EP0151884A2 - Flüssige Reinigungsmittelzusammensetzungen - Google Patents

Flüssige Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0151884A2
EP0151884A2 EP84309004A EP84309004A EP0151884A2 EP 0151884 A2 EP0151884 A2 EP 0151884A2 EP 84309004 A EP84309004 A EP 84309004A EP 84309004 A EP84309004 A EP 84309004A EP 0151884 A2 EP0151884 A2 EP 0151884A2
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EP
European Patent Office
Prior art keywords
composition
electrolyte
stable
composition according
active ingredients
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EP84309004A
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English (en)
French (fr)
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EP0151884A3 (en
EP0151884B1 (de
Inventor
Brian John Akred
William Paul Haslop
Edward Tunstall Messenger
John Michael Allonby
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Solvay Solutions UK Ltd
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Albright and Wilson Ltd
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Priority claimed from GB838334250A external-priority patent/GB8334250D0/en
Priority claimed from GB848415783A external-priority patent/GB8415783D0/en
Priority claimed from GB848421759A external-priority patent/GB8421759D0/en
Application filed by Albright and Wilson Ltd filed Critical Albright and Wilson Ltd
Priority to AT84309004T priority Critical patent/ATE52106T1/de
Publication of EP0151884A2 publication Critical patent/EP0151884A2/de
Publication of EP0151884A3 publication Critical patent/EP0151884A3/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Definitions

  • the present invention relates to novel, aqueous-based, mobile, fluid detergent compositions preferably containing effective quantities of detergent builder.
  • builder is sometimes used loosely in the detergent art to include any non-surfactant whose presence in a detergent formulation enhances the cleaning effect of the formulation. More usually, however, the term is restricted to those typical "builders” -which are primarily useful as a means of preventing or ameliorating the adverse effects on washing of calcium and magnesium ions, e.g. by chelation, sequestering, precipitation or absorption of the ions, and secondarily as a source of alkalinity and buffering.
  • Builder is used herein in the more restricted sense, and refers to additives which ameliorate the effects of calcium to a substantial extent.
  • It includes sodium or potassium tripolyphosphate and other phosphate and condensed phosphate salts such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates, amino tris methylene phosphonates and ethylenediamine tetramethylene phosphonates. It also includes alkali metal carbonates, zeolites and such organic sequestrants as salts of nitrilotriacetic acid, citric acid and ethylene diamine tetracetic acid, polymeric polycarboxylic acids such as polyacrylates and maleic anhydride based copolymers.
  • phosphate and condensed phosphate salts such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates, amino tris methylene phosphonates and ethylenediamine t
  • Builder is used herein to include water soluble alkali metal silicates such as sodium silicate, but excludes additives such as carboxymethyl cellulose, or polyvinyl pyrrolidone whose function is primarily that of soil suspending or anti-redeposition agent.
  • Electrode is used herein to denote those ionic compounds which have a solubility in water at 0°C, expressed as wt% of anhydrous compounds, of at least 5, which dissociate at least partially in aqueous solution to provide ions, and which at the concentrations present tend to lower the total solubility (including micellar concentration) of surfactants in such solutions by a “salting out” effect.
  • It includes water soluble dissociable, inorganic salts such as, for example, alkali metal or ammonium chlorides, nitrates, phosphates, carbonates, silicates, perborates and polyphosphates, and also certain water soluble organic salts which desolubilise or "salt out” surfactants. It does not include salts of cations which form water insoluble precipitates with the surfactants present or which are only sparingly soluble in the composition, such as calcium chloride or sodium sulphate.
  • Electrolyte content or concentration refers to the total dissolved Electrolyte, including any dissolved Builder, if such Builder is also an Electrolyte, but excludes any suspended solid.
  • Hydrotrope denotes any water soluble compound which tends to increase the solubility of surfactants in aqueous solution.
  • Typical Hydrotropes include urea and the alkali metal or ammonium salts of the lower alkyl benzene sulphonic acids such as sodium toluene sulphonate and sodium xylene sulphonate.
  • Electrolyte Whether a particular compound is an Electrolyte or a Hydrotrope may sometimes depend on the Active Ingredients present.
  • Sodium chloride is normally considered a typical Electrolyte, but in relation to sultaines; it behaves as a Hydrotrope.
  • Electrolyte and Hydrotroprope as used herein, must therefore be construed in the context of the particular Active Ingredients.
  • Soap means an at least sparingly water soluble salt of a natural or synthetic aliphatic monocarboxylic acid, which salt has surfactant properties.
  • the term includes sodium, potassium, lithium, ammonium and alkanolamine salts of Cg -22 natural and synthetic fatty acids, including stearic, palmitic, oleic, linoleic, ricinoleic, behenic and dodecanoic acids, resin acids and branched chain monocarboxylic acids.
  • the "Usual Minor Ingredients” includes those ingredients other than Water, Active Ingredients, Builders and Electrolytes which may be included in laundry detergent compositions, typically in proportions up to 5%, and which are compatible in the relevant Formulation with a Pourable, chemically stable non-sedimenting composition.
  • the term includes antiredeposition agents, dispersants, antifoams,perfumes, dyes, optical brightening agents, Hydrotropes, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, scale inhibitors, humectants, enzymes and their stabilizers, bleach . activators, and the like.
  • “Functional Ingredients” means ingredients which are required to provide a beneficial effect in the wash liquor and includes ingredients which contribute to the washing effectiveness of the composition e.g. surfactants, Builders, bleaches, optical brighteners, alkaline buffers, enzymes and anti- redeposition agents, and also anti-corrosives and anti-foams, but excludes water, solvents, dyes, perfume, Hydrotropes, sodium chloride, sodium sulphate, solubilisers and stabilisers whose sole function is to impart stability, fluidity or other desirable characteristics to a concentrated formulation.
  • Payment means the percentage of Functional Ingredients based on the total weight of the composition.
  • Active Ingredients means surface active materials.
  • Separable Phase is used herein to denote components, or mixtures of components of a pourable detergent composition, which are each separable from the composition to form a distinct layer upon Centrifuging. Unless the context requires otherwise all references to the composition of Separable Phases are references to the compositions of the centrifugally separated phases and references to the structure of a composition relate to the uncentrifuged composition.
  • a single Separable Phase may comprise two or more thermodynamically distinct phases, which are not separable from each other on Centrifuging as in, for example, a stable emulsion or floc.
  • Dispersed is used herein to describe a phase which is discontinuously distributed as discrete particles or droplets in at least one other phase.
  • Co-continuous describes two or more interpenetrating phases each of which extends continuously or as a continuous network through a common volume, or else is formed of discreet or Dispersed elements which interact to form a continuous matrix tending to maintain the position of each element in relation to the matrix when the system is at rest.
  • Interspersed describes two or more phases which are either Co-continuous or of which one or more is Dispersed in the other or others.
  • references to “Solid Phases” are to substances actually present in the composition in the solid state at ambient temperature, and including any water of crystallization or hydration unless the context requires otherwise.
  • References to solids include references to microcrystalline and cryptocrystalline solids, i.e. solids whose crystals are not directly observed by optical microscopy but whose presence can only be inferred.
  • a “Solid Layer” is a solid, pasty or non-pourable gelatinous layer formed on Centrifuging.
  • Total Water refers to water present as liquid water in a predominantly aqueous phase, together with any other water in the composition, e.g. water of crystallisation or hydration or water dissolved or otherwise present in any predominantly non-aqueous phase.
  • “Dry Weight” refers to residual weight after drying to constant weight at 1400 C .
  • Formulation is used to describe the combination of ingredients which make up the Dry Weight of a composition.
  • formulation may be exemplified by a number of compositions, differing in their Percentage Dry Weight.
  • Stable means that no layer containing more than 2% of the total volume separates from the bulk of the composition within 3 months at room temperature under normal gravity.
  • the Shear Test means a test in which a sample is passed through a straight 40mm tube having an internal radius of 0.25mm under a pressure of 500 p.s.i.g.
  • the Shear Test was carried out in the case of all measurements described herein, by sucking a sample into a 500ml pressure vessel through a broad aperture tube, replacing the broad aperture tube by the 0.25mm radius tube and applying a nitrogen pressure of 500 p.s.i.g. in the pressure vessel until the latter was empty. The 0.25mm tube was then replaced by the broad aperture tube so that the cycle could be repeated.
  • the above method generates a shear rate of approximately 127,000 sec- 1.
  • Shear Stable means Stable after 3 passes through the Shear Test
  • Shear Unstable means non-Stable after exposure to 3 or less passes through the Shear Test, or to a lower shear rate.
  • Non-Shear Sensitive means not undergoing loss of stability or substantial increase in Viscosity after exposure to moderate shear. Shear Sensitivity was determined using a Contraves "Rheomat 30" viscometer, cone and plate measuring system 2, at 25°C, increasing the shear linearly from 0 to 280 sec -1 over 1 minute (the "upsweep") and immediately decreasing it linearly to 0 sec- 1 over 1 minute (the “downsweep”). A composition is adjudged Non-Shear Sensitive if it is Stable after the cycle and if the Viscosity at 150 sec- 1 on the downsweep is not more than 10% greater than on the upsweep.
  • Temperature Stable means that no layer containing more than 5% of the volume separates from the bulk of the composition within 24 hours of being heated by immersing a 20 g. sample in a water bath maintained at 90°C for 110 minutes, followed by immediate immersion in a water bath maintained at 100°C for 10 minutes.
  • references herein to the "pH" of detergent compositions are to the pH as measured by a Pye Unicam 401 combined glass/calomel electrode.
  • Conductivity refers to specific conductance measured at 25 0 C at a frequency of 50 KHertz. The results quoted were measured on a CDM3 "RADIOMETER” conductivity bridge using a CDC314 flow and pipette cell.
  • the "First Conductivity Minimum” refers to the graph of Conductivity against increasing dissolved Electrolyte concentration in a liquid detergent composition containing a fixed proportion of Active Ingredients to water, wherein the Conductivity, usually having initially risen to a maximum value, declines to a minimum value and then rises again.
  • the term signifies the concentration of Electrolyte corresponding to this minimum value, or the lowest concentration of dissolved Electrolyte corresponding to one of a plurality of such minima.
  • Viscosity except where otherwise stated are to the viscosity as measured on a cup and bob viscometer at 25 0 C after two minutes running using a 20 mm internal diameter flat bottomed cup, 92 mm long, and a 13.7 mm diameter bob, 44 mm long, with conical ends having a 45° horizontal angle, and 4mm diameter spindle.
  • the tip of the bob was 23mm from the base of the cup. This corresponds to Contraves "Rheomat 30" viscometer using measuring system C.
  • “Pourable”, as used herein, means having a Viscosity of less than 2 Pascal seconds at a shear rate of 136 sec -1 .
  • Viscosity Drop means the difference between the Viscosity of a shear thinning composition measured at 21 sec- I and the Viscosity measured at 136 sec- 1 .
  • Yield Points are as measured on an RML Series II Deer Rheometer at 25 0 C, using part No. MG7101.
  • Li phase denotes a clear, fluid, optically isotropic, micellar solution of surfactant in water, which occurs at concentrations above the critical micellar concentration, and wherein the surfactant molecules are believed to aggregate to form spherical, oblate (disc) or prolate (rod) micelles.
  • Bilayer includes a layer of surfactant approximately two molecules thick, which is formed from two adjacent parallel layers, each comprising surfactant molecules which are disposed such that the hydrophobic portions of the molecules are located in the interior of the Bilayer and the hydrophilic portions are located on its outer surfaces.
  • Bilayer is also used herein to include interdigited layers, which are less than two molecules thick. An interdigited layer may be regarded as a Bilayer in which the two layers have interpenetrated allowing at least some degree of overlap between the hydrophobic portions of the molecules of the two layers.
  • Spherulite means a spherical or spheroidal body having dimensions, of from 0.1 to 50 microns. Spherulites may sometimes be distorted into prolate, oblate, pear or dumbell shapes.
  • “Vesicle” means a Spherulite containing a liquid phase bounded by a Bilayer.
  • Multiple Vesicle means a Vesicle which contains one or more smaller Vesicles.
  • “Lamellar Phase” means a hydrated solid, or liquid crystal phase in which a plurality of Bilayers are arranged in a substantially parallel array, separated Dy layers or water or an aqueous solution, and having a sufficiently regular lattice spacing of from 25 to 70 A to be readily detectable by neutron diffraction when present as a substantial proportion of a composition.
  • the expression excludes concentric Multiple Vesicles.
  • G phase refers to a liquid crystal Lamellar Phase, of the type also known in the literature as "neat” phase or “lamellar” phase.
  • the "G” phase for any given surfactant or surfactant mixture normally exists in a narrow range of concentrations. Pure “G” phases can normally be identified by examination of a sample under a polarising microscope, between crossed polarisers. Characteristic textures are observed in accordance with the classic paper by Rosevear, JAOCS Vol. 31 P628 (1954) or in J. Colloid and Interfacial Science, Vol. 30 No. 4, P.500 (1969).
  • Spherical G Phase means Multiple Vesicles formed from substantially concentric shells of surfactant Bilayer alternating with aqueous phase with a "G" phase spacing. Typically conventional G phases may contain a minor proportion of Spherical G Phase.
  • Lye means an aqueous liquid phase containing Electrolyte, which phase separates from, or is Interspersed with, a second liquid phase containing more Active Ingredient and less Electrolyte than the Lye phase.
  • Lamellar Composition means a composition in which a major part of the surfactant is present as a Lamellar Phase, or in which a Lamellar Phase is the principal factor inhibiting sedimentation.
  • Spherulitic Composition means a composition in which a major part of the surfactant is present as Spherulites, or which is principally stabilised against sedimentation by a spherulitic surfactant phase.
  • Liquid detergents have hitherto been used mainly for light duty applications such as dish washing.
  • the market for heavy duty detergents e.g. laundry detergents
  • Such liquids should in theory be cheaper than powder detergents since they would avoid the need to dry and would in many instances replace the sulphate filler conventionally used in powder detergents with water. They also offer the possibilities of greater convenience and more rapid dissolution in wash water than powder.
  • Attempts to provide solutions of the Functional Ingredients have been relatively unsuccessful commercially.
  • One reason for this lack of success has been that the most commonly used and cost effective Builders e.g.
  • sodium tripolyphosphate are insufficiently soluble in aqueous compositions. Moreover due to salting out effects, increasing the amount of dissolved Builder tends to lower the amount of surfactant that can be dissolved and vice versa. Potassium pyrophosphate Builders, together with amine salts of the Active Ingredients, which are more soluble, have been tried as alternatives to the sodium salts but have not been found cost effective.
  • compositions which have been developed commercially many compositions have been proposed in the literature which are not suitable for commercial exploitation in practice. Typically such compositions are unstable, or insufficiently stable to withstand normal storage without undergoing sedimentation, or else are too expensive to manufacture in relation to their washing effectiveness, to be considered for commercial development.
  • compositions in which the Active Ingredients form a network of a Lamellar Phase, separable from the aqueous phase by Centrifuging, which provides a gel structure capable of supporting suspended particles of solid Builder.
  • the gel structure is obtained by addition of sufficient Electrolyte to salt out the Active Ingredient, so as to form an aqueous Lye phase and a Separable Lamellar Phase, and by maintaining the solids content above a threshold for stability and below a ceiling for Pourability.
  • the amount of Electrolyte required depends upon the hydrophilicity and melting point of the surfactant, and whether any solubilising additives such as Hydrotropes or solvents are present.
  • the aforesaid gel compositions tend to be higher in Payload and in the ratio of Builder/Active Ingredient, and to be more cost effective than known commercial liquid compositions. Indeed, the best of the aforesaid Lamellar gel compositions are more cost effective soil removing agents than the best laundry powders.
  • Lamellar Compositions disclosed hitherto exhibit a mobility which is lower than is desirable for some purposes.
  • Preferred embodiments of our invention exhibit at least some of the following advantages compared with products marketed hitherto: High Payload; high Builder to surfactant ratio; improved stability; lower cost due to use of cheaper ingredients and ease of production; high mobility; improved washing performance; high pH and/or alkalinity; good stability at high and/or low storage temperature; and satisfactory behaviour on shearing.
  • a Stable Spherulitic Composition which is . capable of suspending solid particles, such as Builder.
  • our novel compositions appear to be stabilised by surfactant present in a spherulitic, rather than a Lamellar Phase.
  • the second approach is exemplified by G.B. 855893, G.B.948617, G.B.943271, G.B. 1468181, G.B. 1506427, G.B.2028365, E.P.38101, Australian P.522983, U.S.P. 4018720, U.S.P.3232878, U.S.P.3075922 and U.S.P.2920045.
  • the compositions described in these patents are either not stable or are not Temperature Stable or Shear Stable.
  • Commercial products corresponding to examples of two of these patents have been marketed recently in Australia and Europe.
  • a composition corresponding to Australian Patent No. 522983 has enjoyed a measure of commercial success, but has been Shear Sensitive.
  • compositions described exhibit a matrix of Lamellar, solid or liquid crystal surfactant . Such compositions may have Viscosities higher than are desirable for certain uses.
  • a different approach is to suspend solid Builder in an anhydrous liquid non-ionic surfactant e.g. BP 1600981.
  • Such systems are costly, restrictive with regard to choice of surfactant and give unsatisfactory rinsing properties.
  • the level of Builder although high in relation to the total composition is low in relation to the Active Ingredients, and the cost effectiveness is therefore very low.
  • U.S.P.4057506 describes the preparation of clear emulsions of sodium - tripolyphosphate
  • U.S.P.4107067 describes inverse emulsions in which an aqueous solution of Builder is dispersed in a liquid crystal surfactant system.
  • U.S.P.3039971 describes a detergent paste containing the Builder in solution
  • our invention provides a Stable, Pourable, fluid, detergent composition consisting essentially of Active Ingredients, Electrolyte and water and having solid-suspending properties, wherein the proportion of Electrolyte is sufficient to provide a Temperature Stable, Non-Shear-Sensitive, substantially non-Lamellar composition.
  • our invention provides a Stable, Pourable, fluid, detergent composition having solid-suspending properties and comprising water, Active Ingredient and Electrolyte, wherein the proportion of Electrolyte is sufficient to provide a space-filling Spherulitic floc which is Temperature Stable and Non-Shear Sensitive.
  • our invention provides a Stable, Pourable, fluid detergent composition having solid suspending- properties and which comprises water, Active Ingredient and sufficient Electrolyte to form a dispersed Stable phase containing at least part of the Active Ingredients, corresponding to a trough in the graph of Conductivity against Electrolyte concentration, which contains the First Conductivity Minimum, the proportion of said Electrolyte being within the range at which the composition is Temperature Stable and Non-Shear Sensitive.
  • the Electrolyte concentration is sufficient to provide a Shear Stable composition.
  • composition according to each of the foregoing embodiments contain suspended solids, such as Builders and/or abrasives.
  • the suspended solid may be insoluble in the aqueous fluid medium, already present in saturation quantities, or encapsulated in a material which prevents it dissolving in the medium.
  • our invention provides a Stable, Pourable, fluid detergent composition containing water, Active Ingredients, Electrolyte and suspended solids, wherein the proportion of Electrolyte is sufficient to form a Shear Stable Spherulitic composition having a Yield Point of from 1 to 15 dynes cm- 2 .
  • the Yield Point of the composition is greater than 1.5, more preferably greater than 2, most preferably greater than 2.5, e.g. greater than 3, and preferably less than 10 dynes cm- 2 .
  • the Viscosity at 136 sec- 1 is less than 1.5, more preferably less than 1, e.g. from 0.2 to 0.6 Pascal Seconds.
  • our invention provides a Stable, Pourable, fluid, detergent composition consisting essentially of water, from 5 to 25% based on the weight of the composition of Active Ingredients, Electrolyte and suspended,solid Builder, the total weight proportion of Builder to Active Ingredient being from 1.4:1 to 4:1 and the portion of Electrolyte being sufficient to provide a Shear Stable, Non-Lamellar composition.
  • the composition may additionally contain the Usual Minor Ingredients.
  • the Active Ingredients are present in a proportion of 10 to 20%, more preferably 10 to 14% by weight and the total weight ratio and the builder to Active Ingredient is from 1.5:1 to 3:1, e.g. 1.9:1 to 2.5:1.
  • our invention provides a Stable, Pourable, fluid, detergent composition comprising water, from 5 to 25% based on the weight of the composition of Active Ingredients, Electrolyte and suspended solid Builder, and having a Pay Load of at least 35% by weight, wherein the proportion of Electrolyte is sufficient to provide a Shear Stable, Spherulitic composition.
  • our invention provides a Stable, Pourable, fluid, detergent composition containing water from 5 to 25% by weight of Active Ingredients, Electrolyte and suspended solid Builder the total proportion by weight of Builder to Active Ingredients being from 1.5:1 to 4:1-and the proportion of Electrolyte being sufficient to provide a Spherulitic composition Stable to storage at 40 o C.
  • the proportion of Electrolyte is sufficient to render the composition Temperature Stable.
  • our invention provides a Stable, Pourable, fluid, detergent composition
  • a Stable, Pourable, fluid, detergent composition comprising water, 5 to 20% by weight of Active Ingredients, Electrolyte and suspended solid Builder, the total weight ratio of Builder to Active Ingredient being from 1:1 to 4:1 and the proportion of Electrolyte being sufficient to provide a Temperature Stable, Non-Shear Sensitive composition, which on Centrifuging separates into an aqueous layer, containing more than 50% of the total weight of Active Ingredients, and a Solid Layer.
  • our invention provides a Stable, Pourable detergent composition consisting essentially of water, dissolved Electrolyte and from 8 to 14% by weight of the composition of Active Ingredients, together with suspended solid Builder, and optionally the Usual Minor Ingredients, which composition, on Centrifuging, separates into a Solid Layer and a single liquid layer having a Yield Point of greater than 1.5 dynes cm -2 .
  • our invention provides a composition consisting substantially of water, Active Ingredients and Electrolyte and having solid-suspending properties, wherein the Active Ingredients are capable of forming a Stable composition at the First Conductivity Minimum, and the amount of Electrolyte present is sufficient to provide a composition having a Yield Point of greater than 1.5 dynes cm- 2 and a Viscosity measured at 136 sec- I , of less than 0.28 Pascal Seconds.
  • our invention provides a Pourable, Stable, aqueous based detergent composition consisting essentially of water, Electrolyte, Active Ingredient and Builder and comprising a first predominantly aqueous liquid Separable Phase, containing at least part of the Electrolyte in solution and from 50 to 80% of the total weight of Active Ingredients, at least one Dispersed Solid Separable Phase comprising at least part of the Builder as solid.
  • the predominantly aqueous Separable Phase comprises at least 40% usually at least 50% e.g. at least 60% of the Total Water.
  • our invention provides a Pourable, Stable, aqueous based detergent composition having a Pay Load greater than 35% by weight and a pH greater than 9 and comprising water, a dissolved Electrolyte, at least 5% by weight of Active Ingredients and at least 16% by weight of Builder, which Electrolyte is present in a proportion sufficient to render the composition Shear Stable, but insufficient for the Active Ingredients to form a substantial proportion of a Lamellar Phase.
  • our invention provides an aqueous-based, liquid detergent composition, comprising sufficient Active Ingredients to form a space-filling floc of surfactant containing Spherulites Interspersed with an aqueous phase and an amount of Electrolyte not less than that corresponding to the First Conductivity Minimum of the graph of electrical Conductivity against . Electrolyte concentration, but below that which corresponds to the formation of a Lamellar phase, and sufficient to render the composition non-Shear Sensitive.
  • our invention provides a Pourable, Stable detergent composition
  • a Pourable, Stable detergent composition comprising water, Electrolyte, Active Ingredient and Builder, which separates on Centrifuging as defined herein into at least two layers including: a predominantly aqueous layer containing dissolved Electrolyte, at least 10% by weight of the Total Water, and from 80% to 50% by weight of the total Active Ingredient, and a Solid Layer containing at least a proportion of the Builder.
  • our invention provides a Pourable, Stable, fluid, detergent composition consisting essentially of: water; a concentration of from 5 to 25% 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 that is capable of forming stable foams, the proportions of (i) to (ii) being such that if a soluble Electrolyte is added progressively to an aqueous mixture containing said Active Ingredients at said concentration, a First Conductivity Minimum is reached at which the mixture is turbid and Stable; suspended Solid Builder, the total weight ratio of Builder to Active Ingredients being from 1:1 to 4:1; and dissolved Electrolyte in a proportion sufficient to form a Stable composition corresponding to the Conductivity trough containing said First Conductivity Minimum, and greater than any concentration below which the composition is Shear Sensitive but below the maximum concentration at which it is Temperature Stable.
  • our invention provides a Stable, Spherulitic Composition comprising Active Ingredients, Electrolyte and water which does not exhibit a separate, clear, aqueous phase after High G centrifuging, at 20,000 G for 90 minutes.
  • our invention provides Stable, Pourable, . fluid detergent compositions comprising water, Active Ingredients and Electrolyte, all of which compositions exhibit at least some, but not necessarily all, of the following characteristics: they comprise a Spherulitic phase Interspersed with a Lye or L 1 phase and preferably Co-continuous with the Lye or L 1 phase; they are substantially Non-Lamellar; they comprise a floc system which is preferably space-filling; they comprise a floc system which is formed from particles comprising the Active Ingredients which are preferably surfactant-containing Spherulites, typically having concentric shells of surfactant alternating with an aqueous, e.g.
  • Lye phase and having 0 a repeat spacing of from 60 to 100 A, prefered 70 to 90 A, often 75 to 85, e.g. 80 A; they comprise Spherulites of from 0.5-to 5 microns, preferably 0.6 to 5 microns diameter, which show a so-called "Maltese Cross" texture when viewed at suitable magnifications between crossed polarisers; they are shear thinning; they have a Viscosity Drop greater than 0.35, usually greater than 0.4, often greater than 0.45 Pascal seconds, but preferably less than 2 Pascal Seconds, e.g. 0.475 to 1.5, especially 0.48 to 1.1 Pascal seconds; they have a high Payload of Functional Ingredients, typically greater than 20% by weight, e.g.
  • 25 to 75% more usually at least 30% preferably at least 35% most preferably at least 40% by weight; they contain a high ratio of Builder to Active Ingredient e.g. greater than 1:1 preferably 1.2:1 to 4:1, more preferably 1.4:1 to 4:1, most preferably 1.5:1 to 3.5:1; they contain more than 5 and preferably more than 8% by weight of composition of Active Ingredients; they contain less than 25X, preferably less than 20%, usually less than 15%, more preferably less than 14.5%, most preferably less than 14%, e.g.
  • the composition of Active Ingredients from 10 to 13.5% by weight of the composition of Active Ingredients; they form a single aqueous layer and a Solid Layer on Centrifuging wherein the aqueous layer usually has a Yield Point of at least 1, preferably at least 1.5 dynes cm- 2 , e.g. 2 to 10 dynes cm- 2 and typically a Viscosity of less than 1.5 Pascal Seconds at 136 sec- 1 ; the proportion by weight of Active Ingredient in the predominantly aqueous layer formed after Centrifuging based on total Active Ingredient in the composition is greater than 50%, preferably greater than 55% e.g. greater than 60%, . but is less than 90%, preferably less than 85% e.g.
  • the pH of the composition is greater than 8.5, preferably 9 to 13, e.g. 9.5 to 12;
  • the composition produces a wash liquor on dilution with water to 0.5% Dry Weight having a pH greater than 9.7, preferably greater than 10, e.g. 10.9 to 11.1; the alkalinity is sufficient to require at least 0.8ml of N/10 HC to reduce the pH of 100mls wash liquor at 0.5% Dry Weight to 9, preferably lm1 e.g.
  • 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 e.g. 2.0 to 4.5 gram ions per litre of total alkali metal and/or ammonium cations; the concentration of Electrolyte is greater than that corresponding to the First Conductivity Minimum of the graph of Conductivity against Electrolyte concentration; the Conductivity is no more than 2 mS greater than the Conductivity at the First Conductivity Minimum; the concentration of Electrolyte is below that which causes the formation of a substantial proportion of Lamellar phase; the Electrolyte concentration is above the minimum which provides a Stable, and preferably above the minimum which provides a Shear Stable, composition; the composition is Non-Shear Sensitive; the composition is Temperature Stable; the composition is Stable at 40°C; the Conductivity of the composition is below 15 millisiemens per cm; the compositions contain at least 15% by weight,
  • the composition has a Yield Point preferably of at least 1, more preferably at least 1.5; e.g. at least 2, preferably less than 30, e.g. less than 20, most preferably less than 15, usually less than 10 dynes/sq cm;
  • a phase containing Builder comprises solid particles having a maximum particle size below the limit at which the particles tend to sediment;
  • the composition is Shear Stable;
  • the Active Ingredients include at least two components . one of which is a non-ethoxylated anionic surfactant and the other a surfactant which forms stable foams such as an ether sulphate, alkanolamide or amine oxide.
  • the composition typically passes through a series of easily recognised stages, as follows.
  • compositions of Stage I are, in general, clear and stable, but have no capacity to suspend solid particles.
  • stage II eutron diffraction studies are consistent with reduced micellar concentrations and an increasing proportion of larger bodies, but not with the presence of any significant proportion of "G" phase.
  • the compositions of stage II are turbid, and unstable and sediment rapidly.
  • the Conductivity falls to a minimum and then begins to rise.
  • the spaces between the Spherulite flocs disappear and the Spherulites form a space-filling floc extending throughout the liquid phase.
  • High G Centrifuging does not separate an aqueous phase, even when continued for 90 minutes. A Yield Point is observed, rising to a maximum, and the composition becomes shear thinning with a marked Viscosity Drop.
  • compositions in Stage III are Stable and capable of suspending solid particles to form a Stable suspension. Such Stage III compositions constitute our invention.
  • a Lamellar Composition is formed of the type described in E.P.0086614. Viscosity, when the water content is adjusted to the extent required to give a Stable composition, is relatively high.
  • the foregoing sequence is typical of the interactions of Electrolytes with a wide variety of aqueous surfactant mixtures.
  • the composition already contains some dissolved Electrolyte, as in a built detergent containing suspended tripolyphosphate, or where the initial surfactant mixture is not fully soluble in water, the first stage may not be observed.
  • solubility of the Electrolyte is limited, as, for example, in the case of sodium tripolyphosphate or sodium carbonate, addition of further Electrolyte above its saturation limit will not take the composition any further in the sequence.
  • compositions of the present invention lie within the third stage of the above sequence. Between the third stage and the second and fourth stages, respectively, there exist intermediate compositions which are semi-stable. Such compositions exhibit a floc of surfactant Spherulites, which are not completely space-filling as evidenced by the fact that High G Centrifuging continued for 90 minutes results in the formation of a clear aqueous layer, or in which the Spherulites are capable of being irreversibly disrupted. Such compositions, although they may be Stable when allowed to stand at ambient temperature, are often unstable when exposed to various kinds of stress such as high Shear stress, elevated or depressed temperatures or pH changes. Their capacity to suspend particulate solids is often limited. A number of proposed prior art compositions lie in these semi-stable areas.
  • compositions which lie within these semi-stable "borderline” areas may be modified in accordance with the teaching of this patent, by adjusting the Electrolyte and/or Active Ingredient content to bring them more closely into line with the Stable areas of Stage III.
  • the Stage III compositions of the present invention separate into an aqueous layer containing Electrolyte and from 90 to 50% by weight of the total Active Ingredients, typically 80%-50%, more usually 75% to 55%, e.g. 70% to 55% of the total Active Ingredients, and at least one other layer, said at least one other layer preferably containing from 20% to 50% by weight of the total Active Ingredient together with a substantial proportion of the Builder.
  • 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, e.g. 0.25 and 0.6 Pascal Seconds, and the Viscosity Drop is typically between 0.4 and 2, e.g. 0.45 to 1.5 Pascal Seconds.
  • Stage III compositions are Non-Shear Sensitive and usually Shear Stable. In contrast, high shear forces tend to render the semi-stable borderline compositions unstable. The viscosity is often substantially increased by even moderate shear and they may undergo rapid sedimentation. This can present practical difficulties during manufacture and bottling.
  • Stage III compositions of our invention are generally stable to high pH and to storage at temperatures around 40°C or below 5°C, unlike many semi-stable compositions. They are typically Temperature Stable, when heated to 100°C.
  • Stage III compositions typically show no evidence of a Lamellar Phase on analysis by neutron diffraction, although some compositions near the borderline with Stage IV may show evidence of minor amounts of "G" phase.
  • aqueous phases exist, an L 1 and a Lye Phase, which latter phase may also be an L l Phase containing fewer micelles and more Electrolyte than the former.
  • micellar surfactant without substantially reducing the amount of the Spherulites.
  • the lower micellar content reduces the Viscosity, while the Spherulitic phase remains sufficient to maintain stability.
  • the Spherulites are sufficiently closely packed to form an aggregated floe which is substantially space-filling, that is it extends throughout the volume of the liquid.
  • the Spherulites probably interact to form a weak three dimensional matrix sufficiently strong to support suspended particles, but weak enough to break down and flow readily under the influence of shear forces, and to reform when they are withdrawn.
  • the size of the Spherulites appears to correlate with stability compositions with large Spherulites of 5 microns and more being less stable than those in which the majority of surfactant is in Spherulites of from 0.5 to 5 microns.
  • compositions of our invention preferably contain at least 5%, less than 30% and generally less than 25% by weight of surfactants. More preferably the surfactant constitutes from 5 to 20% by weight of the composition, e.g. 8 to 15% by weight, typically 10 to 14.5% especially preferably, less than 14, often less than 13%.
  • the concentration of Active Ingredients may be a critical factor in obtaining compositions of our invention. Below a certain minimum which varies according to the particular Active system, the composition cannot be stabilised by adding more Electrolyte, however, the maximum is also important in order to avoid instability and/or excessively viscous compositions.
  • Prior art semi-stable Spherulitic Compositions have often contained relatively high amounts of Active Ingredients. This has resulted in a relatively high Viscosity of the aqueous suspending medium, which in turn has severely limited the amount of Builder which could be suspended for any given acceptable limit of Viscosity. Thus the overall Builder to Active ratio has been low compared to powders, with consequent poor washing performance.
  • the Active Ingredients in such compositions could be reduced without destabilising the systems totally.
  • the concentration of Active Ingredient may be substantially reduced, to provide aqueous media of equivalent or even greater stability and yet having lower Viscosity.
  • Such media can suspend greater amounts of Builder without losing adequate mobility and the resulting big increases in the ratio of Builder to Active Ingredient produce equally substantial increases in cost effectiveness.
  • mixtures of one or more non-ethoxylated anionic surfactant such as alkyl benzene sulphonate and/or alkyl sulphate with one or more cosurfactants which form stable foams such as alkyl ether sulphates and/or alkanolamides or amine oxides, are generally more suitable than any of the surfactants on their own.
  • Minor amounts of ethoxylated non-ionic surfactants, or of amphoteric surfactants, or cationic fabric softeners, may additionally be present.
  • the surfactant mixture may for example comprise one or more at least sparingly water-soluble salts of sulphonic or mono esterified sulphuric acids e.g. an alkylbenzene sulphonate, alkyl sulphate, alkyl ether sulphate, olefin sulphonate, alkane sulphonate, alkylphenol sulphate, alkylphenol ether sulphate, alkyl ethanol amide sulphate, alkylethanolamide ether sulphate, or alpha sulpho fatty acid or its esters each having at least one alkyl or alkenyl group with from 8 to 22, more usually 10 to 20, aliphatic carbon atoms.
  • sulphonic or mono esterified sulphuric acids e.g. an alkylbenzene sulphonate, alkyl sulphate, alkyl ether sulphate, olefin sulphonate, alkane s
  • Said alkyl or alkenyl groups are preferably straight chain primary groups but may optionally be secondary, or branched chain groups.
  • the expression ether hereinbefore refers to polyoxyethylene, polyoxypropylene, glyceryl and mixed polyoxyethylene-oxy propylene or mixed glyceryl- oxyethylene or glyceryl-oxy propylene groups, typically containing from 1 to 20 oxyalkylene groups.
  • the sulphonated or sulphated surfactant may be sodium dodecyl benzene sulphonate, potassium hexadecyl benzene sulphonate, sodium dodecyl dimethyl benzene sulphonate, sodium lauryl sulphate, sodium tallow sulphate, potassium oleyl sulphate, ammonium lauryl monoethoxy sulphate, or monoethanolamine cetyl 10 mole ethoxylate sulphate.
  • anionic surfactants useful according to the present invention include paraffin sulphonates, olefin sulphonates, fatty alkyl sulphosuccinates, fatty alkyl ether sulphosuccinates, fatty alkyl sulphosuccinamates, fatty alkyl ether sulphosuccinamates, acyl sarcosinates, acyl taurides, isethionates, Soaps such as stearates, palmitates, resinates, oleates, linoleates, and alkyl ether ' carboxylates.
  • Anionic phosphate esters may also be used.
  • the anionic surfactant typically contains at least one aliphatic hydrocarbon chain having from 8 to 22 preferably 10 to 20 carbon atoms, and, in the case of ethers one or more glyceryl and/or from to 20 ethyleneoxy and 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 mixture may optionally contain nonionic surfactants.
  • the nonionic surfactant may be e.g. a C IO - 22 alkanolamide of a mono or di-lower alkanolamine,such as coconut monoethanolamide.
  • nonionic surfactants which may optionally be present, include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and the propoxylated or ethoxylated and propoxylated analogues of all the aforesaid ethoxylated nonionics, all having a C 8-22 alkyl or alkenyl group and up to 20 ethyleneoxy and/or propyleneoxy groups, or any other nonionic surfactant which has hitherto been incorporated in powder or liquid detergent compositions e.g. amine oxides.
  • the latter typically have at least one C 8-22 , preferably C 10-20 alkyl or alkenyl group and up to two lower (e.g
  • the preferred Active Ingredients or mixtures for our invention are for example those having an HLB greater than 7, preferably greater than 8, more preferably greater than 10, most preferably greater than 12 and preferably less than 18, more preferably less than 16, most preferably less than 15.
  • Cationic fabric softeners of value in the invention include quaternary amines having two long chains (e.g. C 12 - 22 typically C 16-20 ) alkyl or alkenyl groups and either two short chains (e.g. C 1-4 ) alkyl groups, or one short chain and one benzyl group. They also include imidazoline and quaternised imidazolines having two long chain alkyl or alkenyl groups, and amido amines and quaternised amido amines having two long chain alkyl or alkenyl groups.
  • the quaternised softeners are all usually salts of anions which impart a measure of water dispersibility such as formate, acetate, lactate, tartrate, chloride, methosulphate, ethosulphate, sulphate or nitrate.
  • Compositions of our invention having fabric softener character may contain smectite clays.
  • compositions of our invention may also contain amphoteric surfactant, which may be included typically in surfactants having cationic fabric softener, but may also be included, usually as a minor component of the Active Ingredients, in any of the other detergent types discussed above.
  • amphoteric surfactant may be included typically in surfactants having cationic fabric softener, but may also be included, usually as a minor component of the Active Ingredients, in any of the other detergent types discussed above.
  • Amphoteric surfactants include betaines, sulphobetaines and phosphobetains formed by reacting a suitable tertiary nitrogen compound having a long chain alkyl or alkenyl group with the appropriate reagent,such as chloroacetic acid or propane sultone.
  • 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 short chain alkyl group; imidazoline having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups.
  • Electrolyte is essential in order to interact with the surfactant to form a space-filling spherulitic system.
  • the Electrolyte concentration is preferably not, however, sufficient to permit substantial stacking of any planar Bilayers, to form non- spherical Lamellar Phases.
  • Such Lamellar Phases may provide non-Stable or Shear Unstable compositions, unless the Pay Load is sufficiently high for the Lamellar Phase to form a stable structure according to E.P.008614A, The relatively strong matrix which characterises the latter compositions, however, generally results in undesirably high Viscosity.
  • a suitable surfactant system at a suitable concentration we have found that it is possible to stabilise the system in accordance with an our invention by including in the composition a suitable quantity of Electrolyte.
  • Electrolyte results in unstable, or shear, or temperature sensitive systems and/or in systems having undesirably high Viscosity.
  • the proportion of Electrolyte must therefore be selected according to the nature of the surfactant and the amount of any Hydrotrope present to provide compositions according to the present invention.
  • the optimum proportion 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 weight Active) and observing one or more of several characteristic properties of the system such as turbidity, Conductivity, Yield Point, appearance under the polarising microscope or with phase contrast or differential interference contrast, or behaviour on High G Centrifuging.
  • the proportion may be optimised within this range by observing the amount required to obtain no clear layer on High G Centrifuging for 90 minutes, and/or to provide Temperature Stable and/or Shear Stable compositions. If the composition is intended for a market in which low Viscosity is of primary importance, the optimised composition may be progressively diluted until a suitable Viscosity is achieved or signs of instability are observed. If the latter occurs, further additions of Electrolyte may be made until a sufficiently stable composition has been obtained.
  • the amount of Electrolyte is preferably greater than that at the First Conductivity Minimum in the Conductivity/Electrolyte concentration graph and corresponds to the amount required to provide a composition having a Yield Point greater than 1.5 dynes cm- 2 .
  • Electrolytes such as carbonates, silicates, pyrophosphates, polyphosphates, nitriloacetates and citrates, all of which are Builders, but the effective concentration of some such Electrolytes, e.g. carbonates, may be undesirably limited by their solubility. In such cases it may prove necessary to add a more soluble Non-Functional Electrolyte. Sodium chloride and sodium nitrate have been found particularly effective in this respect.
  • the proportion of Electrolyte in the at least one predominantly aqueous phase is sufficient to provide a concentration of at least 0.3 preferably at least 1.2 e.g 2.0 to 4.5 gram ions per litre of alkali metal, alkaline earth metal and/or ammonium cations.
  • the Builder in preferred compositions of our invention is . believed to be normally present, at least partially, as discrete solid crystallites suspended in the composition.
  • the crystallites typically have a size of up to 60 eg 1 to 50 microns.
  • Formulations containing sodium tripolyphosphate as Builder exhibit stability and mobility over a wider range of Dry Weight than corresponding Formulations with other Builders. Such formulations are therefore preferred.
  • Our invention also provides compositions comprising other Builders such as potassium tripolyphosphate, carbonates, zeolites, nitrilo triacetates, citrates, metaphosphates, pyrophosphates, phosphonates, EDTA and/or polycarboxylates, optionally but preferably, in admixture with tripolyphosphate.
  • Orthophosphates may be present, preferably as minor components in admixture with tripolyphosphate, as may alkali metal silicates and carbonates.
  • Silicates and carbonates are particularly preferred since they perform several valuable functions. They provide the free alkalinity desirable to saponify fats in the soil, they have an effect as Builders, and in the case of silicates, they inhibit corrosion of aluminium surfaces in washing machines. In addition, they are effective as Electrolytes necessary to form a spherulitic system.
  • silicate typically, where silicate is used to prepare our compositions it has an Na 2 O: SiO2 ratio of from 1:1 to 1:2 or 1:1.5 to 1:1.8. It will however be appreciated that any ratio of Na 2 0 (or other base) to Si0 2 , or even silicic acid, could be used to provide the silicate in the composition, and any necessary additional alkalinity provided by addition of another base such as sodium carbonate or hydroxide. Formulations not intended for use in washing machines do not require silicates provided that there is an alternative source of alkalinity.
  • compositions wherein the Builder is present substantially entirely in solution, e.g. sodium nitrilo triacetate, sodium citrate, sodium silicate or mixtures thereof.
  • the Builder normally constitutes at least 15% by weight of the compositions, preferably at least 20%.
  • the ratio of Builder to surfactant is greater than 1:1 preferably 1.2:1 to 4:1.
  • the cations present should consist, at least predominantly, of sodium.
  • the preferred Builder is sodium tripolyphosphate
  • the preferred anionic surfactants are sodium salts of sulphated or sulphonated anionic surfactants and any anti-redeposition agent, e.g. carboxymethyl cellulose, or alkali, e.g. silicate or carbonate are also preferably present as the sodium salts.
  • Sodium chloride, sodium nitrate or other soluble inorganic sodium salts may be added to increase the Electrolyte concentration.
  • Calcium is only normally present when the Active Ingredients comprise surfactants, such as olefin sulphonates or non-ionics which are tolerant of its presence. Magnesium salts may be present, and are more compatible with surfactants than is calcium.
  • compositions containing high proportions of such cations are, however, unlikely to be cost effective in comparison with conventional laundry powders.
  • compositions of our invention are preferably alkaline, being desirably buffered with an alkaline buffer to provide a pH in the composition as measured on a glass electrode, above 8.5 preferably above 9, most preferably above 9.2, e.g. 9.5 to 12 especially 10 to 11.
  • our compositions should be adapted to provide a pH of greater than 9.7, e.g. greater than 10, especially 10.5 to 11.5 in a wash liquor containing the composition diluted to 0.5% Dry Weight.
  • They desirably have sufficient free alkalinity to require at least 0.4 mls, preferably at least 0.8 mls, most preferably 1 to 12 mls, e.g.
  • compositions having higher alkalinity may also be commercially acceptable.
  • lower alkalinities are less acceptable in commercial practice, although not excluded from the scope of our invention.
  • the alkaline buffer is preferably sodium tripolyphosphate and the alkalinity is preferably provided at least in part by sodium carbonate.
  • Other preferred alkaline buffers include sodium silicate.
  • liquid detergent compositions have commonly contained substantial concentrations of Hydrotropes and/or organic, water- miscible hydroxylic solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol. They are, however, costly and not Functional Ingredients. They may, in certain circumstances promote pourability or permit a surfactant to form a spherulitic phase more readily. 1e do not therefore totally exclude them from all compositions of our invention, but we prefer that their presence be limited to the minimum required to ensure a Spherulitic Composition of adequate Pourability. If not so required we prefer that they be absent. Solvents may sometimes need to be accommodated as components of perfumes or other of the Usual Minor Ingredients.
  • Hydrotropes and/or organic, water- miscible hydroxylic solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol.
  • solvents such as
  • the Dry Weight of the composition affects stability and Pourability. Optimum Dry Weight may vary considerably from one type of Formulation to another and may be selected to provide the required Viscosity. Generally speaking it has not been found possible to guarantee Stable compositions below about 35% by weight Dry Weight, although some types of Formulation can be obtained in a Stable form below 30% Dry Weight, and sometimes as low as 25% Dry Weight. We do not exclude the possibility of making Stable Compositions at Dry Weights down to 20%.
  • a range of Dry Weights can be identified within which the composition is both Stable and Pourable. Generally below this range, sedimentation occurs and above the range, the Formulation is either unstable or too viscous.
  • the acceptable range may be routinely determined for any given Formulation by preparing the suspension using the minimum water required to maintain a stirrable composition, diluting a number of samples to progressively higher dilutions, and observing the samples for signs of sedimentation over a suitable period.
  • the acceptable range of Dry Weights may extend from 30% or 35% to 60 or even 70% by weight for others it may be much narrower, e.g. 40 to 45% by weight.
  • the Formulation should be modified according to the teaching herein e.g. by the addition of more sodium carbonate, sodium silicate solution or other Electrolyte if the composition exhibits Stage or II properties, or by reducing the Electrolyte content or adding Hydrotrope if the composition exhibits Stage IV or V properties.
  • the Active Ingredients may be modified by adding a foam stabilising surfactant, such as alkyl ether sulphate, alkanolamide or amine oxide, if the composition tends to form Stage IV or V, or by adding alkyl benzene sulphonate or alkyl sulphate or other non-ethoxylated anionic surfactant if Stage I or Stage II properties predominate.
  • a foam stabilising surfactant such as alkyl ether sulphate, alkanolamide or amine oxide
  • compositions of our invention can, in many instances be readily prepared by normal stirring together of the ingredients. It is a characteristic of our preferred compositions, however, that they are not destabilised or thickened by subjection to high shear forces.
  • Compositions according to our invention may be typically obtained for any suitable Active Ingredients by first preparing a clear aqueous L 1 solution of the Active Ingredients at a suitable concentration (e.g. 15 to 30% by weight Active) with warming, if necessary, and dissolving Electrolyte in the L 1 solution or adding concentrated Electrolyte solution (preferably Functional Electrolyte) until the mixture becomes opaque. A sample of the mixture is then centrifuged at 20,OOOG for 5 minutes. If a clear aqueous phase is observed, more Electrolyte is added to the mixture until High G Centrifuging no longer gives evidence of a separate, substantially clear, aqueous phase. The weight ratio of Active Ingredient to dissolved Electrolyte is then noted.
  • a suitable concentration e.g. 15 to 30% by weight Active
  • concentrated Electrolyte solution preferably Functional Electrolyte
  • a composition containing all the desired Ingredients and having the Active Ingredient to Electrolyte weight ratio already determined may then be prepared at the desired Percentage Dry Weight (typically 40 to 50%). Formation of a clear aqueous Lye phase on High G Centrifuging indicates the presence of Lamellar or non-space filling Spherical "G" Phase and the amount of Electrolyte is then reduced until no clear phase is observed on High G Centrifuging. Samples of the latter Formulation at different Dry Weights may be prepared to determine the optimum balance of Pay Load/mobi l ity/stabi l ity characteristics. If, on dilution to a desired, low Viscosity, the stability is inadequate, it may often be restored by adding more Electrolyte.
  • the desired Percentage Dry Weight typically 40 to 50%.
  • the -procedure may be repeated using a more soluble Electrolyte, e.g. a non-Functional Electrolyte such as sodium chloride or sodium nitrate.
  • a more soluble Electrolyte e.g. a non-Functional Electrolyte such as sodium chloride or sodium nitrate.
  • the Active system may be modified by addition of surfactants which favour stable dispersions according to our invention, e.g. ether sulphates, amine oxides or alkanolamides, if Stage IV or V properties are observed, or a non-ethoxylated anionic surfactant if Stage I or II properties are more readily obtained.
  • the proportions of surfactant may be adjusted until a mixture is obtained that forms a Stable, turbid, mixture at the First Conductivity Minimum.
  • Formulations are typically based on mixtures of one or more non-ethoxylated anionic surfactant, preferably a sulphated or sulphonated surfactant, with one or more cosurfactant which forms a stable foam such as an ethoxylated anionic surfactant, an amine oxide or a fatty alkanolamide.
  • the first component of the Active Ingredients i.e. the the non ethoxylated anionic surfactant may for example be a C l o - 18 alkyl sulphate and/or C 10-14 alkyl benzene sulphonate.
  • the second component or cosurfactant may be a sodium C 10-20 straight or branched chain alkyl C 1-10 mole ether sulphate or an alkyl phenol ether sulphate, amine ether sulphate, alkanolamide ether sulphate or fatty acid ether sulphate.
  • the second component may comprise an amine oxide or fatty alkylolamide.
  • the total proportion by weight of non-ethoxylated anionic to cosurfactant may typically be from 5:1 to 1:3, preferably 4:1 to 1:2, e.g. 3:1 to 1:1. Small amounts (e.g. up to 1% of the weight of the compositions) of Soap may be present to aid rinsing of the fabric.
  • Nonionic ethoxylates may be present in minor proportions, typically up to 20% by wt. of the total Active Ingredients, preferably less than 15%, usually less than 10%.
  • the sodium alkyl sulphate or alkyl benzene sulphonate may be totally or partially replaced, in the above Formulations by other sulphonated, non-ethoxylated surfactants including fatty alkyl xylene or toluene sulphonates, or by paraffin sulphonates, olefin sulphonates, sulphocarboxylates, and their esters and amides, including sulphosuccinates and sulphosuccinamates.
  • the alkyl ether sulphate may be wholly or partially replaced by other ether sulphates such as alkyl phenyl ether sulphates, fatty acyl monoethanolamide ether sulphates or mixtures thereof.
  • our invention provides a Stable, Pourable, Non-Shear Sensitive Spherulitic Composition having a Pay Load of at least 35% by weight and comprising: water; from 12 to 40% Dry Weight of Active Ingredient based on the Dry Weight of the composition and from 20 to 80% Dry Weight of Builder based on the Dry Weight of the composition, at least partly present as suspended solid and partly as at least part of said dissolved Electrolyte, in a total weight ratio of Builder to Active Ingredients of 1.3:1 to 4:1; and wherein said Active Ingredients consists of (A) from 30 to 80% by weight thereof of a non-alkoxylated anionic sulphated or sulphonated surfactant, and (B) from 20% to 70% by weight of the total surfactant of at least one foam stabilising cosurfactant such as an alkoxylated anionic surfactant, an alkanolamide or an amine oxide.
  • a foam stabilising cosurfactant such as an alkoxylated anionic surfactant, an alkan
  • the aforesaid composition may additionally contain up to 6% by Dry Weight of the composition of Soap.
  • the non-alkoxylated sulphated or sulphonated anionic surfactant consists substantially of alkyl sulphate or alkyl benzene sulphonate, . preferably sodium alkyl benzene sulphonate, e.g. C 10 - 14 alkyl benzene sulphonate.
  • the anionic surfactant may comprise a mixture of alkyl benzene sulphonate, and/or alkyl sulphate with alkyl ether sulphate and/or alkyl phenol ether sulphate in weight proportions of e.g. from 1:3 to 5:1 typically 1:2 to 4:1 preferably 1:1 to 3:1 e.g. 2:1.
  • Low foaming compositions according to our invention may be prepared by using suitable foam-inhibitors.
  • foam-inhibitor requires some care, since certain commercially available foam-inhibitors may lose their effectiveness on storage in compositions of our invention, while others are only effective at concentrations high enough to affect the Viscosity or Stability of the composition.
  • a Stable, Pourable, fluid, aqueous-based, detergent composition comprising: from 12 to 40% based on Dry Weight ther of of Active Ingredients which comprise from 30 to 90% based on the Dry weight of the Active Ingredients of non-alkoxylated sulphated and/or sulphonated anionic surfactant and the balance of alkyl ether sulphate, alkanolamide and/or amine oxide; an aqueous phase containing sufficient Electrolyte in solution to form a space-filling Spherulitic floc comprising at least part of said Active Ingredients and Interspersed with said aqueous phase; suspended particles of Builder; an effective amount of at least one foam inhibitor and optionally the Usual Minor Ingredients.
  • our invention provides a Pourable, Stable, Non-Lamellar detergent composition having a Payload of from 30% to 50% consisting essentially of from 12 to 40% Dry Weight, based on the Dry Weight of the composition, of Active Ingredients, at least 30% Builder, based on the Dry Weight of the composition, a ratio of Builder to Active Ingredient greater than 1.1 to 1, said Active Ingredient consisting essentially of alkyl benzene sulphonate having 8 to 18 aliphatic carbon atoms and an alkyl ethanolamide selected from Cio -18 alkyl monoethanolamides and diethanolamides, in a weight ratio of alkyl benzene sulphonate to ethanolamide of from 1.5:1 to 4:1, said Builder being selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrilo triacetate, sodium silicate and mixtures thereof, such that the amount of dissolved Builder is sufficient to provide a Yield Point of greater than 1.5 dynes cm- 2 .
  • a particularly preferred embodiment of our invention provides a Pourable, Stable, liquid detergent composition, consisting essentially of:
  • the sodium cation in the above composition may optionally, but less preferably, be replaced wholly or in part by potassium, lithium or ammonium.
  • the sodium tripolyphosphate constitutes from 40 to 95% of the total weight of Builder, e.g. 45% to 80%.
  • the composition contains at least one foam-inhibitor if required for automatic washing.
  • composition may optionally contain minor proportions of alkanolamide, such as coconut monoetholamide or diethanolamide, or of ethoxylated non-ionic surfactant, e.g. up to 15% of the total Active Ingredients, preferably less than 10%.
  • alkanolamide such as coconut monoetholamide or diethanolamide
  • ethoxylated non-ionic surfactant e.g. up to 15% of the total Active Ingredients, preferably less than 10%.
  • compositions of the invention may contain the Usual Minor Ingredients. Principal of these are antiredeposition agents, dispersants, optical brightening agents and bleaches.
  • SCMC sodium carboxymethyl cellulose
  • Alternative antiredeposition and/or soil releasing agents include potassium, ammonium and other soluble CMC salts, phosphonates, methylcellulose, poiyvinylpyrrolidone, carboxymethyl starch and similar poly electrolytes, including synthetic polycarboxylates such as polyacrylates all of which may be used in place of SCMC.
  • Optical Brighteners are optional, but preferred, ingredients of the compositions of our invention. Unlike some prior art formulations, our compositions are not dependent on OBA's for stability and we are therefore free to select any convenient and cost effective OBA, or to omit them altogether.
  • OBA may be present in conventional amounts. Typically concentrations of OBA between 0.05 and 0.5% are sufficient e.g. 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 we do not exclude them, are unlikely to prove cost effective and may, in some instances give rise to problems of compatibility.
  • OBA's which may be used in the present invention include : ethoxylated 1, 2-(benzimidazolyl) ethylene; 2- styrylnaphth[1,2d-loxazole; 1,2-bis(5' methyl-2-benzoxazolyl) ethylene; disodium-4,4'-bis(6-methylethanoiamine-3-anilino-1,3,5-triazin-2"-yl)-2,2'-stilbene sulphonate; N-(2-hydroxyethyl-4;4'-bis (benzimidazolyl)stilbene; tetrasodium 4,4'-bis [4"-bis(2"- hydroxyethyl)-amino-6"(3"-sulphophenyl) amino-1", 3", 5"-triazin-2"-yl amino]-2,2'-stilbenedisulphonate; disodium-4-(6"-sulphonaphtho[1',2'-d
  • Bleaches may optionally be incorporated in liquid detergent compositions of our invention subject to chemical stability and compatibility. Encapsulated bleaches may form part of the suspended solid. The action of peroxy bleaches in compositions of our invention may be enhanced by the presence of bleach activators such as tetra acetyl ethylenediamine, in effective amounts. Photoactive bleaches such as zinc or aluminium sulphonated phthalocyanin, may also be present.
  • Perfumes and colourings are conventionally present in laundry detergents in amounts up to 1 or 2%, and may similarly be present in compositions of our invention. Care is sometimes necessary in selecting a suitable perfume since the solvents present may modify the behaviour of the Active Ingredients.
  • Proteolytic and amylolitic enzymes may optionally be present in conventional amounts, together optionally with enzyme stabilizers and carriers. Encapsulated enzymes may be suspended in the composition.
  • Minor Ingredients include defoamers, alkalis, buffers, germicides such as formaldehyde, opacifiers such as vinyl latex emulsion, inert abrasives, such as silica and anticorrosives such as benzotriazole.
  • compositions of our invention are, in general, suitable for laundry use and our invention provides a method of washing clothes by agitating them in a wash liquor containing any composition of the invention as described herein.
  • Low foam compositions herein described are in particular of use in automatic washing machines.
  • the compositions may also be used in the washing of dishes, or the cleaning of hard surfaces, the low foam products being particularly suitable for use in dishwashing machines.
  • High foaming compositions may be of value for shampoo formulations.
  • compositions of our invention may, generally, be used for washing clothes in boiling water, or for washing at medium or cool temperatures, e.g. 50 to 80°C, especially 55 to 68 0 C, or 20 to 50°C especially 30 to 40°C, respectively.
  • the compositions may be added to the washwater at concentrations of 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 invention is illustrated by the examples set out in the following Tables.
  • the Examples were stable and Pourable. They were stable to storage at 40°C and were Non-Shear Sensitive. They were Temperature Stable and, except for Example 83, were Shear Stable.
  • Figure 1 is a graph showing conductivity of an aqueous 20.6% solution of Active Ingredients consisting of 2 parts by weight sodium dodecyl benzene sulphonate and 1 part sodium C 12-18 alkyl 3 mole ethoxy sulphate, with various concentrations of added sodium silicate of Na 2 O:SiO 2 mole ratio 1:1.6.
  • the figures on the horizontal axis refer to the amount of silicate in the composition expressed as weight percent of solids.
  • Stage II compositions are obtained, which are turbid, unstable and comprise non-Space Filling Flocs of Spherulites.
  • Stage III compositions are obtained, according to the invention. These are turbid, Stable compositions containing substantially Space Filling Flocs of Spherulites, exhibiting a Yield Point and showing only a single liquid phase on High G Centrifuging.
  • Stage IV compositions are obtained, containing non-Space Filling Flocs of Spherical G Phase, which are non-Stable. It will be seen that the Stable Stage III compositions are obtained in the Conductivity trough around the First Conductivity Minimum.
  • Figure 2 shows the effect of adding sodium nitrate to the same aqueous Active system. Beyond the point "C” in Stage IV a second Conductivity Maximum is passed, followed by a Second Conductivity Minimum, corresponding to the formation of a Lamellar composition according to Stage V at approximately "D".
  • Figure 3 shows variations in Viscosity, Conductivity and Yield Point when sodium carbonate is added to the same Active system.
  • the left-hand axis indicates Viscosity at 136 sec- l in Pascal Seconds, the figures in parenthesis referring to Conductivity in millisiemens cm- 1 ; the right-hand scale refers to Yield Point in dynes cm- 2 ; 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
  • Figure 4 illustrates the effect of varying the relative proportions of sodium dodecyl benzene sulphonate and coconut monoethanolamide in a composition containing sodium dodecyl benzene sulphonate, sodium tripolyphosphate, sodium carbonate and water in a ratio of 0.2:0.5:0.1:1.0.
  • the horizontal scale represents the Wt. ratio of coconut monoethanolamide to sodium dodecyl benzene sulphonate.
  • the vertical scale represents Conductivity in mS cm- 1 (circles) and also Viscosity in Pascal Seconds X 10 (triangles) .
  • Figure 5 shows a similar relationship wherein the cococnut monoethanolamide is replaced with sodium C 12-18 alkyl 3 mole ethoxy sulphate.
  • the horizontal scale is the weight ratio of the ether sulphate to the alkyl benzene sulphonate.
  • Figures 4 and 5 illustrate how it is possible to prepare compositions of the invention by modifying the Active Ingredients.
  • Figure 6 shows the variation in Conductivity in mS cm -1 when sodium nitrate is added in various proportions to a detergent composition containing suspended Builder and having the formulation:
  • Figure 7 shows the Yield Point for the same system, in dynes cmr2 and Figure 8 shows the Viscosity at 136 cmr 1 (lower curve), 21 curl (upper curve) and the Viscosity drop (middle curve) in Pascal Seconds X10.
  • Figure 9 illustrates the change in Conductivity with varying proportions of sodium silicate in a 20.6% by wt. aqueous solution of sodium dodecyl benzene sulphonate in admixture with coconut monoethanolamide in a weight ratio of 10:4.
  • Figures 10 and 11 are transmission micrographs of Pt/C replicas, after freeze fracturing, at magnifications of X78,000 and X150,000 (lin) respectively.
  • the micrograph shows Spherulites of between 0.2 and 1 micron diameter, which show evidence of being Multiple Vesicles with a concentric structure, having a repeat spacing (including the thickness of one surfactant shell and one adjacent aqueous layer) of 80 + A.

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EP84309004A 1983-12-22 1984-12-21 Flüssige Reinigungsmittelzusammensetzungen Expired EP0151884B1 (de)

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AT84309004T ATE52106T1 (de) 1983-12-22 1984-12-21 Fluessige reinigungsmittelzusammensetzungen.

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GB838334250A GB8334250D0 (en) 1983-12-22 1983-12-22 Liquid detergent compositions
GB8334250 1983-12-22
US57663284A 1984-02-03 1984-02-03
US576632 1984-02-03
GB8415783 1984-06-20
GB848415783A GB8415783D0 (en) 1984-06-20 1984-06-20 Liquid detergent compositions
GB8421759 1984-08-28
GB848421759A GB8421759D0 (en) 1984-08-28 1984-08-28 Liquid detergent compositions

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EP0151884A2 true EP0151884A2 (de) 1985-08-21
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EP0331370A2 (de) * 1988-02-26 1989-09-06 Unilever Plc Detergentzusammensetzung
EP0346993A2 (de) * 1988-06-13 1989-12-20 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0346994A2 (de) * 1988-06-13 1989-12-20 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0354010A2 (de) * 1988-08-05 1990-02-07 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
EP0385522A2 (de) * 1989-02-27 1990-09-05 Unilever N.V. Flüssiges Reinigungsmittel
WO1991005844A1 (en) * 1989-10-12 1991-05-02 Unilever N.V. Liquid detergents
GB2245262A (en) * 1990-06-22 1992-01-02 Unilever Plc Aluminosilicate slurries l
EP0530708A2 (de) * 1991-08-30 1993-03-10 ALBRIGHT & WILSON UK LIMITED Flüssiges Wäschewaschmittel
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EP0658620A1 (de) * 1993-12-15 1995-06-21 ALBRIGHT & WILSON UK LIMITED Strukturierte Tenside
WO1995031528A1 (en) * 1994-05-13 1995-11-23 Unilever N.V. Detergent composition
WO1996024658A1 (en) * 1995-02-06 1996-08-15 Unilever N.V. Liquid compositions
US5597508A (en) * 1989-10-31 1997-01-28 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent composition containing deflocculating polymer with ionic monomers
EP0776965A2 (de) 1995-11-30 1997-06-04 Unilever N.V. Polymerzusammetzungen
WO1997047725A1 (en) * 1996-06-13 1997-12-18 Colgate-Palmolive Company Liquid crystal detergent compositions
WO2000036079A1 (en) * 1998-12-16 2000-06-22 Unilever N.V. Structured liquid detergent composition
US6083897A (en) * 1998-08-28 2000-07-04 Huntsman Petrochemical Corporation Solubilization of low 2-phenyl alkylbenzene sulfonates
US6133217A (en) * 1998-08-28 2000-10-17 Huntsman Petrochemical Corporation Solubilization of low 2-phenyl alkylbenzene sulfonates
US6166095A (en) * 1993-12-15 2000-12-26 Albright & Wilson Uk Limited Method of preparing a drilling fluid comprising structured surfactants
US6617303B1 (en) 1999-01-11 2003-09-09 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
WO2004056957A1 (en) * 2002-12-19 2004-07-08 Unilever Plc Detergent composition
WO2004056950A1 (en) * 2002-12-19 2004-07-08 Unilever Plc Detergent composition
US6897188B2 (en) 2001-07-17 2005-05-24 Ecolab, Inc. Liquid conditioner and method for washing textiles
WO2007001341A2 (en) 2005-06-24 2007-01-04 Rhodia, Inc. Structured surfactant compositions
WO2007085410A1 (en) * 2006-01-24 2007-08-02 Henkel Ag & Co. Kgaa Structured cleaning compositions
WO2008047148A1 (en) * 2006-10-20 2008-04-24 Innovation Deli Limited Skin cleansing compositions
WO2008076693A3 (en) * 2006-12-15 2008-08-07 Colgate Palmolive Co Liquid detergent composition
US7682403B2 (en) 2004-01-09 2010-03-23 Ecolab Inc. Method for treating laundry
US8110537B2 (en) 2003-01-14 2012-02-07 Ecolab Usa Inc. Liquid detergent composition and methods for using
WO2013016031A1 (en) 2011-07-27 2013-01-31 The Procter & Gamble Company Multiphase liquid detergent composition
WO2013064356A1 (de) * 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa STRUKTURIERTES WASCH- ODER REINIGUNGSMITTEL MIT FLIEßGRENZE
WO2013119908A1 (en) 2012-02-10 2013-08-15 Stepan Company Structured surfactant suspending systems
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GB8906234D0 (en) 1989-03-17 1989-05-04 Albright & Wilson Agrochemical suspensions
GB2247028B (en) * 1990-08-15 1994-06-08 Albright & Wilson Dye suspensions
FR2666344B1 (fr) * 1990-09-03 1992-12-18 Total France Procede d'adoucissement en lit fixe de distillats petroliers acides de temperatures de coupe comprises entre environ 125 et environ 350 degre c.
GB9102757D0 (en) * 1991-02-08 1991-03-27 Albright & Wilson Biocidal and agrochemical suspensions
GB2259519B (en) * 1991-08-30 1996-03-06 Albright & Wilson Concentrated aqueous surfactant compositions
SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
IL162227A0 (en) 2001-12-21 2005-11-20 Rhodia Stable surfactant compositions for suspending components
BR112019025357B1 (pt) 2017-06-22 2022-11-01 Ecolab Usa Inc Método de tratamento sanitizante e/ou desinfetante antimicrobiano e branqueamento de roupa para lavar
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EP0328176A2 (de) * 1988-02-10 1989-08-16 Unilever N.V. Wässrige Reinigungsmittel und Verfahren zu deren Herstellung
EP0328176A3 (en) * 1988-02-10 1990-07-18 Unilever Nv Aqueous detergent compositions and methods of forming them
EP0331370A2 (de) * 1988-02-26 1989-09-06 Unilever Plc Detergentzusammensetzung
EP0331370A3 (en) * 1988-02-26 1990-07-25 Unilever Plc Detergent compositions
EP0346993A3 (de) * 1988-06-13 1990-08-16 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0346993A2 (de) * 1988-06-13 1989-12-20 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0346994A2 (de) * 1988-06-13 1989-12-20 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0346994A3 (en) * 1988-06-13 1990-08-22 Unilever Nv Liquid detergent compositions
EP0354010A2 (de) * 1988-08-05 1990-02-07 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
EP0354010A3 (de) * 1988-08-05 1990-04-04 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
US5264143A (en) * 1989-02-22 1993-11-23 The Procter & Gamble Company Stabilized, bleach containing, liquid detergent compositions
EP0385522A2 (de) * 1989-02-27 1990-09-05 Unilever N.V. Flüssiges Reinigungsmittel
EP0385522B1 (de) * 1989-02-27 2001-08-29 Unilever N.V. Flüssiges Reinigungsmittel
WO1991005844A1 (en) * 1989-10-12 1991-05-02 Unilever N.V. Liquid detergents
US5597508A (en) * 1989-10-31 1997-01-28 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent composition containing deflocculating polymer with ionic monomers
GB2245262A (en) * 1990-06-22 1992-01-02 Unilever Plc Aluminosilicate slurries l
EP0530708B2 (de) † 1991-08-30 2002-07-03 Huntsman International Llc Flüssiges Wäschewaschmittel
TR27553A (tr) * 1991-08-30 1995-06-08 Albright & Wilson Uk Ltd Konsantre sulu sürfaktan bilesimleri.
EP0530708A2 (de) * 1991-08-30 1993-03-10 ALBRIGHT & WILSON UK LIMITED Flüssiges Wäschewaschmittel
EP0530708A3 (en) * 1991-08-30 1993-06-09 Albright & Wilson Limited Liquid laundry detergent compositions
US6166095A (en) * 1993-12-15 2000-12-26 Albright & Wilson Uk Limited Method of preparing a drilling fluid comprising structured surfactants
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WO1995031528A1 (en) * 1994-05-13 1995-11-23 Unilever N.V. Detergent composition
WO1996024658A1 (en) * 1995-02-06 1996-08-15 Unilever N.V. Liquid compositions
EP0776965A2 (de) 1995-11-30 1997-06-04 Unilever N.V. Polymerzusammetzungen
WO1997047725A1 (en) * 1996-06-13 1997-12-18 Colgate-Palmolive Company Liquid crystal detergent compositions
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US6083897A (en) * 1998-08-28 2000-07-04 Huntsman Petrochemical Corporation Solubilization of low 2-phenyl alkylbenzene sulfonates
EP1141221B2 (de) † 1998-12-16 2011-11-30 Unilever N.V. Strukturierte flüssige waschmittelzusammensetzung
WO2000036079A1 (en) * 1998-12-16 2000-06-22 Unilever N.V. Structured liquid detergent composition
US6617303B1 (en) 1999-01-11 2003-09-09 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
US6897188B2 (en) 2001-07-17 2005-05-24 Ecolab, Inc. Liquid conditioner and method for washing textiles
WO2004056957A1 (en) * 2002-12-19 2004-07-08 Unilever Plc Detergent composition
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US8110537B2 (en) 2003-01-14 2012-02-07 Ecolab Usa Inc. Liquid detergent composition and methods for using
US7682403B2 (en) 2004-01-09 2010-03-23 Ecolab Inc. Method for treating laundry
EP1988985A4 (de) * 2005-06-24 2011-11-09 Rhodia Strukturierte tensidzusammensetzungen
WO2007001341A2 (en) 2005-06-24 2007-01-04 Rhodia, Inc. Structured surfactant compositions
EP1988985A2 (de) * 2005-06-24 2008-11-12 Rhodia, Inc. Strukturierte tensidzusammensetzungen
WO2007085410A1 (en) * 2006-01-24 2007-08-02 Henkel Ag & Co. Kgaa Structured cleaning compositions
WO2008047148A1 (en) * 2006-10-20 2008-04-24 Innovation Deli Limited Skin cleansing compositions
GB2456965A (en) * 2006-10-20 2009-08-05 Innovation Dell Ltd Skin cleansing compositions
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WO2013064356A1 (de) * 2011-11-02 2013-05-10 Henkel Ag & Co. Kgaa STRUKTURIERTES WASCH- ODER REINIGUNGSMITTEL MIT FLIEßGRENZE
US20140243253A1 (en) * 2011-11-02 2014-08-28 Henkel Ag & Co. Kgaa Structured detergent or cleaning agent having a flow limit
US9187714B2 (en) 2011-11-02 2015-11-17 Henkel Ag & Co. Kgaa Structured liquid detergent or cleaning agent having a flow limit and inorganic salt
WO2013119908A1 (en) 2012-02-10 2013-08-15 Stepan Company Structured surfactant suspending systems
WO2014064005A1 (de) * 2012-10-22 2014-05-01 Henkel Ag & Co. Kgaa Tensid-haltige schäume

Also Published As

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AU576541B2 (en) 1988-09-01
PL251139A1 (en) 1985-11-05
BG68023A (bg) 1993-12-24
IT1179891B (it) 1987-09-16
FR2587355A1 (fr) 1987-03-20
ATE52106T1 (de) 1990-05-15
IE843346L (en) 1985-06-22
IL73917A (en) 1988-11-30
FR2587355B1 (fr) 1991-09-27
EP0151884A3 (en) 1987-09-23
EP0151884B1 (de) 1990-04-18
PT79744B (en) 1986-11-14
GB8432387D0 (en) 1985-02-06
DE3481996D1 (de) 1990-05-23
GB8432487D0 (en) 1985-02-06
KR900000897B1 (ko) 1990-02-17
IL73903A0 (en) 1985-03-31
PL146679B1 (en) 1989-02-28
NZ210707A (en) 1988-09-29
HUT41835A (en) 1987-05-28
PT79744A (en) 1985-01-01
CA1325946C (en) 1994-01-11
YU46364B (sh) 1993-10-20
DK166030C (da) 1993-07-12
BG60382B1 (bg) 1995-01-31
ES8605570A1 (es) 1986-03-16
DK166030B (da) 1993-03-01
HK148294A (en) 1995-01-06
GB2153380A (en) 1985-08-21
GB2153380B (en) 1988-08-10
GR82576B (en) 1985-04-23
NO166724B (no) 1991-05-21
AR244329A1 (es) 1993-10-29
IN163276B (de) 1988-09-03
YU217784A (en) 1989-02-28
FI845098A0 (fi) 1984-12-21
HU214669B (hu) 1998-04-28
FI80473C (fi) 1990-06-11
ES539001A0 (es) 1986-03-16
DK626284D0 (da) 1984-12-21
FI80473B (fi) 1990-02-28
DK626284A (da) 1985-06-23
KR850004611A (ko) 1985-07-25
NO845211L (no) 1985-06-24
IL73917A0 (en) 1985-03-31
FI845098L (fi) 1985-06-23
IE58044B1 (en) 1993-06-16
AU3708684A (en) 1985-07-04
MX167884B (es) 1993-04-20
IT8468278A0 (it) 1984-12-24
BR8406827A (pt) 1985-10-29
NO166724C (no) 1991-08-28

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