EP0354010A2 - Flüssige Reinigungsmittelzusammensetzungen - Google Patents

Flüssige Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0354010A2
EP0354010A2 EP89307841A EP89307841A EP0354010A2 EP 0354010 A2 EP0354010 A2 EP 0354010A2 EP 89307841 A EP89307841 A EP 89307841A EP 89307841 A EP89307841 A EP 89307841A EP 0354010 A2 EP0354010 A2 EP 0354010A2
Authority
EP
European Patent Office
Prior art keywords
composition according
sodium
surfactant
electrolyte
foregoing
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.)
Withdrawn
Application number
EP89307841A
Other languages
English (en)
French (fr)
Other versions
EP0354010A3 (de
Inventor
John Hawkins
John Michael Allonby
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.)
Solvay Solutions UK Ltd
Original Assignee
Albright and Wilson Ltd
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 Albright and Wilson Ltd filed Critical Albright and Wilson Ltd
Publication of EP0354010A2 publication Critical patent/EP0354010A2/de
Publication of EP0354010A3 publication Critical patent/EP0354010A3/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/74Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/044Hydroxides or bases
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to liquid cleaning compositions of the spherulitic type containing sodium tripolyphosphate builder and a non-ionic surfactant.
  • U.S.P. 4,618,446 describes the preparation of liquid detergents comprising an aqueous liquid medium which contains a surfactant and an electrolyte with which the surfactant interacts to form spherulites.
  • the latter can pack together to support suspended solid particles, e.g. builders such as sodium tripolyphosphate.
  • the surfactant used to form the spherulites is an anionic mixture such as a mixture of sodium C8 ⁇ 14 alkyl benzene sulphonate with an alkyl polyethyleneoxy ether sulphate or a olefin or paraffin sulphonate or else a mixture of anionic surfactant with minor amounts of an an alkanolamide or amine oxide.
  • the electrolyte is usually dissolved builder, especially sodium tripolyphosphate, an( sometimes also sodium carbonate and/or sodium silicate.
  • relatively high levels of non-ionic alkoxylates up to 100% of the total surfactant may be included in sodium tripolyphosphate built liquid detergents of the spherulitic type if the composition additionally contains sodium hydroxide or a surfactant desolubilising sodium salt of a monobasic acid.
  • Our invention provides a liquid detergent composition
  • a liquid detergent composition comprising a non-ionic surfactant, suspended sodium tripolyphosphate and a surfactant desolubilising electrolyte of the formula NaX, where X is OH ⁇ , or the anion of a monobasic non-surfactant acid, in an amount sufficient to provide a stable homogeneous non-sedimenting detergent composition.
  • the non-ionic surfactant is preferably an alkoxylate.
  • alkoxylates are preferably ethoxylates or less preferably propoxylates or mixed ethoxylate propoxylate copolymers.
  • the alkoxylate may typically be an alkoxylated C8 ⁇ 18 natural or synthetic alcohol or an alkoxylated fatty acid, C6 ⁇ 18 alkyl phenol, or glycerol or sorbitan ester, preferably with an HLB of from 10 to 18, e.g. 12 to 15.
  • non-ionic surfactants that may be present include alkanolamides, such as coconut diethanolamide or monoethanolamide, amine oxides and alkoxylated amine oxides.
  • the non-ionic surfactant may be present in a proportion of from 10 to 100% by weight of the total surfactant, preferably 15 to 90% more preferably 20 to 70%, e.g. 25 to 40%.
  • the total concentration of nonionic surfactant is typically from 2 to 20% by weight of the composition, preferably 3 to 15%, e.g. 3.5 to 10%.
  • the detergent preferably contains an anionic surfactant.
  • the latter is preferably a sodium linear alkyl benzene sulphonate (e.g. C8 ⁇ 14 alkyl) or a mixture thereof with a sodium alkyl polyoxyethylene sulphate.
  • anionic surfactants which may be used include olefin sulphonates, paraffin sulphonates, alkyl sulphates and mixtures of alkyl benzene sulphonate with alkanolamides.
  • the anionic surfactant is preferably present in a concentration of from 3 to 25% by weight of the composition, especially 5 to 24% e.g. 6 to 20% by weight.
  • compositions containing a high ratio of builder to surfactant are desirable, and the anionic surfactant is typically in the range 5 to 15%, e.g. 6 to 12%.
  • Other markets may require high total surfactant levels, e.g. 15 to 30%.
  • One preferred active system comprises a major proportion of anionic surfactant, preferably sodium alkyl benzene sulphonate or, most preferably a mixture of sodium alkyl benzene sulphonate and sodium alkyl polyoxyalkylene ether sulphate and a minor proportion of non-ionic surfactant comprising an alkylethoxylate and, optionally, but preferably, a mono- or di-ethanolamide such as coconut diethanolamide.
  • the alkylbenzene sulphonate and the ethyl polyoxyethylene sulphate may be present in a relative proportion by weight of from 10:1 to 1:2, preferably 5:1 to 1.5:1, especially 2:1 to 1:1.2, e.g. 1:1.
  • the total of the anionic surfactant is preferably from 12 to 25%, more preferably 15 to 20%, by weight of the composition.
  • the total proportion of nonionic is preferably from 20 to 40%, e.g. 25 to 37%, more usually 30 to 35%, by weight of the total anionic and preferably from 2 to 8%, especially 3 to 6%, e.g. 4 to 5.5%, by weight of the composition.
  • the alkanolamide may typically be present in a proportion of from 0.5 to 5%, e.g. 0.75 to 4%, especially 0.8 to 2% by weight of the composition.
  • the composition preferably contains sufficient total dissolved electrolyte to provide a spherulitic structure. This can usually be identified by centrifuging off the suspended builder and examining the liquid medium by optical or electron microscopy whereupon close packed spherulites may be observed.
  • the total electrolyte concentration is adjusted to form a substantially space filling flocculated system, e.g. one which does not form two or more separate liquid layers when centrifuged for two minutes at 20,000 G.
  • the spherulites are believed to exhibit a concentric structure which exhibits X-ray scattering or neutron diffraction peaks indicative of a 110-140 nm repeat spacing.
  • the surfactant may also be present as an emulsified lamellar phase. This may appear, with some surfactant systems, as droplets resembling spherulites, but distinguishable from them both in appearance and properties at electrolyte concentrations slightly greater than those required to provide true spherulites.
  • the emulsified, lamellar phase shows evidence of the presence of a 30-70nm repeating structural unit under neutron scattering or X-ray diffraction analysis.
  • the emulsion separates on standing into a liquid lye layer and a lamellar liquid crystal ("G" phase) layer unless a stabiliser, e.g. a film forming polymer, such as a polyacrylate, or an emulsifying or dispersing agent, is present. In such systems we prefer that an appropriate emulsifying or dispersing agent should be used.
  • the surfactant may alternatively be present as an open reticular lamellar phase cocontinuous with the lye phase, as described in G.B. 2123846.
  • the total quantity of electrolyte required will depend upon the nature and concentration of surfactant present.
  • the electrolyte comprises dissolved sodium tripolyphosphate and may additionally comprise any builder which is a surfactant-desolubilising, ionisable salt of a monovalent acid or base such as sodium or potasssium nitrilotriacetate, or phosphonate. It is, however, essential to include in the electrolyte, at least a substantial proportion of at least one compound NaX.
  • the latter may for example be sodium hydroxide, a sodium halide such as sodium chloride, sodium fluoride, sodium bromide or sodium iodide, sodium nitrate or a surfactant desolubilising sodium salt of a monobasic organic acid, such as sodium formate, sodium acetate or sodium trichloracetate.
  • a sodium halide such as sodium chloride, sodium fluoride, sodium bromide or sodium iodide, sodium nitrate
  • a surfactant desolubilising sodium salt of a monobasic organic acid, such as sodium formate, sodium acetate or sodium trichloracetate.
  • the compound NaX is present in a concentration of at least 0.5%, typically more than 1%, most preferably more than 1.25% by weight.
  • the compound NaX may constitute the whole of the dissolved electrolyte, other than sodium tripolyphosphate, or preferbaly at least a major part of the total dissolved elecrolyte.
  • Sodium hydroxide used to neutralise any sulphonic or alkyl sulphuric acid present so as to form surfactant in situ does not contribute to the electrolyte content, since it is not present as a non-surfactant electrolyte in the composition.
  • the compound NaX may be present in concentrations up to 10 or even 15% by weight of the composition. We do not exclude the possibility of using higher concentrations, although they will normally be precluded by considerations such as cost, adverse effects on washing performance or on the stability of the spherulitic system or by solubility limitations. usually the compound NaX will be present in total concentration of from 0.75 to 5% by weight of the composition, especially 1 to 3%. Two or more compounds NaX may be present, for instance we have found mixtures of sodium hydroxide and sodium chloride particularly useful.
  • Polyvalent anions are preferably absent or present in concentrations below the minimum at which they cause instability.
  • carbonate, pyrophosphate, orthophosphate, metaphosphate, sulphate and other polyvalent anions are preferably avoided, or maintained at concentrations below 6% preferably below 5%, more preferably below 4% e.g. below 2% especially below 1%, more especially below 0.5%, of the weight of the composition.
  • Sodium silicate has also been found undesirable because of its adverse affect on the physical properties of the system when substantial levels of non-ionic surfactant are present. While we do not exclude the possibility of including sodium silicate, we prefer that it is absent, or maintained within the above limits.
  • Salts which are chemically unstable in the composition are also preferably absent unless they have been protected against decomposition or premature reaction, e.g. by a suitable form of encapsulation or by the inclusion of chemical stabilisers.
  • Such salts include perborates, chlorates, hypochlorites, perchlorates and persulphates.
  • compositions of our invention contain sodium tripolyphosphate in excess of its solubility in the aqueous medium, the excess being present as suspended solid particles.
  • the tripolyphosphate may typically be present in a total proportion between about 10 and about 35% by weight of the composition, e.g. 12 to 30%, preferably 15 to 25% by weight.
  • compositions of our invention may contain any of the usual additives and minor ingredients that are compatible with the formulation, e.g. soil suspending agents such as sodium carboxymethyl cellulose, optical brightening agents, perfumes, dyes, fabric softeners, clays such as bentonite, foaming agents, antifoams enzymes and bleaches.
  • soil suspending agents such as sodium carboxymethyl cellulose, optical brightening agents, perfumes, dyes, fabric softeners, clays such as bentonite, foaming agents, antifoams enzymes and bleaches.
  • solvents such as ethanol, ethyleneglycol, isopropanol, propyleneglycol or glycerol or hydrotropes such as sodium benzene sulphonate, sodium xylene sulphonate or sodium toluene sulphonate
  • hydrotropes such as sodium benzene sulphonate, sodium xylene sulphonate or sodium toluene sulphonate
  • Example A Example B
  • Example C Sodium Linear C 12-14 alkyl benzene sulphonate 9.06 8.96 9.7 Sodium C 12- 14 alkyl 5 mole polyoxyethylene sulphate 7.05 8.96 - C 12-15 synthetic alkyl 7 mole ethoxylate 5.03 4.01 4.8 Cocount diethanolamide - 0.98 - Sodium tripolyphosphate 20.14 18.0 19.4 Potassium carbonate 2.01 2.5 - Sodium chloride 1.15 0.5 - Sodium hydroxide - 1.02 4.0
  • Optical brightener 0.1 0.1 0.1 0.1 Sodium carboxymethyl cellulose 0.1 0.2 0.1 Perfume 0.3 0.3 0.3 % Solids 45.3 45.5 38.4
  • Examples A, B and C were made up by stirring together the specified ingredients, the balance in each case being water.
  • the compositions were pourable, homogenous and stable, showing no sign of sedimentation after three months at laboratory ambient temperature, and gave good performance in washing tests.
  • Automatic diswashing liquids have the following formulae: Example D Example E Example F LF403 6.98 13.5 13.5 NP9 3.48 6.8 6.8 NaCl 2.03 2.2 2.2 K2CO3 6.10 - - S.T.P. 20.35 22.1 22.1 Polyelectrolyte - - 2.0 Perfume - - 0.2 Water Balance Balance Balance (LF 403 is an ethoxylated and propoxylated C 18-15 alcohol NP9 is nonyl phenyl 9 mole ethoxylate. STP is sodium tripolyphosphate).
  • composition was a brilliant white, opaque pourable fluid which gave good performance with low foaming in automatic dishwasher tests.
EP89307841A 1988-08-05 1989-08-02 Flüssige Reinigungsmittelzusammensetzungen Withdrawn EP0354010A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8818704A GB8818704D0 (en) 1988-08-05 1988-08-05 Liquid cleaning compositions
GB8818704 1988-08-05

Publications (2)

Publication Number Publication Date
EP0354010A2 true EP0354010A2 (de) 1990-02-07
EP0354010A3 EP0354010A3 (de) 1990-04-04

Family

ID=10641704

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89307841A Withdrawn EP0354010A3 (de) 1988-08-05 1989-08-02 Flüssige Reinigungsmittelzusammensetzungen

Country Status (2)

Country Link
EP (1) EP0354010A3 (de)
GB (1) GB8818704D0 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004639A1 (en) * 1992-08-11 1994-03-03 Unilever Plc Liquid compositions
WO1996010625A1 (en) * 1994-09-30 1996-04-11 Unilever N.V. Detergent composition
US5952285A (en) * 1990-04-10 1999-09-14 Albright & Wilson Limited Concentrated aqueous surfactant compositions
US6897188B2 (en) 2001-07-17 2005-05-24 Ecolab, Inc. Liquid conditioner and method for washing textiles
US7682403B2 (en) 2004-01-09 2010-03-23 Ecolab Inc. Method for treating laundry
US8110537B2 (en) 2003-01-14 2012-02-07 Ecolab Usa Inc. Liquid detergent composition and methods for using
US10494591B2 (en) 2017-06-22 2019-12-03 Ecolab Usa Inc. Bleaching using peroxyformic acid and an oxygen catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1297037A (fr) * 1961-08-08 1962-06-22 Benckiser Gmbh Joh A Agent de nettoyage alcalin anti-mousse
EP0079646A2 (de) * 1981-11-16 1983-05-25 Unilever N.V. Flüssige Detergenszusammensetzung
EP0151884A2 (de) * 1983-12-22 1985-08-21 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
EP0170091A1 (de) * 1982-02-05 1986-02-05 Albright & Wilson Limited Flüssige Detergenszusammensetzungen
US4597889A (en) * 1984-08-30 1986-07-01 Fmc Corporation Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1297037A (fr) * 1961-08-08 1962-06-22 Benckiser Gmbh Joh A Agent de nettoyage alcalin anti-mousse
EP0079646A2 (de) * 1981-11-16 1983-05-25 Unilever N.V. Flüssige Detergenszusammensetzung
EP0170091A1 (de) * 1982-02-05 1986-02-05 Albright & Wilson Limited Flüssige Detergenszusammensetzungen
EP0151884A2 (de) * 1983-12-22 1985-08-21 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen
US4597889A (en) * 1984-08-30 1986-07-01 Fmc Corporation Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5952285A (en) * 1990-04-10 1999-09-14 Albright & Wilson Limited Concentrated aqueous surfactant compositions
WO1994004639A1 (en) * 1992-08-11 1994-03-03 Unilever Plc Liquid compositions
WO1996010625A1 (en) * 1994-09-30 1996-04-11 Unilever N.V. Detergent composition
US6897188B2 (en) 2001-07-17 2005-05-24 Ecolab, Inc. Liquid conditioner and method for washing textiles
US8110537B2 (en) 2003-01-14 2012-02-07 Ecolab Usa Inc. Liquid detergent composition and methods for using
US7682403B2 (en) 2004-01-09 2010-03-23 Ecolab Inc. Method for treating laundry
US10494591B2 (en) 2017-06-22 2019-12-03 Ecolab Usa Inc. Bleaching using peroxyformic acid and an oxygen catalyst

Also Published As

Publication number Publication date
EP0354010A3 (de) 1990-04-04
GB8818704D0 (en) 1988-09-07

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