WO1997002332A1 - Compositions predetachantes contenant un agent de blanchiment au peroxygene et comprenant des agents stabilisants ameliorant la tenue du tissu et des couleurs - Google Patents

Compositions predetachantes contenant un agent de blanchiment au peroxygene et comprenant des agents stabilisants ameliorant la tenue du tissu et des couleurs Download PDF

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Publication number
WO1997002332A1
WO1997002332A1 PCT/US1996/010234 US9610234W WO9702332A1 WO 1997002332 A1 WO1997002332 A1 WO 1997002332A1 US 9610234 W US9610234 W US 9610234W WO 9702332 A1 WO9702332 A1 WO 9702332A1
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Prior art keywords
composition
integer
compositions
mixtures
fabric
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PCT/US1996/010234
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English (en)
Inventor
Valentina Masotti
Stefano Scialla
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to US08/981,616 priority Critical patent/US6069123A/en
Priority to AU61750/96A priority patent/AU707493B2/en
Priority to JP9505148A priority patent/JPH11508930A/ja
Priority to CA002225804A priority patent/CA2225804C/fr
Priority to BR9609648A priority patent/BR9609648A/pt
Priority to SK1744-97A priority patent/SK174497A3/sk
Publication of WO1997002332A1 publication Critical patent/WO1997002332A1/fr
Priority to MXPA/A/1998/000056A priority patent/MXPA98000056A/xx

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to stable peroxygen bleach-containing compositions suitable to be used as pretreater.
  • Peroxygen bleach-containing compositions have been extensively described in laundry applications as laundry detergents, laundry additives or even laundry pretreaters.
  • liquid peroxygen bleach-containing compositions in laundry pretreatment applications to boost the removal of encrustated stains/soils which are otherwise particularly difficult to remove such as grease, coffee, tea, grass, mud/clay-containing soils and the like.
  • a drawback associated with such liquid peroxygen bleach- containing compositions is the relative instability of said compositions. Indeed, such liquid peroxygen bleach-containing compositions when packaged in containers made out of deformable materials, typically thermoplastic materials, may cause so-called bulging problems.
  • the peroxide bleach in the composition decomposes with time so as to generate oxygen in the composition. The released oxygen builds up pressure inside the container which eventually deforms, i.e., bulges.
  • the rate of decomposition of peroxygen bleach depends on different parameters such as temperature, pH and/or presence of metal ions.
  • metal ions chelating agents e.g., polyaminocarboxylates and/or phosphonate chelating agents, and/or radical scavengers which contribute to reduce peroxygen bleach decomposition and thus to stabilise said compositions.
  • EP-B- 209 2208 discloses the use of metal ions chelating agents such as amino polyphosphonates and radical scavengers such as hydroxybenzene compounds (butylated hydroxy toluene) to stabilise liquid hydrogen peroxide bleaching compositions.
  • liquid peroxygen bleach-containing compositions are not totally satisfactory from a formulator point of view as said compositions all the same tend to be somewhat chemically unstable and consequently all the same tend to bulge the containers into which they may be packaged. In other words, it has been found that there is still room for further improving the chemical stability of a liquid peroxygen bleach-containing composition.
  • peroxygen bleach-containing compositions suitable to be used as pretreater that said compositions are safe to said fabric treated therewith.
  • a drawback associated with such peroxygen bleach-containing compositions is that said compositions may damage fabrics, resulting in loss of tensile strength of the fabric fibres and/or color damage, when used in pretreatment application under stressed conditions, e.g., when applied directly onto the fabrics, and left to act onto said fabrics for prolonged periods of time, i. e., several hours, before washing said fabrics and/or when the fabrics to be pretreated are contaminated with metal ions such as copper and/or iron and/or manganese and/or chromium.
  • An advantage of the present invention is that excellent laundry performance on a broad range of stains and soils such as bleachable stains and/or greasy stains.
  • compositions of the present invention provide also excellent performance when used in other applications, apart from laundry pretreater application, such as in other laundry applications, as a laundry detergent or laundry additive, or even in hard surface cleaning applications or in carpet cleaning applications. Summary of the invention
  • the present invention encompasses a liquid composition comprising a peroxygen bleach and a polyamine as defined hereinafter, or mixtures thereof.
  • the present invention further encompasses a process of pretreating soiled fabrics with a liquid composition comprising a peroxygen bleach and a polyamine as defined hereinafter, or mixtures thereof, and said process comprises the steps of applying said composition in its neat form onto the fabric and allowing said composition to remain in contact with said fabric, before said fabric is washed.
  • the present invention is a liquid composition comprising a peroxygen bleach and a specific polyamine, or mixtures thereof.
  • compositions of the present invention comprise a peroxygen bleach.
  • Preferred peroxygen bleach is hydrogen peroxide, or a water soluble source thereof, or mixtures thereof. Hydrogen peroxide is most preferred to be used in the compositions of the present invention. Indeed, the presence of peroxygen bleach, preferably hydrogen peroxide, provides strong cleaning benefits which are particularly noticeable in laundry applications.
  • a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
  • Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicate, persulphate such as monopersulfate, perborates, peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphtalic acid, perbenzoic and alkylperbenzoic acids, and mixtures thereof.
  • the compositions of the present invention comprise from 0.01 % to 90% by weight of the total composition of said peroxygen bleach, preferably from 2% to 20% and most preferably from 3% to 10%.
  • compositions of the present invention comprise a polyamine having one of the following general structures, or mixtures thereof:
  • n is an integer of from 0 to 15, preferably of from 0 to 10 and more preferably of from 0 to 5 or,
  • n is an integer of from 0 to 8, preferably of from 0 to 3 and m is an integer of from 0 to 8, preferably of from 0 to 3, or
  • n is an integer of from 2 to 20, preferably of from 2 to 10 and more preferably of from 2 to 5 and m is an integer of from 2 to 4, preferably is 2 , or
  • n H2n-m( NH 2) m wherein n is an integer of from 2 to 20, preferably of from 2 to 10 and more preferably of from 2 to 6 and m is an integer of from 2 to 4, preferably is 2 , or n H2n-2-m( NH 2) m wherein n is an integer of from 3 to 20, preferably of from 3 to 10 and more preferably of from 3 to 5 and m is an integer of from 2 to 4, preferably is 2 , or
  • n is an integer of from 4 to 20, preferably of from 4 to 10 and more preferably of from 4 to 6 and m is an integer of from 2 to 4, preferably is 2 , or
  • n is an integer of from 5 to 20, preferably of from 5 to 10 and more preferably of from 5 to 7 and m is an integer of from 2 to 4, preferably is 2.
  • suitable polyamine or mixtures thereof to be used herein include alkyl polyamines in general, such as 1 ,2 alkyl diamine, e.g , 1 ,2 propyl- diamine, 1 ,3 alkyl diamine, e.g., 1 ,3 propyl-diamine, 1 ,4 alkyl diamine, e.g.,
  • polyamines suitable to be used herein may be available from Union Carbide.
  • ethylene diamine may be commercially available under the name EDA® from Union Carbide.
  • compositions of the present invention comprise from 0.01 % to 5.0% by weight of the total composition of said polyamine, or mixtures thereof, preferably from 0.1 % to 3.0% and most preferably from 0.4% to 1.5%.
  • the peroxygen bleach-containing compositions of the present invention are chemically stable.
  • chemically stable it is meant herein that a composition of the present invention comprising a peroxygen bleach does not undergo more than 10% available oxygen loss at 50°C in 2 weeks.
  • concentration of available oxygen can be measured by chemical titration methods known in the art, such as the iodimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the choice of the appropriate method are described for example in "Hydrogen Peroxide", W. C. Schumb, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and “Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.
  • compositions may also be evaluated by a bulging test method as described herein after in the experimental data.
  • the present invention is based on the finding that, peroxygen bleach decomposition is reduced in a peroxygen bleach-containing composition of the present invention comprising a polyamine, as defined herein, or mixtures thereof, thereby preventing the bulging of a deformable container containing it, as compared to the same composition but without said polyamine or mixtures thereof.
  • deformable container it is meant herein any closable container commonly used in the art to package detergent compositions like pretreaters and that can bulge under the pressure generated inside.
  • Such containers include those made of thin metal materials like aluminium sheets or/and of thermoplastic materials (single layer or multilayer materials) including virgin and recycled materials and mixtures thereof, vinyl chloride based resins, polymers and copolymers derived from olefines, acrylic polymers and copolymers, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, or mixtures thereof.
  • a peroxygen bleach-containing composition of the present invention may be packaged in a given deformable container/bottle without compromising the stability of said container/bottle comprising it upon standing, for longer periods of time, as would otherwise be possible by packaging in said given container/bottle the same composition but without said polyamine as defined herein, or mixtures thereof.
  • the present invention is further based on the finding that on top of the improved peroxygen stability properties delivered by the peroxygen bleach- containing compositions of the present invention comprising a polyamine as defined herein, or mixtures thereof, said compositions when used to pretreat soiled fabrics also deliver improved fabric safety, as compared to the use of the same compositions but without said polyamine, or mixtures thereof, to pretreat said fabrics.
  • a peroxygen bleach- containing composition comprising a polyamine as defined herein, or mixtures thereof, allows to considerably reduce the tensile strength loss of a fabric pretreated therewith, even if said composition is left onto said fabric upon a prolonged period of time before washing said fabric, e.g. about 24 hours or more, and said fabric is contaminated by high levels of metal ions such as copper and/or iron and/or manganese, e.g. 30 ppm of copper or more per gram of fabric.
  • the tensile strength loss of a fabric may be measured by employing the Tensile Strength method, as can be seen in the examples herein after. This method consists in measuring the tensile strength of a given fabric by stretching said fabric until it breakes. The force, expressed in Kg, necessary to break the fabric is the "Ultimate Tensile Stress” and may be measured with "The Stress-Strain INSTRON Machine”.
  • tensile strength loss it is to be understood the difference when comparing the tensile strength of a fabric taken as a reference, i.e., a fabric which has not been pre-treated, and the tensile strength of the same fabric after having been pre-treated according to the present invention. A tensile strength loss of zero means that no fabric damage is observed.
  • the present invention is further based on the finding that on top of the improved peroxygen stability properties delivered by the peroxygen bleach- containing compositions of the present invention comprising a polyamine as defined herein, or mixtures thereof, said compositions when used to pretreat soiled colored fabrics also deliver improved color safety, as compared to the use of the same compositions but without said polyamine, or mixtures thereof, to pretreat said fabrics.
  • a peroxygen bleach-containing composition comprising a polyamine as defined herein, or mixtures thereof, allows to considerably reduce the color change and/or decoloration of colored fabrics pretreated therewith, even if said composition is left onto said colored fabrics upon a prolonged period of time before washing said colored fabrics, e.g. about 24 hours or more.
  • compositions according to the present invention are aqueous liquid cleaning compositions.
  • Said aqueous compositions should be formulated in the acidic pH, preferably at a pH of from 0 to 6 and more preferably at a pH of from 2 to 5.
  • Formulating the compositions of the present invention in the acidic pH range contributes to the stability of said compositions.
  • the pH of the compositions of the present invention can be adjusted by using organic or inorganic acids, or alkalinising agents.
  • the present invention encompasses raw material compositions, i.e. compositions based essentially on peroxygen bleach and comprising a polyamine, as defined herein or mixtures thereof, as well as fully formulated detergent compositions, i.e. compositions incorporating further ingredients commonly used in detergent field like other stabiliser, chelating agents, radical scavengers, surfactants, bleach activators, builders, soil suspenders, dye transfer agents, solvents, brighteners, perfumes, foam suppressors or dyes or mixtures thereof.
  • the peroxygen bleach-containing compositions of the present invention may comprise a chelating agent or mixtures thereof, as a highly preferred optional ingredient.
  • Chelating agents suitable to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof.
  • Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1 -hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates. Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987. to Hartman and Perkins.
  • Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa- acetates, ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly preferred chelating agents to be used herein are diethylene triamine methylene phosphonate, ethylene N,N'-disuccinic acid, diethylene triamine pantaacetate, glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof and highly preferred is salicylic acid.
  • Salicylic acid may be commercially available from Rhone-Poulenc under the name Salicylic Acid®.
  • the peroxygen bleach-containing compositions of the present invention may further comprise a radical scavenger, or mixtures thereof, as a highly preferred optional ingredient.
  • Suitable radical scavengers for use herein include the well-known substituted mono and di hydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof.
  • Preferred such radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid, t-butyl catechol, benzylamine, 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert- butyl hydroxy toluene.
  • BHT di-tert-butyl hydroxy toluene
  • hydroquinone di-tert-butyl hydroquinone
  • mono-tert-butyl hydroquinone tert-butyl-hydroxy anysole
  • benzoic acid toluic acid
  • t-butyl catechol benzylamine
  • compositions of the present invention may further comprise any surfactant known to those skilled in the art including nonionic, anionic, cationic, zwitterionic or amphotheric surfactants or mixtures thereof.
  • the peroxygen-bleach containing compositions of the present invention may also comprise a liquid hydrophobic bleach activator, as a highly preferred optional ingredient.
  • bleach activator it is meant herein a compound which reacts with hydrogen peroxide to form a peracid. The peracid thus formed constitutes the activated bleach.
  • hydrophobic bleach activator it is meant herein an activator which is not substantially and stably miscible with water. Typically, such hydrophobic bleach activators have an HLB of below 11.
  • suitable liquid hydrophobic bleach activators typically belong to the class of esters, amides, imides, or anhydrides.
  • ATC acetyl triethyl citrate
  • ATC has the other advantages that it is environmentally friendly in that it eventually degrades into citric acid and alcohol.
  • ATC has good hydrolytical stability in the compositions herein, and it is an efficient bleach activator. Finally, it provides good building capacity to the compositions. It is also possible to use mixtures of liquid hydrophobic bleach activators herein.
  • the compositions herein where a bleach activator is present should comprise from 0.5% to 20% by weight of the total composition of said bleach activator, preferably from 2% to 10%, most preferably from 3% to 7%.
  • the peroxygen bleach-containing compositions according to the present invention further comprise a liquid hydrophobic bleach activator it is highly desired herein for stability purpose to formulate said compositions either as aqueous emulsions of surfactants which comprise said liquid hydrophobic bleach activator, or as microemulsions of said liquid hydrophobic bleach activator in a matrix comprising water, the peroxygen bleach and a hydrophilic surfactant system comprising an anionic and a nonionic surfactant.
  • said peroxygen bleach-containing emulsions comprise a surfactant system of at least two different surfactants, i.e. at least a hydrophobic surfactant having an HLB up to 9 and at least a hydrophilic surfactant having an HLB above 10 in order to emulsify the liquid hydrophobic bleach activator.
  • said two different surfactants in order to form emulsions which are stable must have different HLB values (hydrophilic lipophilic balance), and preferably the difference in value of the HLBs of said two surfactants is at least 1 , preferably at least 3.
  • the emulsions according to the present invention comprise from 2 % to 50 % by weight of the total composition of said hydrophilic and hydrophobic surfactants, preferably from 5 % to 40 % and more preferably from 8 % to 30 %.
  • the emulsions according to the present invention comprise at least from 0.1 % by weight of the total emulsion of said hydrophobic surfactant, or mixtures thereof, preferably at least 3 % and more preferably at least 5 % and at least from 0.1 % by weight of the total emulsion of said hydrophilic surfactant, or mixtures thereof, preferably at least 3 %, and more preferably at least 6 %.
  • hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are the hydrophobic nonionic surfactants and hydrophilic nonionic surfactants.
  • Said hydrophobic nonionic surfactants to be used herein have an HLB up to 9, preferably below 9, more preferably below 8 and said hydrophilic surfactants have an HLB above 10, preferably above 1 1 , more preferably above 12.
  • the hydrophobic nonionic surfactants to be used herein have excellent grease cutting properties, i.e. they have a solvent effect which contributes to hydrophobic soils removal.
  • the hydrophobic surfactants act as carrier of the hydrophobic brighteners onto the fabrics allowing thereby said brighteners to work in close proximity with the fabrics surface since the beginning of the wash.
  • Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols preferably, fatty alcohol ethoxylates and/or propoxylates. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values (hydrophilic lipophilic balance).
  • HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
  • Surfactants catalogs are available which list a number of surfactants including nonionics, together with their respective HLB values.
  • Suitable chemical processes for preparing the nonionic surfactants for use herein include condensation of corresponding alcohols with alkylene oxide, in the desired proportions. Such processes are well known to the man skilled in the art and have been extensively described in the art. As an alternative, a great variety of alkoxylated alcohols suitable for use herein is commercially available from various suppliers.
  • Preferred hydrophobic nonionic surfactants to be used in the emulsions according to the present invention are surfactants having an HLB up to 9 and being according to the formula RO-(C2H4 ⁇ ) n (C3H6 ⁇ ) m H, wherein R is a CQ to C22 alkvl chain or a CQ to C28 alk Y' benzene chain, and wherein n + m is from 0.5 to 5 and n is from 0 to 5 and m is from 0 to 5 and preferably n + m is from 0.5 to 4 and, n and m are from 0 to 4.
  • the preferred R chains for use herein are the Cs to C22 a ' k Yl chains.
  • Dobanol R 23-3 or Dobanol R 23-2, Lutensol R TO3, or mixtures thereof.
  • These Dobanol R surfactants are commercially available from SHELL.
  • These Lutensol R surfactants are commercially available from BASF and these Tergitol R surfactants are commercially available from UNION CARBIDE.
  • Other suitable hydrophobic nonionic surfactants to be used herein are non alkoxylated surfactants.
  • An example is Dobanol R 23 (HLB ⁇ 3 ).
  • Preferred hydrophilic nonionic surfactants to be used in the emulsions according to the present invention are surfactants having an HLB above 10 and being according to the formula RO-(C2H4 ⁇ ) n (C3H6 ⁇ ) m H, wherein R is a Cs to C22 a,k Yl chain or a Cg to C28 alk Yl benzene chain, and wherein n + m is from 5 to 1 1 and n is from 0 to 1 1 and m is from 0 to 1 1 , preferably n + m is from 6 to 10 and, n and m are from 0 to 10.
  • n and m refer to the average degree of the ethoxylation/propoxylation.
  • the preferred R chains for use herein are the Cg to C22 a ' y' chains.
  • Dobanol R 91- 10 or Dobanol R 45-7, Dobanol R 23-6.5, or mixtures thereof .
  • These Dobanol R surfactants are commercially available from SHELL.
  • hydrophilic nonionic surfactants other hydrophilic surfactants may further be used in the emulsions of the present invention such as anionic surfactants described herein after.
  • the emulsions according to the present invention may further comprise other surfactants which should however not significantly alter the weighted average HLB value of the overall emulsion.
  • the emulsifying system meets the equation:
  • X refers to the hydrophobic ingredient to emulsify, if several hydrophobic ingredients are present X refers to all of them, A refers to one of said nonionic surfactants (hydrophilic or hydrophobic), and B refers to the other said nonionic surfactant (hydrophilic or hydrophobic).
  • an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with for instance an HLB of 6, such as a Dobanol R 23-2 and a hydrophilic nonionic surfactant with for instance an HLB of 15, such as a Dobanol R 91-10.
  • said peroxygen bleach-containing microemulsions according to the present invention comprise a hydrophilic surfactant system comprising an anionic surfactant and a nonionic surfactant.
  • a key factor in order to stably incorporate the hydrophobic activator is that at least one of said surfactants must have a significantly different HLB value to that of the hydrophobic activator. Indeed, if all said surfactants had the same HLB value as that of the hydrophobic activator, a continuous single phase might be formed thus lowering the chemical stability of the bleach/bleach activator system.
  • at least one of said surfactants has an HLB value which differs by at least 1.0 HLB unit, preferably 2.0 to that of said bleach activator.
  • Suitable anionic surfactants herein include water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10- 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10- 20 alk Y' component, more preferably a C-
  • Suitable anionic surfactants for use herein are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C- j 0- ⁇ 24 alkyl or hydroxyalkyl group having a C10- 24 alkyl component, preferably a C12-C2O a
  • R is an unsubstituted C- j 0- ⁇ 24 alkyl or hydroxyalkyl group having a C10- 24 alkyl component, preferably a C12-
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12- 18 alkyl polyethoxylate (1.0) sulfate, Ci 2-C ⁇ s (1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate, C-
  • anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C -C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C -C20 linear alkylbenzenesulfonates C8-C22 primary or secondary alkanesulfonates
  • C8-C24 olefinsulfonates C8
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as Ci4_i 6 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -Ci4 diesters), acyl sarcosinates, sulfates of alkylpolylpolylpolyglycolethersul
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • Preferred surfactants for use in the microemulsions herein are the alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.
  • anionic surfactants provide improved cleaning performance.
  • anionic surfactants herein even at low levels, have shown to improve the physical stability of the microemulsions of the present invention, even at higher temperatures (up to 50°C).
  • Suitable nonionic surfactants for use in the microemulsions herein include the hydrophilic nonionic surfactants as defined herein before for the emulsions.
  • the preferred making of the microemulsions of the present invention which comprises a liquid hydrophobic bleach activator includes premixing the surfactants with water and subsequently adding the other ingredients including hydrogen peroxide and said hydrophobic bleach activator. Irrespective of this preferred order of addition, it is important that during the mixing of the ingredients, the microemulsions be constantly kept under stirring under relatively high stirring energies, preferably 30 minutes at 750 rpm, most preferably 30 minutes at 1000 rpm. In the embodiment of the present invention where the compositions are formulated as microemulsions said compositions are macroscopically transparent in the absence of opacifiers and dyes.
  • microemulsions herein showed no phase separation after 15 minutes at 6000 RPM.
  • said microemulsions appeared as a dispersion of droplets in a matrix.
  • the matrix is the hydrophilic matrix described hereinbefore, and the droplets are constituted by the liquid hydrophobic bleach activator.
  • the particles had a size which is typically around or below 3 micron diameter.
  • the peroxygen bleach-containing compositions of the present invention may further comprise an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of Rl , R2 and R3 is independently a C6-C30, preferably a C10-C30, most preferably a C12-C16 hydrocarbon chain.
  • R1 R2R3NO amine oxide surfactant according to the formula R1 R2R3NO, wherein each of Rl , R2 and R3 is independently a C6-C30, preferably a C10-C30, most preferably a C12-C16 hydrocarbon chain.
  • amine oxides should be preferably present in amounts ranging from 0.1 % to 10 % by weight of the total composition, more preferably from 1 % to 3%.
  • the peroxygen bleach-containing compositions of the present invention may further comprise up to 10%, preferably from 2% to 4% by weight of the total composition of an alcohol according to the formula HO - CR'R" - OH, wherein R' and R" are independently H or a C2-C10 hydrocarbon chain and/or cycle .
  • Preferred alcohol according to that formula is propanediol. Indeed, we have observed that these alcohols in general and propanediol in particular also improve the chemical stability of the compositions, i.e. lower the decomposition of the bleach and the bleach activator, if present, as the amine oxides herein above. In addition, said alcohols lower the surface tension of the product, thus preventing superficial film or gel formation.
  • said alcohols improve the aesthetics of the compositions herein. It is believed that the chemical stabilising effect of said alcohols is twofold. Firstly they may work as radical scavengers and secondly they may interact with the hydrogen peroxide preventing or limiting hydrolysis, therefore reducing the rate of peroxide decomposition. It is believed that this improvement in chemical stability obtained by said alcohols is matrix independent.
  • the peroxygen bleach-containing compositions according to the present invention may further comprise a foam suppressors such as 2-alkyl alkanol, or mixtures thereof, as an optional ingredient.
  • a foam suppressors such as 2-alkyl alkanol, or mixtures thereof, as an optional ingredient.
  • Particularly suitable to be used in the present invention are the 2-alkyl alkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 and a terminal hydroxy group, said alkyl chain being substituted in the ⁇ position by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and more preferably 3 to 6.
  • compositions of the present invention comprise up to 2 % by weight of the total composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.05 % to 1.5 % and most preferably from 0.1 % to 0.8 %.
  • the present invention further encompasses a process of pretreating soiled fabrics with a liquid composition comprising a peroxygen bleach and a polyamine as defined herein, or mixtures thereof, said process comprises the steps of applying said composition in its neat form onto the fabric and allowing said composition to remain in contact with said fabric preferably without leaving said composition to dry onto said fabric, before said fabric is washed.
  • Said composition may remain in contact with said fabric, typically for a period of 1 minute to 24 hours, preferably 1 minute to 1 hour and more preferably 5 minutes to 30 minutes.
  • compositions according to the present invention may be rubbed and/or brushed more or less intensively, for example, by means of a sponge or a brush or simply by rubbing two pieces of fabric each against the other.
  • washing it is to be understood herein to simply rinse the fabrics with water, or the fabrics may be washed with conventional compositions comprising at least one surface active agent, this by the means of a washing machine or simply by hand.
  • compositions described herein are applied directly onto the fabrics to be pre-treated without undergoing any dilution, i.e. they are applied as described herein.
  • the liquid compositions used in said process should preferably not be left to dry onto the fabrics. Indeed, it has been found that water evaporation contributes to increase the concentration of free radicals onto the surface of the fabrics and, consequently, the rate of chain reaction. It is also speculated that an auto-oxidation reaction occurs upon evaporation of water when the liquid compositions are left to dry onto the fabrics. Said reaction of auto-oxidation generates peroxy-radicals which may contribute to the degradation of cellulose. Thus, not leaving the liquid compositions, as described herein, to dry onto the fabric, in the process of pretreating soiled fabrics according to the present invention, contributes to the benefits according the present invention, i. e. to reduce the tensile strength loss when pretreating fabrics with liquid peroxygen bleach- containing compositions.
  • compositions described herein may also be used as a laundry detergent or as a laundry detergent booster and as a household cleaner in the bathroom or in the kitchen, for the cleaning of dishes or carpets.
  • compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • ATC is acetyl triethyl citrate.
  • BHT is di-tert-butyl hydroxy toluene marketed by shell under the trade name IONOL CP®.
  • DTPA is diethylene triamine pentaacetate.
  • DETPMP is diethylene triamine penta methylene phosphonate marketed by Monsanto under the trade name DEQUEST®.
  • ATC is acetyl triethyl citrate.
  • BHT is di-tert-butyl hydroxy toluene marketed by shell under the trade name IONOL CP®.
  • compositions I to IV are taken as reference, they comprise hydrogen peroxide and a given chelating agent such as diethylene triamine pentaacetate or diethylene triamine penta methylene phosphonate at different levels.
  • a given chelating agent such as diethylene triamine pentaacetate or diethylene triamine penta methylene phosphonate at different levels.
  • compositions Vll and IX are also taken as reference, they comprise hydrogen peroxide and as a chelating agent, malonic acid or salicylic acid.
  • compositions V and VI are representative of the present invention, they comprise hydrogen peroxide and a polyamine as defined herein, i.e. ethylene diamine (EDA), at different levels.
  • Compositions VIII and X are also representative of the present invention, they comprise hydrogen peroxide and a polyamine as defined herein, i.e. ethylene diamine (EDA), on top of chelating agents, i.e. malonic acid or salicylic acid.
  • a stability test method was carried out with the compositions I to X mentioned herein above. This test method was carried out by filling each of the compositions I to X into identical containers. The containers used were 250ml bottles, of about 200 mm high, about 50 mm deep and about 60 mm wide.
  • the thickness of the walls of the bottles ranged from 1 mm to 3 mm.
  • the containers were closed with an air tight cap with a screw thread. To ensure air tightness during the test, silicone bands were added on the threads and caps were sealed with a tape. The filled and closed containers were then stored at 50°C for the indicated periods. Each composition was tested in 6 different replicates. Bulging is evaluated by visual observation of rocker bottom on said containers.
  • Results are expressed in time requested for the containers to bulge (rocker bottom). Indeed, the first number of the results expressed herein before for the compositions I to X represents the time requested expressed in days, to observe rocker bottom on at least one of the 6 containers tested for a given composition and the second number of said results represents the time requested expressed in days to observe rocker bottom on all of the 6 bottles containers for said composition.
  • compositions of the present invention comprising a polyamine as defined herein, e.g. ethylene diamine
  • exhibit improved chemical stability e.g. the above results demonstrate that the time required to observe bulging (rocker bottom) of a given container under stressed conditions, i.e. storage at 50°C, is increased with the compositions of the present invention, as compared to the same compositions but without ethylene diamine, this both when ethylene diamine is used alone (compositions V and VI versus compositions I, II, III and IV) or on top of chelating agents (composition VIII versus composition Vll and composition X versus composition IX).
  • compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • ATC is acetyl triethyl citrate.
  • BHT is di-tert-butyl hydroxy toluene marketed by shell under the trade name IONOL CP®.
  • DTPA is diethylene triamine pentaacetate.
  • Composition I comprising 1.5% by weight of diethylene triamine pentaacetate is not stable, rocker bottom appears within 1 day only.
  • composition I is taken herein as a reference for tensile strength loss evaluation.
  • Compositions III and V are further taken as reference, they comprise hydrogen peroxide and a chelating agent like salicylic acid or malonic acid.
  • Compositions II, IV and VI are representative of the present invention they comprise hydrogen peroxide and ethylene diamine.
  • a tensile strength test method was carried out with the compositions mentioned herein above. This test method was carried out on metal- polluted fabrics. Indeed, cotton ribbons (dimension 12.5 x 5 cm 2 ) having a copper concentration of 30 ppm per gram of cotton were pre-treated according to the present invention. Indeed, the cotton ribbons were pre- treated with 2 ml of each of the liquid compositions mentioned herein before. The compositions were left in contact with the ribbons for 24 hours, before being rinsed with water. After that, the damage on the fabrics, i.e. cotton ribbons, was evaluated by stretching said ribbons until they broke. The force necessary to break the ribbons, i.e.
  • the tensile strength loss mentioned above for the different compositions tested is expressed in percentage and is obtained by comparing the tensile strength of a given fabric taken as a reference, i.e. a fabric which has not been pre-treated, to the tensile strength of the same fabric measured after said fabric has been pre-treated as mentioned herein before.
  • compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • Salicylic acid — 1.0 — — 1.0 1.0
  • compositions in the examples are according to the present invention.
  • the tensile strength loss is reduced when pretreating fabrics with compositions I to VI, even when leaving said compositions to act onto the fabrics upon a prolonged contact period, i.e., 24 hours, before washing said fabrics and in the presence of high concentration of metal ions on the surface of the fabrics, e.g. about 30 ppm of copper per gram of cotton fabric.
  • compositions I to VI for pretreating colored fabrics no color change and/or discoloration were observed.
  • compositions undergo no more than 3% available oxygen loss when stored for prolonged period of time 20 days at 50°C.

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Abstract

La présente invention se rapporte à des compositions liquides comprenant un agent de blanchiment au peroxygène et une polyamine spécifique, ou des mélanges de ceux-ci. L'invention se rapporte également à un procédé de prétraitement de tissus tachés et/ou de tissus en couleur tachés, ce procédé visant à réduire la perte de résistance à la traction de ces tissus.
PCT/US1996/010234 1995-06-30 1996-06-03 Compositions predetachantes contenant un agent de blanchiment au peroxygene et comprenant des agents stabilisants ameliorant la tenue du tissu et des couleurs WO1997002332A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US08/981,616 US6069123A (en) 1995-06-30 1996-06-03 Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
AU61750/96A AU707493B2 (en) 1995-06-30 1996-06-03 Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
JP9505148A JPH11508930A (ja) 1995-06-30 1996-06-03 改善された布帛／色安全性を与えるポリアミン安定剤を有する過酸素漂白剤含有プレスポッティング組成物
CA002225804A CA2225804C (fr) 1995-06-30 1996-06-03 Compositions predetachantes contenant un agent de blanchiment au peroxygene et comprenant des agents stabilisants ameliorant la tenue du tissu et des couleurs
BR9609648A BR9609648A (pt) 1995-06-30 1996-06-03 Composições de pré-espalhamento contendo alvejante de peroxigênio com estabilizadores que fornecem segurança de cor/tecido aperfeiçoada
SK1744-97A SK174497A3 (en) 1995-06-30 1996-06-03 Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
MXPA/A/1998/000056A MXPA98000056A (en) 1995-06-30 1998-01-07 Pre-treatment compositions against stains containing peroxygen bleacher with polyamine stabilizers that provide improved security to the fabric / co

Applications Claiming Priority (2)

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EP95870079.1 1995-06-30
EP95870079A EP0751214A1 (fr) 1995-06-30 1995-06-30 Compositions de blanchiment stables contenant des agents de blanchiment péroxydés

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DE19750455C1 (de) * 1997-11-14 1999-04-29 Henkel Kgaa Verwendung von peroxidhaltigen Zubereitungen
DE19801086C1 (de) * 1998-01-14 1998-12-17 Henkel Kgaa Wäßrige Bleichmittel in Mikroemulsionsform
EP0995792A1 (fr) * 1998-10-19 2000-04-26 The Procter & Gamble Company Procédé de blanchiment des tissus
US6586382B1 (en) 1998-10-19 2003-07-01 The Procter & Gamble Company Process of bleaching fabrics
EP1001011B2 (fr) † 1998-11-11 2010-06-23 The Procter & Gamble Company Composition de blanchiment comprenant acide benzoique alkoxylé
JP2002318455A (ja) * 2001-04-23 2002-10-31 Tosoh Corp 安定化方法
WO2014190129A1 (fr) * 2013-05-24 2014-11-27 The Procter & Gamble Company Composition de détergent à faible ph

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US4900468A (en) * 1985-06-17 1990-02-13 The Clorox Company Stabilized liquid hydrogen peroxide bleach compositions
US5180514A (en) * 1985-06-17 1993-01-19 The Clorox Company Stabilizing system for liquid hydrogen peroxide compositions

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US3812044A (en) 1970-12-28 1974-05-21 Procter & Gamble Detergent composition containing a polyfunctionally-substituted aromatic acid sequestering agent
DE2437090A1 (de) 1974-08-01 1976-02-19 Hoechst Ag Reinigungsmittel
EP0042187B2 (fr) * 1980-06-17 1988-09-28 THE PROCTER & GAMBLE COMPANY Composition détergente à basse teneur en polyamines substituées
DE3211532A1 (de) * 1982-03-29 1983-09-29 Henkel KGaA, 4000 Düsseldorf Mittel zum waschen und faerbungsschonenden bleichen von textilien
EP0125781B1 (fr) * 1983-04-14 1987-08-12 Interox Chemicals Limited Composés de péroxyde
EP0209228B2 (fr) 1985-06-17 1999-06-09 The Clorox Company Compositions de blanchiment stables liquides de péroxyde d'hydrogène
EP0349153A3 (fr) * 1988-06-28 1990-03-14 The Clorox Company Système stabilisant les compositions liquides d'eau oxygénée et compositions stabilisées de cette manière
JPH0288699A (ja) * 1988-09-26 1990-03-28 Kao Corp 洗濯前処理用液体漂白剤
NZ246258A (en) 1991-12-13 1996-07-26 Procter & Gamble Use of acylated citrate ester derivatives as a hydrogen peroxide activator
ATE163037T1 (de) * 1992-11-16 1998-02-15 Procter & Gamble Reinigungs- und bleichmittelzusammensetzungen

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US4900468A (en) * 1985-06-17 1990-02-13 The Clorox Company Stabilized liquid hydrogen peroxide bleach compositions
US5180514A (en) * 1985-06-17 1993-01-19 The Clorox Company Stabilizing system for liquid hydrogen peroxide compositions

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CA2225804A1 (fr) 1997-01-23
HUP9901101A3 (en) 1999-11-29
JPH11508930A (ja) 1999-08-03
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EP0751214A1 (fr) 1997-01-02
BR9609648A (pt) 1999-03-02
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