WO2007085410A1 - Structured cleaning compositions - Google Patents

Structured cleaning compositions Download PDF

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Publication number
WO2007085410A1
WO2007085410A1 PCT/EP2007/000535 EP2007000535W WO2007085410A1 WO 2007085410 A1 WO2007085410 A1 WO 2007085410A1 EP 2007000535 W EP2007000535 W EP 2007000535W WO 2007085410 A1 WO2007085410 A1 WO 2007085410A1
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WIPO (PCT)
Prior art keywords
composition according
weight
surfactant
salt
less
Prior art date
Application number
PCT/EP2007/000535
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English (en)
French (fr)
Inventor
John Hawkins
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to PL07702946T priority Critical patent/PL1979460T3/pl
Priority to EP07702946A priority patent/EP1979460B1/de
Priority to AT07702946T priority patent/ATE450596T1/de
Priority to DE602007003563T priority patent/DE602007003563D1/de
Publication of WO2007085410A1 publication Critical patent/WO2007085410A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts

Definitions

  • the invention relates to structured cleaning compositions
  • liquid cleaning compositions containing suspended abrasive particles, which are suitable for use as manual dishwashing and scouring liquids
  • EP 0193375 describes dispersing fine particles of sodium carbonate in a viscous, liquid detergent base, relying on the high viscosity of the medium, and the small particle size of the carbonate to retard sedimentation
  • the small particle size gives insufficient abrasive action for an effective pan scourer
  • structured system means a pourable composition comprising water, surfactant, any structurants which may be required to impart suspending properties to the surfactant, and optionally other dissolved matter, which together form a mesophase, or a dispersion of a mesophase in a continuous aqueous medium, and which has the ability to immobilise non-colloidal, water- insoluble particles while the system is at rest, thereby forming a stable, pourable suspension
  • L ⁇ -phases also known as G-phases
  • aqueous layers L ⁇ -phases also known as G-phases
  • Such evidence may comprise first, second and sometimes third order peaks with a d-spacing (2 ⁇ /Q, where Q is the momentum transfer vector) in a simple integral ratio 1 2 3
  • Other types of symmetry give different ratios, usually non-integral
  • the d-spacing of the first peak in the series corresponds to the repeat spacing of the bilayer system
  • the main types of structured system used in practice are based on dispersed lamellar, spherulitic and expanded lamellar phases
  • Dispersed lamellar phases are two phase systems, in which the surfactant bilayers are arranged as parallel plates to form domains of L ⁇ -phase, which are interspersed with an aqueous phase to form an opaque gel-like system They are described in EP 086 614
  • Spherulitic phases comprise well-defined spheroidal bodies, usually referred to in the art as spheruhtes, in which surfactant bilayers are arranged as concentric shells
  • the spherulites usually have a diameter in the range 0 1 to 15 microns and are dispersed in an aqueous phase in the manner of a classical emulsion, but interacting to form a structured system Spherulitic systems are described in more detail in EP 151 884
  • a variant on the spherulitic system comprises prolate or rod shaped bodies sometimes referred to as batonettes These are normally too viscous to be of practical interest
  • Both of the foregoing systems comprise two phases Their stability depends on the presence of sufficient dispersed phase to pack the system so that the interaction between the spheruhtes or other dispersed mesophase domains prevents separation If the amount of dispersed phase is insufficient, e g because there is not enough surfactant or because the surfactant is too soluble in the aqueous phase to form sufficient of a mesophase, the system will undergo separation and cannot be used to suspend solids Such unstable systems are not "structured" for the purpose of this specification
  • a third type of structured system comprises an expanded L ⁇ -phase It differs from the other two types of structured system in being essentially a single phase, and from conventional L ⁇ - phase in having a wider d-spacing
  • Conventional L ⁇ -phases which typically contain 60 to 75% by weight surfactant, have a d-spacing of about 4 to 7 nanometers Attempts to suspend solids in such phases result in stiff pastes which are either non-pourable, unstable or both Expanded L ⁇ -phases with d-spacing greater than 8 nanometres, e g 10 to 15 nm, form when electrolyte is added to aqueous surfactants at concentrations just below those required to form a normal L ⁇ -phase, particularly to surfactants in the H-phase
  • the H-phase comprises surfactant molecules arranged to form cylindrical rods of indefinite length It exhibits hexagonal symmetry and a distinctive texture under the polarising microscope Typical H-phases have so high a viscosity that they appear to be curdy solids H-pha- ses near the lower concentration limit (the L-i/H-phase boundary) may be pourable but have a very high viscosity and often a mucous-like appearance Such systems tend to form expanded L ⁇ -phases particularly readily on addition of sufficient electrolyte.
  • L ⁇ -phases are described in more detail in EP 530 708. In the absence of suspended matter they are generally translucent, unlike dispersed lamellar or spherulitic phases, which are normally opaque. They are optically anisotropic and have shear-dependent viscosity. In this they differ from l_i-phases, which are micellar solutions or microemulsions. L 1 - phases are clear, optically isotropic and are usually substantially Newtonian. They are unstructured and cannot suspend solids.
  • Lrphases exhibit small angle x-ray diffraction spectra which show evidence of hexagonal symmetry and/or exhibit shear dependent viscosity.
  • Such phases usually have concentrations near the l-VH-phase boundary and may form expanded L ⁇ -phases on addition of electrolyte.
  • electrolyte In the absence of any such addition of electrolyte they lack the yield point required to provide suspending properties, and are not, therefore, "structured systems" for the purpose of this specification.
  • Expanded L ⁇ -phases of the above type are usually less robust than spherulitic systems. They are liable to become unstable at low temperatures. Moreover they frequently exhibit a relatively low yield stress, which may limit the maximum size of particle that can be stably suspended.
  • structured surfactants require the presence of a structurant, as well as surfactant and water in order to form structured systems capable of suspending solids.
  • structurant as well as surfactant and water
  • structuralant is used herein to describe any non-surfactant capable, when dissolved in water, of interacting with surfactant to form or enhance (e.g increase the yield point of) a structured system. It is typically a surfactant-desolubiliser, e.g. an electrolyte.
  • stable, pourable, homogeneous, abrasive dishwashing compositions can be obtained by suspending solid particles of common salt in a saturated aqueous solution of said salt, and adding sufficient surfactant to form, in conjunction with said solution, a stable, pourable, solid-supporting structured surfactant system.
  • the saturated salt solution acts as a structurant, interacting with the surfactant to form a suspending system.
  • the excess salt acts as an abrasive when the liquid is applied in the undiluted form, but readily dissolves in water on rinsing.
  • the invention therefore, provides a stable, pourable, homogeneous composition
  • a stable, pourable, homogeneous composition comprising particulate, solid salt suspended in a saturated aqueous solution of said salt, and sufficient surfactant to form, in conjunction with said solution, a stable, pourable, solid-supporting structured surfactant system
  • Salt refers to an alkali metal and/or alkaline earth metal halide composition, which may comprise sodium, potassium, magnesium and/or calcium chloride, but will usually, in practice, consist at least predominantly of sodium chloride
  • the salt may contain minor amounts of the impurities commonly present in naturally occurring salt, such as other halides (e g bromide and/or iodide) and other anions (e g carbonate and/or sulphate)
  • the cationic component consists essentially of alkali metal and/or alkaline earth metal, e g more than 90%, preferably more than 95%, most preferably more than 99% by weight, based on the total weight of cations Preferably at least 40% of the cations by weight are alkali metal
  • at least 50%, more preferably at least 75%, most preferably at least 90% by weight of the cationic component of the salt should be alkali metal
  • the alkali metal consist essentially of sodium and potassium, and that any alkaline
  • Salt is highly soluble, i e more than 30% by weight at 25°C It is highly desirable that the solubility does not vary by a large amount over the normal range of storage temperatures, to avoid unacceptable crystal growth, and destabilisation of the surfactant structure A variation of less than 10% between 0 and 40 0 C is preferred
  • Sodium chloride meets these requirements particularly well It is also cheap, natural and a highly effective hypoallergenic biocide. We have found that cleaning compositions based on saturated brine are self-preserving. Sea salt or rock salt (halite) are very suitable.
  • Saturated brine is a very aggressive medium for surfactants and the choice of structuring surfactant is therefore rather restricted.
  • surfactants with a high HLB or solubility product are suitable.
  • the HLB is preferably greater than 12, more preferably greater than 15, even more preferably greater than 20, most preferably greater than 30.
  • Relatively few surfactants meet these criteria, but one that does is alkyl ether sulphate, which is, fortuitously, one of the preferred surfactants for use in dishwashing formulations.
  • Alkyl ether sulphates having more than one, and more preferably more than two, ethyleneoxy groups are preferred.
  • the alkyl ether sulphate is preferably the product obtained by:
  • the base is typically an alkali metal and/or alkaline earth metal hydroxide or carbonate, usually sodium. However, for Dead Sea salt, with its high magnesium content, a mixed sodium/- magnesium ether sulphate may be preferred.
  • the base may comprise an amine, especially an ethanolamine.
  • Alternative surfactants which may be used include high HLB non-ionic surfactants, such as alcohol or fatty acid ethoxylates with more than 3, preferably more than 5, most preferably more than 10 ethoxy groups. Especially preferred are those with bent chain hydrocarbon groups such as oleyl or isostearyl groups. Non-ionic surfactants may require the presence of a deflocculant, such as an alkyl polyglycoside, in order to be stable.
  • Other surfactants, which may be employed according to the invention include alkyl ether carboxylates and high HLB amphoteric and zwitterionic surfactants and amine oxides.
  • the proportion of surfactant required will depend on the HLB. Higher HLB generally requires more surfactant.
  • the amount of surfactant is greater than 2% by weight, more preferably greater than 4%, most preferably greater than 6%, but less than 25%, more preferably less than 20%, most preferably less than 15%.
  • the surfactant may also comprise minor amounts of other anionic surfactants, such as, for example, C 1 0- 2 0 alkyl sulphate, e.g. C 12 -i8 atkyl sulphate, C 1O - 2 o alky] benzene sulphonate or a C 8 - 2 o aliphatic soap, e.g. C 1O - 2 o aliphatic soap.
  • the soap may be saturated or unsaturated, straight or branched chain. Preferred examples include dodecanoates, myristates, stearates, oleates, linoleates, linolenates, behenates, erucates and palmitates and coconut and tallow soaps.
  • the surfactant may also include other anionic surfactants, such as olefin sulphonates, paraffin sulphonates, taurides, isethionates, ether sulphonates, ether carboxylates, sarcosina- tes, aliphatic ester sulphonates, e.g. alkyl glyceryl sulphonates, sulphosuccinates or sulpho- succinamates.
  • anionic surfactants such as olefin sulphonates, paraffin sulphonates, taurides, isethionates, ether sulphonates, ether carboxylates, sarcosina- tes, aliphatic ester sulphonates, e.g. alkyl glyceryl sulphonates, sulphosuccinates or sulpho- succinamates.
  • any anionic surfactant is typically sodium but may alternatively be, or comprise potassium, lithium, calcium, magnesium, ammonium, or an alkyl or hydroxyalkyl ammonium having up to 6 aliphatic carbon atoms including ethylammonium, isopropylammonium, mono- ethanolammonium, diethanolammonium, and triethanolammonium.
  • Ammonium and ethanol- ammonium salts are generally more soluble than the sodium salts. Mixtures of the above cations may be used.
  • the non-ionic surfactants may typically comprise amine oxides, polyglyceryl fatty esters, fatty acid ethoxylates, fatty acid monoalkanolamides, fatty acid dialkanolamides, fatty acid alkanol- amide ethoxylates, propylene glycol monoesters, fatty alcohol propoxylates, alcohol ethoxylates, alkyl phenol ethoxylates, fatty amine alkoxylates and fatty acid glyceryl ester ethoxylates.
  • non-ionic compounds suitable for inclusion in compositions of the present invent- tion include mixed ethylene oxide/ propylene oxide block copolymers, ethylene glycol mono- esters, alkyl polyglycosides, alkyl sugar esters including alkyl sucrose esters and alkyl oligosaccharide esters, sorbitan esters, ethoxylated sorbitan esters, alkyl capped polyvinyl alcohol and alkyl capped polyvinyl pyrrolidone.
  • the surfactant may comprise an amphoteric or zwitterionic surfactant.
  • the former preferably comprises so-called imidazoline betaines, which are also called amphoacetates, and were traditionally ascribed the zwitterionic formula: CH 2 CH 3
  • R 1 R because they are obtained by treating sodium chloracetate with an imidazoline. It has been shown, however, that they are actually present, at least predominantly, as the corresponding amphoteric linear amidoamines:
  • R preferably has at least 8, more preferably at least 10 carbon atoms but less than 25, more preferably less than 22, even more preferably less than 20, most preferably less than 18.
  • R represents a mixture of alkyl and alkenyl groups, obtained, for example, from coconut or palm oil, and having sizes ranging from 8 to 18 carbon atoms, with 12 predominating, or a fraction of such a feedstock, such as lauryl with at least 90%C 12 .
  • R 1 is preferably an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms, i.e. methyl, ethyl, hydroxyethyl, propyl, iso- propyl, hydroxy propyl, butyl, isobutyl or hydroxybutyl, particularly preferably hydroxyethyl.
  • the zwitterionic surfactant is preferably a betaine, which typically has the formula R"R' 2 + NCH 2 COOH, where R' is an aliphatic group having 1 to 4 carbon atoms and R" is an aliphatic group having from 8 to 25 carbon atoms, preferably a straight or branched chain alkyl or alkenyl group, or more preferably a group of the formula RCONR'(CH 2 ) n, where R and R' have the same significance as before, and n is an integer from 2 to 4.
  • R' is a methyl, carboxymethyl, ethyl, hydroxyethyl, carboxyethyl, propyl, iso- propyl, hydroxypropyl, carboxypropyl, butyl, isobutyl or hydroxybutyl group.
  • the surfactant may comprise cationic surfactants such as fatty alkyl trimethylammonium or benzalkonium salts, amidoamines or imidazolines.
  • the aqueous structured systems formed by the interaction of surfactants with saturated brine include systems which may be in the form of an expanded L ⁇ -phase, such as those described in EP 530 708.
  • the systems of the present invention may comprise structures which preferably show d-spacings greater than 5 nm, more preferably greater than 7 nm, even more preferably greater than 8 nm, more preferably still, greater than 9 nm, most preferably greater than 10 nm.
  • the d-spacing is less than 30 nm, more preferably less than 20 nm, most preferably less than 15 nm.
  • the suspending medium may contain spherulites, e.g. having a d- spacing of 3.5 to 5.5, preferably 4 to 5 nm.
  • spherulites e.g. having a d- spacing of 3.5 to 5.5, preferably 4 to 5 nm.
  • the salt is present in total concentrations greater than saturation at ambient temperature.
  • the composition generally comprises suspended solid salt in amounts greater than 1 %, preferably greater than 3%, more preferably greater than 5%, even more preferably greater than 10%, most preferably greater than 15% by weight, based on the weight of the composition. Amounts of suspended solid greater than 30% by weight are usually undesirably viscous. We prefer that the suspended solid should be less than 25% by weight.
  • the suspended solid salt typically has a relatively coarse granular texture, with a mean particle size greater than 100 microns, preferably greater than 300 microns, more preferably greater than 500 microns, still more preferably greater than 550 microns, most preferably greater than 1 mm, but less than 5mm, preferably less than 3mm, most preferably less than 2mm.
  • Preferably at least 10%, more preferably at least 30%, still more preferably at least 50%, most preferably at least 80%, by weight of the particles are greater than 200microns.
  • the total concentration of salt is greater than 50%, preferably greater than 60%, most preferably greater than 65%, but less than 90%, preferably less than 80%, most preferably less than 75%, by weight, based on the total weight of the composition.
  • the product may optionally contain other common ingredients of dishwashing and scouring liquids, such as builders, essential oils, fragrances, pigments, dyes, and antiseptics. Acids and/or bases can also be added in order to obtain pH values between 4 and 11 if grease- or limescale-removing action is desired.
  • Organic solvents on the other hand, preferably are not among the ingredients as they render the system unstable It is particularly preferred that the composition be preservative-free
  • the product may also contain suspended particles other than salt, especially abrasive particles and/or particles comprising active ingredients
  • the structured surfactant may suspend other abrasive particles to achieve an additional scouring action
  • Abrasive particles which can be used within the scope of this invention preferably have no sharp edges or tips in order to protect the surfaces to be scrubbed, preferably they are spherical or ellipsoidal, which additionally gives the product an aesthetically pleasing appearance
  • These additional abrasive particles are preferably water insoluble
  • the additional abrasives are preferably selected from the group consisting of polymers, hard waxes, natural materials, ceramic particles, inorganic substances and mixtures thereof
  • the abrasives used are polymer particles
  • the polymer is preferably selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyester, polycarbonate, polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate and copolymers and mixtures thereof, polystyrene spheres are particularly preferred
  • a further preferred embodiment comprises abrasives which are obtained from natural materials
  • these include, for example, comminuted shells of hazelnuts, almonds, brazil nuts, walnuts, coconuts and further nuts, and also shells of the stones of various types of fruit, for example apricots, peaches, plums, etc , but also optionally comminuted kernels of grapes and various soft fruits such as strawberries, raspberries, blackberries, etc
  • comminuted roots or pieces of bark may also serve as abrasives
  • it is of particular importance that the formation of sharp-edged particles which under some circumstances attack the surface is prevented
  • the usable inorganic compounds include, for example, alkali metal carbonates, alkali metal bicarbonates and alkali metal sulphates, alkali metal borates, alkali metal phosphates, silicon dioxide, crystalline or amorphous alkali metal silicates and sheet silicates, finely crystalline sodium aluminum silicates, aluminum oxides and calcium carbonate
  • the additional abrasives used may be particles having a diameter of from 0.05 to 4 mm. They preferably have a diameter of from 0.3 to 1.5 mm.
  • composition according to the invention may comprise up to 10% by weight of additional abrasives, preferably up to 5% by weight, especially 0.3 to 2% by weight.
  • the structured cleaning composition may also suspend particles comprising active ingredients. It is preferred that these particles are microcapsules, which consist of an active ingredient in the core and a protective shell.
  • the shell may be composed from any material which can dissolve, be perforated or become friable under mechanical stress, upon dilution, due to a change in pH or chemical or electrical potential when the composition is used in a cleaning operation.
  • the active ingredients may be any kind of active substance which can serve as cleaning and/or surface treatment and/or skincare agent in hard surface cleaning compositions, especially manual dishwashing and/or scouring compositions. Examples of such active substances are bleaching agents, enzymes, essential oils and skin care agents such as emollients, vitamins or plant extracts.
  • composition according to the invention can be used as a manual dishwashing detergent.
  • a manual dishwashing method using the inventive composition is also encompassed by this invention.
  • a method of scouring hard surfaces using the inventive composition also falls under the scope of the invention, as the inventive composition can also be put to use as a scouring liquid.
  • Hard surfaces are all common household surfaces with the exception of carpets, upholstery and other textile surfaces, especially kitchen and bathroom floors, worktops, porcelain, tiles and other surfaces.
  • glass, ceramics, metal, porcelain, wood, stone, plastics, laminated floors, tiles and similar surfaces can be considered hard surfaces falling within the boundaries of this specification.
  • the above composition was a stable, spherulitic, structured surfactant system containing about 7% solid salt in suspension.
  • the composition provided a satisfactory scouring action on encrusted pans, but was fully soluble on dilution with water, leaving no residue. No separation was visible after 1 month's storage at laboratory ambient temperature.
  • the above composition was a stable, structured surfactant system containing about 12.7% solid salt in suspension.
  • the composition provided a satisfactory scouring action on encrusted pans, but was fully soluble on dilution with water, leaving no residue. No separation was visible after 1 month's storage at laboratory ambient temperature.
  • the formulation was self- preserving.
  • the small angle X-ray scattering plot of the product featured a sharp peak at 10.2nm wit ha smaller peak at 4.5 nm.
  • the ratio between these features does not correspond to a specific symmetry. It suggests a spherulitic phase having a d-spacing of 10.2.
  • Electron microscopy confirms the presence of spherulites having a diameter in the range 0.4 to 4 ⁇ m.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
PCT/EP2007/000535 2006-01-24 2007-01-23 Structured cleaning compositions WO2007085410A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PL07702946T PL1979460T3 (pl) 2006-01-24 2007-01-23 Strukturyzowane kompozycje czyszczące
EP07702946A EP1979460B1 (de) 2006-01-24 2007-01-23 Strukturierte reinigungszusammensetzungen
AT07702946T ATE450596T1 (de) 2006-01-24 2007-01-23 Strukturierte reinigungszusammensetzungen
DE602007003563T DE602007003563D1 (de) 2006-01-24 2007-01-23 Strukturierte reinigungszusammensetzungen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0601456.7 2006-01-24
GB0601456A GB2434586A (en) 2006-01-24 2006-01-24 Structured liquid abrasive composition

Publications (1)

Publication Number Publication Date
WO2007085410A1 true WO2007085410A1 (en) 2007-08-02

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ID=36060802

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/000535 WO2007085410A1 (en) 2006-01-24 2007-01-23 Structured cleaning compositions

Country Status (7)

Country Link
EP (1) EP1979460B1 (de)
AT (1) ATE450596T1 (de)
DE (1) DE602007003563D1 (de)
ES (1) ES2336377T3 (de)
GB (1) GB2434586A (de)
PL (1) PL1979460T3 (de)
WO (1) WO2007085410A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010097316A1 (de) 2009-02-26 2010-09-02 Henkel Ag & Co. Kgaa Handgeschirrspülmittel
DE102012222186A1 (de) 2012-12-04 2014-06-05 Henkel Ag & Co. Kgaa Strukturiertes Reinigungsmittel mit Fließgrenze

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2008013501A (es) * 2006-04-21 2008-10-29 Colgate Palmolive Co Composicion para visibilidad e impacto de materiales suspendidos.
WO2013016031A1 (en) 2011-07-27 2013-01-31 The Procter & Gamble Company Multiphase liquid detergent composition

Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0151884A2 (de) * 1983-12-22 1985-08-21 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
WO1994005757A1 (en) * 1992-09-09 1994-03-17 Unilever Plc Improvements to hard surface cleaners
US5633223A (en) * 1995-08-30 1997-05-27 Lever Brothers Company, Division Of Conopco, Inc. Heavy duty liquid compositions comprising structuring solids of defined dimension and morphology

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Publication number Priority date Publication date Assignee Title
GB1370377A (en) * 1971-11-15 1974-10-16 Procter & Gamble Ltd Composition and method for cleaning hard surfaces
GB8504862D0 (en) * 1985-02-26 1985-03-27 Unilever Plc Liquid detergent composition
AU611541B2 (en) * 1988-03-21 1991-06-13 Unilever Plc Liquid detergent composition
HUP0300292A3 (en) * 2000-04-05 2006-07-28 Unilever Nv Solid dispersible abrasive compositions and process for preparing cleaning compositions by their use

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0151884A2 (de) * 1983-12-22 1985-08-21 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
WO1994005757A1 (en) * 1992-09-09 1994-03-17 Unilever Plc Improvements to hard surface cleaners
US5633223A (en) * 1995-08-30 1997-05-27 Lever Brothers Company, Division Of Conopco, Inc. Heavy duty liquid compositions comprising structuring solids of defined dimension and morphology

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010097316A1 (de) 2009-02-26 2010-09-02 Henkel Ag & Co. Kgaa Handgeschirrspülmittel
DE102009001186A1 (de) 2009-02-26 2010-09-02 Henkel Ag & Co. Kgaa Handgeschirrspülmittel
US8329631B2 (en) 2009-02-26 2012-12-11 Henkel Ag & Co. Kgaa Hand dishwashing detergent
KR101730190B1 (ko) 2009-02-26 2017-04-25 헨켈 아게 운트 코. 카게아아 손 식기 세척 세제
DE102012222186A1 (de) 2012-12-04 2014-06-05 Henkel Ag & Co. Kgaa Strukturiertes Reinigungsmittel mit Fließgrenze
WO2014086634A1 (de) 2012-12-04 2014-06-12 Henkel Ag & Co. Kgaa STRUKTURIERTES REINIGUNGSMITTEL MIT FLIEßGRENZE

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DE602007003563D1 (de) 2010-01-14
ES2336377T3 (es) 2010-04-12
GB2434586A (en) 2007-08-01
GB0601456D0 (en) 2006-03-08
ATE450596T1 (de) 2009-12-15
EP1979460B1 (de) 2009-12-02
PL1979460T3 (pl) 2010-07-30
EP1979460A1 (de) 2008-10-15

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