EP0385522A2 - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

Info

Publication number
EP0385522A2
EP0385522A2 EP19900200290 EP90200290A EP0385522A2 EP 0385522 A2 EP0385522 A2 EP 0385522A2 EP 19900200290 EP19900200290 EP 19900200290 EP 90200290 A EP90200290 A EP 90200290A EP 0385522 A2 EP0385522 A2 EP 0385522A2
Authority
EP
European Patent Office
Prior art keywords
detergent composition
composition according
composition
bleach
aqueous detergent
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP19900200290
Other languages
German (de)
French (fr)
Other versions
EP0385522B1 (en
EP0385522A3 (en
Inventor
Cornelis Bernard Donker
Michael Hull
Johannes Cornelis Van De Pas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
Priority claimed from GB898908412A external-priority patent/GB8908412D0/en
Priority to GB898916094A priority Critical patent/GB8916094D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP90200290A priority patent/EP0385522B1/en
Priority to ES90910739T priority patent/ES2060186T3/en
Priority to CA002062781A priority patent/CA2062781C/en
Priority to EP90910739A priority patent/EP0484363B1/en
Priority to PCT/EP1990/001046 priority patent/WO1991000902A1/en
Priority to BR909007519A priority patent/BR9007519A/en
Priority to AU59541/90A priority patent/AU636629B2/en
Priority to DE90910739T priority patent/DE69003683T2/en
Priority to JP2509960A priority patent/JPH0768549B2/en
Priority to TR90/0630A priority patent/TR25827A/en
Priority to ZA905510A priority patent/ZA905510B/en
Priority to MYPI90001456A priority patent/MY105986A/en
Priority to AU61779/90A priority patent/AU647039B2/en
Priority to EP90912561A priority patent/EP0491723B2/en
Priority to JP2511763A priority patent/JPH0774360B2/en
Priority to BR909007641A priority patent/BR9007641A/en
Priority to KR1019920700570A priority patent/KR960004489B1/en
Priority to CA 2064900 priority patent/CA2064900C/en
Priority to ES90912561T priority patent/ES2066216T5/en
Priority to DE69014207T priority patent/DE69014207T3/en
Priority to PCT/EP1990/001461 priority patent/WO1991004314A1/en
Publication of EP0385522A2 publication Critical patent/EP0385522A2/en
Priority to TR00783/90A priority patent/TR27315A/en
Publication of EP0385522A3 publication Critical patent/EP0385522A3/en
Priority to CA002073563A priority patent/CA2073563C/en
Priority to BR919105999A priority patent/BR9105999A/en
Priority to AU71873/91A priority patent/AU652736B2/en
Priority to DE69109273T priority patent/DE69109273T2/en
Priority to JP3503439A priority patent/JPH0772280B2/en
Priority to EP91903330A priority patent/EP0514422B1/en
Priority to BR919106000A priority patent/BR9106000A/en
Priority to PCT/EP1991/000259 priority patent/WO1991012308A1/en
Priority to KR1019920701780A priority patent/KR950008566B1/en
Priority to JP3503735A priority patent/JPH0768542B2/en
Priority to JP50344091A priority patent/JPH05502471A/en
Priority to PCT/EP1991/000258 priority patent/WO1991012307A2/en
Priority to ES91903330T priority patent/ES2072601T3/en
Priority to ES91903653T priority patent/ES2053321T3/en
Priority to DE69102059T priority patent/DE69102059T2/en
Priority to CA 2073445 priority patent/CA2073445A1/en
Priority to EP91903665A priority patent/EP0514434B2/en
Priority to EP91903653A priority patent/EP0513136B1/en
Priority to AU72109/91A priority patent/AU646018B2/en
Priority to DE69126203T priority patent/DE69126203D1/en
Priority to PCT/EP1991/000260 priority patent/WO1991012309A2/en
Priority to AU71874/91A priority patent/AU643503B2/en
Priority to BR919106001A priority patent/BR9106001A/en
Priority to CA002073432A priority patent/CA2073432A1/en
Priority to ZA91956A priority patent/ZA91956B/en
Priority to ZA91955A priority patent/ZA91955B/en
Priority to ZA91957A priority patent/ZA91957B/en
Priority to KR92700065A priority patent/KR950013224B1/en
Priority to KR92701781A priority patent/KR950013223B1/en
Application granted granted Critical
Publication of EP0385522B1 publication Critical patent/EP0385522B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Definitions

  • the present invention relates to liquid detergent compositions which contain a peroxygen bleach compound.
  • the present invention relates to an aqueous structured liquid detergent composition
  • an aqueous structured liquid detergent composition comprising one or more detergent active materials and a peroxygen bleach compound, said detergent composition showing less than 25% volume increase, preferably less than 10 %, more preferred less than 5 % while stored at a temperature of between 20 and 37°C for three months after preparation.
  • the detergent composition comprises less than a structure destabilizing amount, more preferably less than 10% by weight of a water miscible organic solvent.
  • the present invention is concerned with structured liquid detergent compositions, such structured liquids can be "internally structured” whereby the structure is formed by primary ingredients and/or they can be structured by secondary additives such as certain cross-­linked polyacrylates or clays, which can be added as "external structurants" to compositions of the invention.
  • Such structuring is very well known in the art and may be deliberately 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 detergency builders and abrasive particles.
  • lamellar droplets are called "spherulites".
  • 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.
  • Electrolyte may be only dissolved in the aqueous continuous phase or may also be present as suspended solid particles. Particles of solid materials which are insoluble in the aqueous phase may be suspended alternatively or in addition to any solid electrolyte particles.
  • 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. In that case the electrolyte, present to contribute to the structuring of the active material in the dispersed phase, is generally different from the abrasive compounds. In certain cases, the abrasive can however comprise partially soluble salts which dissolve when the product is diluted.
  • the structure is usually used for thickening 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-38,101 whilst examples of those in the second category are described in our specification EP-104,452.
  • Those in the third category are for example, described in US 4,244,840.
  • the dispersed structuring phase in these liquids is generally believed to consist of an onion-life configuration comprising concentric bilayers of detergent active molecules, between which is trapped water (aqueous phase).
  • aqueous phase trapped water
  • These configurations of active material are sometimes referred to as lamellar droplets. It is believed that the close-packing of these droplets enables the solid materials to be kept in suspension.
  • the lamellar droplets are themselves a sub-set of lamellar structures which are capable of being formed in detergent active/aqueous electrolyte systems.
  • detergent compositions of the lamellar droplet type are preferred.
  • compositions according to the present invention comprise a peroxygen bleach.
  • This bleach component may be present in the system in solubilized form, but also possible is that only part of the peroxygen bleach is solubilized, the remaining part being present as solid peroxygen particles which are suspended in the system.
  • peroxygen compounds examples include hydrogen peroxide, the perborates, persulfates, peroxy disulfates, perphosphates and the crystalline peroxyhydrates formed by reacting hydrogen peroxide with urea or alkali metal carbonate.
  • encapsulated bleaches may be used. Preferred bleaches are only partially soluble in the system such as for example diperoxydodecandioic acid (DPDA) or other peracid crystals and perboratetetrahydrate.
  • DPDA diperoxydodecandioic acid
  • the bleach component is preferably added in an amount corresponding to 0.1 to 15% by weight of active oxygen, more preferred from 0.5 to 5% active oxygen, typically from 1.0 to 3.0 % active oxygen.
  • the bleach ingredients may for example be added to the composition as a dry particulate material or as a predispersion of bleach particles. If perborate­tetrahydrate bleaches are used, a suitable commercial available bleach dispersion is Proxsol (ex ICI), alternatively perborate-tetrahydrate crystals may be formed in-situ for example as described in EP 294 904.
  • the detergent active materials 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. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents” published by the McCutcheon division of Manufacturing Confectioners Company or in Tensid-Taschenburch", H. Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 1981.
  • 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 alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C6-C18) 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 ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • salting-out resistant active materials such as for example described in EP 328 177, especially the use of alkyl polyglycoside surfactants, such as for example disclosed in EP 70 074.
  • the level of nonionic surfactants is more than 1 % by weight of the composition, preferably from 2.0 to 20.0 %.
  • 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 detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl 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 (C8-C18) 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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monos
  • the level of the above mentioned non-soap anionic surfactant meterials is from 1-40 % by weight of the composition.
  • the weight ratio of synthetic anionic surfactants to nonionic surfactants is from 10 : 1 to 1 : 10.
  • 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, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil, alk(en)yl succinates e.g. dodecyl succinates or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the level of soap in compositions of the invention is form 1 - 40 % by weight of the composition, more preferred from 5 - 25 %.
  • the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and typically from 10% to 30% by weight.
  • one preferred class of compositions comprises at least 20%, most preferably at least 25% and especially at least 30% of detergent active material based on the weight of the total composition.
  • compositions according to the invention are preferably physically stable in,that they yield no more than 2% by volume phase separation when stored at 25°C for 21 days from the time of preparation. Especially preferred are compositions which do not yield any phase separation upon storage for 21 days at 25 o C.
  • compositions according to the invention preferably have solid-suspending properties in that they yield less than 5% by volume of sediment after storage for 21 at 25°C, more preferably less than 2 % by volume sediment is formed, most preferably substantially no visible sediment is formed.
  • compositions according to the invention comprise less than a structure destabilising amount of water miscible solvent, preferably less than 10% by weight, for example less than 7.5%, more preferred less than 5%, especially preferred less than 2.0%, typically less than 0.5% by weight of a water miscible solvent.
  • water-miscible solvents examples include lower aliphatic monoalcohols, ethers of diethylene glycol and lower monoaliphatic monoalcohols, and mixtures thereof.
  • Liquid detergent compositions according to the invention are volume stable in that they show less than 25% preferably less than 10%, more preferably less than 5% volume increase during storage at a temperature between 20 and 37°C for a period of three months after preparation.
  • liquid detergent compositions according to the invention will be stored in closed bottles, say of 1.5 litre, which optionally may include venting means, for releasing generated oxygen.
  • a solid peroxygen bleach component When a solid peroxygen bleach component is present in an aqueous system, generally part of the bleach material will be solubilized in the form of peracid and/or hydrogen peroxide in the aqueous phase.
  • One of the problems often observed in such systems is the occurence of oxygen evolution, due to the decomposition of this peracid or hydrogen peroxide into acid and/or water and oxygen. The oxygen bubbles formed may either emerge from the liquid or be trapped in the liquid, thereby causing a volume increase.
  • a similar oxygen evolution is observed when the bleach component such as for instance hydrogen peroxide is totally solubilized in the system.
  • the present invention provides liquid detergent compositions wherein the volume increase is kept at an acceptable level of less than 25%, preferably less than 10% , more preferred less than 5 %. during storage of the composition at a temperature between 20 and 37°C for three months after preparation.
  • the parameters to be varied in the composition to bring about the desired volume stability effect may for example be the pH, the physical state of the undissolved bleach particles when present, the amount of dissolved bleach, the presence of stabilising agents, the amount of dissolved bleach activators, the viscosity of the product directly after preparation, the presence of viscosity reducing polymers, the presence of gas bubbles in the composition directly after preparation and the presence of antifoam agents.
  • the choice of an optimum value of these parameters is dependant on the nature and the choice of the active materials which are present in the composition.
  • the half life time of the solubilized peracid or hydrogen peroxide should preferably be increased for increasing the volume stability of the composition. Not only the amount of oxygen formed per time unit is less by increasing the stability of the peracid or hydrogen peroxide, also -and this has been found more important- an increase in the life time of these compounds will allow the oxygen bubbles to be formed upon decomposition of the peracid or hydrogen peroxide to grow in size. An increase in the size of the bubbles to be formed is considered advantageous in that these larger bubbles have been found to be less prone to contribute to the volume increase of the liquid detergent composition, in other words they tend to escape from the liquid rather than being suspended into the system.
  • the half-life time of the hydrogen peroxide or peracid is be more than 3 weeks preferably more than 6 weeks at 37°C at the conditions in the detergent composition, preferably more than 8 weeks especially preferred more than 10 weeks. Most preferred between 10 and 20 weeks.
  • the stability of the peracid or hydrogen peroxide may be increased in several ways such as for instance a decrease in pH of the composition. It has been found that the volume stability of the liquid detergent composition increases by decreasing the pH of the composition. Therefore, for the purpose of formulation volume stable compositions it is preferred to avoid the use of excessive high pH values.
  • the pH of the detergent compositions is less than 12, more preferred less than 11.5, especially preferred between between 6.5 and 11, typically from 7 to 10.
  • the volume stability of the detergent compositions according to the present invention can be improved by using bleach particles which are encapsulated.
  • These encapsulated bleach particles constitute part or all of the bleach present in the composition, the particles are mainly present in the composition in undissolved form.
  • bleach particles in undissolved form is also preferred when the bleach particles are not encapsulated. Higher levels of undissolved bleach are preferred, because it is believed that bleach instability is mainly instability of dissolved bleach. Preferably at least 10% by weight, more preferably at least 30%, especially preferred more than 50%, most preferably more than 75 % or even more than 90 % by weight of the bleach is present in undissolved form. If perborate bleaches are used it has been found that the amount of dissolved bleach is reduced if the pH of the composition is relatively high say from 7-11, more preferably from 7.5 to 10.
  • the weight average diameter of the undissolved bleach particles is from 0.5 to 100 micrometer, especially 5 to 60 micrometer.
  • a method for obtaining these small particles is described in EP 294 904.
  • One way of ensuring that the bleach is present in undissolved form is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the bleach component in the system.
  • Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts and metaborate.
  • Other preferred electrolytes are salting out electrolytes.
  • salting out electrolyte has the same meaning as in EP 79 646, namely those electrolytes which have a lyotropic number of less than 9.5.
  • salting out electrolytes are water-­soluble builder salts, such as alkali metal ortho- and pyroposphates, the alkali metal tripolyphosphates, such as sodium tripolyposphate, the alkali metal silicates, - borates, -carbonates, -sulphates, alkali metal citrates; alkali metal salts of nitriloacetate; alkali metal salts of carboxymethoxy succinate.
  • the alkali metal salts the ammonium salts can be used.
  • Particularly preferred is the use of sodium tripolyphosphate and or sodium (di)silicate as the salting out electrolyte.
  • the dissolved part of the electrolyte constitutes preferably more than 2 % by weight of the composition, more preferred more than 5% by weight, especially preferred between 10 and 50 % by weight.
  • the compositions according to the present invention also comprise a stabilising agent for the bleach component.
  • Suitable stabilisers are well-known in art and include EDTA, Magnesium silicates and phosphonates such as for instance the Dequest range ex Monsanto and Naphthol ex Merck.
  • the amount of stabilising agent is from 0.05 to 5 % by weight of the composition, more preferred from 0.05 to 1% of the composition.
  • compositions of the present invention may comprise one or more bleach activator agents. These materials when combined with a peroxy bleach in the wash, will activate hydrogen peroxide at a low temperature of from 15 to 55°C therewith allowing the effective use of peroxide bleaches at low washing temperatures.
  • the bleach activators used in the present invention often also referred to as peroxyacid bleach precursors are conventionally organic compounds having one or more reactive acyl groups, which at relatively low temperature react with hydrogenperoxide causing the formation of organic peroxyacids, the latter providing for a more effective bleaching action at lower temperatures than hydrogen peroxide itself.
  • N,N,N,N′-tetraacyl ethylene diamine normally referred to as TAED.
  • Another well-known bleach activator is sodium-4-benzoyl oxybenzene sulphonate normally referred to as BOBS, as disclosed in GB 836,988.
  • organic bleach activators are other n-acyl substituted amides, for example tetraacetyl methylene diamine; carboxylic acid anhydrides for example succinic, benzoic and phthalic anhydrides; carboxylic acid esters, for example sodium acetoxy benzene sulphonate; acetates such as glycerol­triacetate, glucose pentaactetate and xylose­tetraacetate and acetyl salicylic acid.
  • carboxylic acid anhydrides for example succinic, benzoic and phthalic anhydrides
  • carboxylic acid esters for example sodium acetoxy benzene sulphonate
  • acetates such as glycerol­triacetate, glucose pentaactetate and xylose­tetraacetate and acetyl salicylic acid.
  • TAED is used as the bleach activator.
  • the preferred level of bleach activator in the liquid detergent is from 0.1 to 10 % by weight preferably from 0.5 to 5 % by weight of the compositions
  • the bleach activator is present in the system in at least partly undissolved form.
  • One way of ensuring that the activator is present in undissolved form is the use of encapsulated activator materials.
  • Another method is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the activator in the system.
  • Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts and metaborate.
  • Other preferred electrolytes are salting out electrolytes as defined hereabove.
  • the dissolved part of the electrolyte constitutes preferably more than 2 % by weight of the composition, more preferred more than 5% by weight, especially preferred between 10 and 50 % by weight.
  • the viscosity of the product directly after preparation it has been found that a lower value for the viscosity generally increases the volume stability of the bleach containing product. Also for lower viscosities are genrally preferred by the consumer. However, for providing solid-suspending properties, low viscosities should preferably be avoided. Therefore in selecting the most appropriate viscosity of the product, a balance should be sought between better stability and consumer-acceptance at lower viscosities and increased solid suspending properties at higher viscosities.
  • the viscosity is preferably less than 2,000 mPas at 21 s ⁇ 1, more preferred less than 1,500, most preferred between 20 and 1,000, especially preferred from 30 to 500.
  • the viscosity is more than 1,000 mPas at 10 ⁇ 4 s ⁇ 1, more preferred more than 10,000, especially preferred more than 100,000.
  • the techniques for obtaining the initial viscosity as desired are well-known in the art, and include for example the appropriate choice of active ingredients, the adaptation of the level of dissolved electrolyte and the inclusion of viscosity modifying agents.
  • a preferred way for regulating the viscosity of the product is the inclusion of polymers in the composition.
  • Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers e.g those having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are described in our copending British patent applications 8813978.7 (corresponding to EP 346 995), 8924479.2, 8924478.4 and 8924477.6.
  • the amount of viscosity regulating polymer, especially deflocculating polymers is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
  • gas bubbles in the detergent composition As to the presence of gas bubbles in the detergent composition according to the invention, it has been found that both the size and the level of gas bubbles are important parameters for determining the volume stability of the composition. Generally gas bubbles in the form of air or oxygen bubbles are introduced into liquid detergent compositions during processing of the composition, which usually involves a mixing stage.
  • the volume fraction of gas bubbles is less than 5.0%, preferably less than 3.5%, most preferred less than 2.0%, especially less than 1 % or even less than 0,5 %.
  • the average diameter of the gas bubbles is above 0.25 mm, more preferred above 0.4 mm, most preferred above 0.5 mm.
  • an antifoam agent both reduces the volume fraction of gas bubbles and increases the size of the bubbles present.
  • the antifoam agents are added at a level above the level commonly used for foam reduction of detergent compositions.
  • the level of antifoam agent is more than 0.2% of the detergent composition, more preferred more than 0.3% of the composition, especially preferred from 0.4 to 2.0% of the composition.
  • Suitable antifoam agents include silicone antifoam agents, such as dimethyl polysiloxanes and/or silica particles.
  • the aqueous continuous phase contains dissolved electrolyte.
  • electrolyte means any ionic water soluble material.
  • the electrolytes may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase.
  • Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
  • salts includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
  • compositions optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent active material.
  • the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
  • some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein.
  • Some or all of the electrolyte may have detergency builder properties.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • the builder material is any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric.
  • Examples of phosphorous-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, 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. Sometimes, however, it is preferred to minimise the amount of phosphorous-containing 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, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid.
  • 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 100ml 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 301,883.
  • the level of non-soap builder material is from 5-50 % by weight of the composition, more preferred from 5 to 35 %.
  • compositions of the present invention contain low levels or are substantially free from hydrotropes.
  • hydrotrope any water soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, 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), germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • fabric softeners such as clays, amines and amine oxides
  • lather depressants inorganic salts such as sodium sulphate
  • fluorescent agents perfumes
  • enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), germicides and colourants.
  • compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions.
  • a preferred method involves the dispersing of the electrolyte (non-builder) -if any- together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material -if any-, the detergent active materials (optionally as a pre-mix) under stirring and thereafter cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes or perfumes and the bleach.
  • the deflocculating polymer -­if any- may for example be added after the elctrolyte ingredient or as the final ingredient.
  • perborate monohydrate When perborate monohydrate is used as the bleaching agent, it may be preferred to cool the final product to a temperature just above the freezing point, in order to accelerate the recrystallisation of the perborate in tetrahydrate form.
  • liquid detergent compositions of the invention will generally be diluted with wash water to form a wash liquor, which may be used for detergency purposes, for example for the washing process in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 % by weight, more preferred from 0.1 to 3 %.
  • a basic liquid detergent composition of the following composition was prepared by addition under stirring of the components in the order listed. Na-Dobs was formed in-situ by combining NaOH and Dobs-acid. Some of the processing water was left behind because the hydrogen peroxide solution used was 27 weight % active. TABLE 1 % by weight Water balance Na-Dobs 13.8 Synperonic 7 4.0 Dequest 2060 0.1 X-Naphtol 0.2 STP thermphos NW 8.6 H2O2 (100%) 5.0 pH1) 7.9-8.1 1) pH adjusted with NaOH if necessary. TABLE 2a Raw material specification Component Supplier Dobs-acid (98%), Marlon AS-3 Hüls Synperonic 7 I.C.I. Dequest 2060 Monsanto X-Naphtol, (p.a.) Merck STP, thermphos NW Hoechst H2O2, 27% Brocacef
  • the basic detergent composition according to example 1 was prepared in several versions of different viscosity direct after preparation.
  • Composition A has a ratio Na-Dobs to Synperonic of 0.74:0.26 and a viscosity of 170 mPas at 21 s ⁇ 1
  • composition B had a ratio Na-Dobs to Synperonic of 0.75:0.25 and a viscosity of 390 mPas
  • composition C had a ratio Na-Dobs to Synperonic of 0.78:0.22 and a viscosity of 1000 mPas.
  • the compositions were stored at 37°C.
  • Composition A showed in the first two days of storage a slight volume increase of about 2% by volume, after 2 two days the volume in decreased to a volume which was about 1% less than the volume of the composition directly after preparation.
  • Composition B showed a sharp volume increase of about 50% by volume in the first three days of storage, followed by a reduction of the volume until at the 5th day the composition had approximately its original volume.
  • Composition C showed during the first 7 days a sharp volume increase of more than 125% by volume (overfoam), a reduction of volume to the original volume of the composition was observed after 15 days.
  • This example illustrates that by lowering the viscosity of the composition, the volume stability of detergent compositions containing solubilized hydrogen peroxide can be increased.
  • Example 1 was prepared by the method as indicated in example 1, with some small modifications.
  • Composition D was prepared according to example 1, the ratio Na-Dobs to Synperonic was 0.77:0.23.
  • Composition E was prepared as composition D, but 0.1% of silicone antifoam was added (corresponding to 0.33 % DB31 ex Dow Corning) before mixing the ingredients.
  • Composition F was prepared as composition D, but the composition was deaerated by centrifuging for 5 min at 4000 G.
  • Composition G was prepared as composition D, but 0.33% of DB31 was added and the composition was de-aerated by centrifuging for 5 min at 4000 G.
  • the viscosity of compositions D-G was 860 mPas after preparation. The compositions were stored at room temperature and the volume increase and the bubble size were monitored.
  • Composition D showed a linear increase in volume up to a maximum of about 75% volume increase after 30 days of storage.
  • the diameter of the gas bubbles present during this period showed a similar increase from very small (about o.1 mm) to about 1.5 mm after 30 days.
  • the volume of the compositions decreased gradually until the composition was back at its original volume after 60 days.
  • the bubble diameter stayed constant at a value of 1.5 mm during this period.
  • Composition E showed a linear increase in volume up to a maximum value of about 55% volume increase after 30 days of storage.
  • the diameter of the gas bubbles present during this period showed a similar increase from very small (around 0.25 mm) to about 1.8 mm after 30 days.
  • the volume of the composition decreased gradually until the composition was back at its original volume after about 60 days.
  • Composition F showed an increase in volume during the first 7 days to a maximum value of about 10% by volume. After 7 days the volume increase decreased to a value of about 0% and remained constant during 60 days of storage. The diameter of the gas bubbles present during this period remained substantially constant at about 1.5 mm.
  • Composition G did not show a substantial increase in volume during storage for 60 days.
  • the diameter of the gas bubbles present during this period showed an increase from 1 mm to 1.8 mm in the first 10 days of storage, and then remained constant during the remaining of the period.
  • This example illustrates that both the presence of an antifoam agent and/or the de-aeration of the composition contribute positively to the stability of the liquid detergent composition.
  • compositions were prepared according to example 1, with some small modifications.
  • Composition H was of the composition of example 1, and had a viscosity of between 400 and 600 mPas, Composition I contained in addition to the components of composition H 0.5% by weight of silicone, corresponding to 1.5 %by weight of DB 31 which was added at the beginning of the mixing process.
  • DB 31 %by weight
  • Composition H contained 5.2% by volume of gas bubbles, the size of the bubbles was between 0.1 and 0.2 mm.
  • Composition I contained 1.9% by volume of gas bubbles, the size of the bubbles was between 0.25 and 0.5 mm.
  • compositions were prepared by adding the electrolyte together with the minor ingredients except for the perfume and the enzymes to water of elevated temperature, followed by the addition of the detergent active material as a premix under stirring and thereafter cooling the mixture and adding the enzymes, perfumes and the bleach.
  • the obtained products had the following characteristics: 5 6 7 8 Volume stability (% volume increase, 3 months 25 o C) 4 3 0 n.m 6 clear layer separation (3 weeks 37 o ) no no no no no solid sedimentation (3 weeks 37 o C) no no no no no no no no no no no Viscosity 21 s ⁇ 1 1,350 710 800 n.m Viscosity 10 ⁇ 4 s ⁇ 1 ⁇ 200,000 n.m n.m n.m dissolved perborates 5) 3 1.5 8 n.m bleach activity % (2 months ambient T) 99 99 96 n.m enzyme activity % (2 months ambient T)2) 65 62 76 n.m

Abstract

An aqueous structured liquid detergent composition comprising detergents active materials and a peroxygen bleach compound, said detergent composition showing less than 25%, preferably less than 10 %, more preferably less than 5 % volume increase while stored at a temperature between 20 and 37°C for three months after preparation.

Description

  • The present invention relates to liquid detergent compositions which contain a peroxygen bleach compound.
  • It has been proposed in EP 293 040 and EP 294 904 to incorporate solid, water-soluble peroxygen bleach compounds in liquid detergent compositions. The compositions as disclosed in these patent applications comprise substantial amounts of water miscible solvents for ensuring that the amount of available oxygen dissolved in the liquid phase is not greater than 0.5%. These high amounts of solvents are however sometimes disadvantageous in that they tend to decrease the solid-­suspending properties of the detergent composition, because they are believed to prevent the internal structuring of the liquid detergent composition.
  • It has now surprisingly been found that stable aqueous liquid bleach containing detergent compositions can be formulated, which are structured. These compositions do not need to contain high -structure destabilizing-­amounts of solvents for bleach stabilisation. Lower amounts of solvents are especially preferred, because it is believed that the absence of high levels of solvents renders it possible to make detergent-structured compositions having good solid-suspending properties.
  • Accordingly the present invention relates to an aqueous structured liquid detergent composition comprising one or more detergent active materials and a peroxygen bleach compound, said detergent composition showing less than 25% volume increase, preferably less than 10 %, more preferred less than 5 % while stored at a temperature of between 20 and 37°C for three months after preparation.
  • Preferably the detergent composition comprises less than a structure destabilizing amount, more preferably less than 10% by weight of a water miscible organic solvent.
  • The present invention is concerned with structured liquid detergent compositions, such structured liquids can be "internally structured" whereby the structure is formed by primary ingredients and/or they can be structured by secondary additives such as certain cross-­linked polyacrylates or clays, which can be added as "external structurants" to compositions of the invention.
  • Such structuring is very well known in the art and may be deliberately 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 detergency builders and abrasive particles.
  • Some of the different kinds of active-structuring which are possible 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. At very low concentrations, the surfactant can exist as a molecular solution, or as a solution of spherical micelles, both of these being isotropic. With the addition of further surfactant and/or electrolyte, structured (antisotropic) systems can form. They are referred to respectively, by various terms such as rod-micelles, planar lamellar structures, lamellar droplets and liquid crystalline phases. Often, different workers have used different terminology to refer to the structures which are really the same. For instance, in European patent specification EP-A-151 884, lamellar droplets are called "spherulites". 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.
  • Electrolyte may be only dissolved in the aqueous continuous phase or may also be present as suspended solid particles. Particles of solid materials which are insoluble in the aqueous phase may be suspended alternatively or in addition to any solid electrolyte particles.
  • Three common product forms in this type are liquids for heavy duty fabrics washing and liquid abrasive and general purpose cleaners. In the first class, 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. In the second class, the suspended solid usually comprises a particulate abrasive, insoluble in the system. In that case the electrolyte, present to contribute to the structuring of the active material in the dispersed phase, is generally different from the abrasive compounds. In certain cases, the abrasive can however comprise partially soluble salts which dissolve when the product is diluted. In the third class, the structure is usually used for thickening 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-38,101 whilst examples of those in the second category are described in our specification EP-104,452. Those in the third category are for example, described in US 4,244,840.
  • The dispersed structuring phase in these liquids is generally believed to consist of an onion-life configuration comprising concentric bilayers of detergent active molecules, between which is trapped water (aqueous phase). These configurations of active material are sometimes referred to as lamellar droplets. It is believed that the close-packing of these droplets enables the solid materials to be kept in suspension. The lamellar droplets are themselves a sub-set of lamellar structures which are capable of being formed in detergent active/aqueous electrolyte systems. For the purpose of the present invention, detergent compositions of the lamellar droplet type are preferred.
  • The peroxygen bleach
  • The compositions according to the present invention comprise a peroxygen bleach. This bleach component may be present in the system in solubilized form, but also possible is that only part of the peroxygen bleach is solubilized, the remaining part being present as solid peroxygen particles which are suspended in the system.
  • Examples of suitable peroxygen compounds include hydrogen peroxide, the perborates, persulfates, peroxy disulfates, perphosphates and the crystalline peroxyhydrates formed by reacting hydrogen peroxide with urea or alkali metal carbonate. Also encapsulated bleaches may be used. Preferred bleaches are only partially soluble in the system such as for example diperoxydodecandioic acid (DPDA) or other peracid crystals and perboratetetrahydrate. The bleach component is preferably added in an amount corresponding to 0.1 to 15% by weight of active oxygen, more preferred from 0.5 to 5% active oxygen, typically from 1.0 to 3.0 % active oxygen.
  • The bleach ingredients may for example be added to the composition as a dry particulate material or as a predispersion of bleach particles. If perborate­tetrahydrate bleaches are used, a suitable commercial available bleach dispersion is Proxsol (ex ICI), alternatively perborate-tetrahydrate crystals may be formed in-situ for example as described in EP 294 904.
  • Detergent active materials
  • In the widest definition the detergent active materials 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. For example, they 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. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in Tensid-Taschenburch", H. Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 1981.
  • 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 alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C₆-C₁₈) 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 ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • Also possible is the use of salting-out resistant active materials, such as for example described in EP 328 177, especially the use of alkyl polyglycoside surfactants, such as for example disclosed in EP 70 074.
  • Preferably the level of nonionic surfactants is more than 1 % by weight of the composition, preferably from 2.0 to 20.0 %.
  • 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. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C₈-C₁₈) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C₉-C₂₀) benzene sulphonates, particularly sodium linear secondary alkyl (C₁₀-C₁₅) benzene sulphonates; sodium alkyl glyceryl 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 (C₈-C₁₈) 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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha­olefins (C₈-C₂₀) with sodium bisulphite and those derived from reacting paraffins with SO₂ and Cl₂ and then hydrolysing with a base to produce a random sulponate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C₁₀-C₂₀ alpha-olefins, with SO₃ and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C₁₁-C₁₅) alkyl benzene sulphonates and sodium (C₁₆-C₁₈) alkyl sulphates.
  • Generally the level of the above mentioned non-soap anionic surfactant meterials is from 1-40 % by weight of the composition.
  • Preferably the weight ratio of synthetic anionic surfactants to nonionic surfactants is from 10 : 1 to 1 : 10.
  • 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, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil, alk(en)yl succinates e.g. dodecyl succinates or mixtures thereof. The sodium or potassium soaps of these acids can be used. Preferably the level of soap in compositions of the invention is form 1 - 40 % by weight of the composition, more preferred from 5 - 25 %.
  • In many (but not all) cases, the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and typically from 10% to 30% by weight. However, one preferred class of compositions comprises at least 20%, most preferably at least 25% and especially at least 30% of detergent active material based on the weight of the total composition.
  • Compositions according to the invention are preferably physically stable in,that they yield no more than 2% by volume phase separation when stored at 25°C for 21 days from the time of preparation. Especially preferred are compositions which do not yield any phase separation upon storage for 21 days at 25 oC.
  • Compositions according to the invention, preferably have solid-suspending properties in that they yield less than 5% by volume of sediment after storage for 21 at 25°C, more preferably less than 2 % by volume sediment is formed, most preferably substantially no visible sediment is formed.
  • Preferably compositions according to the invention comprise less than a structure destabilising amount of water miscible solvent, preferably less than 10% by weight, for example less than 7.5%, more preferred less than 5%, especially preferred less than 2.0%, typically less than 0.5% by weight of a water miscible solvent.
  • Depending on the other ingredients of the composition, it is however sometimes possible to incorporate low levels of water miscible solvents, say from 0.1 to 8 % by weight, more preferred from 2 to 6 %, without the occurence of structure destabilisation. In particular it has been found that these low levels of water miscible solvents may advantageously be used in combination with relatively high levels of dissolved electrolyte, say more than 2 % by weight, more preferred more than 5 % by weight, especially preferred between 10 and 50 % by weight. Bleach containing compositions comprising water miscible solvents at levels which do not prevent the formation of structuring, in particular internal structuring, are also embraced within the scope of the present invention.
  • Examples of water-miscible solvents are lower aliphatic monoalcohols, ethers of diethylene glycol and lower monoaliphatic monoalcohols, and mixtures thereof.
  • Volume-Stability
  • Liquid detergent compositions according to the invention are volume stable in that they show less than 25% preferably less than 10%, more preferably less than 5% volume increase during storage at a temperature between 20 and 37°C for a period of three months after preparation.
  • Although the type of container for storage is believed not to be critical, generally liquid detergent compositions according to the invention will be stored in closed bottles, say of 1.5 litre, which optionally may include venting means, for releasing generated oxygen.
  • When a solid peroxygen bleach component is present in an aqueous system, generally part of the bleach material will be solubilized in the form of peracid and/or hydrogen peroxide in the aqueous phase. One of the problems often observed in such systems is the occurence of oxygen evolution, due to the decomposition of this peracid or hydrogen peroxide into acid and/or water and oxygen. The oxygen bubbles formed may either emerge from the liquid or be trapped in the liquid, thereby causing a volume increase. A similar oxygen evolution is observed when the bleach component such as for instance hydrogen peroxide is totally solubilized in the system.
  • The present invention provides liquid detergent compositions wherein the volume increase is kept at an acceptable level of less than 25%, preferably less than 10% , more preferred less than 5 %. during storage of the composition at a temperature between 20 and 37°C for three months after preparation.
  • The parameters to be varied in the composition to bring about the desired volume stability effect may for example be the pH, the physical state of the undissolved bleach particles when present, the amount of dissolved bleach, the presence of stabilising agents, the amount of dissolved bleach activators, the viscosity of the product directly after preparation, the presence of viscosity reducing polymers, the presence of gas bubbles in the composition directly after preparation and the presence of antifoam agents. The choice of an optimum value of these parameters is dependant on the nature and the choice of the active materials which are present in the composition.
  • The half life time of the solubilized peracid or hydrogen peroxide should preferably be increased for increasing the volume stability of the composition. Not only the amount of oxygen formed per time unit is less by increasing the stability of the peracid or hydrogen peroxide, also -and this has been found more important- an increase in the life time of these compounds will allow the oxygen bubbles to be formed upon decomposition of the peracid or hydrogen peroxide to grow in size. An increase in the size of the bubbles to be formed is considered advantageous in that these larger bubbles have been found to be less prone to contribute to the volume increase of the liquid detergent composition, in other words they tend to escape from the liquid rather than being suspended into the system.
  • Preferably the half-life time of the hydrogen peroxide or peracid is be more than 3 weeks preferably more than 6 weeks at 37°C at the conditions in the detergent composition, preferably more than 8 weeks especially preferred more than 10 weeks. Most preferred between 10 and 20 weeks.
  • The stability of the peracid or hydrogen peroxide may be increased in several ways such as for instance a decrease in pH of the composition. It has been found that the volume stability of the liquid detergent composition increases by decreasing the pH of the composition. Therefore, for the purpose of formulation volume stable compositions it is preferred to avoid the use of excessive high pH values. Preferably the pH of the detergent compositions is less than 12, more preferred less than 11.5, especially preferred between between 6.5 and 11, typically from 7 to 10.
  • It has also been found that the volume stability of the detergent compositions according to the present invention can be improved by using bleach particles which are encapsulated. These encapsulated bleach particles constitute part or all of the bleach present in the composition, the particles are mainly present in the composition in undissolved form.
  • The presence of bleach particles in undissolved form is also preferred when the bleach particles are not encapsulated. Higher levels of undissolved bleach are preferred, because it is believed that bleach instability is mainly instability of dissolved bleach. Preferably at least 10% by weight, more preferably at least 30%, especially preferred more than 50%, most preferably more than 75 % or even more than 90 % by weight of the bleach is present in undissolved form. If perborate bleaches are used it has been found that the amount of dissolved bleach is reduced if the pH of the composition is relatively high say from 7-11, more preferably from 7.5 to 10.
  • Preferably the weight average diameter of the undissolved bleach particles is from 0.5 to 100 micrometer, especially 5 to 60 micrometer. A method for obtaining these small particles is described in EP 294 904.
  • One way of ensuring that the bleach is present in undissolved form is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the bleach component in the system. Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts and metaborate. Other preferred electrolytes are salting out electrolytes.
  • For the purpose of the present invention the expression salting out electrolyte has the same meaning as in EP 79 646, namely those electrolytes which have a lyotropic number of less than 9.5.
  • Typical examples of salting out electrolytes are water-­soluble builder salts, such as alkali metal ortho- and pyroposphates, the alkali metal tripolyphosphates, such as sodium tripolyposphate, the alkali metal silicates, - borates, -carbonates, -sulphates, alkali metal citrates; alkali metal salts of nitriloacetate; alkali metal salts of carboxymethoxy succinate. Instead of the alkali metal salts the ammonium salts can be used. Particularly preferred is the use of sodium tripolyphosphate and or sodium (di)silicate as the salting out electrolyte.
  • For ensuring an adequate reduction in solubility of the bleach component, the dissolved part of the electrolyte constitutes preferably more than 2 % by weight of the composition, more preferred more than 5% by weight, especially preferred between 10 and 50 % by weight.
  • For obtaining good volume stability, preferably the compositions according to the present invention also comprise a stabilising agent for the bleach component. Suitable stabilisers are well-known in art and include EDTA, Magnesium silicates and phosphonates such as for instance the Dequest range ex Monsanto and Naphthol ex Merck. Preferably the amount of stabilising agent is from 0.05 to 5 % by weight of the composition, more preferred from 0.05 to 1% of the composition.
  • Compositions of the present invention may comprise one or more bleach activator agents. These materials when combined with a peroxy bleach in the wash, will activate hydrogen peroxide at a low temperature of from 15 to 55°C therewith allowing the effective use of peroxide bleaches at low washing temperatures.
  • The bleach activators used in the present invention, often also referred to as peroxyacid bleach precursors are conventionally organic compounds having one or more reactive acyl groups, which at relatively low temperature react with hydrogenperoxide causing the formation of organic peroxyacids, the latter providing for a more effective bleaching action at lower temperatures than hydrogen peroxide itself.
  • The best known organic bleach activator of practical importance is N,N,N,N′-tetraacyl ethylene diamine, normally referred to as TAED. Another well-known bleach activator is sodium-4-benzoyl oxybenzene sulphonate normally referred to as BOBS, as disclosed in GB 836,988.
  • Examples of other organic bleach activators are other n-acyl substituted amides, for example tetraacetyl methylene diamine; carboxylic acid anhydrides for example succinic, benzoic and phthalic anhydrides; carboxylic acid esters, for example sodium acetoxy benzene sulphonate; acetates such as glycerol­triacetate, glucose pentaactetate and xylose­tetraacetate and acetyl salicylic acid.
  • Preferably TAED is used as the bleach activator. The preferred level of bleach activator in the liquid detergent is from 0.1 to 10 % by weight preferably from 0.5 to 5 % by weight of the compositions
  • Preferably the bleach activator is present in the system in at least partly undissolved form. Preferably at least 10% by weight, more preferably at least 30%, especially preferred,more than 50% by weight of the activator is present in undissolved form.
  • One way of ensuring that the activator is present in undissolved form is the use of encapsulated activator materials. Another method is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the activator in the system. Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts and metaborate. Other preferred electrolytes are salting out electrolytes as defined hereabove.
  • For ensuring an adequate reduction in solubility, the dissolved part of the electrolyte constitutes preferably more than 2 % by weight of the composition, more preferred more than 5% by weight, especially preferred between 10 and 50 % by weight.
  • As to the viscosity of the product directly after preparation, it has been found that a lower value for the viscosity generally increases the volume stability of the bleach containing product. Also for lower viscosities are genrally preferred by the consumer. However, for providing solid-suspending properties, low viscosities should preferably be avoided. Therefore in selecting the most appropriate viscosity of the product, a balance should be sought between better stability and consumer-acceptance at lower viscosities and increased solid suspending properties at higher viscosities.
  • Generally it is preferred that for good volume stability and good consumer-acceptance, the viscosity is preferably less than 2,000 mPas at 21 s⁻¹, more preferred less than 1,500, most preferred between 20 and 1,000, especially preferred from 30 to 500. For good solid suspending properties, it is preferred that the viscosity is more than 1,000 mPas at 10⁻⁴ s⁻¹, more preferred more than 10,000, especially preferred more than 100,000.
  • The techniques for obtaining the initial viscosity as desired are well-known in the art, and include for example the appropriate choice of active ingredients, the adaptation of the level of dissolved electrolyte and the inclusion of viscosity modifying agents. A preferred way for regulating the viscosity of the product is the inclusion of polymers in the composition.
  • Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers e.g those having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are described in our copending British patent applications 8813978.7 (corresponding to EP 346 995), 8924479.2, 8924478.4 and 8924477.6.
  • Other polymers which could advantageously be used for viscosity regulation are described in EP 301,882 (Unilever PLC) and EP 301,883 (Unilever PLC). Preferably the amount of viscosity regulating polymer, especially deflocculating polymers, is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
  • As to the presence of gas bubbles in the detergent composition according to the invention, it has been found that both the size and the level of gas bubbles are important parameters for determining the volume stability of the composition. Generally gas bubbles in the form of air or oxygen bubbles are introduced into liquid detergent compositions during processing of the composition, which usually involves a mixing stage.
  • It has been found that it is generally preferred to reduce the amount of gas which is present in the composition just after preparation. Preferably the volume fraction of gas bubbles is less than 5.0%, preferably less than 3.5%, most preferred less than 2.0%, especially less than 1 % or even less than 0,5 %.
  • It has also been found that when gas bubbles are present, the volume stability of the liquid detergent composition increases when at constant gas content the average diameter of the gas bubbles in increased.
  • Preferably the average diameter of the gas bubbles is above 0.25 mm, more preferred above 0.4 mm, most preferred above 0.5 mm.
  • Several techniques can be used for reducing the amount of gas bubbles and for increasing the size of the gas bubbles.
  • For example the presence of an antifoam agent both reduces the volume fraction of gas bubbles and increases the size of the bubbles present. Preferably the antifoam agents are added at a level above the level commonly used for foam reduction of detergent compositions. Preferably the level of antifoam agent is more than 0.2% of the detergent composition, more preferred more than 0.3% of the composition, especially preferred from 0.4 to 2.0% of the composition. Suitable antifoam agents include silicone antifoam agents, such as dimethyl polysiloxanes and/or silica particles.
  • Furthermore it has been found that the use of lower shear-rates in the mixing of the detergent compositions of the invention, decreases the amount of gas bubbles in the composition. A similar decrease can be observed when mixing the detergent composition under deaerated conditions, by centrifuging the detergent composition after mixing, by leading a stream of large gas bubbles through the composition during or after mixing and by vacuum deaeration of the product after mixing. Especially preferred for obtaining the desired result is the centrifuging of the composition in the absence of suspended solids and/or the vacuum deaeration of the composition.
  • It should be noted that the choice of the values of the optimum set of values of the above mentioned parameters should be determined for each detergent composition individually while using the above given guidelines. For certain compositions it may not be necessary to optimise all of the above given parameters. For instance for some detergent compositions it may appear that if the amount and size of the gas bubbles present in the composition is adequately controlled, then a greater flexibility in choosing the viscosity and or pH of the system may be obtained, while still resulting in compositions satisfying the required stability requirement. It is however believed to be well within the ability of a skilled man on the basis of the above teaching to determine for each detergent composition an acceptable set of values for the above-mentioned parameters.
  • Optional ingredients
  • When the compositions are of lamellar structure then in many cases it is preferred for the aqueous continuous phase to contain dissolved electrolyte. As used herein, the term electrolyte means any ionic water soluble material. However, in lamellar dispersions, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g. the order of addition of components. On the other hand, the term "salts" includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
  • The only restriction on the total amount of detergent active material and electrolyte (if any) is that in the lamellar compositions embraced in the present invention, together they must result in formation of an aqueous lamellar dispersion. Thus, within the ambit of the present invention, a very wide variation in surfactant types and levels is possible. The selection of surfactant types and their proportions, in order to obtain a physically stable liquid with the required structure will be fully within the capability of those skilled in the art. However, it can be mentioned that an important sub-class of useful compositions is those where the detergent active material comprises blends of different surfactant types. Typical blends useful for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-­alkoxylated anionic and/or an alkoxylated anionic surfactant.
  • In the case of blends of surfactants, the precise proportions of each component which will result in such physical stability and viscosity will depend on the type(s) and amount(s) of the electrolytes, as is the case with conventional structured liquids.
  • The compositions optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent active material. Preferably though, the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte. Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646. Optionally, some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein. Some or all of the electrolyte (whether salting-in or salting-out), or any substantially water insoluble salt which may be present, may have detergency builder properties.
  • In any event, it is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. The builder material is any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric.
  • Examples of phosphorous-containing inorganic detergency builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, 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. Sometimes, however, it is preferred to minimise the amount of phosphorous-containing builders.
  • Examples of 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.
  • Examples of 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, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid.
  • In the context of organic builders, it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP 301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that would occur if substantially all were dissolved.
  • It is further possible to include in the 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 100ml 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 301,883.
  • Preferably the level of non-soap builder material is from 5-50 % by weight of the composition, more preferred from 5 to 35 %.
  • Although it is possible to incorporate minor amounts, of hydrotropes other than water-miscible solvents, we prefer that the compositions of the present invention contain low levels or are substantially free from hydrotropes. By hydrotrope is meant any water soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
  • Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, 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), germicides and colourants.
  • Compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions. A preferred method involves the dispersing of the electrolyte (non-builder) -if any- together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material -if any-, the detergent active materials (optionally as a pre-mix) under stirring and thereafter cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes or perfumes and the bleach. The deflocculating polymer -­if any- may for example be added after the elctrolyte ingredient or as the final ingredient.
  • When perborate monohydrate is used as the bleaching agent, it may be preferred to cool the final product to a temperature just above the freezing point, in order to accelerate the recrystallisation of the perborate in tetrahydrate form.
  • In use the liquid detergent compositions of the invention will generally be diluted with wash water to form a wash liquor, which may be used for detergency purposes, for example for the washing process in a washing machine. The concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 % by weight, more preferred from 0.1 to 3 %.
  • The invention will now be illustrated by way of the following Examples. In all Examples, unless stated to the contrary, all percentages are by weight.
  • Example 1
  • A basic liquid detergent composition of the following composition was prepared by addition under stirring of the components in the order listed. Na-Dobs was formed in-situ by combining NaOH and Dobs-acid. Some of the processing water was left behind because the hydrogen peroxide solution used was 27 weight % active. TABLE 1
    % by weight
    Water balance
    Na-Dobs 13.8
    Synperonic 7 4.0
    Dequest 2060 0.1
    X-Naphtol 0.2
    STP thermphos NW 8.6
    H₂O₂ (100%) 5.0
    pH¹) 7.9-8.1
    ¹) pH adjusted with NaOH if necessary.
    TABLE 2a
    Raw material specification
    Component Supplier
    Dobs-acid (98%), Marlon AS-3 Hüls
    Synperonic 7 I.C.I.
    Dequest 2060 Monsanto
    X-Naphtol, (p.a.) Merck
    STP, thermphos NW Hoechst
    H₂O₂, 27% Brocacef
  • Example 2
  • By varrying the Na-Dobs/Synperonic weight ratio and keeping the total amount of actives constant, the basic detergent composition according to example 1 was prepared in several versions of different viscosity direct after preparation.
  • Composition A has a ratio Na-Dobs to Synperonic of 0.74:0.26 and a viscosity of 170 mPas at 21 s⁻¹, composition B had a ratio Na-Dobs to Synperonic of 0.75:0.25 and a viscosity of 390 mPas and composition C had a ratio Na-Dobs to Synperonic of 0.78:0.22 and a viscosity of 1000 mPas. The compositions were stored at 37°C.
  • Composition A showed in the first two days of storage a slight volume increase of about 2% by volume, after 2 two days the volume in decreased to a volume which was about 1% less than the volume of the composition directly after preparation.
  • Composition B showed a sharp volume increase of about 50% by volume in the first three days of storage, followed by a reduction of the volume until at the 5th day the composition had approximately its original volume.
  • Composition C showed during the first 7 days a sharp volume increase of more than 125% by volume (overfoam), a reduction of volume to the original volume of the composition was observed after 15 days.
  • This example illustrates that by lowering the viscosity of the composition, the volume stability of detergent compositions containing solubilized hydrogen peroxide can be increased.
  • Example 3
  • The composition of example 1 was prepared by the method as indicated in example 1, with some small modifications.
  • Composition D was prepared according to example 1, the ratio Na-Dobs to Synperonic was 0.77:0.23. Composition E was prepared as composition D, but 0.1% of silicone antifoam was added (corresponding to 0.33 % DB31 ex Dow Corning) before mixing the ingredients. Composition F was prepared as composition D, but the composition was deaerated by centrifuging for 5 min at 4000 G. Composition G was prepared as composition D, but 0.33% of DB31 was added and the composition was de-aerated by centrifuging for 5 min at 4000 G. The viscosity of compositions D-G was 860 mPas after preparation. The compositions were stored at room temperature and the volume increase and the bubble size were monitored.
  • Composition D showed a linear increase in volume up to a maximum of about 75% volume increase after 30 days of storage. The diameter of the gas bubbles present during this period showed a similar increase from very small (about o.1 mm) to about 1.5 mm after 30 days. After 30 days the volume of the compositions decreased gradually until the composition was back at its original volume after 60 days. The bubble diameter stayed constant at a value of 1.5 mm during this period.
  • Composition E showed a linear increase in volume up to a maximum value of about 55% volume increase after 30 days of storage. The diameter of the gas bubbles present during this period showed a similar increase from very small (around 0.25 mm) to about 1.8 mm after 30 days. After 30 days the volume of the composition decreased gradually until the composition was back at its original volume after about 60 days.
  • Composition F showed an increase in volume during the first 7 days to a maximum value of about 10% by volume. After 7 days the volume increase decreased to a value of about 0% and remained constant during 60 days of storage. The diameter of the gas bubbles present during this period remained substantially constant at about 1.5 mm.
  • Composition G did not show a substantial increase in volume during storage for 60 days. The diameter of the gas bubbles present during this period showed an increase from 1 mm to 1.8 mm in the first 10 days of storage, and then remained constant during the remaining of the period.
  • This example illustrates that both the presence of an antifoam agent and/or the de-aeration of the composition contribute positively to the stability of the liquid detergent composition.
  • Example 4
  • Compositions were prepared according to example 1, with some small modifications. Composition H was of the composition of example 1, and had a viscosity of between 400 and 600 mPas, Composition I contained in addition to the components of composition H 0.5% by weight of silicone, corresponding to 1.5 %by weight of DB 31 which was added at the beginning of the mixing process. For both compositions the amount and the size of the gas bubbles in the liquid detergent just after preparation was measured.
  • Composition H contained 5.2% by volume of gas bubbles, the size of the bubbles was between 0.1 and 0.2 mm.
  • Composition I contained 1.9% by volume of gas bubbles, the size of the bubbles was between 0.25 and 0.5 mm.
  • This examples shows that the amount and size of gas bubbles in the detergent composition can positively be influenced by incorporation of an antifoam agent during processing.
  • Examples 5-8
  • The following compositions were prepared by adding the electrolyte together with the minor ingredients except for the perfume and the enzymes to water of elevated temperature, followed by the addition of the detergent active material as a premix under stirring and thereafter cooling the mixture and adding the enzymes, perfumes and the bleach.
    INGREDIENT (% WT) 5 6 7 8
    Na-Dobs 21 21 23.3 21
    Synperonic 7 9 9 10 9
    Glycerol 3.5 -- 3.9 --
    Metaborate 2.6 2.6 2.9 2.6
    Nacitrate/ Citric acid¹) 9.8 9.8 11.1 9.8
    Dequest 2060S (as 100%) 0.4 0.4 0.4 0.4
    Na-perborate tetrahydrate³) 20 20 -- 20
    Na-perborate monohydrate -- -- 7.2 --
    Enzyme, Alcalase 0.8 0.8 0.8 0.8
    CaCl₂.2H₂O 0.2 0.2 0.2 0.1
    Fluorescer, Tinopal CBSX 0.1 0.1 0.1 0.1
    Silicon, Dow Corning DB100 0.3 0.3 0.3 0.3
    Perfume 0.3 0.3 0.3 0.3
    deflocculating polymer⁴) 1 1 1.1 1
    ethanol -- -- -- 2.5
    water balance
    pH 9 9 9 9
    ¹) This mixture is used to adjust the final pH
    ²) Expressed as % of analysed enzyme level in the frsh sample
    ³) as 100 % perborate, added as a dispersion (Proxsol ex ICI, approximate 65% perborate dispersion in water with an average perborate particle size of 40 micrometer.
    ⁴) deflocculating polymer of formula I of EP 346 995, wherein x=50, y=0, R⁵=H, R⁶=CH₃, R¹= -CO-O, R² and R³ are absent, R⁴=-C₁₂H₂₅, mW= 7,500.
    5) wt% -approximate- of total perborate, obtained by removal of the undissolved bleach particles by mild centrifugation.
    6) not measured
  • The obtained products had the following characteristics:
    5 6 7 8
    Volume stability (% volume increase, 3 months 25 oC) 4 3 0 n.m6
    clear layer separation (3 weeks 37 o) no no no no
    solid sedimentation (3 weeks 37 oC) no no no no
    Viscosity 21 s⁻¹ 1,350 710 800 n.m
    Viscosity 10⁻⁴ s⁻¹ ≈200,000 n.m n.m n.m
    dissolved perborates5) 3 1.5 8 n.m
    bleach activity % (2 months ambient T) 99 99 96 n.m
    enzyme activity % (2 months ambient T)²) 65 62 76 n.m

Claims (14)

1. An aqueous structured liquid detergent composition comprising detergents active materials and a peroxygen bleach compound, said detergent composition showing less than 25%, preferably less than 10 %, more preferably less than 5 % volume increase while stored at a temperature between 20 and 37°C for three months after preparation.
2. An aqueous detergent composition according to claim 1, wherein the structure is formed by the detergent active materials.
3. An aqueous detergent composition according to claim 1, wherein the structure is formed by external structurants.
4. An aqueous detergent composition according to one or more of the preceding claims having solid suspending properties.
5. An aqueous detergent composition according to claims 1-4, comprising less than a structure destabilizing amount, preferably less than 10% by weight of a water miscible solvent.
6. An aqueous detergent composition according to claims 1-5 having a pH between 6.5 and 11.
7. An aqueous detergent composition according to one or more of the preceding claims, wherein the composition further comprises an amount of electrolyte which is sufficiently high to effect that at least 30%, preferably more than 50 %, more preferably more than 75 % by weight of the bleach is present in undissolved form.
8. An aqueous detergent composition according to one or more of the preceding claims comprising one or more stabilising agents for the bleach compound.
9. An aqueous detergent composition according to one or more of the preceding claims, comprising a bleach activator.
10. An aqueous detergent composition according to one or more of the preceding claims having a viscosity at 21 s⁻¹ of between 20 and 1,000 mPas, and a viscosity at 10 ⁻⁴ s⁻¹ of more than 10,000 mPas.
11. An aqueous detergent composition according to one or more of the preceding claims comprising 0.1 to 5.0 % of a deflocculating polymer.
12. An aqueous detergent composition according to one or more of the preceding claims comprising just after preparation less than 5.0% by volume of gas bubbles, said gas bubbles having an average diameter of more than 0.25 mm.
13. An aqueous detergent composition according to one or more of the preceding claims comprising more than 0.2% by weight of an antifoam agent.
14. Method for the washing of fabrics, comprising the contacting of the fabrics with a wash liquor comprising from 0.1 to 10 % of a detergent composition according to one or more of the preceding claims.
EP90200290A 1989-02-27 1990-02-08 Liquid detergent composition Expired - Lifetime EP0385522B1 (en)

Priority Applications (52)

Application Number Priority Date Filing Date Title
GB898916094A GB8916094D0 (en) 1989-07-13 1989-07-13 Liquid bleach composition
EP90200290A EP0385522B1 (en) 1989-02-27 1990-02-08 Liquid detergent composition
ES90910739T ES2060186T3 (en) 1989-07-13 1990-06-27 LIQUID WHITENING COMPOSITION.
CA002062781A CA2062781C (en) 1989-07-13 1990-06-27 Liquid bleach composition
EP90910739A EP0484363B1 (en) 1989-07-13 1990-06-27 Liquid bleach composition
PCT/EP1990/001046 WO1991000902A1 (en) 1989-07-13 1990-06-27 Liquid bleach composition
BR909007519A BR9007519A (en) 1989-07-13 1990-06-27 LIQUID DETERGENT COMPOSITION READY FOR USE, AND WASHING PROCESS
AU59541/90A AU636629B2 (en) 1989-07-13 1990-06-27 Liquid bleach composition
DE90910739T DE69003683T2 (en) 1989-07-13 1990-06-27 Liquid bleaching composition.
JP2509960A JPH0768549B2 (en) 1989-07-13 1990-06-27 Liquid bleach composition
TR90/0630A TR25827A (en) 1989-07-13 1990-07-11 A WATER-BASED DETERGENT ACTIVE SUBSTANCES AND A LIQUID-BASING SUBSTANCE LIQUID DETERGENT COMPOSITION
ZA905510A ZA905510B (en) 1989-07-13 1990-07-13 Liquid bleach composition
MYPI90001456A MY105986A (en) 1989-09-13 1990-08-27 Liquid detergents.
AU61779/90A AU647039B2 (en) 1989-09-13 1990-08-28 Liquid detergents
EP90912561A EP0491723B2 (en) 1989-09-13 1990-08-28 Liquid detergents
JP2511763A JPH0774360B2 (en) 1989-09-13 1990-08-28 Liquid detergent
BR909007641A BR9007641A (en) 1989-09-13 1990-08-28 LIQUID DETERGENT COMPOSITION AND USE OF A HYDROTROPISM MATERIAL AS A STABILIZER FOR THE SAME
KR1019920700570A KR960004489B1 (en) 1989-09-13 1990-08-28 Liquid detergents
CA 2064900 CA2064900C (en) 1989-09-13 1990-08-28 Liquid detergents
ES90912561T ES2066216T5 (en) 1989-09-13 1990-08-28 LIQUID DETERGENTS.
DE69014207T DE69014207T3 (en) 1989-09-13 1990-08-28 LIQUID SURFACE ACTIVE AGENTS.
PCT/EP1990/001461 WO1991004314A1 (en) 1989-09-13 1990-08-28 Liquid detergents
TR00783/90A TR27315A (en) 1989-09-13 1990-09-10 Liquid detergents.
CA002073563A CA2073563C (en) 1990-02-08 1991-02-07 Liquid bleach composition
BR919105999A BR9105999A (en) 1990-02-08 1991-02-07 LIQUID DETERGENT COMPOSITION AND WASHING PROCESS
AU71873/91A AU652736B2 (en) 1990-02-08 1991-02-07 Liquid bleach composition
DE69109273T DE69109273T2 (en) 1990-02-08 1991-02-07 LIQUID BLeach.
JP3503439A JPH0772280B2 (en) 1990-02-08 1991-02-07 Liquid bleaching composition
EP91903330A EP0514422B1 (en) 1990-02-08 1991-02-07 Liquid bleach composition
BR919106000A BR9106000A (en) 1990-02-08 1991-02-07 PROCESS FOR PREPARING A LIQUID DETERGENT COMPOSITION AND LIQUID DETERGENT COMPOSITION
PCT/EP1991/000259 WO1991012308A1 (en) 1990-02-08 1991-02-07 Liquid bleach composition
KR1019920701780A KR950008566B1 (en) 1990-02-08 1991-02-07 Liquid breach composition
JP3503735A JPH0768542B2 (en) 1990-02-08 1991-02-07 Liquid bleaching composition
JP50344091A JPH05502471A (en) 1990-02-08 1991-02-07 liquid bleaching composition
PCT/EP1991/000258 WO1991012307A2 (en) 1990-02-08 1991-02-07 Liquid bleach composition
ES91903330T ES2072601T3 (en) 1990-02-08 1991-02-07 LIQUID WHITENING COMPOSITION.
ES91903653T ES2053321T3 (en) 1990-02-08 1991-02-07 LIQUID WHITENING COMPOSITION.
DE69102059T DE69102059T2 (en) 1990-02-08 1991-02-07 LIQUID BLeach.
CA 2073445 CA2073445A1 (en) 1990-02-08 1991-02-07 Liquid bleach composition
EP91903665A EP0514434B2 (en) 1990-02-08 1991-02-07 Liquid bleach composition
EP91903653A EP0513136B1 (en) 1990-02-08 1991-02-07 Liquid bleach composition
AU72109/91A AU646018B2 (en) 1990-02-08 1991-02-07 Liquid bleach composition
DE69126203T DE69126203D1 (en) 1990-02-08 1991-02-07 LIQUID BLeach
PCT/EP1991/000260 WO1991012309A2 (en) 1990-02-08 1991-02-07 Liquid bleach composition
AU71874/91A AU643503B2 (en) 1990-02-08 1991-02-07 Liquid bleach composition
BR919106001A BR9106001A (en) 1990-02-08 1991-02-07 LIQUID DETERGENT COMPOSITION
CA002073432A CA2073432A1 (en) 1990-02-08 1991-02-07 Liquid bleach composition
ZA91956A ZA91956B (en) 1990-02-08 1991-02-08 Liquid bleach composition
ZA91955A ZA91955B (en) 1990-02-08 1991-02-08 Liquid bleach composition
ZA91957A ZA91957B (en) 1990-02-08 1991-02-08 Liquid bleach composition
KR92700065A KR950013224B1 (en) 1989-07-13 1992-01-13 Liquid bleach composition
KR92701781A KR950013223B1 (en) 1990-02-08 1992-07-28 Liquid breach composition

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP89200492 1989-02-27
EP89200492 1989-02-27
GB8908412 1989-04-13
GB898908412A GB8908412D0 (en) 1989-04-13 1989-04-13 Liquid detergent compositions
EP90200290A EP0385522B1 (en) 1989-02-27 1990-02-08 Liquid detergent composition

Publications (3)

Publication Number Publication Date
EP0385522A2 true EP0385522A2 (en) 1990-09-05
EP0385522A3 EP0385522A3 (en) 1991-01-09
EP0385522B1 EP0385522B1 (en) 2001-08-29

Family

ID=26120979

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90200290A Expired - Lifetime EP0385522B1 (en) 1989-02-27 1990-02-08 Liquid detergent composition

Country Status (8)

Country Link
EP (1) EP0385522B1 (en)
JP (1) JPH089719B2 (en)
AU (1) AU629910B2 (en)
BR (1) BR9000882A (en)
CA (1) CA2010442C (en)
DE (1) DE69033783T2 (en)
ES (1) ES2162785T3 (en)
TR (1) TR24976A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430330A2 (en) * 1989-11-24 1991-06-05 The Procter & Gamble Company Suspending liquid detergent compositions
EP0471410A2 (en) * 1990-08-15 1992-02-19 Unilever N.V. Structured liquid detergent compositions containing subtilisin mutants
EP0619368A1 (en) * 1993-04-06 1994-10-12 The Procter & Gamble Company Concentrated liquid detergent compositions
EP0636691A2 (en) * 1993-07-30 1995-02-01 National Starch And Chemical Limited Bleach compositions
WO1996033258A1 (en) * 1995-04-20 1996-10-24 Albright & Wilson Uk Limited Stabilised aqueous suspensions of bleach containing perborate particles
US6080710A (en) * 1993-11-16 2000-06-27 Warwick International Group Limited Bleach activator compositions
US6187221B1 (en) 1999-05-12 2001-02-13 National Starch And Chemical Investment Holding Corporation Controlled release bleach thickening composition having enhanced viscosity stability at elevated temperatures

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994011484A1 (en) * 1992-11-18 1994-05-26 Kao Corporation Liquid bleach composition

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
EP0030096A1 (en) * 1979-12-04 1981-06-10 Imperial Chemical Industries Plc Detergent composition
EP0037184A2 (en) * 1980-04-01 1981-10-07 Interox Chemicals Limited Liquid detergent compositions, their manufacture and their use in washing processes
EP0086511A1 (en) * 1982-02-03 1983-08-24 THE PROCTER & GAMBLE COMPANY Oxygen-bleach-containing liquid detergent compositions
EP0151884A2 (en) * 1983-12-22 1985-08-21 Albright & Wilson Limited Liquid detergent compositions
EP0241137A2 (en) * 1986-03-10 1987-10-14 The Clorox Company Liquid hydrogen peroxide bleach containing a peracid activator
EP0293040A1 (en) * 1987-05-27 1988-11-30 The Procter & Gamble Company Liquid detergent containing solid peroxygen bleach
EP0301882A1 (en) * 1987-07-31 1989-02-01 Unilever Plc Liquid detergent compositions
EP0346995A2 (en) * 1988-06-13 1989-12-20 Unilever N.V. Liquid detergents
EP0359308A2 (en) * 1988-09-16 1990-03-21 Unilever N.V. Liquid detergents
EP0368575A2 (en) * 1988-11-11 1990-05-16 Imperial Chemical Industries Plc Bleach formulation and aqueous detergent compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8411161D0 (en) * 1984-05-01 1984-06-06 Unilever Plc Multiple compartment pack
EP0201958B1 (en) * 1985-05-07 1988-06-29 Akzo N.V. Pourable detergent and bleach compositions
CA1294510C (en) * 1986-03-31 1992-01-21 Stanton Lane Boyer Stable liquid diperoxyacid bleach
JPS63387A (en) * 1986-06-19 1988-01-05 Neos Co Ltd Method for coating coal
GB8713756D0 (en) * 1987-06-12 1987-07-15 Procter & Gamble Liquid detergent

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
EP0030096A1 (en) * 1979-12-04 1981-06-10 Imperial Chemical Industries Plc Detergent composition
EP0037184A2 (en) * 1980-04-01 1981-10-07 Interox Chemicals Limited Liquid detergent compositions, their manufacture and their use in washing processes
EP0086511A1 (en) * 1982-02-03 1983-08-24 THE PROCTER & GAMBLE COMPANY Oxygen-bleach-containing liquid detergent compositions
EP0151884A2 (en) * 1983-12-22 1985-08-21 Albright & Wilson Limited Liquid detergent compositions
EP0241137A2 (en) * 1986-03-10 1987-10-14 The Clorox Company Liquid hydrogen peroxide bleach containing a peracid activator
EP0293040A1 (en) * 1987-05-27 1988-11-30 The Procter & Gamble Company Liquid detergent containing solid peroxygen bleach
EP0301882A1 (en) * 1987-07-31 1989-02-01 Unilever Plc Liquid detergent compositions
EP0346995A2 (en) * 1988-06-13 1989-12-20 Unilever N.V. Liquid detergents
EP0359308A2 (en) * 1988-09-16 1990-03-21 Unilever N.V. Liquid detergents
EP0368575A2 (en) * 1988-11-11 1990-05-16 Imperial Chemical Industries Plc Bleach formulation and aqueous detergent compositions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430330A2 (en) * 1989-11-24 1991-06-05 The Procter & Gamble Company Suspending liquid detergent compositions
EP0430330A3 (en) * 1989-11-24 1991-12-18 The Procter & Gamble Company Suspending liquid detergent compositions
TR25074A (en) * 1989-11-24 1992-11-01 Procter & Gamble SUSPENSIVE LIQUID DETERGENT COMPOSITIONS.
EP0471410A2 (en) * 1990-08-15 1992-02-19 Unilever N.V. Structured liquid detergent compositions containing subtilisin mutants
EP0471410A3 (en) * 1990-08-15 1992-07-01 Unilever Nv Structured liquid detergent compositions containing subtilisin mutants
EP0619368A1 (en) * 1993-04-06 1994-10-12 The Procter & Gamble Company Concentrated liquid detergent compositions
EP0636691A2 (en) * 1993-07-30 1995-02-01 National Starch And Chemical Limited Bleach compositions
EP0636691A3 (en) * 1993-07-30 1996-05-01 Nat Starch Chem Corp Bleach compositions.
US6080710A (en) * 1993-11-16 2000-06-27 Warwick International Group Limited Bleach activator compositions
WO1996033258A1 (en) * 1995-04-20 1996-10-24 Albright & Wilson Uk Limited Stabilised aqueous suspensions of bleach containing perborate particles
US6187221B1 (en) 1999-05-12 2001-02-13 National Starch And Chemical Investment Holding Corporation Controlled release bleach thickening composition having enhanced viscosity stability at elevated temperatures

Also Published As

Publication number Publication date
EP0385522B1 (en) 2001-08-29
JPH089719B2 (en) 1996-01-31
CA2010442A1 (en) 1990-08-27
BR9000882A (en) 1991-02-13
DE69033783T2 (en) 2002-04-18
JPH02269800A (en) 1990-11-05
EP0385522A3 (en) 1991-01-09
ES2162785T3 (en) 2002-01-16
DE69033783D1 (en) 2001-10-04
AU629910B2 (en) 1992-10-15
AU5010490A (en) 1990-08-30
CA2010442C (en) 1996-10-01
TR24976A (en) 1992-09-01

Similar Documents

Publication Publication Date Title
US5160655A (en) Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
EP0526539B1 (en) Liquid detergent compositions
US5397493A (en) Process for making concentrated heavy duty detergents
EP0385522B1 (en) Liquid detergent composition
EP0514422B1 (en) Liquid bleach composition
EP0518870B1 (en) Liquid detergents
EP0514434B2 (en) Liquid bleach composition
AU636629B2 (en) Liquid bleach composition
EP0513136B1 (en) Liquid bleach composition
US5573701A (en) Liquid detergent composition
AU647039B2 (en) Liquid detergents
CA2064900C (en) Liquid detergents

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE ES FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19901128

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

17Q First examination report despatched

Effective date: 19931105

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI NL SE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69033783

Country of ref document: DE

Date of ref document: 20011004

ET Fr: translation filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20060116

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060217

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060223

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060224

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20060227

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060228

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060331

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070208

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20071030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070901

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070901

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20060227

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070208

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070208