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EP0498806B1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
EP0498806B1
EP0498806B1 EP90914713A EP90914713A EP0498806B1 EP 0498806 B1 EP0498806 B1 EP 0498806B1 EP 90914713 A EP90914713 A EP 90914713A EP 90914713 A EP90914713 A EP 90914713A EP 0498806 B1 EP0498806 B1 EP 0498806B1
Authority
EP
European Patent Office
Prior art keywords
weight
polymer
viscosity
alkyl
liquid 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.)
Expired - Lifetime
Application number
EP90914713A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0498806A1 (en
Inventor
Johannes Cornelis Van De Pas
Frederik Jan Schepers
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
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Filing date
Publication date
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Publication of EP0498806A1 publication Critical patent/EP0498806A1/en
Application granted granted Critical
Publication of EP0498806B1 publication Critical patent/EP0498806B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3711—Polyacetal carboxylates
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to liquid detergent compositions, in particular to liquid detergent compositions which comprise a dispersion of lamellar droplets in an aqueous continuous 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', 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 lamellar 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-140 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplet 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.
  • a deflocculating polymer consisting of alternating hydrophobic and hydrophilic groups; these polymers have one of the following general structures: wherein A represents a hydrophobic group, B a hydrophilic group and z is an integer which is preferably zero.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising a dispersion of lamellar droplets in an aqueous continuous phase and a block copolymer consisting of alternating hydrophobic and hydrophilic moieties, wherein the equivalent composition, minus the polymer has a significantly higher viscosity and/or becomes unstable.
  • the deflocculating polymer allows, if desired, the incorporation of greater amounts of surfactants and/or electrolytes than would otherwise be compatible with the need for a stable, low-viscosity product. It also allows (if desired) the incorporation of greater amounts of certain other ingredients to which, hitherto, lamellar dispersions have been highly stability-sensitive. Further details of these are given hereinbelow.
  • the present invention allows formulation of stable, pourable products wherein the volume fraction of the lamellar phase is 0.5- 0.6 or higher, but with combinations or concentrations of ingredients not possible hitherto.
  • a method of determining the volume fraction of the lamellar phase is described in our copending European patent application 89201530.6.
  • compositions of the present invention to have solid-suspending properties (i.e. capable of suspending solid particles).
  • the term 'deflocculating' in respect of the polymer means that the equivalent composition, minus the polymer, has a significantly higher viscosity and/or becomes unstable. It is not intended to embrace polymers which would increase the viscosity but not enhance the stability of the composition. It is also not intended to embrace polymers which would lower the viscosity simply by a dilution effect, i.e. only by adding to the volume of the continuous phase. Nor does it include those polymers which lower viscosity only by reducing the volume fraction (shrinking) of the lamellar droplets, as disclosed in our UK Patent Application N° 8718217 (corresponding to EP 301 883).
  • relatively high levels of the deflocculating polymers can be used in those systems where a viscosity reduction is brought about; levels as low as from about 0.01% by weight to about 1.0% by weight can be capable of considerably reducing the viscosity at 21 s ⁇ 1.
  • the reduction in viscosity at a polymer level of 1.0% by weight is more than 10%, more preferred 20% or more, especially preferred more than 30%.
  • compositions of the present invention exhibit less phase separation on storage and have a lower viscosity than an equivalent composition without any of the deflocculating polymer.
  • compositions of the present invention will yield no more than 10%, more preferred no more than 5 %, especially preferred no more than 2 % by volume phase separation as evidenced by appearance of 2 or more phases when stored at 25 °C for 21 days from the time of preparation.
  • the viscosity of compositions according to the invention is preferably less than 3.5 Pas, more preferably less than 2.5 Pas and especially not greater than 1,500 mPas at a shear rate of 21 s-1.
  • the Applicants have hypothesised that the polymers exert their action on the composition by the following mechanism.
  • the hydrophobic group(s) could be incorporated in the outer bi-layer of the lamellar droplets, leaving the hydrophilic groups over the outside of the droplets and/or the polymers could be incorporated deeper inside the droplet.
  • the composition according to the invention may contain only one, or a mixture of deflocculating polymer types.
  • the term 'polymer types' is used because, in practice, nearly all polymer samples will have a spectrum of structures and molecular weights and often impurities.
  • any structure of deflocculation polymers described in this specification refers to polymers which are believed to be effective for deflocculation purposes as defined hereabove. In practice these effective polymers may constitute only part of the polymer sample, provided that the amount of deflocculation polymer in total is sufficient to effect the desired deflocculation effects.
  • any structure described herein for an individual polymer type refers to the structure of the predominating deflocculating polymer species and the molecular weight specified is the weight average molecular weight of the deflocculation polymers in the polymer mixture.
  • the hydrophilic groups of the polymer are preferably composed of hydrophilic monomer units, which can be selected from a variety of units available for the preparation of polymers. Suitable hydrophilic monomer units are for instance described in our copending European patent application 89201530.6. Particularly preferred hydrophilic groups are polyethoxy groups preferably comprising from 4 to 50 ethylene oxide groups, polyglycerol, condensation polymers of polyglycerol and citric acid anhydride and condensation polymers of alpha-hydroxy acids or polyacetals.
  • the hydrophobic groups of the polymer are preferably selected from saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms, preferably from 6 to 18, most preferred from 8 to 16 carbon atoms, and are optionally bonded to the adjacent hydrophilic groups via an alkoxylene or polyoxyalkylene linkage, for example a polypropoxy or butyloxy linkage having from 1 to 50 alkoxylene groups.
  • Other suitable hydrophobic groups are polyoxyalkylene groups comprising from 4 to 50 propylene oxide and/or butylene oxide groups.
  • hydrophilic groups may be linked to the hydrophobic groups by any possible chemical link, although the following types of linkages are preferred: -CO-, -CO-O-or -O-.
  • R1 represents a C6 ⁇ 24 alkyl or alkenyl group
  • R2 represents -CO-
  • R3 represents -CO-O- or -O-
  • A is -H, or -CO-CH2-C(OH)CO2A1-CH2-CO2A1, or may be a branching point whereto other poly glycerol molecules are attached
  • A1 is independently selected from hydrogen, alkalimetals, alkaline earth metals, ammonium and amine bases and C1 ⁇ 4 alkyl or alkenyl groups
  • S is selected from -H, -COOA1, -CH(COOA1)2, x is from 4 to 1,000, preferably from 6 to 250.
  • compositions according to the present invention have a pH of less than 12.5, more preferred less than 11.0. Most preferred from 7.0 to 10.5.
  • the polymers of formula (I-III) and their salts it is preferred to have a weight average molecular weight in the region of from 500 to 500,000, most preferably from 1,000 to 250,000, especially from 2,000 to 30,000, when measured by GPC using polyacrylate standards or by S.V. measurements.
  • the molecular weights of the standards are measured by the absolute intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.
  • compositions of the present invention may be prepared in analogy of conventional polymerisation methods, eg condensation reactions. Those skilled in the art will be capable of adapting these methods for preparing other polymers for use in the present invention.
  • the deflocculating polymer will be used at from 0.01% to 5.0% by weight of the composition, most preferably from 0.1% to 2.0%.
  • the aqueous continuous phase may contain dissolved electrolyte.
  • electrolyte means any ionic water-soluble material.
  • the electrolyte 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.
  • 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 level of electrolyte is more than 1%, more preferred more than 2%, especially preferred from 5-40% by weight of the composition.
  • a very wide variation in surfactant types and levels is possible.
  • the selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will be fully within the capability of those skilled in the art.
  • 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.
  • 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.
  • 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, München & 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.
  • 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 neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane
  • Suitable surfactants also include stabilising surfactants preferably having a salting out resistance - as defined in our copending European patent application EP 328 177- of more than 6.4.
  • Some preferred classes of stabilising surfactants are : alkyl amine oxides; alkyl polyalkoxylated carboxylates; alkyl polyalkoxylated phosphates; alkyl polyalkoxylated sulphosuccinates; dialkyl diphenyloxide disulphonates; and alkyl polysaccharides (sometimes called alkyl polyglucosides or polyglycosides); selected as those which have a salting out resistance of at least 6.4.
  • stabilising surfactants for example the alkyl polysaccharides described in European patent specification nos. EP-A-70 074; 70 075; 70 076; 70 077; 75 994; 75 995; 75 996 and 92 355.
  • the use of these materials is especially preferred for environmental reasons.
  • 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 according to the present invention 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 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 and the dispersion of the fabric softening clay material.
  • 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.
  • 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.
  • 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, tartrate mono succinate, tartrate di succinate, CMOS, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
  • compositions of the present invention particularly advantageous the use of polymers as described in EP 301 883.
  • compositions of the present invention are substantially free from hydrotropes.
  • hydrotrope any water soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
  • ingredients already mentioned may also be present, for 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.
  • 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
  • These agents cause a problem because they tend to promote flocculation of the lamellar droplets.
  • fluorescers like Blankophor® RKH, Tinopal® LMS, and Tinopal® DMS-X and Blankophor® BBM as well as metal chelating agents, especially of the phosphonate type, for example the Dequest® range sold by Monsanto.
  • compositions of the invention may be prepared in analogy to conventional methods for the preparation of liquid detergent compositions.
  • a preferred method of preparing compositions of the present invention involves the addition of the water-soluble electrolyte -if any- to water, followed by the addition of any water-insoluble material such as aluminosilicates, followed by the polymer ingredients and finally the surfactant ingredients.
  • Another preferred method of preparing a composition of the present invention involves the addition of the surfactant ingredients to water at ambient temperature, followed by the addition of the polymer ingredients, and the cooling of the mixture to below 30 °C, whereafter the remaining ingredients are added. Finally, if necessary, the pH of the composition may be adjusted, e.g. by the addition of small quantities of caustic materials.
  • Table 1 Composition of basic formulation i.e without deflocculating polymers.
  • Ingredient Basic formulation 1 2 Na Dobs 26.1 26.3 Synperonic® A7 10.5 10.6 Na citrate 10.9 8.8 water 52.5 54.3 polymer weights additional to basic formulation

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  • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
EP90914713A 1989-10-31 1990-10-05 Detergent compositions Expired - Lifetime EP0498806B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB8924479 1989-10-31
GB898924479A GB8924479D0 (en) 1989-10-31 1989-10-31 Detergent compositions
PCT/EP1990/001679 WO1991006622A1 (en) 1989-10-31 1990-10-05 Detergent compositions

Publications (2)

Publication Number Publication Date
EP0498806A1 EP0498806A1 (en) 1992-08-19
EP0498806B1 true EP0498806B1 (en) 1994-06-22

Family

ID=10665458

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90914713A Expired - Lifetime EP0498806B1 (en) 1989-10-31 1990-10-05 Detergent compositions

Country Status (7)

Country Link
EP (1) EP0498806B1 (es)
CA (1) CA2069928A1 (es)
DE (1) DE69010215T2 (es)
ES (1) ES2055447T3 (es)
GB (1) GB8924479D0 (es)
NO (1) NO180203C (es)
WO (1) WO1991006622A1 (es)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4237337A1 (de) * 1992-11-05 1994-05-11 Basf Ag Blockcopolyacetale, Verfahren zu ihrer Herstellung und ihre Verwendung in Wasch- und Reinigungsmitteln
SK53294A3 (en) * 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
GB9309475D0 (en) * 1993-05-07 1993-06-23 Albright & Wilson Concentrated aqueous based surfactant compositions
DE69431841D1 (de) * 1994-09-30 2003-01-16 Procter & Gamble Blockkopolymere für verbesserte Viskositätsstabilität in konzentrierten Weichspülmitteln
US5595968A (en) * 1995-05-23 1997-01-21 Basf Corporation Polymeric dispersants for soda ash based detergent slurries
US5733861A (en) * 1995-05-23 1998-03-31 Basf Corporation Hydrophilic copolymers for reducing the viscosity of detergent slurries
US5618782A (en) * 1995-05-23 1997-04-08 Basf Corporation Hydrophilic copolymers for reducing the viscosity of detergent slurries
EP0776965A3 (en) 1995-11-30 1999-02-03 Unilever N.V. Polymer compositions
US6194364B1 (en) 1996-09-23 2001-02-27 The Procter & Gamble Company Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222557B1 (en) * 1985-10-31 1993-10-13 The Procter & Gamble Company Liquid detergent composition
DE3541535A1 (de) * 1985-11-25 1987-05-27 Henkel Kgaa Verwendung von polyglykoldialkylethern als viskositaetsregler fuer waessrige aniontensidloesungen
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
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents

Also Published As

Publication number Publication date
DE69010215T2 (de) 1994-10-13
WO1991006622A1 (en) 1991-05-16
EP0498806A1 (en) 1992-08-19
NO921685D0 (no) 1992-04-29
ES2055447T3 (es) 1994-08-16
CA2069928A1 (en) 1991-05-01
NO180203C (no) 1997-03-05
NO921685L (no) 1992-06-29
DE69010215D1 (de) 1994-07-28
GB8924479D0 (en) 1989-12-20
NO180203B (no) 1996-11-25

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