EP0702714B1 - Waschmittelzusammensetzung - Google Patents

Waschmittelzusammensetzung Download PDF

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Publication number
EP0702714B1
EP0702714B1 EP94917684A EP94917684A EP0702714B1 EP 0702714 B1 EP0702714 B1 EP 0702714B1 EP 94917684 A EP94917684 A EP 94917684A EP 94917684 A EP94917684 A EP 94917684A EP 0702714 B1 EP0702714 B1 EP 0702714B1
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EP
European Patent Office
Prior art keywords
weight
aqueous liquid
composition
droplets
viscosity
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EP94917684A
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English (en)
French (fr)
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EP0702714A1 (de
EP0702714B2 (de
Inventor
Peter Robert Garrett
Adam Jan Kowalski
Philippus Cornelis Van Der Hoeven
Andrew John Prescott
John William H. Yorke
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP94917684A priority Critical patent/EP0702714B2/de
Publication of EP0702714A1 publication Critical patent/EP0702714A1/de
Publication of EP0702714B1 publication Critical patent/EP0702714B1/de
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the present invention relates to substantially non-aqueous liquid cleaning products, especially detergent compositions and to a method of preparing a non-aqueous liquid.
  • Non-aqueous liquids are those containing little or no water, usually less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight of the composition.
  • Non-aqueous liquid detergent compositions are known in the art and have been described in quite a number of patent publications, e.g. in US-A-4,316,812, US-A-4,874,537 and EP-A-0,484,095.
  • Non-aqueous liquids provide a way of concentrating liquid detergents without giving in on washing performance.
  • Non-aqueous liquid detergent compositions normally comprise a non-aqueous liquid phase having incorporated therein as dispersion, solution or combination thereof, the usual detergent components and adjuncts depending on the purpose of use, primarily surfactants and builders.
  • the liquid phase often comprises a nonionic surfactant as major component, which apart from acting as carrier liquid for the detergent components, usually and preferably also has detergent-active properties, thereby acting wholly or in part as the surfactant ingredient.
  • the liquid phase may comprise a nonionic surfactant and/or surfactant mixtures, such as mixtures of C13-C15 alcohols with an average of 3 ethoxy groups and C13-C15 alcohols with an average of 7 ethoxy groups and liquid phases as described in GB-A-1,462,134, WO 91/12313, WO 91/14765 and EP-A-0,510,762.
  • EP-A-510,762 discloses non-aqueous liquids comprising solid dispersed particles and a polymer material to overcome physical stability.
  • WO 93/24603, WO 94/01525 and WO 94/01524 disclose non-aqueous liquids with DB100® a low viscosity silicone polymer material having a viscosity of 3,000 mPa.s at 21s -1 at 25°C.
  • EP-A-515,418 and EP-A-515,435 disclose the use of silicone material in non-aqueous liquids.
  • Non-aqueous liquids of the prior art comprising silicone polymer material may suffer from sedimentation, clear layer formation or poor dispersibility. Surprisingly we have found that one or more of these disadvantages can be overcome.
  • the invention provides a non-aqueous liquid cleaning composition
  • a non-aqueous liquid cleaning composition comprising a non-aqueous liquid phase, from 1 to 90% by weight of solid particles and dispersed droplets comprising silicone polymer and hydrophobic particles, said droplets having a high viscosity.
  • the viscosity of the droplets is of from 5,000 to 60,000 mPa.s at 21s -1 at 25°C.
  • the dispersed droplets according to the invention comprise silicone polymer and hydrophobic particles and have a viscosity of at least 5,000 mPa.s at 21s -1 at 25°C, preferably at least 10,000, more preferably at least 15,000, most preferably at least 20,000.
  • the viscosity of the dispersed droplets is at most 60,000 mPa.s at 21s -1 at 25°C, preferably at most 50,000 mPa.s at 21s -1 at 25°C, more preferably at most 40,000 mPa.s, most preferably at most 35,000 mPa.s.
  • the droplets may be of a viscosity of more than 3,000 mPa.s at 21s -1 at 25°C.
  • the dispersed droplets also comprise alkoxypoly-dimethyl stabilising agents, e.g. DC-198 (ex Dow Corning), which is believed to be able to further improve the properties of the non-aqueous liquids as to sedimentation, clear layer formation and/or poor dispersibility.
  • alkoxypoly-dimethyl stabilising agents e.g. DC-198 (ex Dow Corning)
  • DC-198 Ex Dow Corning
  • the weight ratio of the silicone polymer to the hydrophobic particles is from 70:30 to 99:1, preferably from 80:20 to 98:2, more preferably from 90:10 to 95:5.
  • the dispersed droplets are present in amounts of from 0.1 to 5.0% by weight of the composition, preferably 0.3 to 3.0% by weight, preferably from 0.5 to 2.0% by weight.
  • the particle size of the droplets is from 0.5-50 ⁇ m (in terms of D(1.0), being the number mean diameter as described by M. Alderliesten, Anal. Proc. Vol. 21, May, 1984, 167-172, as can be microscopically determined using a fluorescence imagin technique; images can be digitised so that droplet areas and diameters can be measured and counted using image analysis), preferably from 1-30 ⁇ m.
  • the silicone polymer comprises an organosiloxane polymer, more preferably a polydimethylsiloxane.
  • the polymer may also consist of a mixture of polymers, e.g. a mixture of a polymer that has a high viscosity (due to branching or to a high molecular weight) per se, e.g. more than 5.000 mPa.s at 21s-1 at 25°C, and a polymer that has a low viscosity per se, e.g. say lower than 5.000 mPa.s at 21 s-1 at 25°C.
  • An example of a high viscosity polymer is polydimethylsilixone of a weight average molecular weight of 137,000 that has a viscosity of 60,000 mPa.s at 21 s-1 at 25°C.
  • DB100® (ex Dow Corning) comprises a polydimethylsiloxane with a weight average molecular weight of 37,000. These two polymers could for example be mixed in a 50/50 w/w ratio.
  • the hydrophobic particles are selected from hydrophobic silica, hydrophobed metal oxide (e.g. aluminium, titanium and magnesium), ⁇ -w dialkylamide alkane, polyvalent metal salt of an alkyl phosphoric acid and polyvalent metal salt of an alkyl carboxylic acid.
  • hydrophobic silica hydrophobed metal oxide (e.g. aluminium, titanium and magnesium), ⁇ -w dialkylamide alkane, polyvalent metal salt of an alkyl phosphoric acid and polyvalent metal salt of an alkyl carboxylic acid.
  • hydrophobic silica hydrophobic silica
  • the particle size of the hydrophobic particles is smaller than 10 ⁇ m, more preferably smaller than 1 ⁇ m.
  • the non-aqueous liquid phase of the compositions according to the present invention may comprise surfactant and other liquid materials, such as liquid bleach precursors solvents and deflocculant material.
  • the non-aqueous liquid phase will generally be present in amounts of at least 10%, preferably 20%, more preferably 30% most prefereably 35% by weight of the non-aqueous liquid composition and generally at most 90%, preferably 70%, more preferably 60% and most preferably 50% by weight of the composition.
  • non-aqueous liquid detergent products have a free water content of less than 5% by weight, preferably less than 2% by weight, more preferably substantially nil.
  • liquid phase of non-aqueous liquid detergent compositions often and preferably comprises a liquid nonionic surfactant as major component.
  • Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilizing polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof), preferably having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
  • alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms
  • dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms
  • primary, secondary or tertiary aliphatic alcohols or alkyl-capped derivatives thereof
  • fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
  • the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
  • the polyalkoxylene moiety preferably consists of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups.
  • particularly preferred are those described in EP-A-225,654, especially for use as all or part of the liquid phase.
  • ethoxylated nonionics which are the condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with from 3 to 11 moles of ethylene oxide.
  • condensation products of C 11-13 alcohols with (say) 3 or 7 moles of ethylene oxide may be used as the sole nonionic surfactants or in combination with those of the described in the last-mentioned European specification, especially as all or part of the liquid phase.
  • Suitable nonionics comprise the alkyl polysaccharides (polyglycosides/oligosaccharides) such as described in any of specifications US 3,640,998; US 3,346,558; US 4,223,129; EP-A-92,355; EP-A-99,183; EP 70,074, '75, '76, '77; EP 75,994, '95, '96.
  • nonionic surfactants are quite effective at oily and greasy soil removal (e.g. sebum), particulate soils, such as clay soils and the like, may be more effectively removed by anionic surfactants.
  • anionic surfactants may be more effectively removed by anionic surfactants.
  • composition within the invention normally comprise blends of different surfactant types.
  • Typical blends include those where the primary surfactants comprise a nonionic and/or non-alkoxylated anionic and/or alkoxylated anionic surfactant.
  • Cationic, zwitterionic and amphoteric surfactants may also be present usually in minor amounts as desirable.
  • liquid bleach precursors such as for example glyceroltriacetate, solvent materials for example ethanol and dodecanol and deflocculant material, as described in EP-A-266199 (Unilever), e.g. deflocculants selected from Bronsted acids and Lewis acids.
  • the level of liquid bleach precursors is preferably 0-20% by weight, more preferably 1-25%, most preferably 2-10%.
  • the level of solvents other than nonionic surfactants is preferably from 0-20%, most preferably 0-15%, more preferably 0-10% by weight.
  • compositions may comprise a solid dispersed phase.
  • the solid phase may be present in amounts as low as 1% by weight, however at least 10% is preferred and more preferably 20%, most preferably 30% by weight of the composition and preferably at most 90%, more preferably 80% and most preferably 70% and particularly preferred 60% by weight of the composition.
  • the solid phase may comprise one or more ingredients selected from bleach materials, solid bleach activators, builders, abrasives, fabric softening material, enzymes and minor ingredients such as fluorescers, which particles size may not necessarily be the same as that of the biopolymer material.
  • the particle size of the solid phase defined in terms of D(3,2) will be less than 100 ⁇ m, preferably not more than 30 ⁇ m, more preferably up to 10 ⁇ m.
  • the D(3,2) of the solid phase is more than 0.1 ⁇ m, preferably at least 1 ⁇ m and more preferably at least 2.5 ⁇ m.
  • references to the D(3,2) average particle diameter refer to the D(3,2) particle size, which is the average surface weighted, volume/weight mean diameter calculated as described by M. Alderliesten, Anal. Proc. Vol. 21, May, 1984, 167-172.
  • the particle size can for example be determined by using a Malvern Mastersizer or a Coulter LS 130, as appropriate.
  • Bleaches include the halogen, particularly chlorine bleaches such as are provided in the form of alkalimetal hypohalites, e.g. hypochlorites.
  • the oxygen bleaches are preferred, for example in the form of an inorganic persalt, preferably with a bleach precursor or as a peroxy acid compound.
  • the ratio by weight of the peroxybleach compound to the activator is from about 20:1 to about 1:1, preferably from about 10:1 to about 1.5:1.
  • the preferred level of the peroxybleach compound in the composition is from 0-30% by weight, more preferably 2-20%, most preferably 4-15%, while the preferred level of the activator is from 0-20% by weight, more preferably 1-10%, most preferably 2-8%.
  • Suitable peroxybleach compounds are alkalimetal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate and sodium percarbonate are preferred.
  • a preferred bleach activator is TAED.
  • a further preferred class of bleach activators is that of hydrophobic peroxy acid bleach precursors, such as sodium nonanoyloxy benzene sulphonate and sodium -3,5,5- trimethyl hexanoyloxy benzene sulphonate. These activators are deemed to cause less (local) dye damage.
  • a bleach catalyst such as a transition metal compound or complex and the sulphonimines as described in US Patents 5,041,232 and 5,047,163, which may be used instead of or together with said bleach activators.
  • a specifically preferred bleach catalyst for use herein is a manganese complex of formula [Mn IV 2 ( ⁇ -O) 3 (Me-MeTACN) 2 ](PF 6 ) 2 as described in EP-A-0,458,397 and EP-A-0,458,398.
  • Another preferred bleach catalyst is a manganese complex as described in EP-A-549,272 (co-pending GB patent application 9127060.3).
  • the ligand and a manganese source can be separately added such as is described in EP-A-549,271 (co-pending GB application 9204706.7).
  • a stabiliser for the bleach or bleach system for example hydroxyethylidene-1,1-diphosphonic acid, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonate or salt thereof, such as the Dequest@ range hereinbefore described.
  • These stabilisers can be used in acid or salt form, such as the calcium, magnesium, zinc or aluminium salt form.
  • the stabiliser may be present at a level of up to about 1% by weight, preferably between about 0.1% and about 0.5% by weight.
  • the inorganic builders comprise the various phosphate-, carbonate-, silicate-, borate- and aluminosilicates-type materials, particularly the alkali-metal salt forms. Mixtures of these may also be used.
  • Examples of phosphorus-containing 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.
  • non-phosphorus-containing inorganic builders when present, include water-soluble alkali metal carbonates, bicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates.
  • specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates such as sodiummetasilicate and zeolites.
  • suitable organic builders include the higher molecular weight polymers and co-polymers known to have builder properties, for example appropriate polyacrylic acid, polymaleic acid and polyacrylic/polymaleic acid co-polymers and their salts, such as those sold by BASF under the Sokalan® Trade Mark. Polyacrylates or their derivatives may also be useful for their anti-ashing properties.
  • the level of builder materials is from 5-50% by weight of the composition, more preferably 10-40%, most preferably 15-35%.
  • ingredients comprise those remaining ingredients which may be used in liquid cleaning products, such as fabric conditioning agents, enzymes, perfumes (including deoperfumes), fluorescent agent, micro-biocides, colouring agents, soil-suspending agents (anti-redeposition agent), corrosion inhibitors, enzyme stabilising agents, and lather depressants.
  • fabric conditioning agents such as fabric conditioning agents, enzymes, perfumes (including deoperfumes), fluorescent agent, micro-biocides, colouring agents, soil-suspending agents (anti-redeposition agent), corrosion inhibitors, enzyme stabilising agents, and lather depressants.
  • fabric conditioning agents which may be used, either in fabric washing liquids or in rinse conditioners, are fabric softening materials such as fabric softening clays, quaternary ammonium salts, imidazolinium salts, fatty amines and cellulases.
  • the total amount of the fluorescent agent or agents used in a detergent composition is generally from 0.02-2% by weight.
  • anti-redepostion agents When it is desired to include anti-redepostion agents in the liquid cleaning products, the amount thereof is normally from about 0.1% to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the total liquid composition.
  • Preferred anti-redeposition agents include carboxy derivatives of sugars and celluloses, e.g. sodium carboxymethyl cellulose, anionic poly-electrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • Composition in accordance with the present invention may be used for several detergency purposes, for example the cleaning of surfaces and the washing of fabrics.
  • an aqueous liquor containing 0.1 to 10 %, more preferably 0.2 to 2%, of the non-aqueous detergent composition of the invention is used.
  • the non-aqueous liquid During manufacture of the non-aqueous liquid, it is preferred that all raw materials should be dry and (in the case of hydratable salts) in a low hydration state, e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • a low hydration state e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • the dry, substantially anhydrous solids are blended with the liquid phase in a dry vessel. If deflocculant materials are used, these should preferably -at least partly- be mixed with the liquid phase, prior to the addition of the solids. In order to minimise the rate of sedimentation of the solids, this blend is passed through a grinding mill or a combination of mills, e.g.
  • a colloid mill a corundum disc mill, a horizontal or vertical agitated ball mill.
  • a preferred combination of such mills is a colloid mill followed by a horizontal ball mill since these can be operated under the conditions required to provide a narrow size distribution in the final product.
  • particulate material already having the desired particle size need not be subjected to this procedure and if desired, can be incorporated during a later stage of processing.
  • the particles comprising carrier material and dye material associated thereto, according to the invention can be prepared separately, as discussed above, whereafter they are dispersed in the non-aqueous phase of the non-aqueous cleaning product, e.g. by mixing using high shear or using a mill.
  • the D(3,2) particle size is of from 0.1 ⁇ m to 2000 ⁇ m in the non-aqueous phase.
  • the non-aqueous liquid of the Example showed good properties with regard to sedimentation and dispersibility.
  • Example 1 The formulation of Example 1 (without enzymes and perfume) was prepared with the following chances:
  • compositions were compared in a model experiment in which clear layer formation was measured with stoppered glass 100 cm 3 measuring cylinders containing 80cm 3 of the product. These were suspended vertically in a glass-sided water bath and thermostatted at 37°C. Compositions A, 1, 2 and 3 were stored for 12 weeks and compositions B and 4 were stored for 4 weeks. The height in centimeters of the liquid meniscus and the clear layer separation layer was measured in dulpo using a cathetometer (clear layer separation of Composition 2 was only determined once).
  • compositions 1, 2, 4 and in particular 3 have a lower clear layer separation than of the comparative compositions A and B.
  • a high viscosity silicone polymer composition can be made by blending a conventional silicone polymer with a high viscosity fluid.
  • the solid content of the composition e.g. hydrophobic particles, can be adjusted.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Liquid Crystal (AREA)

Claims (8)

  1. Nichtwässeriges flüssiges Reinigungsmittel, umfassend eine nichtwässerige flüssige Phase, 1 bis 90 Gewichtsprozent Feststoffteilchen und dispergierte Tröpfchen, umfassend Siliconpolymer und hydrophobe Teilchen, wobei die Tröpfchen eine Viskosität von mehr als 3000 mPa·s bei 21 s-1 bei 25°C aufweisen.
  2. Mittel nach Anspruch 1, wobei die Tröpfchen eine Viskosität von 5000 bis 60000 mPa·s bei 21 s-1 bei 25°C aufweisen.
  3. Mittel nach Ansprüchen 1-2, wobei die hydrophoben Teilchen hydrophobes Siliciumdioxid sind.
  4. Mittel nach Ansprüchen 1-3, wobei das Siliconpolymer Polydimethylsiloxan ist.
  5. Mittel nach Ansprüchen 1-4, wobei die Tröpfchen in einer Menge von 0,1 bis 5,0 Gewichtsprozent des Mittels vorliegen.
  6. Mittel nach Ansprüchen 1-5, wobei das Gewichtsverhältnis des Siliconpolymers zu den hydrophoben Teilchen 70:30 bis 99:1 ist.
  7. Mittel nach Ansprüchen 1-6, wobei das Polymer ein Gemisch von Polydimethylsiloxan hoher Viskosität und Polydimethylsiloxan geringer Viskosität umfaßt.
  8. Verfahren zur Herstellung eines nichtwässerigen flüssigen Reinigungsmittels, umfassend eine nichtwässerige flüssige Phase, 1 bis 90 Gewichtsprozent Feststoffteilchen und dispergierte Tröpfchen, wobei die Tröpfchen Siliconpolymer und hydrophobe Teilchen umfassen und eine Viskosität von mehr als 3000 mPa·s bei 21 s-1 bei 25°C aufweisen, wobei die Feststoffteilchen mit der nichtwässerigen flüssigen Phase vermischt werden und gegebenenfalls vorher, während oder nach dem Mischen mit der nichtwässerigen flüssigen Phase vermahlen werden, wonach die Tröpfchen in der nichtwässerigen flüssigen Phase dispergiert werden.
EP94917684A 1993-06-11 1994-06-01 Waschmittelzusammensetzung Expired - Lifetime EP0702714B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP94917684A EP0702714B2 (de) 1993-06-11 1994-06-01 Waschmittelzusammensetzung

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP93304581 1993-06-11
EP93304581 1993-06-11
EP94917684A EP0702714B2 (de) 1993-06-11 1994-06-01 Waschmittelzusammensetzung
PCT/EP1994/001791 WO1994029427A1 (en) 1993-06-11 1994-06-01 Detergent composition

Publications (3)

Publication Number Publication Date
EP0702714A1 EP0702714A1 (de) 1996-03-27
EP0702714B1 true EP0702714B1 (de) 1997-08-13
EP0702714B2 EP0702714B2 (de) 2001-02-21

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EP94917684A Expired - Lifetime EP0702714B2 (de) 1993-06-11 1994-06-01 Waschmittelzusammensetzung

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EP (1) EP0702714B2 (de)
JP (1) JPH08511048A (de)
AU (1) AU682044B2 (de)
BR (1) BR9406773A (de)
DE (1) DE69404988T3 (de)
ES (1) ES2106546T5 (de)
WO (1) WO1994029427A1 (de)
ZA (1) ZA944063B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1595939B1 (de) * 2004-05-11 2007-06-13 The Procter & Gamble Company Portionierte Wasch- und Reinigungsmittelzubereitung enthaltend Silikonöl
ATE364678T1 (de) * 2004-05-11 2007-07-15 Procter & Gamble Portionierte wasch- und reinigungsmittelzubereitung enthaltend silikonöl
US8635732B2 (en) * 2006-09-15 2014-01-28 Reckitt Benckiser Llc Cleaning article comprising melamine foam sponge
US9376648B2 (en) * 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075118A (en) † 1975-10-14 1978-02-21 The Procter & Gamble Company Liquid detergent compositions containing a self-emulsified silicone suds controlling agent
US4395352A (en) † 1978-06-29 1983-07-26 Union Carbide Corporation High efficiency antifoam compositions and process for reducing foaming
GB2237813A (en) * 1989-10-31 1991-05-15 Unilever Plc Liquid detergent
WO1991012312A1 (en) * 1990-02-16 1991-08-22 Unilever N.V. Liquid cleaning products
FI924296A7 (fi) * 1990-03-28 1992-09-25 Unilever Nv Nestemäiset puhdistustuotteet
GB9108665D0 (en) * 1991-04-23 1991-06-12 Unilever Plc Liquid cleaning products
GB9127178D0 (en) † 1991-12-21 1992-02-19 Dow Corning Sa Suds-controlling composition for aqueous compositions

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Publication number Publication date
ZA944063B (en) 1995-12-11
DE69404988T3 (de) 2001-05-23
ES2106546T5 (es) 2001-05-16
DE69404988D1 (de) 1997-09-18
AU682044B2 (en) 1997-09-18
ES2106546T3 (es) 1997-11-01
BR9406773A (pt) 1996-02-27
JPH08511048A (ja) 1996-11-19
EP0702714A1 (de) 1996-03-27
DE69404988T2 (de) 1998-01-22
EP0702714B2 (de) 2001-02-21
AU6930994A (en) 1995-01-03
WO1994029427A1 (en) 1994-12-22

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