EP0491723A1 - Detergents liquides. - Google Patents

Detergents liquides.

Info

Publication number
EP0491723A1
EP0491723A1 EP90912561A EP90912561A EP0491723A1 EP 0491723 A1 EP0491723 A1 EP 0491723A1 EP 90912561 A EP90912561 A EP 90912561A EP 90912561 A EP90912561 A EP 90912561A EP 0491723 A1 EP0491723 A1 EP 0491723A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
hydrotroping
materials
electrolyte
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
EP90912561A
Other languages
German (de)
English (en)
Other versions
EP0491723B1 (fr
EP0491723B2 (fr
Inventor
Mario Bulfari
De Pas Johannes Cornelis Van
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 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27233406&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0491723(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from GB8920716A external-priority patent/GB8920716D0/en
Priority claimed from EP90200290A external-priority patent/EP0385522B1/fr
Priority claimed from PCT/EP1990/001046 external-priority patent/WO1991000902A1/fr
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP90912561A priority Critical patent/EP0491723B2/fr
Publication of EP0491723A1 publication Critical patent/EP0491723A1/fr
Publication of EP0491723B1 publication Critical patent/EP0491723B1/fr
Application granted granted Critical
Publication of EP0491723B2 publication Critical patent/EP0491723B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • the present invention is concerned with aqueous liquid detergent compositions which contain, sufficient detergent-active material and, optionally, sufficiently dissolved electrolyte to result in a structure of lamellar droplets dispersed in a continuous aqueous phase.
  • Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial Applications 1 , J. Wiley & Sons, Letchworth 1980.
  • Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplets are called *spherulites* .
  • lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and electron microscopy.
  • the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase) . Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.
  • the viscosity and stability of the product depend on the volume fraction of the liquid which is occupied by the droplets. Generally speaking, when the volume fraction is around 0.6, the droplets are just touching (space ⁇ filling) . This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 2.0 Pas, more preferably no more than 1 Pas at a shear rate of 21s" 1 ) . This volume fraction also endows useful solid-suspending properties.
  • a problem in the formulation of liquid detergent compositions is to have a relatively high volume fraction of lamellar droplets without the occurence of flocculation of the droplets.
  • flocculation occurs between the lamellar droplets at a given volume fraction, the viscosity of the corresponding product will increase due to the formation of a network throughout the liquid.
  • Flocculation may also lead to instability reflected in phase separation of the product.
  • a first embodiment of the present invention relates to a physically stable liquid detergent composition
  • a physically stable liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising from 0.05 to 4.0 % by weight of a hydrotroping material, wherein the corresponding composition minus the hydrotroping agent is physically unstable when stored at 25 °C for 21 days from the day of preparation.
  • a second aspect of the present invention is the discovery that low levels of hydrotroping agents can be used for the stabilisation of active structured liquid detergent compositions.
  • the present invention relates to the use of from 0.05 to 4.0 % by weight based on the total composition, of a hydrotroping material as a stabiliser for liquid detergent compositions comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase.
  • hydrotroping materials these materials may for example be included for providing secondary benefits, for example anti- wrinkling properties or perfume benefits or for providing other benefits such as a decrease in solubility of certain ingredients which may be prone to decomposition in sollubilised form.
  • hydrotroping materials tend to "dissolve" the detergent active materials from the lamellar droplets into the aqueous phase, therewith possibly reducing the physical stability and/or solid suspending properties.
  • a third aspect of the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising at least 1.0 % by weight of a hydrotroping material and an effective amount of a salting out electrolyte.
  • a fourth aspect of the present invention is the discovery that relatively high levels of hydrotroping agents can be incorporated into liquid detergent compositions of the lamellar droplet type, when this composition also comprises relatively high levels of a salting-out electrolyte.
  • the present invention also relates to a liquid detergent composition
  • a liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous c .tinuous phase, said composition comprising from 1.0 to 50.0 % by weight of a hydrotroping material and from 1.0 to 50.0 % by weight of a salting out electrolyte.
  • compositions of the invention are preferably physically stable. Furthermore compositions according to the invention which contain low levels of hydrotroping materials are preferably physically unstable in the absence of hydrotropes.
  • physical stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the "stable* compositions will yield no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
  • Liquid detergent compositions according to the invention are preferably 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 for three months after preparation.
  • a hydrotroping material is a component, which, when added to a standard lamellar droplet type liquid detergent compositions, in a large amount (say 5% by weight) without the addition of an effective amount of salting-out electrolyte, destabilises the dispersed lamellar phase, therewith causing the -at least partly- breaking down of this phase into an L 2 , active rich L- ⁇ or isotropic micellar structure.
  • 2 and L- ⁇ phases are for example described by G.J.T. Tiddy, in Physical Reports 57, No 1 (1980) 1- 46. The presence of such an isotropic micellar structure may in so.
  • micellar structure is present in the continuous aqueous base of the product, then the presence may be evidenced by the fact that the aqueous phase -when isolated- contains more than 1% by weight of surfactant materials.
  • the preferred standard composition for distinguishing between hydrotroping materials and non-hydrotroping materials has the following formulation:
  • the level of Na-Citrate in the standard composition is at least 5 parts by weight, more preferably however the level of Na-Citrate is 10 parts by weight.
  • Suitable hydrotroping materials for use in compositions of the present invention may for example be selected from the class of hydrotroping materials which have hitherto been suggested for use in isotropic detergent compositions.
  • suitable materials are: (i) the alkali metal aryl sulphonates, preferably the sodium aryl sulphonates for example sodium xylene sulphonate, sodium toluene sulphonate, sodium cumene sulphonate, sodium tetralin sulphonate, sodium naphtalene sulphonate and the short chain alkyl derivatives thereof.
  • mono- or di-hydric alcohols or derivatives thereof such as lower alcohols such as ethanol or isopropanol, propyleneglycol, ethylene glycol; alcohol derivative such as mono- or triethanolamine or 1,2 propylene glycol dibuthyl ether; and higher alcohols, such as C 3 _ 10 alcohols preferably having a carbon chain length which is at least 4 carbon atoms shorter than the average chain length of the hydrocarbyl chain of the surfactant materials used in the composition.
  • Hydrocarbon materials such as for example C 8 _ 12 parafins (e.g. SHELL SOLT ex SHELL) , preferably for these materials the carbon chain length of the hydrocarbon chain is at least 2 carbon atoms shorter than the average chain length of the hydrocarbyl chain of the surfactants uses in the composition.
  • Organic solvent materials such as limonene, linalol, benzyl alcohol, diglyme, dibuthyl phtalate and terpene.
  • hydrotroping agents may be used.
  • glycerol is not a hydrotroping agent.
  • Preferred hydrotroping materials are the lower alcohols such as ethanol.
  • the level of hydrotroping material in compositions of the present invention can be varried in a wide range but for obtaining a stabilising effect the preferred levels of hydrotroping materials are in the range from 0.05 to 4.0 % by weight of the composition, more preferred from 0.1 to 3.0%, especially preferred from 0.15 to 2.0 % by weight of the composition, most preferred from 0.2 to 1.0 %.
  • the preferred level of hydrotoping materials is at least 1.0 % by weight and less than 50 % by weight, more preferably from 4.0 to 40.0 %, especially preferred from 6.0 to 30.0 % by weight of the composition, most preferred from 8.0 to 20.0 %.
  • Co positi ns of the invention also comprise detergent active materials, preferably at a level of from 1 to 70% by weight of the composition, more preferred a level of 5 to 50 % by weight, most preferred from 10 to 40 % by weight.
  • the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • surfactants may be chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents* Vol.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-Taschenbuch' , H.Stache, 2nd Edn. , Carl Hanser Verlag, M ⁇ nchen & 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 (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products f 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
  • alkyl poly glycoside surfactants such as for example disclosed in EP 70 074.
  • the level of nonionic surfactants is more than 1 % of the composition, preferably from 2.0 to 20.0% by weight of the composition, more preferred from 3.0 to 6.0 %.
  • Especially preferred nonionic materials for use in compositions of the present invention are ethoxylated alcohols comprising from 2 to 10 EO groups.
  • Advantageous materials are for instance Synperonic A7, Synperonic A5 and Synperonic A3 (ex ICI) or mixtures thereof.
  • compositions of the present invention preferably contain anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials.
  • Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic 10 anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (Cg-C 0 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 ⁇ c 15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the hie _ar alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C 18 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acids
  • 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 or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • compositions preferably also contain a salting out electrolyte.
  • the salting out electrolytes are optional, though preferred ingredients.
  • the salting-out electrolyte is present in an effective amount.
  • This effective amount can be determined by adjusting the amount of electrolyte while keeping the relative amounts of the other ingredients constant.
  • the level of electrolyte is chosen such that after centrifuging the composition for 17 h at 750 G the level of surfactant in the aqueous phase is less than 5% by weight, more preferably less than 2%, most preferably less than 1%.
  • the level of salting-out electrolytes is preferably from 1 to 50 % by weight.
  • the same levels of salting-out electrolytes are preferred for the other embodiments of the invention. More preferably the level of salting-out electrolytes is from 5 to 45%, most preferably from 10 to 35 % by weight.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is those materials having a lyotropic number of less than 9.5.
  • some salting-in electrolyte (as defined in the latter specification) may also be included.
  • Preferred salting-out electrolytes are for example citrates, borates, formates and tripolyphosphates.
  • Preferred salting-in electrolytes are NaCl and Na- acetate.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • Examples of phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, 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.
  • 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.
  • the stabilising effect of the hydrotroping agent is especially noticeable in compositions containing zeolite builders, especially in compositions containing high levels of zeolite builders, for example of from 10 to 30 % by weight of the compositions, more preferred from 15 to 20%.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • electrolytes which promote the solubility of other electrolytes
  • potassium salts to promote the solubility of sodium salts.
  • 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, 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
  • compositions according to the present is preferably less than 2500 mPas, especially preferred less than 2000 mPas, more preferred less than 1500 Pas, most preferred between 30 and 1000 mPas at 21 s -1 .
  • One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
  • Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our copending European application 89201530.6. (EP 346 995).
  • compositions of the invention have solid suspending properties, most preferably they do not yield any visible sedimentation after storage for 3 weeks at 21°C when 10% of a solid particulate material e.g. calcite or zeolite is incorporated.
  • a solid particulate material e.g. calcite or zeolite
  • compositions of the invention preferably contain from 10-80% by weight of water, more preferably 15-60%, most preferably 20-50%.
  • 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, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo) , 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 oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate
  • An especially preferred embodiment of the present invention relates to the combined use of bleach ingredients and hydrotroping materials in liquid detergent compositions of the lamellar droplet type.
  • the use of relatively high levels of hydroptroping materials enhances the stability of the bleach ingredient, especially when partially insoluble bleaches such as sodium perborate are used.
  • the level of bleach material, especially of peroxygen bleach material, more preferably of perborate or percarbonate bleach material is from 1- 25 % by weight of the composition, more preferred from 3- 20 %, most preferred from 5 - 15 %.
  • the hydrotroping material is a polyhydric alcohol used at a level of from 1-20 % of the composition, then the composition does not comprise a bleach material in combination with a metaborate electrolyte;
  • composition comprises minor amounts of hydrotrope other than water-miscible solvents, then the composition does not comprise a peroxygen bleach compound and shows less than 25 % volume increase when stored at .0-37 °C for three months.
  • compositions comprise salting-out electrolyte, water and hydrotrope, wherein the weight ratio of water to hydrotrope is between 20:1 and 1:1, more preferably between 10:1 and 3:1.
  • the weight ratio of salting out electrolyte to hydrotrope is preferably from 20:1 to
  • the weight ratio of water to electrolyte is preferably from 10:1 to 1:1, more preferably 8:1 to 2:1, most preferably 6:1 to 4:1.
  • 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 ingredient 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, the hydrotroping material and the detergent active material under light stirring and finally cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes, perfumes etc.
  • the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.
  • the liquid detergent compositions should be alkaline, and it is preferred that they should provide a pH within the range of about 8.5 to 12, preferably about 9 to about 11, when used in aqueous sr ⁇ utions of the composition at the recommended concentration.
  • the undiluted liquid composition should also be of a pH above 7, for example about pH 7.5 to about 12.5. It should be noted that an excessively high pH, e.g. over about pH 13, is less desirable for domestic safety. If hydrogen peroxide is present in the liquid composition, then the pH of the composition is generally from 7.5 to 10.5, preferably 8 to 10, and especially 8.5 to 10, to ensure the combined effect of good detergency and good physical and chemical stability.
  • any such highly alkaline detergent composition should, of course, be chosen for alkaline stability, especially for pH-sensitive materials such as enzymes, and a particularly suitable proteolytic enzyme.
  • the pH may be adjusted by addition of a suitable alkaline material.
  • Liquid detergent compositions of the following formulation were prepared by heating the water to 50 °C and mixing the fluorescer, the Calcium chloride,
  • compositions A and B were both lamellar structured liquid detergent compositions having solid suspending properties.
  • Composition A outside the scope of the present invention, had direct after preparation a viscosity of 1270 mPas at 21 s" 1 . After three weeks storage at 25 °C the compositions showed 10 % by volume phase sep j-ation.
  • Composition B according to the invention had an initial viscosity of 890 mPas at 21 s "1 and showed no visible phase separation after storage for three weeks at 25 °C.
  • compositions were stable liquid detergents having a lamellar structure.
  • the corresponding compositions minus the hydrotroping material were physically unstable (some phase separation upon storage) Example III
  • compositions were made by mixing the ingredients in the order as indicated.
  • Component Composition (in parts bv weight) 1 2 3 4
  • the following formulation was prepared by adding the ingredients to water in the order listed.
  • compositions were made by adding the ingredients in the listed order to water under stirring.
  • Tinopal CBS-X polymer 1 water ⁇ balance >
  • 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 mat rial as a premix under stirring and thereafter cooling the mixture and adding the enzymes, perfumes and the bleach.
  • volume stability (% volume 0 0 increase, 3 months 25 °C) clear layer separation no no
  • a composition as described in example IX of EP 293 040 (P&G) was prepared by adding the following ingredients in the order listed under stirring:
  • compositions as disclosed in EP 293 040 are difficult to reproduce and suffer from an unacceptable high viscosity and/or volume instability and/or physical instability.
  • a compositiom according to example 70 of US 4,618,446 (A&W) was prepared by adding the NaOH to the water at ambient temperature, followed by the addition of the surfactants, the remaining electrolytes and the remaining ingredients.
  • composition was prepared wherein the SXS was omitted. Both compositions were stored for 21 and 42 days at 25 °C.
  • composition without the SXS ingredient was physically stable (no phase separation after storage)
  • composition with SXS was physically stable after 21 days of storage, but unstable after 6 weeks.
  • the viscosity of the composition without SXS was 2,750 mPas at 21 s" 1
  • the viscosity of the composition with SXS was 3,800 mPas.
  • compositions as disclosed in US 4,618,446 do not comprise SXS as a stabiliser; furthermore compositions according to this patent appear of high viscosity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Composition stable de détergent liquide comportant une dispersion de gouttelettes lamellaires de matériaux à activité détergente en phase continue aqueuse. Cette composition comprend un matériau hydrotrope et de préférence un électrolyte relargeant.
EP90912561A 1989-09-13 1990-08-28 Detergents liquides Expired - Lifetime EP0491723B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP90912561A EP0491723B2 (fr) 1989-09-13 1990-08-28 Detergents liquides

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
GB8920716 1989-09-13
GB8920716A GB8920716D0 (en) 1989-09-13 1989-09-13 Liquid detergents
EP90200290 1990-02-08
EP90200290A EP0385522B1 (fr) 1989-02-27 1990-02-08 Composition détergente liquide
PCT/EP1990/001046 WO1991000902A1 (fr) 1989-07-13 1990-06-27 Composition de blanchiment liquide
EP90201701 1990-06-27
EP90201701 1990-06-27
WOPCT/EP90/01046 1990-06-27
EP90912561A EP0491723B2 (fr) 1989-09-13 1990-08-28 Detergents liquides
PCT/EP1990/001461 WO1991004314A1 (fr) 1989-09-13 1990-08-28 Detergents liquides

Publications (3)

Publication Number Publication Date
EP0491723A1 true EP0491723A1 (fr) 1992-07-01
EP0491723B1 EP0491723B1 (fr) 1994-11-17
EP0491723B2 EP0491723B2 (fr) 1998-12-23

Family

ID=27233406

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912561A Expired - Lifetime EP0491723B2 (fr) 1989-09-13 1990-08-28 Detergents liquides

Country Status (9)

Country Link
EP (1) EP0491723B2 (fr)
JP (1) JPH0774360B2 (fr)
KR (1) KR960004489B1 (fr)
AU (1) AU647039B2 (fr)
BR (1) BR9007641A (fr)
DE (1) DE69014207T3 (fr)
ES (1) ES2066216T5 (fr)
TR (1) TR27315A (fr)
WO (1) WO1991004314A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996033258A1 (fr) * 1995-04-20 1996-10-24 Albright & Wilson Uk Limited Suspensions aqueuses stabilisees d'agent de blanchiment contenant des particules de perborate

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1569617A (en) * 1976-03-08 1980-06-18 Procter & Gamble Liquid detergent composition
ES475852A1 (es) * 1977-12-09 1980-03-01 Albright & Wilson Un metodo para la manufactura de una composicion acuosa ten-soactiva concentrada
GB2021141B (en) * 1977-12-09 1982-06-16 Albright & Wilson Concentrated aqueous surfactant compositions
GB2031941B (en) * 1978-02-07 1982-06-30 Albright & Wilson Concentrated aqueous surfactant compositions
DE2921366A1 (de) * 1978-05-26 1979-12-06 Albright & Wilson Konzentrierte waessrige oberflaechenaktive zubereitung
GB2023637B (en) * 1978-05-26 1982-06-23 Albright & Wilson Concentrated aqueous surfactant compositions
FR2521135B1 (fr) * 1982-02-05 1986-05-09 Oreal Composes polyanioniques, procede pour les preparer et compositions les contenant
GB8334250D0 (en) * 1983-12-22 1984-02-01 Albright & Wilson Liquid detergent compositions
GB8713574D0 (en) * 1987-06-10 1987-07-15 Albright & Wilson Liquid detergent compositions
GB8718217D0 (en) * 1987-07-31 1987-09-09 Unilever Plc Liquid detergent compositions
GB8718215D0 (en) * 1987-07-31 1987-09-09 Unilever Plc Liquid detergent compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9104314A1 *

Also Published As

Publication number Publication date
AU6177990A (en) 1991-04-18
ES2066216T3 (es) 1995-03-01
DE69014207D1 (de) 1994-12-22
EP0491723B1 (fr) 1994-11-17
WO1991004314A1 (fr) 1991-04-04
JPH0774360B2 (ja) 1995-08-09
BR9007641A (pt) 1992-07-07
AU647039B2 (en) 1994-03-17
DE69014207T3 (de) 1999-03-18
JPH05500075A (ja) 1993-01-14
DE69014207T2 (de) 1995-03-23
ES2066216T5 (es) 1999-04-01
KR960004489B1 (ko) 1996-04-06
TR27315A (tr) 1995-01-12
EP0491723B2 (fr) 1998-12-23

Similar Documents

Publication Publication Date Title
US5160655A (en) Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
AU651825B2 (en) Liquid detergent compositions
EP0346993A2 (fr) Composition détergentes liquides
AU646018B2 (en) Liquid bleach composition
CA1335646C (fr) Compositions de detergents liquides
WO1991006622A1 (fr) Compositions detergentes
US5672580A (en) Liquid detergent compositions
AU647039B2 (en) Liquid detergents
EP0385522A2 (fr) Composition détergente liquide
EP0495858A1 (fr) Detergents liquides.
EP0514434B2 (fr) Composition de blanchissage liquide
CA2064900C (fr) Detergents liquides
EP0504159A1 (fr) Detergents liquides.
AU636629B2 (en) Liquid bleach composition
CA2076970C (fr) Detergents liquides
AU7187391A (en) Liquid bleach composition

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

17P Request for examination filed

Effective date: 19920226

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19920918

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

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19941117

REF Corresponds to:

Ref document number: 69014207

Country of ref document: DE

Date of ref document: 19941222

ITF It: translation for a ep patent filed
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2066216

Country of ref document: ES

Kind code of ref document: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: UNILEVER N.V.

26 Opposition filed

Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V.

Effective date: 19950817

NLR1 Nl: opposition has been filed with the epo

Opponent name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER N.V.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

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

Ref country code: CH

Payment date: 19960724

Year of fee payment: 7

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: 19970831

Ref country code: CH

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

Effective date: 19970831

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: SE

Payment date: 19980715

Year of fee payment: 9

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

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

Ref country code: NL

Payment date: 19980817

Year of fee payment: 9

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19981223

AK Designated contracting states

Kind code of ref document: B2

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: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

ITF It: translation for a ep patent filed
ET3 Fr: translation filed ** decision concerning opposition
NLR2 Nl: decision of opposition
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 19990212

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990830

EUG Se: european patent has lapsed

Ref document number: 90912561.9

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

Ref country code: ES

Payment date: 20010808

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: FR

Payment date: 20020731

Year of fee payment: 13

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

Ref country code: GB

Payment date: 20020821

Year of fee payment: 13

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

Ref country code: DE

Payment date: 20020830

Year of fee payment: 13

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

Ref country code: GB

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

Effective date: 20030828

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: 20030829

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: 20040302

GBPC Gb: european patent ceased through non-payment of renewal fee
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: 20040430

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030829

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050828