WO1996024656A1 - Composition detergente contenant de la zeolithe map et mineral d'argile - Google Patents

Composition detergente contenant de la zeolithe map et mineral d'argile Download PDF

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Publication number
WO1996024656A1
WO1996024656A1 PCT/US1996/001031 US9601031W WO9624656A1 WO 1996024656 A1 WO1996024656 A1 WO 1996024656A1 US 9601031 W US9601031 W US 9601031W WO 9624656 A1 WO9624656 A1 WO 9624656A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
composition according
zeolite map
clay
clay mineral
Prior art date
Application number
PCT/US1996/001031
Other languages
English (en)
Inventor
Jonathan Richard Clare
Michael Alan John Moss
Original Assignee
The Procter & Gamble Company
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 The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP96903677A priority Critical patent/EP0808356A4/fr
Publication of WO1996024656A1 publication Critical patent/WO1996024656A1/fr

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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • 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
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

  • the present invention relates to a detergent composition and, in particular, to improvements in the detergency performance of laundry detergent compositions comprising zeolites as sequestering agents for water hardness.
  • Detergent compositions for fabric washing conventionally contain detergency builders which lower the concentration of calcium and magnesium water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soft water.
  • inorganic phosphates such as sodium tripolyphosphate
  • alkali metal aluminosilicate ion-exchangers particularly crystalline sodium aluminosilicate zeolite A
  • crystalline sodium aluminosilicate zeolite A have been proposed as replacements for the inorganic phosphates.
  • EP 21 491 A (Procter & Gamble) discloses detergent compositions containing a building system which includes zeolite A, X or P (B) or a mixture thereof.
  • EP 384070 A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes its use as a detergency builder. To date, however, zeolite A is the preferred aluminosilicate detergency builder in commercially available products.
  • zeolite MAP particularly when present as small particles, such as those having a particle size of less than 1 ⁇ m, may abrade coloured patterns from printed fabrics.
  • This problem of coloured pattern abrasion can surprisingly be solved by the inclusion of a clay mineral component together with the zeolite MAP component.
  • the present invention provides a detergent composition comprising:
  • a surfactant selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof;
  • a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP);
  • an additive component for a detergent comprising zeolite MAP and a clay mineral.
  • Such an additive may optionally also include a clay flocculating agent.
  • the detergent composition according to the invention contains, as an essential ingredient, one or more surfactants selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof.
  • surfactants are well known and described in the literature, for example, in "Surface- Active Agents and Detergents", Volumes I and II by Schwartz, Perry and Berch.
  • alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of Cg-C ⁇ ; C12-C15 primary alkyl sulphates; olefin sulphonates; alkyl xylene sulphonates and their ethoxylated analogues containing from 0.25 to 6 moles of ethylene oxide per mole of alkyl sulphate; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of from 3 to 10 alkylene oxide groups per molecule.
  • Preferred alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule, for example less than 4 alkylene oxide groups per molecule e.g. 3.5 and usefully 3 alkylene oxide groups per molecule or less and usefully also greater than 0.5, or 1, or 2 alkylene oxide groups per molecule.
  • Alkylene oxide adducts of fatty alcohols useful as hydrophobic alkoxylated nonionic surfactants in the present invention can suitably be chosen from those of the general formula:
  • R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is preferably from about 0.5 to about 3.5 and n is 2 or 3.
  • Preferred nonionic surfactants include primary C11-C15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight.
  • a particularly preferred aliphatic alcohol ethoxylate is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
  • suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • composition comprises an aliphatic alcohol ethoxylate as the hydrophobic nonionic surfactant it is present in an amount of at least 1 wt. %, preferably from 1 wt. % to 10 wt. % and more preferably 1 wt. % to 6 wt. % of the composition.
  • the detergent composition of the invention generally contains a detergent surfactant in a range of from 1 to 60 wt. % , preferably 4 to 40 wt. % and most preferably from 7 to 25 wt. % of the composition.
  • the detergency builder system is based on zeolite MAP, optionally in conjunction with one or more supplementary builders.
  • the amount of zeolite MAP employed may range, for example, from 1 to 60 wt. %, more preferably from 10 to 40 wt. % .
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • Zeolite P having a Si:Al ratio of 1.33 or less may be prepared by the following steps:
  • Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel).
  • the calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
  • zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
  • the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt. % .
  • a preferred zeolite MAP for use according to the present invention has a d5o of from 1.0 to 5.0 micrometres, for example 2.25 to 5 micrometres, more particularly 2.75 to 5 micrometres.
  • the quantity "d5o" indicates that 50 wt. % of the particles have a diameter smaller than that figure.
  • the zeolite MAP detergent builder is in powder form.
  • the material may be granulated by conventional techniques such as spray drying or by a non- tower method such as an agglomeration method to form larger particles.
  • the detergent composition according to the invention comprises, as an essential component, a clay mineral.
  • the clay mineral is preferably present in the detergent composition according to the invention in a proportion of from 0.05 % to 40% , more preferably from 0.5% to 30%, most preferably from 2% to 20% by weight of the composition.
  • the weight ratio of Zeolite MAP to clay mineral is preferably from 1:10 to 10:1 , more preferably from 1 :5 to 5:1 , most preferably from 1 :3 to 3:1.
  • the clay mineral is preferably a smectite clay.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A-299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company.
  • smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice.
  • Typical smectite clay compounds include the compounds having the general formula Al2(Si2 ⁇ 5)2(OH)2-nH2 ⁇ and the compounds having the general formula M 3(Si2 ⁇ 5)2(OH)2.nH2 ⁇ . Smectite clays tend to adopt an expandable three layer structure.
  • Suitable smectite clays include those selected from the classes of the montmorillonites, hectorites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure.
  • Sodium or calcium montmorillonite are particularly preferred.
  • Suitable smectite clays are sold by various suppliers including English China Clays, Laviosa, Georgia Kaoli and Colin Stewart Minerals.
  • Clays for use herein preferably have a largest particle dimension of from 0.01 ⁇ m to 800 ⁇ m, more preferably from 1 ⁇ m to 400 ⁇ m, most preferably from 5 ⁇ m to 200 ⁇ m.
  • Particles of the clay mineral may be included as components of agglomerate particles containing other detergent compounds.
  • the term "largest particle dimension" of the clay mineral refers to the largest dimension of the clay mineral component as such, and not to the agglomerated particle as a whole.
  • Substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups ca typically take place within the crystal lattice structure of the smectite clays.
  • a clay may be chosen for its ability to preferentially absorb one cation type, such ability being assessed by measurements of relative ion exchange capacity.
  • the smectite clays suitable herein typically have a cation exchange capacity of at least 50 meq/lOOg.
  • U.S. Patent No. 3,954,632 describes a method for measurement of cation exchange capacity.
  • the crystal lattice structure of the clay mineral may have, in a preferred embodiment, a cationic fabric softening agent substituted therein.
  • a cationic fabric softening agent substituted therein Such substituted clays have been termed 'hydrophobically activated' clays.
  • the cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1 :200 to 1 : 10, preferably from 1 : 100 to 1 :20.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 Oi l 340.
  • a preferred commercially available "hydrophobically activated" clay is a bentonite clay containing approximately 40% by weight of a dimethyl ditallow quaternary ammonium salt sold under the tradename Claytone EM by English China Clays International.
  • compositions of the invention preferably contain a clay flocculating agent, preferably present at a level of from 0.005 % to 10% , more preferably from 0.05% to 5% , most preferably from 0.1 % to 2% by weight of the composition.
  • the weight ratio of clay mineral to clay flocculating agent is preferably from 300: 1 to 1 : 1 , more preferably from 80: 1 to 10: 1 , most preferably from 60: 1 to 20: 1.
  • the clay flocculating agent functions such as to bring together the particles of clay in the wash solution and hence to aid their deposition onto the surface of the fabrics in the wash. This functional requirement is hence different from that of clay dispersant compounds which are commonly added to laundry detergent compositions to aid the removal of clay soils from fabrics and enable their dispersion within the wash solution.
  • Preferred as clay flocculating agents herein are organic polymeric materials having an average molecular weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.
  • Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are preferred.
  • EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.
  • Inorganic clay flocculating agents are also suitable herein, typical examples of which include lime and alum.
  • the detergency builder can be zeolite MAP alone or a combination of zeolite MAP with an organic or inorganic cobuilder.
  • Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form.
  • Suitable inorganic cobuilders include carbonates and amorphous and crystalline lamellar sodium silicates. Suitable crystalline lamellar silicates have the composition:
  • M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • the synthetic material is commercially available from Hoechst AG as -Na2 Si2 ⁇ 5 (SKS6) and is described in US Patent No. 4664830.
  • the total amount of detergency builder in the composition preferably ranges from 1 to 80 wt.% , more preferably from 5 to 60 wt% and most preferably from 10 to 45 wt. %.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • the bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a precursor.
  • Suitable persalts include sodium perborate monohydrate and tetrahydrate, with sodium percarbonate being most preferred.
  • Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); and peroxybenzoic acid precursors such as sodium benzoyloxybenzene sulphonate (BOBS) and benzoyl caprolactam (BZCL).
  • Other materials which may be present in the detergent composition of the invention include, for example, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, fabric softening agents, pigments, perfumes and coloured speckles.
  • the detergent compositons of the invention are in one preferred aspect in solid form.
  • Preferred forms include granules, powders and tablets. Granular compositions are especially preferred.
  • the detergent compositions of the invention may be prepared by any suitable method, for example by any tower (spray-drying) or non- tower process, including agglomeration.
  • a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).
  • the zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower.
  • the lamellar silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
  • granular detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
  • the granular detergent compositions of the invention may be prepared to any suitable bulk density.
  • the compositions preferably have a bulk density of at least 400 g/1 preferably at least 550 g/1, most preferably at least 700 g/1 and, with particular preference at least 800 g/1.
  • powders of high bulk density for example, of 700 g/1 or above.
  • Such powders may be prepared either by post-tower densification of spray- dried powder, or by wholly non-tower methods such as dry mixing and agglomeration; in both cases a high-speed mixer/granulator may advantageously be used.
  • Processes using high-speed mixer/granulators are disclosed, for example, in EP340 013A, EP 367 339A, EP 390 251 A and EP 420 317A (Unilever).
  • the detergent composition according to the invention generally has a pH (as measured with a 1 % solution in distilled water) of above 9.0, preferably above 9.5 and with particular preference about 10.
  • the invention provides use of a composition comprising zeolite MAP and clay, optionally in combination with a clay flocculating agent as an additive for a detergent composition.
  • compositions according to the present invention are presented in the following Examples.
  • PEG polyethylene glycol
  • Lipase Lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S with an activity of 165 KLU/g
  • Clay Calcium montmorillonite Granular Suds 12% Silicone/silica, 18% stearyl alcohol, 70%

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)

Abstract

On décrit une composition détergente contenant un tensioactif, un adjuvant pour améliorer la détergence, comprenant de la zéolithe P selon un rapport silicium sur aluminium ne dépassant pas 1.33 (zéolithe MAP) et un minéral d'argile, ainsi qu'éventuellement un agent capable de faire floculer l'argile. La composition permet de mieux conserver les motifs en couleur de tissus.
PCT/US1996/001031 1995-02-07 1996-01-24 Composition detergente contenant de la zeolithe map et mineral d'argile WO1996024656A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96903677A EP0808356A4 (fr) 1995-02-07 1996-01-24 Composition detergente contenant de la zeolithe map et mineral d'argile

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9502321A GB2297977A (en) 1995-02-07 1995-02-07 Detergent composition containing Zeolite MAP
GB9502321.4 1995-02-07

Publications (1)

Publication Number Publication Date
WO1996024656A1 true WO1996024656A1 (fr) 1996-08-15

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ID=10769183

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/001031 WO1996024656A1 (fr) 1995-02-07 1996-01-24 Composition detergente contenant de la zeolithe map et mineral d'argile

Country Status (3)

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EP (1) EP0808356A4 (fr)
GB (1) GB2297977A (fr)
WO (1) WO1996024656A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436889B1 (en) 1999-07-30 2002-08-20 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6881717B1 (en) 1999-04-01 2005-04-19 The Procter & Gamble Company Fabric softening component
GB2348435A (en) * 1999-04-01 2000-10-04 Procter & Gamble Softening compositions
EP1048721A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes
EP1561804B1 (fr) * 2004-02-03 2008-08-13 The Procter & Gamble Company Composition pour le linge comprenant de l'argile et un polydiméthylsiloxane
ES2340276T3 (es) * 2004-02-03 2010-06-01 THE PROCTER & GAMBLE COMPANY Composicion detergente para lavar la ropa, solida en particulas, que comprende arcilla y polidimetilsiloxano.

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US5259981A (en) * 1992-01-17 1993-11-09 Lever Brothers Company Detergent compositions
US5409627A (en) * 1993-03-18 1995-04-25 Lever Brothers Company, Division Of Conopco, Inc. Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst
US5431846A (en) * 1993-05-20 1995-07-11 Lever Brothers Company, Division Of Conopco, Inc. Copolymers and detergent compositions containing them

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CA2001927C (fr) * 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
DE4009618A1 (de) * 1990-03-26 1991-10-02 Henkel Kgaa Spruehgetrocknetes, avivierend wirkendes waschmitteladditiv
GB9008462D0 (en) * 1990-04-12 1990-06-13 Ecc Int Ltd Granules for detergent compositions
CA2083331C (fr) * 1991-11-26 1998-08-11 Johannes H. M. Akkermans Compositions pour detergent
WO1994000545A1 (fr) * 1992-06-25 1994-01-06 Unilever N.V. Composition pour le lavage en machine de la vaisselle
AU669900B2 (en) * 1992-07-20 1996-06-27 Colgate-Palmolive Company, The Stabilized built aqueous liquid softergent compositions
EP0627484A1 (fr) * 1993-06-02 1994-12-07 The Procter & Gamble Company Agglomérats d'argiles revêtus des matériaux particulaires finement divisés

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Publication number Priority date Publication date Assignee Title
US5259981A (en) * 1992-01-17 1993-11-09 Lever Brothers Company Detergent compositions
US5409627A (en) * 1993-03-18 1995-04-25 Lever Brothers Company, Division Of Conopco, Inc. Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst
US5431846A (en) * 1993-05-20 1995-07-11 Lever Brothers Company, Division Of Conopco, Inc. Copolymers and detergent compositions containing them

Non-Patent Citations (1)

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Title
See also references of EP0808356A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436889B1 (en) 1999-07-30 2002-08-20 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions

Also Published As

Publication number Publication date
GB9502321D0 (en) 1995-03-29
EP0808356A1 (fr) 1997-11-26
GB2297977A (en) 1996-08-21
EP0808356A4 (fr) 1999-12-01

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