WO1996000276A1 - Composition detergente - Google Patents

Composition detergente Download PDF

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Publication number
WO1996000276A1
WO1996000276A1 PCT/EP1995/002298 EP9502298W WO9600276A1 WO 1996000276 A1 WO1996000276 A1 WO 1996000276A1 EP 9502298 W EP9502298 W EP 9502298W WO 9600276 A1 WO9600276 A1 WO 9600276A1
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WO
WIPO (PCT)
Prior art keywords
clay
liquid detergent
detergent composition
weight
surfactant
Prior art date
Application number
PCT/EP1995/002298
Other languages
English (en)
Inventor
Johannes Cornelis Van De Pas
David Machin
Lili Fausia Brouwn
Deborah Ann Roberts
Andrew Paul Chapple
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to EP95924229A priority Critical patent/EP0767828B1/fr
Priority to AU28823/95A priority patent/AU2882395A/en
Priority to BR9508150A priority patent/BR9508150A/pt
Priority to DE69505531T priority patent/DE69505531T2/de
Priority to CA002191579A priority patent/CA2191579A1/fr
Publication of WO1996000276A1 publication Critical patent/WO1996000276A1/fr

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Classifications

    • 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
    • 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
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions

Definitions

  • the present invention relates to liquid detergent compositions, in particular to structured liquid detergent compositions.
  • Liquid detergent compositions are well-known in the art and offer several advantages over solid compositions. For example, liquid compositions are easier to measure, to dispense and to dissolve into a laundering liquor. Further, liquid compositions give more confidence to the consumer of being safer and less harsh to the washed or laundered textile than solid compositions. This may be the reasons why heavy duty and light duty built laundry liquid detergent products are gaining in popularity ever since their introduction on the market at the expense of powdered detergent products.
  • Isotropic liquids are liquids in which all ingredients are dissolved and, contrary to structured liquids, there is no structure present in isotropic liquid.
  • Structured liquids are well-known in the art. They can either be internally structured, whereby the structure is formed by primary ingredients, preferably by surfactant material, and/or by providing a three dimensional matrix structure using secondary additives, preferably polymers and/or silicate material. Structuring may be brought about to endow properties such as consumer preferred flow properties and/or turbid appearance. Many structured liquids are also capable of suspending particulate solids, such as particles of clay that may be used to provide a fabric-softening effect to fabrics.
  • EP-A-0,225, 142 discloses aqueous liquid detergent compositions comprising surfactant and builder material and a clay material which has lov; swellability in sodium tripolyphosphate solutions and high swellability in water. There is no direct disclosure of the use of clay material in structured compositions. Liquids according to this reference may be or may become viscous.
  • EP-A-0, 291, 261 discloses aqueous structured liquid detergent composition comprising a fabric softening clay material, wherein the viscosity of the liquid is reduced by incorporation of a non-peptising/non-building electrolyte.
  • electrolytes are formate, acetate, halide and sulphate.
  • WO 91/08281 discloses aqueous structured liquid detergent compositions comprising a dispersion of lamellar droplets of surfactant material materials in an aqueous continuous phase and clay material wherein the viscosity and stability of the liquid is improved by incorporation of a deflocculating polymer.
  • EP-A-0, 580, 245 discloses aqueous liquid detergent compositions comprising surfactants, electrolyte and clay material. As indicated on page 3 lines 5-10, these liquids do not contain surfactant-desolubilising electrolyte (or salting-out electrolyte) and they do not contain a structure.
  • the present invention relates to an aqueous structured liquid detergent composition
  • an aqueous structured liquid detergent composition comprising surfactant material, electrolyte material and suspended clay particles, characterised in that the composition further comprises sodium and potassium ions in a molar ratio of 10:1 or lower.
  • the molar ratio between Na + and K + in the liquid according to the invention is 10:1 or lower, e.g. 9:1 or lower, more preferably 8:1 or lower, most preferably 5:1 or lower, or even 3 : 1 or lower or in particular 1.5:1 or lower.
  • Suitable ratios are 1.3:1 or lower, 1: 1 or lower and 0.8:1 or lower.
  • the ratio is 1:20 or higher, more preferably 1:5 or higher, most preferably 1:3 or higher.
  • the K + ions are added in the form of a soluble salt.
  • soluble salts are citrate, hydroxide, (bi)carbonate, anionic surfactant material, nitrate, sulphate and chloride.
  • the Na + and K + concentrations in the structured liquid are defined as the concentrations that are determined in the liquid phase of the product and also include the Na + and K + ions that are present in solid materials that are capable of contributing ions to the structured liquid, e.g. zeolite. Inert solid materials, which do not contribute to ion-exchange are not included when determining the Na + and K + concentrations.
  • the clay material according to the present invention is suspended in particle form in the structured liquid.
  • Clays of interest in the present invention are swelling types, which expand and delaminate in liquid media. These clays belong to the group of phyllosilicates and are three- layer sheet type crystalline materials.
  • the sheet structures are composed of three layer arrangements of tetrahedral silica, octahedral alumina and tetrahedral silica.
  • the central layer may be dioctahedral or triotahedral and the three layer sheet structures are separated by an interlamellar space.
  • Clays are defined as crystalline and amorphous hydrated silicates of Al, Mg Li and Fe. They comprise fine colloidal particles. The following key features distinguish the different varieties on: a) chemical composition; and b) the degree of isomorphic substitution (replacement of one framework ion with another of similar size, usually of different valence) .
  • Point b offers the opportunity for a permanent charge on the lattice which must be balanced by cations present in close proximity.
  • M+ refers to the charge balancing cations introduced as a result of the isomorphic substitution.
  • the degree of isomorphic substitution determines the magnitude of the layer charge, a crucial factor in the swelling of clays.
  • the layer structure has many variants in nature.
  • the central octahedral layer may have the two aluminium ions (Al 3+ ) (dioctahedral) replaced by three magnesium ions (Mg 2+ ) (trioctahedral) or the octahedral layer may be partially occupied by the substitution of one Al 3+ for one Mg 2+ (dioctahedral) or one Mg + for one Li + (trioctahedral) resulting in a residual surplus of negative charge in the structure.
  • a residual surplus of negative charge can also arise when silicon ions (Si 4+ ) in the tetrahedra layer are replaced by aluminium ions (Al 3+ ) .
  • the surplus of negative charge requires the present of balancing cations which are located in the interlamellar space between the sheet structures
  • a measure of the degree of the surplus charge is given by the number of exchangeable cations, as reflected by the cation exchange capacity (CEC) of the pure mineral.
  • CEC cation exchange capacity
  • X n+ is a balancing exchangeable cation which can be univalent or divalent;
  • y + b is the lattice charge deficiency of the mineral per half unit cell;
  • M 111 is a trivalent metal ion e.g. Al 3+ , Fe 3+ and Cr 3+ ;
  • N 11 is a divalent metal ion e.g. Mg 2+ , Fe 2+ , Ni 2+ and Zn 2+ ;
  • L 11 is a univalent metal ion e.g. Li + ; y is zero or a positive number less than four; and a and b are separately or together zero or positive numbers.
  • CEC measurements indirectly determine the number of X n+ y+b n present in lOOg and quote these as meg.
  • the value of y+b (the lattice charge deficiency) in gram equivalents per half unit cell is therefore directly related to CEC.
  • Swelling is the process in which solvent molecules penetrate the inter layer space between individual crystals, and occurs very readily in clays containing exchangeable cations such as hectorites and montmorillonites.
  • the factors which most influence the swelling behaviour is aqueous suspension are:
  • Point i) is important because substitution in the tetrahedral layer creates a localised charge and in the octahedral layer a delocalised charge. The latter interacts only weakly with water molecules.
  • Clays used in through the wash fabric softening are generally montmorillonites. Although it has been shown that softening performance is a function of lattice charge, the detailed mechanism of the action of clays in fabric softening is not fully understood. Both delamination (swelling) behaviour, and electrostatic forces between the clay particles and the fabric substrate are thought to govern the overall process, and both are influenced by layer charge.
  • Montmorillonites occur in nature with a range of layer charges (see point ii) ) , and optimum softening is observed with a limited number of clays of poor colour which have layer charges at the lower end of the range.
  • the lattice charge of clays can, however, be modified by chemical treatment. Controlled incorporation of Li + cations in the crystal lattice (by ion exchange/calcination) is described in EP-A-O, 401, 047 (Unilever) and leads to an improvement in the performance of the clay through charge reduction.
  • Layer charge reduction of montmorillonite requires neutralisation of a delocalised negative charge. This is thought to be achieved when Li cations penetrate the crystal lattice upon dehydration. They are thought to move into octahedral vacancies in the aluminous region of the montmorillonite lattice. This process requires an expensive calcination step to achieve the dehydration of the Li + cation before penetration into the lattice can take place.
  • Potassium is the most closely studied ion. Its ionic diameter closely matches the diameter of the ring of six oxygen atoms characteristic of clay crystal surfaces. Good coordination of potassium by the clay surface can therefore be reasonably expected.
  • the clay material is selected from Bentonite, Kaolinite, Attapulgite, Hectorite, and derivative thereof. Most preferably the clay material is a Bentonite clay.
  • the clay material particles in the product have an average weight particle size (D(3,2)) of at least 0.1 ⁇ m, more preferably at least l ⁇ m, most preferably at least 5 ⁇ m and preferably at most 100 ⁇ m, more preferably at most 50 ⁇ m, most preferably at most lO ⁇ m.
  • D(3,2) average weight particle size
  • the clay has a white colour.
  • the level of clay material is at least 0.5% by weight of the composition, preferably at least 1%, more preferably at least 3%, most preferably at least 5%.
  • the clay level is at most 20%, more preferably at most 10%, most preferably at most by weight of the composition.
  • compositions of the invention also comprise surfactant materials, preferably at a level of at least 1% by weight of the composition, more preferred at least 5% by weight, most preferred at least 10% by weight of the composition; and preferably at a level of at most 70% by weight, more preferably at most 40%, most preferably at most 35% by weight.
  • the surfactant material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • surfactants may be chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkyl oxides, especially ethylene oxide, either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-di-amine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long- chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the surfactant material comprises nonionic surfactant, in particular ethoxylated nonionic surfactants.
  • the composition then comprises at most 25%, more preferably at most 20%, most preferably at most 15%, in particular at most 10% by weight of the total ethoxylated nonionic surfactants of long chain EO (ethylene oxide) nonionic surfactants.
  • Long chain EO nonionic surfactants are defined as comprising 15 or more EO groups, preferably 10 or more EO groups, more preferably 8 or more EO groups per nonionic molecule. It is noted that commercially available ethoxylated nonionics always represent a nonionic mixture.
  • nonionic surfactants with a long chain of ethylene oxide groups form a complex with the clay material, in particular in the environment of concentrated liquids, in such a way that the complex tends to increase the viscosity of the structured liquid.
  • the level of nonionic surfactant materials is from 1 to 40 % by weight of the composition, more preferred from 2 to 20%.
  • Compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials.
  • Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic surfactant compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C 8 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glycerol ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amide
  • the level of the above mentioned non-soap anionic surfactant materials is from 1-40 % by weight of the composition, more preferred from 2 to 25 %. It is also possible, and sometimes preferred, to include an alkali metal soap of a mono- or di-carboxylic acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, alk(en)yl succinate for example dodecyl succinate, and fatty acids derived from castor oil, rapeseed oil, groundnut oil,coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the level of soap in compositions of the invention is from 1-35% by weight of the composition, more preferred from 5-25%.
  • salting out resistant active materials such as for example described in EP-A-0, 328, 177, especially the use of alkylpolyglycoside surfactants such as for example disclosed in EP-A-0, 070, 074.
  • alkyl mono glucosides may be used.
  • alkyl glucose ether may be used and/or polyhydroxy fatty acid amides as described in WO 92/06157, more particular the amides used in the Examples thereof.
  • compositions according to the invention comprise electrolyte material, some or all of which may be builder material.
  • the total level of electrolyte is from 1 to 60% by weight of the composition, more preferably from 5 to 45% by weight, most preferably from 10 to 30% by weight.
  • the level of dissolved electrolytes is from 1 to 45% by weight of the composition, more preferably from 5 to 35% by weight, most preferably from 10 to 25% by weight.
  • the term electrolytes including builder material is from 5 to 40 % by weight of the composition, more preferred from 5 to 25 % by weight of the composition.
  • compositions according to the invention preferably contain a salting-out electrolyte that is able to bring about internal structuring of the liquid, preferably in the form of lamellar droplets of the surfactant material.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-0, 079, 646, i.e. salting-out electrolytes have a lyotropic number of less than 9.5, preferably less than 9.0. Examples are sulphate, citrate, NTA and carbonate.
  • some salting-in electrolyte may also be included.
  • the compositions contain from 1% to 60%, especially from 10 to 45% of salting-out electrolyte.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • detergency builder material some or all of which may be electrolyte.
  • surfactant materials such as for example soaps, also have builder properties.
  • Examples of phosphorous containing inorganic detergency builders include the water-soluble salts, especially alkali etalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. It may however be preferred to minimise the amount of phosphate builders.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds) , potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid. Citric acids or salts thereof are preferred builder materials for use in compositions of the invention.
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100 ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000.
  • Use of such polymers is generally described in our EP-A-0, 301, 883. Typical levels are from 0.5 to 4.5% by weight.
  • a deflocculating polymer is incorporated in liquid detergent compositions according to the present invention to further improve viscosity and stability.
  • WO 91/06622 describes deflocculating polymers being a block copolymer consisting of alternating hydrophobic and hydrophillic groups
  • WO 91/06623 describes deflocculating polymers consisting of nonionic monomers and ionic monomers
  • GB-A- 2,237,813 describes deflocculating polymers consisting of a hydrophobic backbone and one or more hydrophillic side- chains.
  • WO 91/09109 discloses liquid detergent compositions comprising deflocculating polymers that are biodegradable.
  • EP/93/01882 discloses deflocculating polymer having a ketone group.
  • deflocculating polymer are described in EP-A-0, 346,995 having a hydrophillic backbone and one or more hydrophobic side- chains.
  • the deflocculating polymer will be used at levels of from 0.01 to 5 % by weight of the composition, more preferably from 0.1 to 3.0, especially preferred from 0.25 to 2.0 %.
  • lather boosters such as alkanola ides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo) , enzyme stabilizers, anti-redeposition agents, germicides and colorants.
  • biodegradable materials are preferred for environmental reasons.
  • PRODUCT FORM As indicated, structured liquids, internally as well as externally, are well-known in the art. Some of the different kinds of liquids, that are internally structuring with surfactant material, are described in the reference H.A. Barnes, “Detergents”, Ch.2. in K. Walters (Ed), “Rheometry: Industrial Applications”, J. Wiley & Sons, Letchworth 1980. In general, the degree of ordering of such systems increases with increasing surfactant and/or electrolyte concentrations.
  • the surfactant can exist as a molecular solution, or as a solution of spherical micelles, both of these solutions being isotropic, i.e. they are not structured.
  • surfactant and/or electrolyte structures of surfactant material may form.
  • Various forms of such structures exists, e.g. bi-layers. They are referred to by various terms such as rod-micelles, anisotropic surfactant phase, planar lamellar structures, lamellar droplets and liquid crystalline phases.
  • rod-micelles e.g. rod-micelles
  • anisotropic surfactant phase planar lamellar structures
  • lamellar droplets e.g. bi-layers.
  • lamellar droplets are called ⁇ pherulites.
  • lamellar structures are lamellar droplets of surfactant material.
  • the dispersed structuring phase in such liquids is generally believed to consist of an onion ⁇ like configuration comprising concentric bilayers surfactant molecules, between which water is trapped, the aqueous phase.
  • Liquids with a lamellar droplets structure are preferred as systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid- suspending properties with useful flow properties, i.e. low viscosity with stability.
  • Such liquids have for example been described in A. Jurgens, Microstructure and Viscosity of Liquid Detergent, Tenside Surfactants Detergent 26 (1989) 222 and J.C. van de Pas, Liquid Detergents, Tenside Surfactants Detergents 28 (1991) 158.
  • the presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, X-ray or neutron diffraction, and sometimes, electron microscopy.
  • Externally structured liquids may provide a high viscosity, especially upon storage. Therefore, internally structured liquids are preferred over externally structured.
  • the most preferred structured liquids are liquid detergent compositions comprising lamellar droplets of surfactant material.
  • Liquid compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 s-1, more preferred less than 1,500 mPas, most preferred less than 1,000 mPas and preferably higher than 100, more preferably higher than 500 mPas at 21 s-1.
  • Liquid compositions according to the invention are physically stable.
  • physical stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable 1 compositions will yield no more than 10 %, preferably no more than 5 %, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
  • the suspended solid can comprise suspended solids which are substantially the same as the dissolved electrolyte, being an excess of same beyond the solubility limit.
  • This solid is usually present as a detergency builder, i.e. to counteract the effects of calcium ion water hardness in the wash.
  • the suspended solid usually comprises a particulate abrasive, insoluble in the system.
  • the electrolyte present to contribute to the structuring of the active material in the dispersed phase, is generally different from the abrasive compounds.
  • the abrasive can however comprise partially soluble salts which dissolve when the product is diluted.
  • the structure is usually thickens the product to give consumer-preferred flow properties, and sometimes to suspend pigment particles.
  • compositions of the first kind are described in for example our patent specification EP-A-0, 038, 101 whilst examples of those in the second category are described in our specification EP-A-0, 104 , 452.
  • Those in the third category are for example, described in US-A-4 , 244 , 840.
  • the compositions of the present invention are concentrated. Therefore, the water level in the liquid detergent compositions according to the present invention is preferably at least 10%, more preferably at least 20%, most preferably at least 30% by weight of the composition and preferably at most 60% by weight, more preferably at most 50%, most preferably at most 40% by weight of the composition.
  • liquid compositions according to the invention have a product pH of at least 6, more preferably at least 6.5, most preferably at least 7 and preferably at most 14, more preferably at most 13, most preferably at most 12.
  • the pH is at least 6, more preferably at least 7.5, most preferably at least 8.
  • the pH is at most 12, more preferably at most 10, most preferably at most 9.
  • Liquid compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions.
  • a further embodiment of the present invention relates to a method of preparing a structured aqueous liquid detergent composition
  • a method of preparing a structured aqueous liquid detergent composition comprising surfactant material, electrolyte and suspended clay material by mixing electrolytes, water, surfactant and clay material wherein the composition comprises sodium and potassium ions in a molar ratio of 10:1 or lower and the clay material is a Bentonite clay.
  • the preferred method for example involves the dispersing of the electrolyte ingredient together with the minor ingredients except for the temperature and pH sensitive ingredients, such as enzymes, perfumes, etc -if any- in water of elevated temperature, followed by the addition of the builder material -if any-, the surfactant material (possibly as a premix) under stirring and thereafter cooling the mixture and adding any temperature and pH sensitive minor ingredients.
  • the deflocculating polymer may for example be added after the electrolyte ingredient or as the final ingredient. Preferably the deflocculating polymer are added prior to the formation
  • At least 25% by weight of the total amount of clay material is added to the liquid after addition of at least 25% by weight of the total of electrolytes to further minimise swelling and/or delamination, more preferably at least 50% by weight of the total amount of clay material, most preferably at least 75% by weight, in particular 100% of clay is added after the electrolytes.
  • the clay is added after addition of at least 50% by weight of the total of electrolytes, more preferably at least 75% by weight, most preferably 100% by weight of the total of electrolyte material.
  • the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.
  • the order of addition to water was citric acid, NaOH and/or KOH (for neutralising the citric acid and LAS-acid) , polymer, premix of LAS-acid and Synperonic A7 , and clay (if present) .
  • the preparation was done without external heating. The temperature during processing rose to about 60°C due to release of neutralisation heat and heat of mixing.
  • compositions were physically stable, i.e. showed no phase separation over a storage period of 1 month at room temperature.
  • Viscosity (mPas at 590 512 600 1500 540 1050 570 1060 810 1160
  • the polymer is the source of the low level of Na+ in the formulation
  • the swellability of the clay (QC200) in electrolyte solutions representing product conditions and wash solution conditions were measured. 5% clay material was stirred for 5 minutes in a 25% citrate solution, representing the electrolyte concentration in the product. Another 5% clay material was stirred for 5 minutes in a 25% citrate solution, after which the dispersion was washed out in such a way that the citrate concentration was decreased while retaining the clay material in the dispersion.
  • the clay dispersions were poured into a measuring cylinder. The clay sedimentation was measured after 2 weeks with the same method as described in EP-A-0,225, 142. The amount of clay swelling was calculated by dividing the height of the clay sediment by the total height of the dispersion in the cylinder and multiplying that figure with 100%.
  • the swelling of the clay in the high electrolyte solution is, however, lower in the K + -containing compositions.
  • composition 7 was made (ingredients by weight %) :
  • the Na + /K + molar ratio is 0.43:1
  • the viscosity is 820 mPas at 21 s "
  • the order of addition to water was citric acid, glycerol, borax, fluorescer, caustic, clay, polymer, Synperonic A7 , fatty acids premix and LAS acid. Then after cooling from ca
  • Nonionic 1 7) 4.7 4.5 4.5 5.2 - 4.8
  • Nonionic 3 9) — - — - 9.4 - Oleic acid 10> 4.7 4.5 4.5 4.7 4.7 4.8
  • the D50% of the clay particles in the liquids was in the region of 10 to 20 microns.
  • the liquids of these Examples are low viscous and have good stability.

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Abstract

L'invention se rapporte à une composition détergente liquide, aqueuse, comprenant un tensioactif, un électrolyte et des particules d'argile en suspension. Cette composition comprend également des ions sodium et potassium dans un rapport molaire spécifique afin d'améliorer la viscosité et la stabilité du liquide.
PCT/EP1995/002298 1994-06-27 1995-06-15 Composition detergente WO1996000276A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP95924229A EP0767828B1 (fr) 1994-06-27 1995-06-15 Composition detergente
AU28823/95A AU2882395A (en) 1994-06-27 1995-06-15 Detergent composition
BR9508150A BR9508150A (pt) 1994-06-27 1995-06-15 Composição detergente líquida e processo de preparação da mesma
DE69505531T DE69505531T2 (de) 1994-06-27 1995-06-15 Waschmittel
CA002191579A CA2191579A1 (fr) 1994-06-27 1995-06-15 Composition detergente

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP94304673.0 1994-06-27
EP94304673 1994-06-27

Publications (1)

Publication Number Publication Date
WO1996000276A1 true WO1996000276A1 (fr) 1996-01-04

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ID=8217753

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/002298 WO1996000276A1 (fr) 1994-06-27 1995-06-15 Composition detergente

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EP (1) EP0767828B1 (fr)
AU (1) AU2882395A (fr)
BR (1) BR9508150A (fr)
CA (1) CA2191579A1 (fr)
DE (1) DE69505531T2 (fr)
ES (1) ES2124567T3 (fr)
WO (1) WO1996000276A1 (fr)
ZA (1) ZA955283B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110139703A (zh) * 2017-03-07 2019-08-16 栗田工业株式会社 水处理药品及其调制方法、以及聚酰胺系反渗透膜的清洗方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0003625A1 (fr) * 1978-02-08 1979-08-22 THE PROCTER & GAMBLE COMPANY Compositions de nettoyage liquides contenant de l'hypochlorite et des sulfonates de paraffine
EP0004111A1 (fr) * 1978-03-13 1979-09-19 THE PROCTER & GAMBLE COMPANY Compositions pour traitement de tissu contenant de l'argile smectite et de l'amidon végétal gélatinisé
EP0050887A1 (fr) * 1980-10-16 1982-05-05 Unilever N.V. Suspensions détergentes stables liquides
EP0541203A1 (fr) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Composition détergente liquide aqueuse à visco-élasticité linéaire pour lave-vaisselle automatique
EP0580245A2 (fr) * 1992-07-20 1994-01-26 Colgate-Palmolive Company Compositions détergentes-adoucissantes liquides aqueuses renforcées stabilisées

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0003625A1 (fr) * 1978-02-08 1979-08-22 THE PROCTER & GAMBLE COMPANY Compositions de nettoyage liquides contenant de l'hypochlorite et des sulfonates de paraffine
EP0004111A1 (fr) * 1978-03-13 1979-09-19 THE PROCTER & GAMBLE COMPANY Compositions pour traitement de tissu contenant de l'argile smectite et de l'amidon végétal gélatinisé
EP0050887A1 (fr) * 1980-10-16 1982-05-05 Unilever N.V. Suspensions détergentes stables liquides
EP0541203A1 (fr) * 1991-11-08 1993-05-12 Colgate-Palmolive Company Composition détergente liquide aqueuse à visco-élasticité linéaire pour lave-vaisselle automatique
EP0580245A2 (fr) * 1992-07-20 1994-01-26 Colgate-Palmolive Company Compositions détergentes-adoucissantes liquides aqueuses renforcées stabilisées

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110139703A (zh) * 2017-03-07 2019-08-16 栗田工业株式会社 水处理药品及其调制方法、以及聚酰胺系反渗透膜的清洗方法
CN110139703B (zh) * 2017-03-07 2020-08-07 栗田工业株式会社 水处理药品及其调制方法、以及聚酰胺系反渗透膜的清洗方法

Also Published As

Publication number Publication date
ZA955283B (en) 1996-12-27
DE69505531D1 (de) 1998-11-26
EP0767828B1 (fr) 1998-10-21
CA2191579A1 (fr) 1996-01-04
DE69505531T2 (de) 1999-04-22
EP0767828A1 (fr) 1997-04-16
BR9508150A (pt) 1997-08-12
ES2124567T3 (es) 1999-02-01
AU2882395A (en) 1996-01-19

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