositions of the ninth invention preferably contain at least 5%, less than 30% and generally less than 25% by weight of surfactants. More preferably the surfactant comprises from 5 to 20% by weight of the composition, for example 8 to 15% by weight, typically 10 to 14.5%, especially and preferably less than 14, often less than 13% .

The concentration of the active ingredients may be a key factor in obtaining compositions of the present invention. Below a certain minimum which varies according to the particular active system, the composition can not be stabilized by addition of more electrolyte, however, the maximum is also important in order to avoid excessively viscous compositions.

The semi-stable spherolytic compositions of the prior art often have relatively high amounts of active ingredients. This has resulted in a relatively high viscosity of the aqueous suspension medium, which in turn has energetically limited the amount of additive that can be suspended for any given acceptable viscosity limit. Thus, the ratio of the total additive to the active ingredient has itself. of the low am compared to powders, with the consequent poor washing behavior.

It was largely unobvious that the active ingredients in such compositions could be reduced without totally destabilizing the systems. We have surprisingly found that if the electrolyte concentration is sufficiently high, the concentration of active ingredient can be substantially reduced, to provide aqueous media with equivalent or even

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-29 higher stability and still lower viscosity. Such means can suspend larger amounts of additive without loss of convenient mobility and the resulting large increases in the ratio of additive to active ingredient also produces substantial increases in price capability.

In general it is easier to prepare spherolytic flakes from mixed surfactants than from simple surfactants. Thus mixtures of one or more non-ethoxylated anionic surfactants such as alkyl benzene sulfonate and / or alkyl sulfate with one or more surfactant which form stable foams such as alkyl ether sulfates and / or ethoxylates nonionic or alkanolamides or amine oxides are generally more convenient than any of the surfactants themselves. Lower amounts of ethoxylated nonionic surfactants or amphoteric surfactants or cationic fabric softeners may additionally be present.

The surfactant mixture may for example comprise at least one or more poorly water-soluble salts of monoesterified sulfonic or sulfuric acids, for example an alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, olefin sulfonate, alkylphenol ether sulphate, alkyl phenol ether sulphate, alkyl ether sulphate, alkyl ether sulphate ether or alpha sulfo fatty acid or esters thereof each having at least one alkyl or alkenyl group having from 8 to 22, more usually 10 to 20 aliphatic carbon atoms. Said alkyl or alkenyl groups are preferably straight-chain primary groups but may optionally be secondary or branched chain groups. The term "ether" above refers to admixed polyoxyethylene, polyoxypropylene, glyceryl and polyoxyethylene-oxypropylene groups, or mixed glyceryloxyethylene or glyceryl oxypropylene groups, typically containing from 1 to 20 oxyalkylene groups, for example the sulfonated surfactant or sulphate may be sodium dodecyl benzene sulfonate, sulphate

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"Liquid Detergent Compositions"

d

THE

i>

-30-

hexadecyl benzene potassium sulfate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, sodium tallow sulfate, potassium oleyl sulfate, lauryl sulfate monoethoxy ammonium, or cetyl monoethanolamine sulfate (10 moles) ethoxylate.

Other anionic surfactants useful in accordance with the present invention include paraffin sulfonates, olefin sulfonates, alkyl fatty sulfosuccinates, fatty alkyl alkyl sulfosuccinates, fatty alkyl sulfosuccinamate, fatty alkyl alkyl sulfosuccinamates, acyl sarcosinates, acyl, isethionates, soaps such as stearate, palmitates, resinates, oleates, linoleates and alkyl ether carboxylates. Anionic phosphate esters may also be used. In each case the anionic surfactant typically contains at least one chain of aliphatic hydrocarbons containing 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, and in the case of ethers one or more glyceryls and / or of up to 20 ethyleneoxy or propyleneoxy groups.

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

The surfactant blend may optionally contain or, less preferably, consist of nonionic surfactants. The nonionic surfactant may for example be an alkanolamide ^{of a} lower ^{mono or} dialkanolamine such as monoethanolamide. Other nonionic surfactants which may optionally be present include ethoxylated alcohols, carboxylic ethoxylated acids, ethoxylated amines, alkylolamides, ethoxylates, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters and propoxylated esters or ethoxylated and propoxylated analogues of all heretofore mentioned nonionic ethoxylated, all having an alkyl or alkenyl £ q ~ ® 22 ^a to 20 groups

21.

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-31-

ethyleneoxy and / or propyleneoxy or any other nonionic trifluoroacetic agent which has heretofore been incorporated into powder or liquid detergent compositions, for example amine oxides. The latter have typically at least one alkyl or

alkenyl ^C g_22 ^'d8 P ^refer6ncia i0-20 ^{C and two at} 9 ^ ^{ru al} q P ⁰⁸ ° ^IWU lower (e.g. Preference ^d ®

The preferred active ingredients or mixtures for our invention are for example those with an HL8 range of greater than 7, preferably greater than 12 and less than 18, more preferably less than 16 and more preferably less than 15.

Some of our detergents may contain cationic surfactants, and especially cationic and / or bactericidal tissue emollients usually as a minor proportion of the total active material. Ethyl tissue emollients of value for the present invention include quaternary amines having two long chain alkyl or alkenyl groups

(e.g. ± £ ^ti P 2-22 ^icamen '^ ^rt ^ 16-20 ^{and two} P ^ru 9 ° lquilo ^{8 to} short chains (sxsmplo C ^ _ ^) or a short chain and one benzyl group. The same also include quaternized imidazoline and imidazolines having two long chain alkyl or alkenyl groups, and amide amines and quaternized amide amines having two long chain alkyl or alkenyl groups. The quaternized emollients are all usually salts of anions which transmit a measure such as formate, lactate, tartrate, chloride, methosulfate, ethosulfate, sulfate or nitrate. Compositions of our invention having a fabric softening nature may contain smectite clays.

Compositions of our invention may also contain amphoteric surfactant, which may typically be included in cationic surfactants, but may also be included, usually as a minor component of the active ingredients, in any of the other types of detergents pre-examined.

Amphoteric surfactants include betaines, sulfobetaines and phosphobetaines formed by the reaction of a compound

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Suitable tertiary nitrogen with a long chain alkyl or alkenyl group with the appropriate reagent, such as chloroacetic acid or propane sultone. Examples of suitable tertiary nitrogen-containing compounds include: tertiary amines having one or two long chain alkyl or alkenyl groups, optionally a benzyl group and any other substituent a lower alkyl group imidazoline having one or two long chain alkyl or alkenyl groups and amidoamines with one or two long chain alkyl or alkenyl groups

Those skilled in the art of detergents should recognize that the specific types of surfactants des. above are only exemplary of the common type surfactants suitable for use in accordance with the present invention. Any tene-active agent capable of performing a useful function in the wash liquor may be included. A full disclosure of the principal types of surfactants that are commercially available from the current edition of MaCutcheon's Emulsifiers & Detergent, published by the MaCutheon division of the Manufacturing Confectioners Publishing Company.

Electrolyte

The electrolyte is essential in order to act reciprocally with the surfactant to form a spherotic system. The concentration of the electrolyte is preferably, however, not sufficient to permit substantially accumulation of any bilayers located on the same piano for non-spherical phase and lamellar phases. Such lamellar phases may provide compositions which are unstable or unstable to the cut, salt and and payload is sufficiently high for the lamellar phase to form a stable structure according to PE

008614A. The relatively strong matrix characterizing the latter compositions, however, results in an undesirable high viscosity. For a convenient surfactant system at a suitable concentration, we find that it is possible to stabilize the system according to our invention by including in the composition a suitable amount of electrolyte.

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Insufficient electrolyte results in unstable or cut-off or temperature sensitive systems and / or in systems with undesirable high viscosity. The proportion of electrolyte must therefore be chosen according to the nature of the surfactant and the amount of any hydrotrope present to provide compositions in accordance with the present invention.

The optimum ratio of electrolyte may generally be determined by making progressive additions of electrolyte to an aqueous micellar solution of the active ingredients (typically about 15 to 20% by active weight) and observing one or more of the various characteristic properties of the system such as turbidity, conductivity, yield strength, polarizing microscope appearance or high spin behavior G. ¹

When the characteristics of Step III properties as described above are detected, for example a cloudy composition at or near a first minimum conductivity, with a flake of spheroliths showing no clear isotropic areas and not showing any clear to high centrifugation, then the spherolytic range was identified.

The proportion can be optimized within this range by obviating the amount required for not obtaining clear layer at high G centrifugation for 90 minutes. If the position is intended for a market in which the low viscosity is most important, say shelf life at low temperature, the optimized composition may be progressively reduced. diluted until a suitable viscosity is achieved or signs of instability are observed. If any of the above occurs, further additions of electrolyte may be made until a sufficiently stable composition is obtained.

The amount of electrolyte is preferably higher than the first conductivity minimum of the conductivity / Electrolyte concentration plot and corresponding to the amount required to provide a composition having a yield point greater than 1.5 dynes cm-1.

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»

-34-

We prefer the use of functional electrolytes such as carbonates, silicates, pyrophosphates, polyphosphates, nitrile acetates and citrates, all of which are additives, but the effective concentration of some such electrolytes, for example carbonates, may be undesirably limited by their solubility. In such cases it proves necessary to add a more soluble non-functional electrolyte. Sodium chloride and sodium nitrate were found to be particularly effective in this regard.

Often the ratio of electrolyte in at least one predominantly aqueous phase is sufficient to provide a concentration of at least 0.3, preferably at least 1.2, for example 2.0 to 4.5 gram per liter of calcium metal , alkaline earth metal and / or ammonium cations.

Additions

The additive in preferred compositions of our invention is generally considered to be present at least partially as discontinuous solid crystallites suspended in the composition. The crystallites typically have a size of up to 60, for example 1 to 50 microns.

We have found that formulations containing sodium tripolyphosphate as an additive, or at least the greater proportion of sodium tripolyphosphate in admixture with other additives, exhibit stability and mobility over a wider range of dry weight than the corresponding formulations with other additives. Such flormulations are therefore preferred. Our invention, however, also provides compositions which comprise other additives such as tripolyphosphate, carbonates, zeolites, nitrile triacetates, citrates, metaphosphates, pyrophosphates, potassium phosphonates, EDTAs / o-carbonol carboxylates, optionally but preferably in admixture with tripolyphosphate. Orthophosphates may be present, preferably as secondary components in admixture with tripolyphosphate, such as alkali metal silicates and carbonates.

The silicates and carbonates are particularly preferred since they perform several valuable functions. They provide desirable free alkalinity to saponify fats in the

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soil, have effect as additives, and in the case of silicates, inhibit corrosion of aluminum surfaces in washing machines. Moreover, they are effective as electrolytes necessary to form a spherolytic system.

Typically, in the case of silicate being used to prepare our compositions, it has a Na2 Q: SiO2 ratio of 1: 1 to 1: 2 or 1: 1.5 to 1: 1.8. It will be appreciated, however, that any ratio of the (or other base) to SiO2, or even silicic acid, may be used to provide the silicate in the composition and any necessary additional alkalinity performed by the addition of another base such as sodium carbonate or hydroxide. Formulations not intended for use in washing machines do not require silicates provided there is an alternative alkalinity source.

We do not exclude compositions where the additive is substantially completely present in solution, for example sodium nitrile triacetate, sodium citrate, sodium silicate or mixtures thereof.

The additive generally constitutes at least 15% by weight of the compositions, preferably at least 20%. We prefer the ratio of additive to surfactant to be greater than 1: 1 preferably 1.2: 1 to 4: 1.

Causes

For economic reasons it is generally preferred that the cations present should consist, at least predominantly, of sodium. Thus, for example the preferred additive is sodium tripolyphosphate, the preferred anionic surfactants are sodium salts of sulfated or sulfonated anionic surfactants and any anti-redeposition agent for example carboxymethyl cellulose, or alkali, for example silicate or carbonate salts are also preferably present as sodium chloride, sodium chloride, sodium nitrate or other soluble inorganic sodium salts may be added to increase the concentration of the electrolyte. Calcium is only generally present when the active ingredients comprise tertiary-active agents, such as olefin or nonionic sulfonates which

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are tolerant of their presence. Magnesium salts may be present, and are more compatible with the surfactants than calcium *

It is possible, alternatively, but less preferably, to choose potassium, ammonium, lower amine, alkanolamine, or mixed cations salts. Compositions containing strong proportions of such cations are, however, unlikely to be cost effective compared to conventional laundry powders.

Alkalinity

The compositions of our invention are preferably alkaline, desirably buffered with an alkaline buffer to provide a pH of the composition when measured on a calomel glass electrode, above 8.5, preferably above 9, more preferably above 9.2, for example 9.5 to 12, specifically 10 to 11. We particularly prefer that our compositions should be adapted to provide a pH of greater than 9.7, for example greater than 10, specifically 10.5 to 11.5 in a wash liquor containing the diluted dry weight composition. They will desirably have free alkalinity / to require at least 0.4 ml, preferably at least 0.8 ml, more preferably 1 to 12 ml, for example 3 to 10 ml, typically 4 to 9 ml of N / reducing the pH of 100 ml of a diluted solution of the composition containing 0.5% dry weight to 9, although the compositions with higher alkalinity may also be commercially acceptable. In general, lower alkalinities are less acceptable in practice and commercial, although not excluded from the scope of our invention.

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

Solubilladoras

Heretofore, the liquid detergent compositions have usually contained substantial concentrations of hydrotropes and / or

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water-miscible organic hydroxylic solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol. They are, however, expensive and are not functional ingredients. They may, in certain circumstances, produce verifiability or allow a surface active agent to form a spherolytic phase more easily. We do not therefore exclude them altogether from all compositions of our invention, but we prefer that their presence be limited to the minimum necessary to ensure a spherical composition with suitable vertibility. If it is not necessary, we prefer that they are absent. Solvents may sometimes need to be adapted as perfume components or other customary side ingredients.

Dry weight

The dry weight of the composition affects stability and vertibility. The optimum dry weight can vary considerably from one type of formulation to another and may be chosen to provide the required viscosity. Generally speaking, it has not been found possible to provide stable compositions below about 35% by weight dry weight, although some types of formulations can be obtained in a stable form below 30% dry weight, and often as low as 25% dry weight. We did not exclude the possibility of making compositions stable at dry weights below 20%.

For any given formulation according to the present invention a range of dry weights can be identified within which the composition is both stable and watertight. Generally it lowers from this range, it gives sedimentation and above the range, the formulation is too viscous. The acceptable range can usually be determined for any given formulation by preparing the suspension using the minimum water necessary to keep the composition agitated by diluting a number of samples at progressively higher dilutions and observing the samples per se. sedimentation during a convenient period. For some formulations the acceptable range of dry weights may range from 30% or 35% to 60% or even 70% by weight, while others may be much more limited from 40 to 45% by weight.

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If no stable and pourable range can be determined by the foregoing processes, the formulation should be modified according to the teachings of the masters for example by the addition of more sodium carbonate, sodium silicate solution or other electrolyte if the composition properties of Eta I or II or by reduction of the electrolyte content or by the addition of hydrotrope if the composition has properties of Step IV or V. Alternatively, if problems are encountered in obtaining a stable spherolytic system, only by altering the The active ingredients may be modified by the addition of a foam stabilizing surfactant such as alkyl ether sulfate, amine oxide alkanolamide, if the composition is to be employed in step IV or V, or by the addition of alkyl benzene or alkyl sulfate if step I or II is predominant

Preparation

The compositions of our invention may in many cases be readily prepared by normal stirring together with the ingredients. It is a feature of our preferred compositions, however, that they are not destabilized or thickened by subjection to high shear forces.

The order is mixing conditions of the ingredients are sometimes important for the preparation of a stable structured mix according to our invention.

The compositions according to our invention may typically be obtained for any suitable active ingredients by first preparing a clear aqueous solution Lj of the active ingredients at a convenient concentration (for example 15 to 30% by weight active) with heating, if necessary, and dissolving □ the electrolyte in the Lj solution or by adding a solution of the concentrated electrolyte (preferably functional electrolyte) until the mixture becomes opaque. A sample of the mixture is then centrifuged at 20,000 G for 5 minutes. If a clear aqueous phase is observed, more electrolyte is added to the mixture until the high centrifugation G no longer provides evidence of a sub-ethanically separated aqueous phase

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clear The weight ratio of the active ingredient to dissolved electrolyte is then noted.

The composition containing all of the desired ingredients and the weight ratio of the active ingredient to the already determined electrolyte may then be prepared at the desired dry weight percent (typically 40-50%). Formation of a clear phase of aqueous lye at high centrifugation G indicates the presence of β-lamellar phase the amount of electrolyte is then reduced until no clear phase is observed by high centrifugation G. Samples of the latter formulation at different dry feet may be prepared to determine optimal mobility / stability characteristics.

If it is difficult to determine a suitable active / electrolyte ratio in the first step of the preceding step the operating mode may be repeated using a more soluble electrolyte, for example a non-functional electrolyte such as sodium chloride or sodium nitrate. Alternatively, the active system may be modified by the addition of surfactants favoring stable dispersions according to our invention, for example ether sulfates, amine oxides or alkaliamides, if the properties of step IV or V are observed, or a surfactant anionic, non-ethoxylic activity of the properties of step I β II are obtained more rapidly.

Typically, mixing is carried out at ambient temperature in the case of compatible dispersion, certain ingredients, for example nonionic surfactants such as coco monoethanolamide, require gentle heating for example 408 for convenient dispersion. This degree of heating can usually be achieved by heating or hydrating sodium tripolyphosphate. To ensure sufficient heating, it is preferred to add the tripolyphosphate in the anhydrous form containing a sufficiently high proportion of the high temperature increase modification generally referred to as " Phase I ". The preceding operative mode is only one of the dj.

which processes can be satisfactorily used for all or most of the compositions of our invention. Some

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formulations are more sensitive to the mixing order and temperature than to others.

Formulation

In view of the different types of formulation according to our invention in greater detail, we particularly distinguish high foaming formulations of sulphate or sulphonate foam and low foaming formulations.

High foaming formulations can be used. These compositions may be based on mixtures of one or more non-ethoxylated anionic surfactants, preferably a sulfated or sulphonated surfactant, with one or more surface-active surfactant co-surfactants such as surface- anionic ethoxylated actives an amine oxide or a fatty alkanolamide. The first component is the active ingredients, i.e. the ethoxylated anionic surfactant, for example a ^C18 - ^C18 alkyl sulfate, or alkyl benzene sulfonate of the second component or co-surfactant -alkyl may be a straight chain

or branched alkyl ether sulphate or an alkylphenol ether sulphate, ether amine sulfate, fatty acid ether or sulfate alkanolamide. Alternatively or additionally, the second component may comprise an amine oxide or fatty alkylamide. The total weight ratio of non-ethoxylated cosurfactant to anionic surfactant may typically be 5: 1 to 1: 3 , preferably 4: 1 to 1: 2, for example 3: 1 to 1: 1. Small amounts (for example up to 1% of the composition weight) of soap may be present to aid the hard rinse of the fabric. Ethoxylates may be present in minor proportions, typically up to 20% by weight of the total active ingredients, preferably less than 15%, usually less than 10%.

The sodium alkyl sulfate or the alkyl benzyl sulfonate may not be wholly or partially substituted in the formulas the other sulfonates, surfactants. non-ethoxylated alkyls including xylene alkyl or toluene fatty sulfonates, or by paraffin sulfonates, olefin sulfonates, sulfocarboxylates and their esters and amides, including

63 318

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"Liquid Detergent Compositions"

Sulfosuccinates and sulfosuccinamates. The alkyl ether sulfate may be wholly or partially substituted by other ether sulfates such as alkyl ether phenyl sulfates, ether sulfonate ether sulfonates or mixtures thereof

According to a specific embodiment, therefore, our invention provides a stable and pourable spherolytic composition comprising: water, from 12 to 40% dry weight of active ingredient based on the dry weight of the concentration and from 20 to 80% of dry weight of the additive based on the dry weight of the composition, at least partially present as a suspended solid and at least partially as part of said dissolved electrolyte; and wherein said active ingredients consist of (A) from 30 to 80% by weight of a sulfated or sulfonated anionic non-alkoxylated surfactant, β (θ) of 20% to 70% by weight of the surfactant, active agent of at least one foam stabilizer surfactant and / or a nonionic surfactant.

The above composition may optionally further contain up to 6% dry weight of the soap composition. Preferably the nonionic, sulfated or sulfonated anionic surfactant substantially consists of alkyl sulfate or benzene alkyl benzene sulphonate sodium benzene alkyl sulfonate, for example sulphonate alkyl benzene.

Alternatively, the anionic teneioactive agent may comprise a mixture of the alkyl benzene sulfonate and / or alkyl sulfate with alkyl ether sulfate and / or alkyl phenol ether sulfate in weight proportions of, for example, from 1: 3 to 5: 1 typically 1: 2 to 4: 1, preferably 1: 1 to 3: 1 for example 2: 1.

The low foaming compositions according to our invention may be prepared using suitable foam inhibitors. The choice of foam inhibitors needs some care, since certain commercially available inhibitors of the art may lose their storage efficiency of the compositions of our invention, whereas other

63 318

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"Liquid Detergent Compositions"

are only efficient at very high concentrations to affect the viscosity or stability of the composition. Particularly effective blends of organopolysiloxane and colloidal silica are found.

Our invention provides, according to a further specific embodiment, a stable, pourable, fluid aqueous detergent composition comprising: from 12 to 40% based on the dry weight thereof of active ingredients comprising from 30 to 90% based on the dry weight of the active ingredients of sulfated and / or sulphonated non-alkoxylated anionic surfactant and the weight equality of an alkyl ether sulphate surfactant and / or an alkanolamide or amine oxide; an aqueous phase containing electrolyte in solution sufficient to form a confluent spherolytic flake comprising said active ingredients and intercalated with said aqueous phase; particles, suspension of additive; an effective amount of at least one foam inhibitor and optionally the usual secondary ingredients.

According to another specific embodiment the nos. the invention provides a stable pourable detergent composition having a payload of 30% to 50% consisting essentially of 12 to 40% by dry weight, based on the dry weight of the composition, active ingredients, at least 30% of additive, based on the dry weight of the composition, an additive to active ingredient ratio of greater than 1: 1 to 1, said active ingredient consisting essentially of aliphatic alkyl benzene sulfonate having 8 to 18 carbon atoms and an alkyl ethanolamide selected from alkyl monoethanolamides and diethanolamides in a

weight ratio of alkyl benzene sulfonate to ethanol amide of from 1.5: 1 to 4: 1, said additive being selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrile triacetate, sodium silicate and mixtures thereof, of such that the amount of the dissolved additive is sufficient to

_2

elasticity of more than 1,5 cm.

A particularly preferred embodiment of our invention provides a liquid, liquid detergent composition

stable, which consists essentially of:

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

A mixture of (i) a sodium benzene alkylbenzene sulfonate of 10 to 18, preferably 10 to 14 aliphatic carbon atoms with (ii) a sodium alkyl sulfate having an alkyl group with an average of 8 to 18, preferably 10 to 14 carbon atoms, β of 1 to 20, preferably 2 to 10, for example 3 to 5 ethyleneoxy and / or propyleneoxy groups in the ratio of (i) :( ii), between 10: 1 to 1:10, especially 10: 1.5 to 10.5 for example 10: 2 to 10: 4;

An additive selected from sodium tripolyphosphate, zeolite, sodium nitrilotriacetate and mixtures of dosages in a B: A weight ratio of from 1.1: 1 to 4: 1, preferably 1.2: 1 to 3.5: 1 , for example 2: 1 to 3: 1.

C - In an electrolyte selected from sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof in a concentration of 2 to 15% by weight of the composition; said composition having a payload of 30 to 50% by weight, preferably 35 to 50% by weight, for example 38 to 45% by weight; said composition preferably containing minor but effective amounts of anti-redeposition agents, preferably sodium carboxymethyl cellulose, aromatics, colorants and optical brightening agents.

The sodium cation of the preceding composition may optionally, but less preferably, be substituted in whole or in part by potassium, lithium or ammonium. Preferably the tripolyphosphate salt constitutes 40-95% of the total weight of the additive, for example 45% to 80%. Preferably the composition contains at least one foam inhibitor, if necessary for automatic washing.

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

Secondary Inequalities

The compositions of the present invention may contain the

usual secondary ingredients. The main ones of these are the

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"Liquid Detergent Compositions"

-44 anti-redeposition agents, dispersants, optical brightening agents and bleaching agents

The anti-redeposition agent most commonly used to make sodium carboxymethylcellulose (SCMC) detergents, which may be present in the composition of the present invention, for example in effective amounts compatible with the desired viscosities, stability and stability · Generally; speaking, SCMC is effective at concentrations of about 1% and we prefer not to exceed normal effective concentrations, since SCMC in larger amounts. increases the viscosity of a very conspicuous liquid composition. and can also affect stability.

An alternative anti-redeposite and / or soil release agents include potassium, ammonium and other CMC soluble salts, foephonates, methylcellulose, polyvinylpyrrolidone, carboxymethyl starch and similar polyelectrolytes, all of which may be used in place of SCMC.

Optical brightness agents (ABO) are optional but are preferred ingredients of the compositions of our invention. Except for some formulations of the prior art, our compositions are not dependent on ABO for stability and are therefore free to choose any convenient and cost effective ABO, or to omit them altogether. We have found that any fluorescent ink up to now recommended for use as ABO mm liquid detergents may be employed, as can many inks generally suitable for use in powder detergents. The ABO may be present in conventional amounts. Typically ABO concentrations between 0.05 and 0.5% are sufficient, for example 0.075 to 0.3%, typically 0.1 to 0.2%. Lower concentrations could be used but are unlikely to be effective, while higher concentrations, while not excluding them, are unlikely to prove effective pricing and may in some cases lead to compatibility problems.

Typical examples of ABO that may be used in the pre-

The compounds of the present invention comprise: 1,2- (benzimidazolyl) ethylene ethoxyl

(2-methyl-2-benzofuran-2-yl)

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

»

-4-oxazole) ethylene; (2-hydroxyethyl-4,4'-bis (6-methylethanolamine-3-anilino-1,3,5-triazin-2 "-yl) -2,2'-stilbene sulfonate; bis (2 "-hydroxystil) -amino-6" - (3 "-sulfophenyl) amino-1", 3 ", 5-triazin-2" -yl 2-yl) -2-stilbenesulfonate disodium 4,4'-bis [4 '- ((S) -dimethylphenylsulfonate); 2 "-hydroxyethoxy) -6" -amino-1 ", 3", 5 "-triazin-2-yl) amino] -2,2'-stilbenedisulfonate;4-methyl-7-dimethylammarmarin; and 4,4 ' (benzimidazolyl) sphene.

Bleaches may optionally be incorporated into liquid detergent compositions of our invention, subject to stability and chemical compatibility. Capsju bleach sides may form part of the suspended solids. The action of peroxy chelators in compositions of our invention can be enhanced by the presence of bleach activators such as tetracethyl ethylenediamide in effective amounts. Photoactive bleach such as zinc or sulfonated aluminum phthalocyanine may also be present.

Aromatics and colorants are conventionally present in laundry detergents in amounts of up to 1 or 2%, and may likewise be present in compositions of our invention. Care is often required in choosing a convenient aroma, since the solvents present may modify the behavior of the active ingredients.

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

Other secondary ingredients include defoamers, al. calis, buffers, germicides such as formaldehyde, opacifiers, such as vinyl latex emulsion, inert abrasives, such as silica and anticorrosives such as benzotriazole.

The compositions of our invention are in general convenient for laundry use and our invention provides a

fabric washing process by stirring the same in a ds liquor

washing composition containing any composition of the present invention as

63 318

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"Liquid Detergent Compositions"

Described herein. Low-foam compositions described herein are particularly useful for use in automatic washing machines. The composition may also be used in dishwashing, the cleaning of hard surfaces, the low foam products being particularly suitable for use in washing machines. These uses constitute another aspect of the present invention.

The compositions of our invention may generally be used for washing fabrics in boiling water, or for washing at medium or cold temperatures, for example 50 to 800C. particularly 55 to 68 ° C, or 20 to 50 ° C especially 30 to 40 ° C, respectively. Typically the compositions may be added to the wash water at concentrations between 0.05 and 3% dry weight based on the wash water preferably 0.1 to 2%, more usually 0.3 to 1% e.g. 0.4 to 0.8%.

The present invention is elucidated by the examples set forth in the following Tables.

The examples were stable and veritable. They remained stable to storage at 40 ° C and were unaffected by cutting. They were stable at temperature and, except for example 83, stable at cut.

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

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MPD252 / RGMS / AER

'• Liquid Detergant Compositions "

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63 318

MPD252 / RGMS / AER

«Liquid Detergent Compositions»

-54-

IA IA IA tn IA - · » * » • X UI Ch CM <r IA IA IA IA fc » fc • XI IA IA CJ \ CM r-4 • X UI CM IA or -4 1 tn • X UI ι-1 fA O -1 1 1 • X or IA The rl 1 OX xi 1

IA

IA

CM

CM

CM

CM

CM

rr

IA

CM

C? -I

X

UI

Ch

CM

•

X

UI

LA II

CM

CM

1Λ

*

CM

I

IA

r- ι

ιλ ι

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Hi rl

P (0 O W •H rl X O -4 □ rl -P Rl m P <-1 O O O -P | 00 O P Rl Rl O yl O O d (I.e. W rl 1 □ u rm (I.e. CJ CM O O • r | 0 □ r-4 rl d O X O Rl oo O (I.e. (I.e. O Rl 0 u r-1 *O d +1 TJ D (I.e. Rl □ n d (I.e. d (I.e. 0 3 * O <-L (I.e. 0 O CT <0 Rl O rl d CD -P d yl 3 (I.e. AND TJ rl 0 d TJ <0 ® cr d r | 1 n 4- (I.e. yl xx ι-1 e CMx-x 0 O O d to O d rl 0 < O O -P P d W rl U d -P Ck. d A.D O yl d O rl O d Rl + » CD -P O +1 W rl -P W l-1 d σ ν d e d d ο ε Rl O O O <uc '- O +> O -4 XI Q. d -4 ® -4 tn W m U00 (I.e. P • r | Rl 3 XI 3 x r O • r | r- | xx d d P P cn cn ΣΣ O (I.e. N CJ 1- 1-

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

00 κν CN K K THE • 00 1 GRANDFATHER X CN Ul

CN

The

00

KV • 4 ¹ A cn * <N 'k 00 A • r •-1 rH <t 1 X CN

UJ

NJ

A Ι-I

GRANDFATHER

KV

•

X

Ul

in

UV ι

i

H

and

m

c

Rl X

rn

(D r-1 O O t CO u Rl α (I.e. O XJ rn « O "O cj CN O co rN O "-1 O O CJ XI XI CD O «· r-1 •H (I.e. XJ Rl (I.e. •H XJ O 0 0 XJ K 3 O "-1 XJ O (I.e. "-1 cr <0 • H (D • r, P CO ri □ XJ e "The K (0 CD cr here u- The" O XJ (Z "> H 0) XJ 0 (0 O η n O X O + J O ω W Ct- O Z β W OH 0 O Rl -P (I.e. W O T the -P P 0 c a O N ca CD Rl O O W U O r-I The Rl • r | rn O η κν W (I.e. Rl cn □ jO □ O O P Rl cn cn Σ N 1- cn

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-56

x

Ul

tn <t

O O 00 i-4 v0 O- rd tn - •B •B •B •B •B - K 00 grandfather 03 CO 1 O O O r4

M tn v0 w b) 4b ro · » • Hello a b m 0 • k X tn Γ- rd 1 1o O σ 1 Ul Ol

ro σν O O O· O tn ο- tn rd O • (I.e. * · » H, •B ι * K X α ro tn 1 H O O 1 rd

Ul rd <N

Ol

T

•

X

UI

rd

rd 00 co rd ro r "4 i-4 σ K K M- K - · » · » "B v0 ro 40 Ov l rd ι α * -4 O 1-d

rd

•

X

UI

O in <r 0V Ch *B K · » •B K W- to i-4 ι α HI

40

The rd

· · · »

Hello

O

K

rd

X

Ul

m OO O CM ro grandfather CM • -4 α K k K "B K •B K GRANDFATHER T • 3- Q the α O 1 rd

Ol

Ov tn tn □ O The O O 0- • K "B •B K "B •B * » X tn OVER THERE tn co H O Ul Ol

tn

rd

K

α

tn

· »

οιι

P □ 1 rd 1 β D O D □ O TJ XI •P -P W (I.e. O ro ro D ro ro AND D rd AND ro 1 ro TJ rd W 00 rd O 1 D O rd | D ro rd rd O 1 O O O The ro D O D grandfather W rd O (I.e. O +3 N +3 rd O u O ro rd ro ro The ω O O O O AND TJ grandfather D O O D O rd 1 D O rd rd D O The TJ (D rd AND O rd D D TJ TJ GRANDFATHER O | D x D ro □ (I.e. ot O O rd □ O cr 0) ro +3 O XI <-S D cr +> O rd TJ O and the D O □ P rd ro TJ (0 O D n '- d ro rd XI ro you- TJ AND ro P | D ro ro O 0 O O et ro Ol +3 ro D O •P + » O rd +3 Ass. e O TJ The 4- W (0 W O to D O D O O ro W O W W d -P X + » TJ ro O ro s □ N β O O D O fl D O 3 Ck- W + » j0 Q. rd n 0- AND W O TJ The rd O ID (d D (I.e. P rd ro ro W ro ro □ (I.e. D OK P O ro □ 1 cn O P (D tn ω H N CJ cn «X 5Z Q

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-57

»

CO * (I.e. OVER THERE O O σ α α (I.e. UV • · » (I.e. - (I.e. * - X O β- 1 Ch σν σν (I.e. σ ld rl r- |

Γ- α or or or X or (I.e. ιη • (I.e. - (I.e. - · » · » - X (I.e. <τ ι σ \ σν OK (I.e. α ld r- | ι- |

GRANDFATHER

•

X

Ld

αο UV r σν - - w- - · » 00 KV <± v-H (I.e.

KV <t

<-I <t

- -

hi

n

d

(D

W

•H

or 00 (I.e. (I.e. or (I.e. (I.e. «-Η I u (I.e. rl (I.e. 1 (I.e. or Τ3 X (I.e. (I.e. hi or (I.e. X +> <-Ι CJ (I.e. α. α (I.e. φ or · » (I.e. (I.e. or or Α (I.e. (I.e. (I.e. r * | or d -4 (I.e. (I.e. (I.e. (I.e. (I.e. (I.e. «-4 ass (I.e. Τ3 d (I.e. Α (I.e. χ: · 4 co □ (I.e. • π (I.e. (I.e. (I.e. X (I.e. □ or σ (0 (I.e. (I.e. (I.e. (I.e. cr Ass γ β (I.e. d U • -ι d (I.e. d η ASS (I.e. or X d φ (I.e. 1-I φ (I.e. 04 or or α or or d (I.e. (I.e. (I.e. +> or W χ> Ass (I.e. (i.e. XJ (I.e. d d W d d (I.e. (I.e. +1 β » W d -μ W ι-4 +> d 04 (I.e. (I.e. □ or (I.e. φ or □ (I.e. or or +> 4J U W σ Χ3 CL Γ- | (I.e. (I.e. W (I.e. φ · -I (I.e. W U (I.e. (I.e. ι-4 ιη φ W (I.e. □ XI or d (I.e. (I.e. σι or e ιη SE or (I.e. (I.e. ιη et 5u

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-58

CN

« the e O • faith - O the O A rH X Hi ι tn ιη ι 1M 1Λ O Ul r-1 CN

lh

"faith

ο I

rn α O O O α in rH • •faith •faith •faith "faith •faith (I.e. X O ι tn in 1 rl IA O Ul "H CN

α

(I.e. O O α α Rd (I.e. O • THE •faith •faith The •faith The •faith X α 1 Ch Ch 1 1o O 1 1 ΙΛ Ul rl r-4

Ch • st (I.e. CN -1 NJ rl (I.e. Ch • The The THE THE •faith •faith THE X Ch 1 1 03 CD 1 ισ or 1 1 CN Ul rH

powder

(I.e.

D

* r4 0 O rn O Rl 0 rl TJ TJ CD TJ 0 (I.e. r-1 O O O rl (I.e. Rl 0 O | u • r | 0 O | 0 □ Rl O O TJ 0 O Rl MJ Rl cr 0 (I.e. r-1 O XJ O O •P rl P 0 TJ xj CJ 0 rl O CL CJ O P u 0 0 O □ O *O P -P s-' Rl O O TJ Rl 0 "-1 O 0 O O O P "-1 rl YOU YOU 0 0 □ rl 0- Tl +3 •P •P Rl TJ 0 O CJ TJ x: Rl 0 0 □ XJ u 0 O rl □ O O 0 W O cr m •H •P O 0 Rl cr 0- •P W O TJ rl AND 0 0 TJ P ·-1 0 Rl 0- (0 O 0 TJ 0- Rl Rl XI 0 0 W AND 0 O τι i-1 0 •P AND O •H 0 O -P O O O O «X 0 0 0 Rl TJ u Rl Ο- 0 -P 0 W | .S 0- AND rH TJ TJ 0 O TJ (I.e. 0- co W 0 0 •H O Rl O P □ O W 0 W O + » W rl P X W 0 0 (I.e. 0 W 0 O O N 0 □ □ Rl O 0 •P P □ 0 + » Ο- 0- W O J3 (X rl XJ +> W O 0 Ο- rl 0 (I.e. r-1 0 W P •H X3 P 0 0 W Rl ι-1 Rl AND •P □ XJ O 0 H 0 0 Rl cn O e □ -P Sr P cn e CJ l N CJ Q SC 2E cn Ul α

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

59

00 in grandfather r- NJ (I.e. you X O H <r UJ H

cb O CM THE you O 1 H -1

(I.e.

• NJ · » rte I'm going to X O Hi <r UJ ·-1

Ov O O CN you - you you <r O H -1 H

NJ UN N3 un • you ** X O CN 1 UJ

Γ- O α r - you you you you N) ia Cb O

Hi

UN UN NJ UN • you X O CJ UJ H

r- O Γ- THE (I.e. * η NJ Hi Cb 1 O

UN NJ r- NJ * you n X O Hi • ÍÍ · UJ -1

Ov O O CM you you you you xt C3 H H Hi H

KN UN grandfather UN • you you X O CN UJ H

• σ O σ O r- - you you you * NJ KN Cb •H α

PON \

0 · Η x_x

τι ® -1 O □ 1 u •P ® co O O TJ CO r-1 H O O O 1 O ff) •P CN α O (I.e. □ r-1 O O TJ Rl O (I.e. ® tp CJ iH •H (I.e. •H NJ •The ® •P (I.e. 0 (I.e. τι - O □ O □ (I.e. TJ 0) O rn O rH Rl cr frog • r | ro -P O Rl τι (I.e. e O X here xN □ (I.e. (0 CD m τι frog O & Rl cr frog (I.e. (I.e. tj CN (0 -P •P O O O CO O <x O 0 CD P O W -P O z <P e TJ 0 W 0 (0 -P (I.e. •P O •P O W O +> W co CN (I.e. •P X -P XX □ N 0 O O O O •P O 0 The Cl_ W O XI •P •P CL <P XJ <P I-1 Q> W P > P cn •P (I.e. P P O □ XJ O here •P P CD 0 □ e cn Σ The cn 1- INI ω cn

Optical brightness agent 0.14 0.14 0.14 0.14 0.14 0.14

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-60 IA MJ Of the X u CM w Ch IA IA CO *> IA CD Λ o CM 1 CM »» O "d- MJ <T CM IA CO Ch ι-1 rl • (I.e. • \ - - - ·. X th IA IA CO 1 O O UI CM IA MJ d Ch CM MJ 00 rl * * (I.e. T X co IA IA Γ- 1 t α Ld η CM MJ IA <1 H- Ch IA rl • * (I.e. · « M · » X Ch CM IA Ch 1 1 (I.e. UJ CM rl MJ d- IA tf Ch r- rl • (I.e. - ·> ·. X Ch CM IA Ch 1 1 O UI CM O MJ d IA IA CO O α (I.e. ♦ - * T n · » X Ch IA IA CO <-I 1 O UI H r | Ch ia d- IA IA CO O ri • T w λ λ • fc X Ch IA IA Ch 1 1 O

u cm

ρ

(0

D

W

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TJ

(I.e.

»

you

• d · rl 1 o • r | You oo O O TJ w Rl rl O O (I.e. O -P CJ •H O co r-I α YOU O O 3 O O O Rl you r-1 rl 0 O n YOU you O Rl TJ O u X □ ® co O rl CT TJ (0 -P O Rl r | TJ you you r-1 P Yes O Rl TJ fi- Rl X W AND co -P O O SJ O O <x you you + » N H -P u. e TJ SI W □ you Rl □ Rl O W W rl -P X you O JQ you O O Rl □ -P U +> XI α rl XI W r-1 O you P • r | (I.e. P CD 3 TJ Rl you P you you CT cn Q CJ (- N CJ «X

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

f

-61

P- P * th * Rk K • fc co -k (I.e. X Ch O O 1 ΙΛ M Ul rd

th MD the co (I.e. α θ ' (I.e. • K * * K X CO O O 1 r Ul -1

03 MD rd (I.e. Ch (I.e. CM CM O • K * K • fc X 00 O α 1 Ul you

P- MD th 00 CO « K · » W x ι i ι r » H IA Ul •H

MD MD rd Γ- H « n • fc K • fc X 1 1 1 Ch (I.e. (I.e. THE- Ul H

(4 0 or O W ts D rd α W <r O rl (I.e. (I.e. | • r | (I.e. (I.e. (I.e. τι X r- | CJ (I.e. CJ (I.e. m (I.e. (I.e. or (I.e. □ α D ω O α ι-1 (I.e. φ τι τ> (I.e. (I.e. (I.e. TJ TD (I.e. T3 03 □ (I.e. 03 or (I.e. <r σ 03 (0 4J O CO or rd ι-1 (I.e. 0) β> O (I.e. I (0 (I.e. Rl η 4- D O or TJ e (0 10 (I.e. (I.e. ι-1 (I.e. (I.e. or or -1 +> CJ +> (I.e. rd +> 4- □ O (0 C0 W (I.e. (0 D + » W or W β » W W <-1 O □ (I.e. or (I.e. β □ (I.e. TJ * 4 4- σ 4- W ρ jC3 α. -d TJ -1 (I.e. <-1 (0 ffl (4 (I.e. O D □ 03 □ XJ D (0 14 fct X cn ω CJ 1-

th rk Ch p • 4 H 1 S0 rH ♦ 4 α the 4 ' 1 rd • k (I.e. (I.e. (I.e. rd (I.e. th * K K K σ \ rl 1 O rl 1 CM (I.e. MD rl MD O - K K K K Ch rl 1 O rl 1 (I.e. (I.e. 00 MD rl O r- | • St O K - K K K K rd O CM O O rl 1 rl d P- U \ i rl rl <r Ch K K K K r rl O 1 O O O 1 r-1 O TJ O CO •P O co 14 LOL • r | O □ rd TJ rl P O D (I.e. O » CD X CO e Rl Rl O e W -P ® (I.e. at TJ • _ » 00 Rl O H 1 CD 00 CJ 1 O The CO rl Rl MD w co O 1 •P r- | W rd rl CM CJ □ □ rl (I.e. co and rl CJ □ e CD O rl □ co O O O X • r | CL rl Rl <-1 □ CO □ D TJ Rl σ 10 00 rl □ (I.e. P rd r-1 • r | CT CO XI (0 (0 1 •P rl •The CM OC 03 10 ffl (D • r | rd e TJ YOU TJ O P CJ O Rl O -P O + i X + » Rl (D CD RJ TJ rd Rl O 10 X -P 4- D O rd XI 4- O W O 03 X3 O (I.e. (4 rd •P (D W O D CJ 03 (0 □ (0 cn O 4- W rd N CJ cn «X Σ 1-4 "W

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-62

(I.e. You CM r- 00 • 44 - "B •B 0b XI grandfather O CN (I.e. σν CN

ΙΛ CO 1Λ VO * 1 CN * 1 (I.e. • co 04 r X \ £> O CN K \ Ov Ul CN

ρ

0

0

W

• r |

•H

<r Il O 1 • r | The O XJ rl O (I.e. u O 0 O oo 0 O r- | (I.e. 0 XI O Rl H XJ XI • r | xj D O XJ (I.e. cr 0 0 P (I.e. O n "-1 XJ 0 0 u 0 0 Rl 4- •H σ XI 6 0 0 0 xj O 0 O XJ rl •POWDER rl 4- O O 0 C O • r | 0 +> CO W -1 -P O 0 ON 0 O 0 XJ P 4- C -P The. 14 Rl XJ rl 0 0 •H O O Rl □ XI Rl P • -I bc X cn Ω 1- U

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-63

0x

UJ

CD

•s

nvO

04

fl

(I.e.

(I.e. •H O O r-1 > - - T - KV irv rm O (I.e. 04 O

3

σ

P O β Rl β TJ fl W D (I.e. •P • r4 X fl W 1-4 0 fl -P O P O XJ O r-1 O O u CD Rl fl O frog rH H (I.e. co Rl O i-1 • O O -P n CJ 04 O fl 1- | CL H Rl O 3 (I.e. (D O O U TJ (D Rl r-1 TJ 1-1 •H (I.e. (I.e. •O fl O Rl (I.e. O frog (I.e. O x: fl □ (I.e. rl O fl 1-1 3 Of 0) Rl CD P □ Rl cn r- | 3 (I.e. fl fl ι-1 P Cfl α fl cr ASS- TJ Rl X) tJ r ***! <-X CO -P - O fl O O O O (D O •P □ CD ass -P AND •The O α W O r4 •H fl • r | Rl W O •P □ W X O -P O N fl e O 0 O +> Cfl ass W 4- CL XI X) W e ι- | fl r-4 KV •H P ρ (D 0 □ XI 3 x- ^ fc fl fl CT P tn cn F " CJ CJ «X "W

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

-64-

it's the O O • THE THE X Ov UJ

UV

KV co O • THE X UV

i <J · CN THE THE THE THE KV KV α 1

Ul

CN

00-V

• A

xr-

hi

THE

KV

Ov CN OV rn Ov THE THE THE K · » N> 1 1 OR 1 CN O O O

ri 00 GRANDFATHER grandfather KV • THE THE THE X Ov O 1 1 CN hi

grandfather O Ov rn Ov THE THE THE K UV 1 rN | CN α O O

O 00 CM cn • · » (I.e. X rH UJ H

Ts

GRANDFATHER CO O rn K THE K THE grandfather CN 1 C- 1 R N 1o

Ov W- O Ov • THE THE THE X Ov CN | O Ul

00 uv O O uv rN K THE K K THE grandfather <r 1 Ov cn 1o

00 r- O σ O • THE THE THE X GRANDFATHER KV 1 CN UJ

uv O O O UV rN THE THE THE THE THE r- UV 1 00 CN ι α rn

r- O O • THE THE X (I.e. KV UJ

O O O I laugh K k k K OVER THERE 1 00 <T 1 O ri

O

GRANDFATHER £ » α σ • K THE X * ' Γ- KV UJ

O O uv THE K THE uv IA 1 rN CN

UV

00 Ov νθ KV Ov r- grandfather ri K THE THE THE THE THE THE THE λ 00 CN rn 1 1 1 1 ο- CN O r ^ · rN 1 O 00 Χ-χ O rn O □ O 00 0 O | • r | 0 O W rn 0 O O O grandfather XJ 0 Ri • | rn O CJ rn rn (I.e. O •P N CN 0 O O Rl CJ O r-. 0 rn CL W rn XJ e O 0 •P P or rn O *O OO u XJ 0 O 0 Rl O " 0 rn «Η X) • r, co 0 e rN * - XJ • POW O XJ 0 O •H O X XJ 0 O • rl 0 (I.e. XJ a Rl O JX P rn O XJ (I.e. □ □ 0 Rn • σ 0 "H σ * © Rl •P 00 0 •H XJ XJ cr- 0 (I.e. -P O •H r-4 β □ 0 rn XJ e 0 vo rn 0 THE 0 0 rn P (0 C cr I Rl 0 0 0 0 0 (I.e. 0 k- Rl OJ "H rH X CN O AND rn O XI CN 0 0 P The river 0 0 rN XJ 0 □ O 0 • H XJ O 0 XJ O <x 0 © (I.e. O CJ 0 rn W • P XJ XJ 0 -P O 2 k- ε «rl tj gj TI O rn rn O 0 0 P 0 -P ·· O *P O Rl XJ Chuck -P T the rN "rl W -P CP T the W 0 CN P rn •P X T t CO 0 R OX 0 0 O 0 -P O OO O O Rl O 0 +> Ass. O k- XJ oo + » O k- +> O 0 jj • rl -rl £ · < Q. rn XJ W . rn KV VO or + » 0 W rN 0 C1- P rn cn O •P (I.e. P 0 © □ O XJ □ sza rN 0 Rl O □ V® ο ε 0 rn P O 0 XJ cn cn Q Σ. cn e CJ cn CJ N CJ «X

grandfather

THE

O

D

W

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Rl

rn

Rl

0

O

XJ

O

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0

and

□

CL

0

0

Q

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

The drawings represent variations in conductivity, yield strength and viscosity with variations in concentration of the electrolyte and active ingredient.

Figure 1 is a graph showing the conductivity of a 20.6% aqueous solution of active ingredients consisting of 2 parts by weight of sodium dodecyl benzene sulfonate and a portion of sodium sulfate various concentrations of sodium silicate with a ratio of 1.6: 1 NagOiSiOg. The figures on the horizontal axis refer to the amounts of silicate in the composition expressed as cent in solids.

From 0 to 7% the added silicate solution produces a substantially clear optically isotropic composition typical of Step I as described hereinbefore. Between the points marked "A" and "B" are obtained compositions of Step II, which are turbid, unstable and comprise non-obstructing flakes of spherolites. Between "8" and "C" are obtained compositions of Step III, according to the present invention. These are stable β-beaved compositions containing substantially spherolytic blocking flakes, which have a yield point and show only an ionic liquid phase by centrifugation G. Beyond "C" are obtained compositions of Step IV, containing non-blocking flakes of spherical phase G, which are non-stable. It should be noted that the Stable compositions of Step III are obtained in the conductivity depression around the first minimum conductivity.

Figure 2 shows the effect of adding sodium nitrate to the same aqueous active system. In addition to the "C" point of Step 4, a second maximum conductivity has passed corresponding to the formation of a lamellar composition according to Step V in approximately "D".

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

The left-hand axis indicates the viscosity at 136 ° F

63 318

MPD252 / RGMS / AER

"Liquid Datergent Compositions"

-66 seconds Pascal, the figures in parenthesis referring to

conductivity mm millisemens cm * "¹; the right hand scale -2

refers to the tensile strength in cm; the horizontal axis represents the total percentage of sodium carbonate present expressed as dry weight of sodium carbonate based on the total weight of the composition.

In the case of sodium carbonate, no minimum was observed in the conductivity curve (dashed line). This is because the solubility limit of sodium carbonate has been reached, so that more carbonate additions to the suspension does not increase the concentration of dissolved electrolyte. No Step IV can therefore be observed. The sharp rise in the elasticity limit (right-hand maximum) coincides with the principle of Step III at point "B". This is typical of compositions of our invention.

Figure 4 represents the effect of varying the relative proportions of sodium dodacylobenzene sulfonate and coconut monoethanolamine in a composition containing sodium dodecyl benzene sulfonate, sodium tripolyphosphate, sodium carbonate and water in a ratio of 0.2: 0.5: 0 , 1: 1.0. The horizontal scale represents the weight ratio of monoethanolamide of coconut sulfonate to sodium dodecyl benzene. The vertical scale represents conductivity in mS cm ^-1 (circles) and also viscosity in seconds Pascal x 10 (triangles).

Figure 5 shows an analogous relationship in which the monoethane of coconut amide is replaced by alkyl sulphate (3 moles)

sodium ethoxy. The horizontal scale is the weight ratio of ether sulfate to the alkyl benzene sulfonate.

Figures 4 and 5 show how it is possible to prepare compositions of the present invention by modifying the active ingredients.

Figure 6 shows the conductivity variation in mS cm ^-1

when sodium nitrate is added in various proportions to

a detergent composition containing suspending additive and fo

tion:

by weight

9

4

1

0.6

0.5

0.15

19

12

63 318

MPD252 / RGMS / AER

"Liquid Detergent Compositions"

Sodium dodecyl benzenesulfonate

^L j2-18 alkyl sulfate mol) sodium ethoxy

Aromatic silicone cleanser

Mixed alkyl monoesters

phosphate

Optical brightness agent Sodium tripolyphosphate Zeolite A

Because of the dissolved tripolyphosphate already present, Stage I is not observed in this curve. The conductivity falls from maximum "A" to the beginning of Step III in "B".

Figure 7 shows the elasticity limit for the same system, cm2.

Figure 8 shows the viscosity at 136 cnT (lower curve), 21 cm ^-1 (upper curve) and viscosity drop (middle curve) in Pascal x 10 seconds.

Figure 9 shows the change in conductivity with varying proportions of sodium silicate in a 20.6% by weight aqueous solution of sodium dodecyl benzene sulfonate in admixture with coconut monoethanolamide in a weight ratio of 10: 4.

Again, no Step I is observed this time because the active ingredients are not completely soluble in water at room temperature. The composition is thus clouded and unstable with the absence of electrolyte.

Figures 10 and 11 copies of Pt / G transmission micrographs after freeze fracture at X45.QQ0 β X110,000 (lines) enlargements respectively.

The micrographs that were prepared at the University

63 318

MPD252 / RGHS / AER

"Liquid Detergent Compositions"

-68 from Lencastsr both represent an electron microscope transmission of a sample having the composition:

% by weight

sodium dodecyl benzene sulfonate 11.8

alkyl sulfate ^and j2-18 ^mo -'- ^s) 5.2 Sodium stoxi

Sodium silicate (Na2 O: SiO2, 1.6: 1) 17.4

Water supplement

The micrograph shows spherolites of between 0.2 and 1 micron in diameter, which evidently show multiple vesicles having a concentric structure, having a repeating spacing (including the thickness of a surfactant shell and an adjacent aqueous layer) of 80 A.

Claims (65)

A process for the preparation of a stable, pourable, flowable detergent composition consisting essentially of active ingredients, electrolyte and water and having solids suspension properties, in which the ratio of electrolyte is sufficient to provide a temperature stable composition, sensitive, substantially non-lamellar. 2. A process for the preparation of a stable, pourable, flowable detergent composition having solids suspension properties and comprising water, electrolyte active ingredients, wherein the ratio of electrolyte is sufficient to provide an obstructing spheroletic flake which is stable temperature and not sensitive to cutting. A process for the preparation of a stable, pourable, flowable detergent composition having solids suspension properties which comprises water, active ingredients and sufficient electrolyte to form a stable dispersed phase containing at least part of the active ingredients, corresponding to a channel in the graph of conductivity versus concentration 63 318 MPD252 / RGMS / AER "Liquid Detergent Compositions" Electrolyte, which contains the first minimum conductivity, the ratio of electrolyte being within the range at which the composition is temperature stable and non-shear sensitive. Process according to any one of claims 1 to 3, characterized in that the proportion of electrolyte is sufficient to render the composition stable at temperature. A process according to any one of the preceding claims, characterized in that the composition contains suspended solid. 6. A process according to claim 5, the solid is an additive or an abrasive. A process for the preparation of a stable, pourable, liquid detergent composition containing water, active ingredients, electrolyte and suspended solids, characterized in that the ratio of electrolyte is sufficient to form a stable, spherolytic cut composition having a limit of elasticity of 1 to 15 dynes cm. A process for the preparation of a stable, pourable, flowable, liquid detergent composition consisting essentially of water of 5 to 25% based on the weight of the active ingredient composition, electrolyte and suspended solid additive, the total weight ratio of additive to ingredient active ratio of 1.4: 1 to 4: 1 and the ratio of electrolyte being sufficient to provide a non-lamellar, shear stable composition. A process for the preparation of a stable, pourable, flowable, liquid detergent composition comprising water, 5 to 25% based on the weight of the active ingredient composition, electrolyte and suspended solid additive, and having a payload of at least 35% by weight in which the ratio of electrolyte is sufficient to provide a stable, lytic spherical cut composition. A process for the preparation of a stable, pourable, liquid detergent composition containing water, from 5 to 25 / in 63 318 MPD252 / RGMS / AER "Liquid Datergent Compositions" JBg " «4Br -70 weight of active ingredients, electrolyte and suspended solid additive, the total weight ratio of additive for active ingredients being from 1.5: 1 to 4: 5 and the ratio of electrolyte being sufficient to provide a stable spherolytic composition p, storage at 4Â ° C, 11. A process for the preparation of a stable, pourable, fluid, stable, water-containing composition comprising 5 to 20% by weight of active ingredients, electrolyte and suspended solid additive, the total weight ratio of additive to active ingredient being 1: 1 to 4: 1 and the ratio of electrolyte being sufficient to provide a non-cut sensitive temperature stable composition which in centrifugation separates into an aqueous layer containing more than 50% of the total weight of active ingredients and a solid layer. Process for the preparation of a detergent composition people stable, vertlvel consisting essentially of water, dissolved electrolyte from 8 to 14% by weight of the composition of active ingredients, together with suspended solid additive, and, optionally the usual minor ingredients whose composition, under centrifugation, separates into a solid layer and a layer having a yield point greater than -2 1.5 dines cm · 13. A process for the preparation of a composition consisting essentially of water, active ingredients and electrolyte and having solids suspension properties in which the active ingredients are capable of forming a composition stable at the first minimum conductivity and wherein the amount , the amount of electrolyte present is sufficient to provide one with position having a yield strength greater than 1,5 di-2-1 cm and a viscosity measured at 136 sec, less than 0.28 seconds of Pascal. 14. A process for the preparation of a stable, water-based, stable, water-soluble composition comprising essentially water, electrolyte, active ingredient and additive comprising a predominantly aqueous first separable liquid phase containing at least part of the electrolyte in solution 63 318 MPD252 / RGMS / AER '• Liquid Detergent Compositions " -71e from 50 to 80% of the total weight of active ingredients, and at least one separable phase of dispersed solid comprising at least part of the additive as a solid 15. A process for the preparation of a composition comprising: water-soluble, stable, water-soluble people having a pH greater than 9 s comprising water, a dissolved electrolyte, at least 5% by weight of active ingredients and at least 16% by weight of additive, the electrolyte being present in a proportion sufficient to render the composition stable to shear, but insufficient for the active ingredients to form a substandard portion of a lamellar phase 16. A process for the preparation of an aqueous-based liquid particulate composition comprising active ingredients sufficient to form a surfactant-containing flocculant floc containing intercalated aqueous phase at an amount of electrolyte not less than that corresponding to the prior art. minimum of conductivity of the graph of conductivity versus electrolyte concentration, but below that corresponding to the formation of a lamellar phase, and sufficient to render the composition non-sensitive to the cut 17. A process for the preparation of a stable, veritable, stable, water soluble, water soluble, electrolyte, active, and additive composition which is separated by centrifugation as defined in at least two layers comprising: a further predominantly aqueous layer containing dissolved electrolyte, at least 10% by weight of the total water, and 85% to 50% by weight of the total active ingredient, and a solid layer containing at least a proportion of the additive 18. A process for the preparation of a stable spherolytic composition comprising active ingredients, electrolyte and water, which does not have a clear, separated aqueous phase after high G-centrifugation at 20,000 G for 90 minutes. A process for the preparation of a composition according to any one of the preceding claims, characterized in that it has a viscosity drop of more than 0.35 seconds Pascal. 63 318 MPD252 / RGMS / AER "Liquid Detergent Compositions" A process for the preparation of a composition according to claim 19, characterized in that it has a viscosity drop of 0.45 to 2 seconds Pascal. A process according to any one of the preceding claims, characterized in that the composition has a payload of 25 to 75% by weight. 22. A composition according to any one of the preceding claims, wherein the composition has a weight ratio of the additive to the active ingredient to 1.2: 1. A process according to claim 22, characterized in that the composition has an additive to active ingredient weight ratio of from 1.4: 1 to 4: 1. A method according to any one of the preceding claims, characterized in that the composition contains from 10 to 13.5% based on the weight of the active ingredient composition A process according to any one of the preceding claims, characterized in that, under centrifugation, the composition provides a solid layer to a single aqueous layer _2 sa having a yield point of 2 to 10 dynes cm · A composition according to any one of the preceding claims, wherein, upon centrifugation, the composition provides a solid layer and a single aqueous layer containing from 60 to 90% of the total weight of active ingredients. A process according to any one of the preceding claims, characterized in that the composition has a pH of from 9 to 13. A process as claimed in any one of the preceding claims, wherein the composition has sufficient alkalinity to require at least 0.8 ml SCI Ν / 10 to reduce the pH to 100 ml of an aqueous solution of said diluted composition to 0.5 # dry weight, to 9. 29. A composition according to claim 28, wherein the composition, when diluted to 0.5% by weight 63 31Β MPD252 / RGMS / AER "Liquid Detergent Compositions" Dry, require 4.7 to 8.6 ml HCl / 10 to reduce 100 ml to pH 9 * A process according to any one of the preceding claims, characterized in that the composition has a conductivity of not more than 2 milliSiemens cm- ¹ than the yield of the composition. responding to the first minimum conductivity. Process according to any one of the preceding claims, characterized in that the composition has a conductivity of less than 10 milliSiemens per cm- ¹ . Method according to any one of the preceding claims, characterized in that the electrolyte is a water-soluble carbonate, silicate, tripolyphosphate, pyrophosphate, nitrilotriacetate, citrate, chloride and / or nitrate. A process according to any one of the preceding claims, wherein the active ingredients comprise a mixture of (A) a non-alkoxylated anionic surfactant with (B) a co-surfactant which forms foams. A process as claimed in claim 33, wherein component (A) comprises a benzyl alkyl sulfonate containing 8 to 22 carbon atoms. A process according to any one of claims 33 and 34, characterized in that component (A) comprises an alkyl sulfate having 8 to 22 carbon atoms. A process according to any one of claims 33 to 35, characterized in that component (A) comprises an olefin sulfonate, alkane sulfonate, alkylphenol sulfate, alkyl etanolamide sulfate, sulfocarboxylic acid. and / or sulfocarboxylic ester, having 8 to 22 carbon atoms. A process according to any one of claims 33 to 36, characterized in that component (B) is an alkyl polyethoxy sulfate having a C alquilo alquilo grupo alkyl group and up to 20 ethylsnoxy groups. 63 318 MPD252 / RGMS / AER "Liquid Detergent Compositions" A process according to any one of claims 33 to 37, characterized in that component (B) comprises a polyethyleneoxy alkylphenol sulphate, and / or a polyethyleneoxyalkylethanolol sulphate having a C 22 alkyl group ^and up to 20 groups ethyleneoxy. 39 - Process according to any one of claims tions 33-38, characterized in that component (B) with one alkyl preender ^rnono8 ^ © iq_22 ^year ^ ^am ^ ^c * ^{to or} diethanolamide. A method according to any one of the claims Compounds 33 to 39, characterized in that component (B) comprises a mono-amine oxide. 41 - Process according to any one of claims tions 33 to 40, characterized in that the active ingredients further comprise an alcohol © θ_22 ° ^^ P ^ ^{x and} ^ ed, ICE. carboxylic acid, amine alkylolamide, glyceryl ester, each having up to 20 ethyleneoxy groups in a proportion up to 20 percent of the total weight of active ingredients. Method according to any one of claims 33 to 41, characterized in that the ratio of (A) :( B) is from 5: 1 to 1: 3. A process according to claim 42, characterized in that the ratio of (A) :( B) is from 4: 1 to 1: 2. A process according to claim 43, characterized in that the ratio of (A) :( B) is from 3: 1 to 1: 1. A process according to claim 41, characterized in that the proportion of nonionic ethoxylated compound is from 2 to 10% of the total weight of active ingredients. A process according to any one of claims 1 to 44, characterized in that the composition contains a foam inhibitor. A process according to claim 46, wherein the foam inhibitor comprises a mixture of organopolysiloxane foam inhibitor and fumed silica. 6 3 318 MPD252 / RGMS / AER "Liquid Detergent Compositions" A process according to any one of the preceding claims, characterized in that the composition contains suspended particles of sodium tripolyphosphate and / or zolodite. A process for the preparation of a stable, pourable, non-cut sensitive spherolytic composition having an elastomeric charge of at least 35% by weight and comprising: water; from 12 to 40 / active ingredients based on the dry weight of the composition; dissolved electrolyte; and from 20 to 80 / total dry weight of additive based on the dry weight of the composition at least partially present as suspended solid, and partially as at least part of said dissolved electrolyte, in a ratio total active ingredient additive weight from 1.3: 1 to 4: 1; in which said active ingredients are comprised of (A) 30 to 80% by weight of at least one non-alkoxylated sulfonated or sulfated anionic surfactant; and (B) from 20 to 70% by weight of the total active ingredient, at least one non-ionic anionic surfactant and / or nonionic surfactant. A process for the preparation of a stable, flowable, stable, watertight basic composition comprising: from 12 to 40 / based on its dry weight active ingredients which comprises 30 to 90% based on the dry weight of the active ingredients sulfated surfactant and / or sulfonated anionic surfactant and the balance of alkyl ether sulfate and / or a non-ionic surfactant; an aqueous phase containing sufficient electrolyte in solution to form an obstructive spherolytic flake comprising at least part of said active ingredients and intercalated with said aqueous phase; suspended particulate additive; an effective amount of at least one foam inhibitor and optionally minor usju ingredients. A process for the preparation of a composition comprising: non-lamellable, stable, pourable, having a payload of 30 to 50%, consisting essentially of 12 to 40 weight percent, based on the dry weight of the composition, active ingredients, 63 318 MPD252 / RGMS / AER "Liquid Detargent Compositions" Based on the dry weight of the composition, an additive to active ingredient ratio of greater than 1.1 to 1, said active ingredient consisting essentially of alkyl benzene sulfonate having 8 to 18 aliphatic carbon atoms and an alkyl ethanolamide selected from 1 to 6 carbon atoms monoethanolamides and distanolamides in a weight ratio of alkyl benzene to ethanolamide sulfonate of 1.5: 1 to 4: 1, said additive being selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrile triacetate, sodium silicate and mixtures thereof, so that the amount of the dissolved additive is sufficient to provide with a yield point greater than 1.5 cm. A process for the preparation of a stable, liquid, stable disposable composition consisting essentially of: A mixture of (i) a sodium alkylbenzene sulfonate having 10 to 18 aliphatic carbon atoms with (ii) a sodium alkyl ether sulfate having an alkyl group having an average of 8 to 18 carbon atoms, and 1 to 20 ethyleneoxy and / or propyleneoxy groups; in a ratio of (i) :( ii) between 10: 1 and 1:10; B - An additive selected from sodium tripolyphosphate, zeolite, sodium nitrilotriacetate, and mixtures thereof, in a B: A weight ratio of from 1.1: 1 to 4: 1; An electrolyte selected from sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof in a concentration of 2 to 20% by weight of the composition. dog; said composition having a payload of 30 to 50% by weight. 53. A process according to claim 52, wherein the ratio of (i) :( ii) is from 10: 1.5 to 10: 5. A process according to claim 53, characterized in that the ratio of (i) :( ii) is from 10: 2 to 10: 4. A process according to any one of claims 52 to 54, characterized in that the ratio B: A is from 1.2: 1 to 3.5: 1. 63 318 MPD252 / RGHS / AER "Liquid Detergent Compositions" A process as claimed in claim 55, characterized in that the B: A ratio is from 2: 1 to 3: 1. A method according to any one of the claims 52 to 56, characterized in that C is present at a concentration of 3 to 18% by weight based on the weight of the composition. A process according to claim 57, wherein C is present in a concentration of 7 to 15% by weight. A method according to any one of claims 52 to 58, characterized in that the payload is 38 to 45%. Process according to claims 52 to 59, characterized in that the composition contains small but effective amounts of carboxymethylcellulose, perfume, colorant and optical brightness element. A method according to any one of the claims (ii) has an alkyl group and from 3 to 6 ethyleneoxy groups. A process according to any one of claims 52 to 61, characterized in that the electrolyte is sodium carbonate and / or sodium silicate together with dissolved sodium triphosphate, the additive comprises sodium tripoli phosphate in suspension. A process according to any one of claims 52 to 62, wherein the ratio of electrolyte is sufficient to provide a temperature-stable composition. A process according to any one of the preceding claims, characterized in that the composition contains capsulated bleaches and / or enzymes in suspensions. A process according to any one of the preceding claims, wherein a majority of the active ingredients are present as spherolites of from 0.1 to 5 microns in diameter. 63 318 MPD252 / RGMS / AER "Liquid Detergent Compositions" A process according to claim 65, characterized in that a greater proportion by weight of the active ingredient is present as spherolites of 0.2 to 2 microns in diameter A method as claimed in claim 66, characterized in that a greater proportion by weight of the active ingredient is present in spherolites of 0.2 to 1 micron in diameter. A process according to any one of the preceding claims, characterized in that the composition comprises spherulites which are multiple vesicles having a concentric structure with a mean truss spacing of 60 to 100 X. A method according to claim 68, characterized in that the lattice spacing is 70 to 90%. A process for the preparation of a detergent composition; people, fluid, stable, pourable, consisting essentially of: water! a concentration of 5 to 25 percent by weight of the composition of active ingredients which consist essentially of (i) at least one non-ethoxylated anionic surfactant and (II) at least one cosurfactant which is capable of forming stable foams, the ratios of (i) to (II) being such that a progressively soluble electrolyte to an aqueous mixture containing said active ingredients at said concentration, a first minimum conductivity is achieved at which the mixture is turbid and stable: solid additive suspended, the total weight ratio of active ingredient additive being 1: 1 to 4: 1, and electrolyte dissolved in a proportion sufficient to form a stable composition corresponding to the conduit vessel containing said first conductivity minimum, and greater than any concentration below which the composition is sensitive to shear, but below the maximum concentration at which is stable at temperature. 63 318 MPD252 / RGMS / AER "Liquid Detergent Compositions" A fabric washing process which comprises agitating the fabric in a wash liquid containing a composition according to any one of the preceding claims.