EP0918841B1 - Aqueous bleaching agents - Google Patents

Aqueous bleaching agents Download PDF

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Publication number
EP0918841B1
EP0918841B1 EP97924975A EP97924975A EP0918841B1 EP 0918841 B1 EP0918841 B1 EP 0918841B1 EP 97924975 A EP97924975 A EP 97924975A EP 97924975 A EP97924975 A EP 97924975A EP 0918841 B1 EP0918841 B1 EP 0918841B1
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alkyl
carbon atoms
acid
formula
weight
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German (de)
French (fr)
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EP0918841A1 (en
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Mercedes Mendoza
Maite Canellas
Jaume Jose
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the invention relates the use of polyacrylic acid compounds as Sequestrant against the Deposition of metals on fabrics in aqueous bleaches.
  • EP-A 0 274 885 recommends the use of mixtures of linear and branched amine oxides for the production of viscous hypochlorite bleaches.
  • EP-A 0 145 084 Unilever
  • mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose.
  • EP-A 0 137 551 and EP-A 0 447 261 disclose the use of amine oxides with soap or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or alkyl benzene sulfonates as a thickening component for hypochlorite solutions.
  • EP-A 0 156 438 reports on the use of alkylarylsulfonates as thickeners in aqueous bleaches which contain certain stilbene dyes as optical brighteners.
  • ES-A 8801389 (Henkel Ibérica) are bleaching agents based on aqueous hypochlorite solutions, which mainly contain alkyl ether sulfates and small amounts of amine oxides as surfactant components.
  • aqueous bleaching compositions containing sodium hypochlorite and anionic surfactants are also known.
  • the hypochlorite concentration of these agents is 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine.
  • German patent DE-C1 43 33 100 the applicant finally proposed aqueous bleaching and cleaning agents based on hypochlorites, fatty alcohol ether sulfates, amine oxides and amine oxide phosphonic acids.
  • the complex object of the invention has been to provide aqueous bleaches to provide, which are chlorine-stable, gentle on textiles and as skin-friendly as possible, one have sufficiently high viscosity and with high stain removal capacity the deposition of Prevent metal traces on the fabric reliably.
  • the invention relates to the use of polyacrylic acid compounds, selected from the group of homopolymers of acrylic acid and methacrylic acid, in amounts of 0.01 to 1 wt .-% as a sequestering agent against Deposition of metals on fabrics in aqueous bleaches with a content - related on the means - from 1 to 10% by weight of alkali hypochlorite and 0.1 to 1% by weight Amine oxidephosphonic acid and alkali or alkaline earth metal silicate and optionally further usual auxiliaries and additives.
  • Alkali hypochlorites are to be understood as lithium, potassium and in particular sodium hypochlorite.
  • the Hypochlorites can preferably in amounts of 1.5 to 8 and in particular 4 to 6 wt .-% - based on the funds - are used.
  • Polyacrylic acid compounds include homopolymers of acrylic acid and methacrylic acid to understand. Polyacrylic acid compounds with special advantageous stabilizing effects are present as alkali salts and have an average Molecular weight in the range of 1,000 to 10,000 and in particular 4,000 to 6,000 daltons. The preferred application range is 0.02 to 0.05% by weight.
  • Alkyl ether sulfates are known anionic surfactants which are obtained by sulfation of nonionic surfactants of the alkylpolyglycol ether type and subsequent neutralization.
  • the alkyl ether sulfates which are suitable for the purposes of the invention follow the formula (I) R 1 O- (CH 2 CH 2 O) n SO 3 X (I) in which R 1 is an alkyl radical having 12 to 18, in particular 12 to 14, carbon atoms, n is numbers 2 to 5, in particular 2 to 3 and X is sodium or potassium.
  • Typical examples are the sodium salts of sulfates of the C 12/14 cocoalcohol-2, -2,3- and -3-EO adduct.
  • the alkyl ether sulfates can have a conventional or narrow homolog distribution.
  • the alkyl ether sulfates are preferably used in amounts of 1 to 8, preferably 1.5 to 6 and in particular 2 to 4% by weight, based on the composition.
  • Amine oxides are also known substances, which are occasionally attributed to the cationic, but usually the nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and are oxidized in the presence of hydrogen peroxide.
  • the amine oxides which are suitable for the purposes of the invention follow the formula (II) in which R 2 represents a linear or branched alkyl radical having 12 to 18 carbon atoms and R 3 and R 4 independently of one another are R 2 or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
  • Amine oxides of the formula (II) are preferably used in which R 2 and R 3 are C 12/14 and C 12/18 cocoalkyl radicals and R 4 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (II) in which R 2 is a C 12/14 or C 12/18 cocoalkyl radical and R 3 and R 4 are methyl or hydroxyethyl.
  • the amine oxides are preferably used in amounts of 1.5 to 6, preferably 2 to 4,% by weight, based on the composition.
  • Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (III) R 5 O- [G] p (III) in which R 5 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0 301 298 and WO 90/03977 .
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 5 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • Alkyl oligoglucosides with chain length C 8 - are preferred.
  • the alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred. The glycosides are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.
  • the agents may contain fatty acid salts of the formula (IV) as further surfactants R 6 CO-OX (IV) in which R 6 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
  • R 6 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
  • Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their mixtures, and their mixtures the pressure splitting of technical fats and oils.
  • Salts of technical coconut or tallow fatty acids are preferably used. Since the recipes are strongly alkaline, the fatty acids can be used instead of the salts, which are neutralized in situ when added to the mixture. Preferably, those agents contain, as an optional component, fatty acid salts in which a particular low foam level is desired.
  • the soaps are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.
  • the agents usually have a non-aqueous content of 5 to 35 and preferably 8 to 15 wt .-% and are suitable for the treatment of textile fabrics, such as for example yarns, webs of fabric and in particular textiles. They are usually used at low temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C).
  • the means stand out not only by excellent stain removal, but also reliably prevent deposits traces of metal on the fibers and thus prevent yellowing.
  • the real one Use the agent aimed at removing stains when washing they can also be used for other purposes in which hypochlorite solutions are used, for example for cleaning and disinfecting hard surfaces.
  • auxiliaries and additives include, for example, other chlorine-stable surfactants or hydrotropes such as alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, xylene sulfonates, sarcosinates, Taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid N-alkylglucamides.
  • the sum of all surfactants preferably makes at most 10 to 15% by weight. the total amount of ingredients in the recipe.
  • the funds can Contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with their
  • the pH of the recipes can be adjusted to an optimal value from 12.5 to 14.
  • the agents contain amine oxidephosphonic acids as further stabilizers and alkali or alkaline earth silicates, preferably sodium and / or potassium silicates with a modulus in the range of 1.0 to 3.0 and preferably 1.5 to 2.0, the amount used the stabilizers based on the agent is 0.1 to 1 and in particular 0.2 to 0.5% by weight. They are special in terms of additional corrosion protection then an advantage if the exposure time of the agents is very long.
  • the agents can be active chlorine-stable fragrances, optical brighteners, dyes and Pigments in a total of 0.01 to 0.5 wt .-% - based on the agent - contain.
  • active chlorine-resistant include, for example, monocyclic and bicyclic Monoterpene alcohols and their esters with acetic or propionic acid (e.g. isobomeal, dihydroterpene oil, Isobornyl acetate, dihydroterpenyl acetate).
  • the optical brighteners can be, for example the potassium salt of 4,4'-bis- (1,2,3-triazolyl) - (2-) - stilbin-2,2-sulfonic acid act under the brand name Phorwite® BHC 766 is sold.
  • the color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz) in question.
  • the preparation is made by stirring. If necessary, the obtained Decant or filter product to remove foreign bodies and / or agglomerates.
  • the agents also have a viscosity above 100 mPas - measured at 20 ° C in one Brookfield viscometer - on.
  • soiled fabric was treated with bleach solutions.
  • the yellowing of the tissue was determined photometrically, the initial value of the soiled tissue serving as the standard (100%).
  • the measurements were carried out in a liquor with a metal ion content of 300 ppb Fe and 100 ppb Mn; the water hardness was 1000 ppm CaCl 2 , the hydrogen carbonate content was 0.013% by weight.
  • the liquor ratio (tissue: water) was 1:50, the exposure time was 30 minutes at a temperature of 40 ° C.
  • Table 1 The results are summarized in Table 1; the quantities are understood as% by weight:

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft die Verwendung von Polyacrylsäureverbindungen als Sequestriermittel gegen die Ablagerung von Metallen auf Geweben in wäßrigen Bleichmitteln.The invention relates the use of polyacrylic acid compounds as Sequestrant against the Deposition of metals on fabrics in aqueous bleaches.

Stand der TechnikState of the art

Während zur Wäsche stark verschmutzter Textilien in vielen Staaten Europas pulverförmige oder flüssige Vollwaschmittel eingesetzt werden, die ihr Leistungsvermögen erst bei höheren Temperaturen erreichen, wird beispielsweise von den Verbrauchern in den USA und Spanien die Kaltwäsche vorgezogen, bei der man neben einem Waschmittel zur Entfernung besonders schwieriger Flecken ein flüssiges Bleichmittel, vorzugsweise auf Hypochloritbasis, zusetzt.While heavily soiled textiles for washing in many European countries are powdered or Liquid heavy-duty detergents are used, their performance only at higher temperatures For example, consumers in the U.S. and Spain prefer cold washing, where, in addition to a detergent to remove particularly difficult stains, a liquid Bleach, preferably based on hypochlorite, is added.

Aus dem Stand der Technik sind eine Vielzahl von flüssigen Bleichmitteln bekannt. So wird beispielsweise in der EP-A 0 274 885 (ICI) der Einsatz von Mischungen linearer und verzweigter Aminoxide zur Herstellung viskoser Hypochloritbleichmittel empfohlen. Gemäß der Lehre der EP-A 0 145 084 (Unilever) können für diesen Zweck auch Mischungen von Aminoxiden mit Seifen, Sarkosinaten, Tauriden oder Zuckerestem eingesetzt werden. Aus den Schriften EP-A 0 137 551 und EP-A 0 447 261 (Unilever) ist der Einsatz von Aminoxiden mit Seife oder Sarcosinat und weiteren anionischen Tensiden, beispielsweise Alkylsulfaten, Alkylethersulfaten, sekundären Alkansulfonaten oder Alkylbenzolsulfonaten als verdickende Komponente für Hypochloritlösungen bekannt. Über die Verwendung von Alkylarylsulfonaten als Verdickungsmitteln in wäßrigen Bleichmitteln, die bestimmte Stilbenfarbstoffe als optische Aufheller enthalten, wird in der EP-A 0 156 438 berichtet. Gegenstand der ES-A 8801389 (Henkel Ibérica) sind Bleichmittel auf Basis von wäßrigen Hypochloritlösungen, die als Tensidkomponente überwiegend Alkylethersulfate und daneben kleine Anteile an Aminoxiden enthalten. Aus der EP-A1 0 447 261 sind weiterhin wäßrige Bleichmittelzusammensetzungen mit einem Gehalt an Natriumhypochlorit und anionischen Tensiden bekannt. Die Hypochloritkonzentration dieser Mittel liegt jedoch bei 0,1 bis 8 und vorzugsweise 0,5 bis 5 Gew.-% Aktivchlor. Im Deutschen Patent DE-C1 43 33 100 hat die Anmelderin schließlich wäßrige Bleich- und Reinigungsmittel auf Basis von Hypochloriten, Fettalkoholethersulfaten, Aminoxiden und Aminoxidphosphonsäuren vorgeschlagen.A large number of liquid bleaching agents are known from the prior art. For example, EP-A 0 274 885 (ICI) recommends the use of mixtures of linear and branched amine oxides for the production of viscous hypochlorite bleaches. According to the teaching of EP-A 0 145 084 (Unilever), mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose. The documents EP-A 0 137 551 and EP-A 0 447 261 (Unilever) disclose the use of amine oxides with soap or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or alkyl benzene sulfonates as a thickening component for hypochlorite solutions. EP-A 0 156 438 reports on the use of alkylarylsulfonates as thickeners in aqueous bleaches which contain certain stilbene dyes as optical brighteners. The subject of ES-A 8801389 (Henkel Ibérica) are bleaching agents based on aqueous hypochlorite solutions, which mainly contain alkyl ether sulfates and small amounts of amine oxides as surfactant components. From EP-A1 0 447 261 aqueous bleaching compositions containing sodium hypochlorite and anionic surfactants are also known. However, the hypochlorite concentration of these agents is 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine. In German patent DE-C1 43 33 100 , the applicant finally proposed aqueous bleaching and cleaning agents based on hypochlorites, fatty alcohol ether sulfates, amine oxides and amine oxide phosphonic acids.

An Bleichmittel der genannten Art werden vom Verbraucher hohe Anforderungen gestellt: Sie müssen textilverträglich sein, d.h. durch die Behandlung mit der an sich aggressiven Chemikalie Hypochlorit müssen die Flecken ohne Angriff des Gewebes entfernt werden. Da ein Hautkontakt mit den Bleichmitteln nicht ausgeschlossen ist, müssen die Zubereitungen femer so dermatologisch verträglich wie nur eben möglich sein. Ein weiteres Problem besteht darin, daß Hypochloritlösungen auch Metalle angreifen und die gelösten Metallspuren auf den Textilfasern während der Wäsche abgelagert werden können, was sich letztendlich in einer Vergilbung des Gewebes widerspiegelt. Mittel des Marktes versuchen zwar diese Redeposition durch die Mitverwendung von Silicaten zu verhindern, in der Praxis erweist sich diese Maßnahme jedoch nicht immer als zufriedenstellend.High demands are placed on bleaches of the type mentioned: consumers have to be compatible with textiles, i.e. by treatment with the intrinsically aggressive chemical hypochlorite the stains must be removed without attacking the tissue. Because skin contact with the bleach is not excluded, the preparations must also be as dermatologically tolerated as possible just be possible. Another problem is that hypochlorite solutions also attack metals and the dissolved metal traces can be deposited on the textile fibers during washing, which is ultimately reflected in the yellowing of the fabric. Try means of the market to prevent this redeposition by using silicates in practice However, this measure does not always prove to be satisfactory.

Demzufolge hat die komplexe Aufgabe der Erfindung darin bestanden, wäßrige Bleichmittel zur Verfügung zu stellen, die gleichzeitig chlorstabil, textilschonend und möglichst hautverträglich sind, eine ausreichend hohe Viskosität aufweisen und bei hohem Fleckentfernungsvermögen die Ablagerung von Metallspuren auf dem Gewebe zuverlässig verhindern.Accordingly, the complex object of the invention has been to provide aqueous bleaches to provide, which are chlorine-stable, gentle on textiles and as skin-friendly as possible, one have sufficiently high viscosity and with high stain removal capacity the deposition of Prevent metal traces on the fabric reliably.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist die Verwendung von Polyacrylsäureverbindungen, ausgewählt aus der Gruppe der Homopolymere der Acrylsäure und Methacrylsäure, in Mengen von 0,01 bis 1 Gew.-% als Sequestriermittel gegen die Ablagerung von Metallen auf Geweben in wäßrigen Bleichmitteln mit einem Gehalt - bezogen auf die Mittel - von 1 bis 10 Gew.-% Alkalihypochlorit und 0,1 bis 1 Gew.-% Aminoxidphosphonsäure und Alkali- bzw. Erdalkalisilikat sowie gegebenenfalls weiteren üblichen Hilfs- und Zusatzstoffen.The invention relates to the use of polyacrylic acid compounds, selected from the group of homopolymers of acrylic acid and methacrylic acid, in amounts of 0.01 to 1 wt .-% as a sequestering agent against Deposition of metals on fabrics in aqueous bleaches with a content - related on the means - from 1 to 10% by weight of alkali hypochlorite and 0.1 to 1% by weight Amine oxidephosphonic acid and alkali or alkaline earth metal silicate and optionally further usual auxiliaries and additives.

Überraschenderweise wurde gefunden, daß der Zusatz geringer Mengen Polyacrylsäureverbindungen zu den Hypochloritlösungen die Ablagerung von Metallen auf dem Gewebe während der Wäsche signifikant vermindert und der Vergilbung der Fasern entgegenwirkt. Die Erfindung schließt die Erkenntnis ein, daß die Mitverwendung von milden, chlorstabilen Tensiden wie vorzugsweise Alkylethersulfaten, Aminoxiden, Alkyl- und/oder Alkenyloligoglykosiden und Fettsäuresalzen zu einer weiteren Verbesserung der Reinigungsleistung und der dermatologischen Verträglichkeit führt. Die Mittel weisen schließlich eine ausreichend hohe Viskosität auf, so daß eine Dosierung durch den Verbraucher problemlos möglich ist.Surprisingly, it was found that the addition of small amounts of polyacrylic acid compounds to the hypochlorite solutions, the deposition of metals on the fabric during washing significantly reduced and counteracts the yellowing of the fibers. The invention closes the knowledge that the use of mild, chlorine-stable surfactants such as preferably alkyl ether sulfates, Amine oxides, alkyl and / or alkenyl oligoglycosides and fatty acid salts for a further improvement cleaning performance and dermatological compatibility. The Finally, agents have a sufficiently high viscosity so that dosing by the consumer is easily possible.

Alkalihypochloritealkali metal hypochlorites

Unter Alkalihypochloriten sind Lithium-, Kalium- und insbesondere Natriumhypochlorit zu verstehen. Die Hypochlorite können vorzugsweise in Mengen von 1,5 bis 8 und insbesondere 4 bis 6 Gew.-% - bezogen auf die Mittel - eingesetzt werden.Alkali hypochlorites are to be understood as lithium, potassium and in particular sodium hypochlorite. The Hypochlorites can preferably in amounts of 1.5 to 8 and in particular 4 to 6 wt .-% - based on the funds - are used.

Polyacrylsäureverbindungenpolyacrylic acid

Unter Polyacrylsäureverbindungen sind Homopolymere der Acrylsäure und der Methacrylsäure zu verstehen. Polyacrylsäureverbindungen mit besonders vorteilhafter stabilisierender Wirkung liegen als Alkalisalze vor und weisen ein durchschnittliches Molekulargewicht im Bereich von 1.000 bis 10.000 und insbesondere 4.000 bis 6.000 Dalton auf. Der bevorzugte Einsatzbereich liegt bei 0,02 bis 0,05 Gew.-%.Polyacrylic acid compounds include homopolymers of acrylic acid and methacrylic acid to understand. Polyacrylic acid compounds with special advantageous stabilizing effects are present as alkali salts and have an average Molecular weight in the range of 1,000 to 10,000 and in particular 4,000 to 6,000 daltons. The preferred application range is 0.02 to 0.05% by weight.

Alkylethersulfatealkyl ether

Alkylethersulfate stellen bekannte anionische Tenside dar, die durch Sulfatierung von nichtionischen Tensiden vom Typ der Alkylpolyglycolether und nachfolgende Neutralisation erhalten werden. Die im Sinne der Erfindung in Betracht kommenden Alkylethersulfate folgen der Formel (I), R1O-(CH2CH2O)nSO3X   (I) in der R1 für einen Alkylrest mit 12 bis 18, insbesondere 12 bis 14 Kohlenstoffatomen, n für Zahlen 2 bis 5, insbesondere 2 bis 3 und X für Natrium oder Kalium steht. Typische Beispiele sind die Natriumsalze von Sulfaten des C12/14-Kokosalkohol-2, -2,3- und -3-EO-Adduktes. Die Alkylethersulfate können eine konventionelle oder eingeengte Homologenverteilung aufweisen. Vorzugsweise werden die Alkylethersulfate in Mengen von 1 bis 8, vorzugsweise 1,5 bis 6 und insbesondere 2 bis 4 Gew.-% - bezogen auf die Mittel - eingesetzt.Alkyl ether sulfates are known anionic surfactants which are obtained by sulfation of nonionic surfactants of the alkylpolyglycol ether type and subsequent neutralization. The alkyl ether sulfates which are suitable for the purposes of the invention follow the formula (I) R 1 O- (CH 2 CH 2 O) n SO 3 X (I) in which R 1 is an alkyl radical having 12 to 18, in particular 12 to 14, carbon atoms, n is numbers 2 to 5, in particular 2 to 3 and X is sodium or potassium. Typical examples are the sodium salts of sulfates of the C 12/14 cocoalcohol-2, -2,3- and -3-EO adduct. The alkyl ether sulfates can have a conventional or narrow homolog distribution. The alkyl ether sulfates are preferably used in amounts of 1 to 8, preferably 1.5 to 6 and in particular 2 to 4% by weight, based on the composition.

Aminoxideamine oxides

Auch Aminoxide stellen bekannte Stoffe dar, die gelegentlich den kationischen, in der Regel jedoch den nichtionischen Tensiden zugerechnet werden. Zu ihrer Herstellung geht man von tertiären Fettaminen aus, die üblicherweise entweder einen langen und zwei kurze oder zwei lange und einen kurzen Alkylrest aufweisen, und oxidiert sie in Gegenwart von Wasserstoffperoxid. Die im Sinne der Erfindung in Betracht kommenden Aminoxide folgen der Formel (II),

Figure 00040001
in der R2 für einen linearen oder verzweigten Alkylrest mit 12 bis 18 Kohlenstoffatomen sowie R3 und R4 unabhängig voneinander für R2 oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen stehen. Vorzugsweise werden Aminoxide der Formel (II) eingesetzt, in denen R2 und R3 für C12/14- bzw. C12/18-Kokosalkylreste stehen und R4 einen Methyl- oder einen Hydroxyethylrest bedeutet. Ebenfalls bevorzugt sind Aminoxide der Formel (II), in denen R2 für einen C12/14- bzw. C12/18-Kokosalkylrest steht und R3 und R4 die Bedeutung eines Methyl- oder Hydroxyethylrestes haben. Vorzugsweise werden die Aminoxide in Mengen von 1,5 bis 6, vorzugsweise 2 bis 4 Gew.-% - bezogen auf die Mittel - eingesetzt.Amine oxides are also known substances, which are occasionally attributed to the cationic, but usually the nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and are oxidized in the presence of hydrogen peroxide. The amine oxides which are suitable for the purposes of the invention follow the formula (II)
Figure 00040001
in which R 2 represents a linear or branched alkyl radical having 12 to 18 carbon atoms and R 3 and R 4 independently of one another are R 2 or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms. Amine oxides of the formula (II) are preferably used in which R 2 and R 3 are C 12/14 and C 12/18 cocoalkyl radicals and R 4 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (II) in which R 2 is a C 12/14 or C 12/18 cocoalkyl radical and R 3 and R 4 are methyl or hydroxyethyl. The amine oxides are preferably used in amounts of 1.5 to 6, preferably 2 to 4,% by weight, based on the composition.

Alkyl- und/oder AlkenyloligoglykosideAlkyl and / or alkenyl oligoglycosides

Alkyl- und Alkenyloligoglykoside stellen bekannte nichtionische Tenside dar, die der Formel (III) folgen, R5O-[G]p    (III) in der R5 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-A1 0 301 298 und WO 90/03977 verwiesen. Die Alkylund/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (III) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R5 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestem oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden, Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R5 kann sich femer auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3. Vorzugsweise werden die Glykoside in Mengen von 1,5 bis 6, vorzugsweise 2 bis 4 Gew.-% - bezogen auf die Mittel - eingesetzt. Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (III) R 5 O- [G] p (III) in which R 5 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0 301 298 and WO 90/03977 . The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (III) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R 5 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides with chain length C 8 - are preferred. C 10 (DP = 1 to 3), which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of C 12 alcohol, and alkyl oligoglucosides based technical C 9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred. The glycosides are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.

Fettsäuresalzefatty acid salts

Als weitere Tenside können die Mittel Fettsäuresalze der Formel (IV) enthalten, R6CO-OX   (IV) in der R6CO für einen Acylrest mit 12 bis 22 Kohlenstoffatomen und X für ein Alkalimetall steht. Typische Beispiele sind die Natrium- und/oder Kaliumsalze der Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie bei der Druckspaltung technischer Fette und Öle anfallen. Vorzugsweise werden Salze technischer Kokos- oder Talgfettsäuren eingesetzt. Da die Rezepturen stark alkalisch eingestellt sind, können anstelle der Salze auch die Fettsäuren eingesetzt werden, die beim Eintragen in die Mischung in situ neutralisiert werden. Vorzugsweise enthalten diejenigen Mittel als fakultative Komponente Fettsäuresalze, bei denen eine besondere Schaumarmut erwünscht ist. Vorzugsweise werden die Seifen in Mengen von 1,5 bis 6, vorzugsweise 2 bis 4 Gew.-% - bezogen auf die Mittel - eingesetzt.The agents may contain fatty acid salts of the formula (IV) as further surfactants R 6 CO-OX (IV) in which R 6 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal. Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their mixtures, and their mixtures the pressure splitting of technical fats and oils. Salts of technical coconut or tallow fatty acids are preferably used. Since the recipes are strongly alkaline, the fatty acids can be used instead of the salts, which are neutralized in situ when added to the mixture. Preferably, those agents contain, as an optional component, fatty acid salts in which a particular low foam level is desired. The soaps are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.

Gewerbliche AnwendbarkeitIndustrial applicability

Die Mittel weisen in der Regel einen nicht-wäßrigen Anteil von 5 bis 35 und vorzugsweise 8 bis 15 Gew.-% auf und eignen sich für die Behandlung von textilen Flächengebilden, wie beispielsweise Garnen, Stoffbahnen und insbesondere Textilien. Üblicherweise erfolgt ihre Anwendung bei niedrigen Temperaturen, d.h. im Bereich der Kaltwäsche (ca. 15 bis 25°C). Die Mittel zeichnen sich nicht nur durch eine ausgezeichnete Fleckentfernung aus, sondern verhindern zuverlässig die Ablagerung von Metallspuren auf den Fasern und beugen somit auch der Vergilbung vor. Obschon die eigentliche Verwendung der Mittel auf die Entfernung von Flecken bei der Wäsche gerichtet ist, eignen sie sich grundsätzlich auch für andere Zwecke, in denen Hypochloritlösungen Anwendung finden, beispielsweise für die Reinigung und Desinfektion harter Oberflächen.The agents usually have a non-aqueous content of 5 to 35 and preferably 8 to 15 wt .-% and are suitable for the treatment of textile fabrics, such as for example yarns, webs of fabric and in particular textiles. They are usually used at low temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C). The means stand out not only by excellent stain removal, but also reliably prevent deposits traces of metal on the fibers and thus prevent yellowing. Although the real one Use the agent aimed at removing stains when washing they can also be used for other purposes in which hypochlorite solutions are used, for example for cleaning and disinfecting hard surfaces.

Als weitere Hilfs- und Zusatzstoffe kommen beispielsweise weitere chlorstabile Tenside bzw. Hydrotrope in Betracht, wie etwa Alkylsulfate, Alkylsulfonate, Alkylbenzolsulfonate, Xylolsulfonate, Sarcosinate, Tauride, Isethionate, Sulfosuccinate, Betaine, Zuckerester, Fettalkoholpolyglycolether und Fettsäure-N-alkylglucamide. Vorzugsweise macht die Summe aller Tenside höchstens 10 bis 15 Gew.-% der Gesamtmenge an Inhaltsstoffen in der Rezeptur aus. Die Mittel können Alkalimetallverbindungen enthalten, vorzugsweise Natriumhydroxid oder Kaliumhydroxid, mit deren Hilfe der pH-Wert der Rezepturen auf einen optimalen Wert von 12,5 bis 14 eingestellt werden kann. Die Mittel enthalten als weitere Stabilisatoren Aminoxidphosphonsäuren und Alkali- bzw. Erdalkalisilicate, vorzugsweise Natrium- und/oder Kaliumsilicate mit einem Modul im Bereich von 1,0 bis 3,0 und vorzugsweise 1,5 bis 2,0, wobei die Einsatzmenge der Stabilisatoren bezogen auf die Mittel 0,1 bis 1 und insbesondere 0,2 bis 0,5 Gew.-% beträgt. Sie sind im Sinne eines zusätzlichen Korrosionsschutzes besonders dann von Vorteil, wenn die Einwirkungszeit der Mittel sehr lang ist.Additional auxiliaries and additives include, for example, other chlorine-stable surfactants or hydrotropes such as alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, xylene sulfonates, sarcosinates, Taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid N-alkylglucamides. The sum of all surfactants preferably makes at most 10 to 15% by weight. the total amount of ingredients in the recipe. The funds can Contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with their The pH of the recipes can be adjusted to an optimal value from 12.5 to 14. The agents contain amine oxidephosphonic acids as further stabilizers and alkali or alkaline earth silicates, preferably sodium and / or potassium silicates with a modulus in the range of 1.0 to 3.0 and preferably 1.5 to 2.0, the amount used the stabilizers based on the agent is 0.1 to 1 and in particular 0.2 to 0.5% by weight. They are special in terms of additional corrosion protection then an advantage if the exposure time of the agents is very long.

Darüber hinaus können die Mittel aktivchlorstabile Duftstoffe, optische Aufheller, Farbstoffe und Pigmente in Mengen von insgesamt 0,01 bis 0,5 Gew.-% - bezogen auf die Mittel - enthalten. Zu den als aktivchlorbeständig bekannten Duftstoffen zählen beispielsweise monocyclische und bicyclische Monoterpenalkohole sowie deren Ester mit Essig- oder Propionsäure (z.B. Isobomeal, Dihydroterpenöl, Isobornylacetat, Dihydroterpenylacetat). Bei den optischen Aufhellern kann es sich beispielsweise um das Kalisalz der 4,4'-bis-(1,2,3-Triazolyl)-(2-)-Stilbin-2,2-sulfonsäure handeln, das unter der Marke Phorwite® BHC 766 vertrieben wird. Als Farbpigmente kommen u.a. grüne Chlorophthalocyanine (Pigmosol® Green, Hostaphine® Green) oder gelbes Solar Yellow BG 300 (Sandoz) in Frage. Die Herstellung der Mittel erfolgt mittels Umrühren. Gegebenenfalls kann das erhaltene Produkt zur Abtrennung von Fremdkörpern und/oder Agglomeraten dekantiert oder filtriert werden. Die Mittel weisen zudem eine Viskosität oberhalb von 100 mPas - gemessen bei 20°C in einem Brookfield-Viskosimeter - auf. In addition, the agents can be active chlorine-stable fragrances, optical brighteners, dyes and Pigments in a total of 0.01 to 0.5 wt .-% - based on the agent - contain. To the fragrances known to be active chlorine-resistant include, for example, monocyclic and bicyclic Monoterpene alcohols and their esters with acetic or propionic acid (e.g. isobomeal, dihydroterpene oil, Isobornyl acetate, dihydroterpenyl acetate). The optical brighteners can be, for example the potassium salt of 4,4'-bis- (1,2,3-triazolyl) - (2-) - stilbin-2,2-sulfonic acid act under the brand name Phorwite® BHC 766 is sold. The color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz) in question. The The preparation is made by stirring. If necessary, the obtained Decant or filter product to remove foreign bodies and / or agglomerates. The agents also have a viscosity above 100 mPas - measured at 20 ° C in one Brookfield viscometer - on.

BeispieleExamples

Zur Untersuchung der Bleichwirkung wurde verschmutztes Gewebe mit Bleichmittellösungen behandelt. Die Vergilbung des Gewebes wurde photometrisch bestimmt, wobei der Ausgangswert des verschmutzten Gewebes als Standard (100 %) diente. Die Messungen wurden in einer Flotte mit einem Metallionengehalt von 300 ppb Fe und 100 ppb Mn durchgeführt; die Wasserhärte betrug 1000 ppm CaCl2, der Gehalt an Hydrogencarbonat 0,013 Gew.-%. Das Flottenverhältnis (Gewebe : Wasser) lag bei 1 : 50, die Einwirkzeit betrug 30 min bei einer Temperatur von 40°C. Die Ergebnisse sind in Tabelle 1 zusammengefaßt; die Mengenangaben verstehen sich als Gew.-%:

Figure 00080001
To investigate the bleaching effect, soiled fabric was treated with bleach solutions. The yellowing of the tissue was determined photometrically, the initial value of the soiled tissue serving as the standard (100%). The measurements were carried out in a liquor with a metal ion content of 300 ppb Fe and 100 ppb Mn; the water hardness was 1000 ppm CaCl 2 , the hydrogen carbonate content was 0.013% by weight. The liquor ratio (tissue: water) was 1:50, the exposure time was 30 minutes at a temperature of 40 ° C. The results are summarized in Table 1; the quantities are understood as% by weight:
Figure 00080001

Die Verwendung dieser Mittel fällt nicht unter den Schutzumfang der Ansprüche.The use of these funds is not within the scope of the claims.

Man erkennt, daß der Zusatz von Polyacrylaten zu den alkalischen Hypochloritlösungen zu einer deutlichen Aufhellung des Gewebes führt, die durch den Zusatz von Silicaten noch weiter gesteigert werden kann. Demgegenüber ist der Zusatz von Silicaten als alleinigen Stabilisatoren im Vergleich zu reinen Hypochloritlösungen sogar eher noch von Nachteil.It can be seen that the addition of polyacrylates to the alkaline hypochlorite solutions leads to a clear Lightening of the tissue leads, which are further increased by the addition of silicates can. In contrast, the addition of silicates as sole stabilizers compared to pure ones Hypochlorite solutions are even more of a disadvantage.

Claims (7)

  1. The use of polyacrylic acid compounds selected from the group of homopolymers of acrylic acid and methacrylic acid in quantities of 0.01 to 1% by weight as sequestering agents against the deposition of metals on fabrics in water-based bleaching preparations containing - based on the preparation - 1 to 10% by weight of alkali metal hypochlorite and 0.1 to 1% by weight of amine oxide phosphonic acid and alkali metal or alkaline earth metal silicate and optionally other typical auxiliaries and additives.
  2. The use claimed in claim 1, characterized in that the preparations contain sodium hypochlorite.
  3. The use claimed in claim 1 or 2, characterized in that the preparations contain alkyl ether sulfates corresponding to formula (I): R1O-(CH2CH2O)nSO3X in which R1 is a C12-18 alkyl group, n has a value of 2 to 5 and X stands for sodium or potassium.
  4. The use claimed in any of claims 1 to 3, characterized in that the preparations contain amine oxides corresponding to formula (II):
    Figure 00110001
    in which R2 is a linear or branched alkyl group containing 12 to 18 carbon atoms and R3 and R4 independently of one another have the same meaning as R2 or represent an optionally hydroxysubstituted alkyl group containing 1 to 4 carbon atoms.
  5. The use claimed in any of claims 1 to 4, characterized in that the preparations contain alkyl and/or alkenyl oligoglycosides corresponding to formula (III): R5O-[G]p in which R5 is an alkyl and/or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10.
  6. The use claimed in one or more of claims 1 to 5, characterized in that the preparations contain fatty acid salts corresponding to formula (IV): R6CO-OX in which R6CO is an acyl group containing 12 to 22 carbon atoms and X is an alkali metal.
  7. The use claimed in any of claims 1 to 6, characterized in that the preparations have a viscosity above 100 mPas, as measured at 20°C in a Brookfield viscosimeter.
EP97924975A 1996-05-31 1997-05-22 Aqueous bleaching agents Expired - Lifetime EP0918841B1 (en)

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DE19624843A DE19624843C2 (en) 1996-05-31 1996-06-21 Use of aqueous bleaching compositions
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0606707A1 (en) * 1993-01-11 1994-07-20 The Clorox Company Thickened hypochlorite solutions with reduced bleach odor and methods of manufacture and use
WO1997043395A1 (en) * 1996-05-10 1997-11-20 The Clorox Company Sequesterants as hypochlorite bleach enhancers

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US3663442A (en) * 1970-02-09 1972-05-16 Purex Corp Ltd Household bleach having stable opacifier
US3689421A (en) * 1971-04-09 1972-09-05 Purex Corp Ltd Household hypochlorite bleach with stable latex opacifier
GB1548379A (en) * 1975-05-19 1979-07-11 Jeyes Group Ltd Bleach compositions
US4867896A (en) * 1988-02-17 1989-09-19 Lever Brothers Company Cleaning compositions containing cross-linked polymeric thickeners and hypochlorite bleach
CA2003857C (en) * 1988-12-15 1995-07-18 Lisa Michele Finley Stable thickened aqueous bleach compositions
GB9027372D0 (en) * 1990-12-18 1991-02-06 Cussons Int Ltd Detergent composition
DE4333100C1 (en) * 1993-09-29 1994-10-06 Henkel Kgaa Bleaching and disinfecting compositions
ES2169062T3 (en) * 1994-02-22 2002-07-01 Procter & Gamble HIPOCLORITE WHITENING COMPOSITIONS.

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EP0606707A1 (en) * 1993-01-11 1994-07-20 The Clorox Company Thickened hypochlorite solutions with reduced bleach odor and methods of manufacture and use
WO1997043395A1 (en) * 1996-05-10 1997-11-20 The Clorox Company Sequesterants as hypochlorite bleach enhancers

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