EP1001010B1 - Bleichmittelzusammensetzungen - Google Patents

Bleichmittelzusammensetzungen Download PDF

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Publication number
EP1001010B1
EP1001010B1 EP98870263A EP98870263A EP1001010B1 EP 1001010 B1 EP1001010 B1 EP 1001010B1 EP 98870263 A EP98870263 A EP 98870263A EP 98870263 A EP98870263 A EP 98870263A EP 1001010 B1 EP1001010 B1 EP 1001010B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
styrene
compositions
mixtures
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98870263A
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English (en)
French (fr)
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EP1001010A1 (de
Inventor
Andrea Briatore
Oreste Todini
Michael Alan John Moss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT98870263T priority Critical patent/ATE239779T1/de
Priority to EP98870263A priority patent/EP1001010B1/de
Priority to ES98870263T priority patent/ES2195306T3/es
Priority to DE69814398T priority patent/DE69814398D1/de
Priority to DE69932580T priority patent/DE69932580T3/de
Priority to AT99870211T priority patent/ATE335068T1/de
Priority to EP99870211A priority patent/EP1001011B2/de
Priority to ES99870211T priority patent/ES2270572T5/es
Priority to US09/831,192 priority patent/US6894015B1/en
Priority to AU18168/00A priority patent/AU1816800A/en
Priority to CO99070900A priority patent/CO5210994A1/es
Priority to CO99070882A priority patent/CO5221050A1/es
Priority to AU18165/00A priority patent/AU1816500A/en
Priority to PCT/US1999/026605 priority patent/WO2000027972A1/en
Priority to TR2001/01308T priority patent/TR200101308T2/xx
Priority to PCT/US1999/026588 priority patent/WO2000027978A1/en
Publication of EP1001010A1 publication Critical patent/EP1001010A1/de
Priority to MA26186A priority patent/MA25309A1/fr
Application granted granted Critical
Publication of EP1001010B1 publication Critical patent/EP1001010B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • 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
    • 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
    • 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
    • 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
    • C11D3/24—Organic compounds containing halogen
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur

Definitions

  • the present invention relates to cleaning compositions suitable for use in various laundry applications including hand and machine laundry methods, comprising a radical scavenger.
  • Cleaning compositions are well known in the art. Such compositions generally comprise a number of active components that provide the cleaning function of the composition. When selecting components of the composition, it is therefore preferred that the components are stable in the composition so as not to lose cleaning effectiveness. In certain instances however, some ingredients of a cleaning composition for example oxidising agents can decompose leading to a reduction in the concentration of oxidising agent over time and consequently to the reduction of the cleaning and whitening performance of the composition.
  • Cleaning compositions can also comprise, in addition to the oxidising agent, a number of other components that provide additional cleaning and whitening performance benefits.
  • the components are stable in the composition, i.e., do not react with the oxidising agent, further reducing the concentration of oxidising agent in the composition.
  • the reaction or interaction of components of the composition with the oxidising agent is inevitable. As a consequence of this, the premature decomposition of the oxidising agent and the other actives present in the composition occurs, leading to the reduction of the cleaning and/or whiteness effectiveness of the composition.
  • decomposition of the oxidising agent and the interaction or reaction of the different ingredients of the composition with the oxidising agent can proceed via one electron and/or two electron chemistry.
  • One electron chemistry reactions are initiated by the formation of radicals from the parent oxidising agent.
  • the radicals formed are more reactive and better oxidising species than the parent and thus accelerate the decomposition kinetics of the oxidising agents and its reaction or interaction with the other actives ingredients present in the composition. Thereby enhancing the decomposition of the oxidising agent and the other actives ingredients.
  • brighteners are components of the composition
  • decomposition thereof can be initiated by one and/or two electron processes, resulting in the loss or decreased of whiteness performance benefit, normally expected when incorporating a brightener.
  • the brightener oxidation via one electron processes is believed to proceed faster than the two electron oxidation.
  • EP-A-668345 discloses hypochlorite-containing compositions comprising a source of strong alkalinity, a pH buffering means (silicate/carbonate) and radical scavengers.
  • the radical scavengers of the present invention are not disclosed therein.
  • compositions of the present invention are stable on storage and provide improved whiteness and cleaning performance in any laundry application even on ageing of the composition, i.e. when used after prolonged periods of storage, as compared to the whiteness and cleaning performance delivered by the same composition under the same conditions but without any radical scavenger. More particularly, it has been found that the stability of the oxidising agent and/or the other actives ingredients (where present), are improved when the radical scavenger of the present invention is present versus when it is not.
  • compositions of the present invention are suitable for the cleaning of different types of fabrics including natural fabrics (e.g., fabrics made of cotton, viscose, linen, silk and wool), synthetic fabrics such as those made of polymeric fibers of synthetic origin as well as those made of both natural and synthetic fibers.
  • natural fabrics e.g., fabrics made of cotton, viscose, linen, silk and wool
  • synthetic fabrics such as those made of polymeric fibers of synthetic origin as well as those made of both natural and synthetic fibers.
  • liquid bleaching compositions of the present invention are suitable for various laundry cleaning applications both when used in diluted conditions, e.g. as a detergent additive or a fully formulated laundry detergent composition, and when used in neat condition, e.g. as a liquid pretreater (spotter).
  • compositions comprising sodium hypochlorite and polystyrene sulfonated polymer.
  • WO 98/06814 describes hypohalite bleaching compositions comprising a pH buffering compound and an ingradient having the ability to prevent the precipitation of the salts of said buffering component upon dilution of the composition in water.
  • WO 99/35227 (relevant for novelty only) describes an acidic composition comprising up to 5% of hydrogen peroxide and up to 0.5% of polystyrene sulfonate.
  • the present invention relates to a liquid cleaning composition
  • a liquid cleaning composition comprising an oxidising agent and a radical scavenger which is selected from the group consisting of: 2,3,4,5 tetramethoxy benzoic acid; 2,3,4,5,6 pentamethoxy benzoic acid; polystyrene; styrene:maleic acid copolymer; styrene:acrylic acid copolymer; styrene:ethylene glycole graft polymers; poly(ethyleneglycol) di-toluene sulfonate; poly hydroxy styrene; poly methyl stryrene; polystyrene divinyl benzene; poly vinyl phenol; and mixtures thereof.
  • a radical scavenger which is selected from the group consisting of: 2,3,4,5 tetramethoxy benzoic acid; 2,3,4,5,6 pentamethoxy benzoic acid; polystyrene; sty
  • compositions of the present invention further comprise one or more surfactants and/or a brightener.
  • Liquid cleaning compositions :
  • compositions according to the present invention are in liquid form.
  • the compositions of the present invention are thickened. Thickening can be achieved by the addition of thickening components for example surfactants, more particularly anionic surfactants.
  • the compositions are in aqueous form. More preferably, they comprise water in an amount of from 60% to 98% by weight, more preferably of from 80% to 97% and most preferably of from 85% to 97% by weight of the total aqueous liquid bleaching composition.
  • the oxidising agent of the present invention can be any known oxidising agent. Suitable oxidising agent include peroxygen or hypohalite bleaching agent.
  • Suitable peroxygen bleaches to be used herein are hydrogen peroxide, water soluble sources thereof, or mixtures thereof.
  • a hydrogen peroxide source refers to any compound that produces perhydroxyl ions when said compound is in contact with water.
  • Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicates, persulphates such as monopersulfate, perborates, peroxyacids such as diperoxydodecandioic acid (DPDA), perphtalic acid, perlauric acid, perbenzoic and alkylperbenzoic acids, hydroperoxides, aliphatic and aromatic diacyl peroxides, and mixtures thereof.
  • Preferred peroxygen bleaches herein are hydrogen peroxide, hydroperoxide and/or diacyl peroxide. Hydrogen peroxide is the most preferred peroxygen bleach herein.
  • Suitable hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydroperoxide.
  • Such hydroperoxides have the advantage to be particularly safe to fabrics and color while delivering excellent bleaching performance when used in any laundry application.
  • Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof.
  • Suitable aromatic dicayl peroxide for use herein is for example benzoyl peroxide.
  • Such diacyl peroxides have the advantage to be particularly safe to fabrics and color while delivering excellent bleaching performance when used in any laundry application.
  • the oxidising agent of the invention is a hypohalite bleach.
  • Hypohalite bleaches may be provided by a variety of sources, including bleaches that are oxidative bleaches and subsequently lead to the formation of positive halide ions as well as bleaches that are organic based sources of halides such as chloroisocyanurates.
  • Suitable hypohalite bleaches for use herein include the alkali metal and alkaline earth metal hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
  • oxidising agents of the present invention are the alkali metal and/or alkaline earth metal hypochlorites selected from the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites, and mixtures thereof. Most preferably the oxidising agent is sodium hypochlorite.
  • the liquid compositions according to the present invention comprise said oxidising agent such that the content of active oxidising agent in the composition is from 0.1% to 20% by weight, more preferably from 0.25% to 8% by weight, most preferably from 0.5% to 6% by weight of the composition.
  • compositions of the present invention comprise a radical scavenger.
  • the radical scavengers herein are selected from the group consisting of 2,3,4,5 tetramethoxy benzoic acid; 2,3,4,5,6 pentamethoxy benzoic acid; polystyrene; styrene:maleic acid copolymer; styrene:acrylic acid copolymer; styrene:ethylene glycole graft polymers; poly(ethyleneglycol) di-toluene sulfonate; poly hydroxy styrene; poly methyl stryrene; polystyrene divinyl benzene; poly vinyl phenol; and mixtures thereof.
  • compositions of the present invention may comprise from 0.001% to 10% by weight of the total composition of a radical scavenger, or a mixture thereof, preferably from 0.01% to 8%, more preferably from 0.1% to 6% and most preferably from 0.2% to 4%.
  • compositions of the present invention may comprise a mixture of the radical scavengers or a combination of at least one radical scavenger of the present invention and another radical scavenger known in the art or those described in EP-A-0 905 224.
  • compositions of the invention are stable on storage.
  • stable on storage it is to be understood that the compositions of the present invention typically do not undergo more than 25% loss of available oxidising agent after 5 days of storage at 50°C ⁇ 0.5°C and more preferably not more than 20%.
  • the % loss of available chlorine may be measured using the method described, for instance, in “Analyses des Eaux et Extraits de Javel” by "Lachner syndicalerance de L'eau de Javel et des building connexes", pages 9-10 (1984). Said method consists in measuring the available oxidising agent in the fresh compositions, i.e. just after they are made, and in the same compositions after 5 days at 50°C.
  • a preferred optional component of the invention is a brightener. Any brightener known in the art may be used herein including both hydrophobic and hydrophilic brighteners and mixtures thereof.
  • Brighteners are compounds which have the ability to fluoresce by absorbing ultraviolet wave-lengths of light and re-emitting visible light. Brighteners, also referred to as fluorescent whitening agents (FWA), have been extensively described in the art, see for instance EP-A-0 265 041, EP-A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening agents" by A.K. Sarkar, published by MERROW, especially page 71-72.
  • FWA fluorescent whitening agents
  • optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanine, dibenzothiophene-5,5-dioxide, azole, 5- and 6-membered-ring heterocycle, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical brighteners which may also be used in the present invention include naphthlimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof. Particularly preferred brighteners for use herein are the derivatives of stilbene and mixtures thereof.
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE® series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal-UNPA®, Tinopal CBS® and Tinopal 5BM® available from Ciba-Geigy; Artic White CC® and Artic White CWD®; the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • brighteners useful herein include 4-methyl-7-diethylamino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[1,2-d]oxazole; 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole, 3-phenyl-7-(isoindolinyl) coumarin; 3-methyl-7-(isoindolinyl) coumarin; 3-chloro-7-(isoindolinyl) coumarin; 4-(isoindolinyl)-4'-methylstilbene; 4-(isoindolinyl)-4'-methoxystilbene; sodium 4-(isoindolinyl)-4'-stilbenesulfonate; 4-(isoindolinyl)-4'-phenylstilbene; 4-((is
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R 1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Optiblanc BRB available from 3V sigma.
  • substituted stilbene 2,2'-disulfonic acid derivatives also include 4-4'-bis (2-2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy under the trade name Brightener 49® or other hydrophilic brighteners like for example Brightener 3® or Brightener 47®, also commercially available from Ciba-Geigy.
  • hydrophobic brighteners useful in the present invention include the polycyclic oxazole derivatives such as benzo-oxazole derivatives, or mixtures thereof and particularly preferred herein the benzo-oxazole derivatives.
  • An example of such a brightener is benzoxazole,2,2'-(thiophenaldyl)bis having the following formula C18H10N2O2S, commercially available from Ciba-Geigy under the trade name Tinopal SOP®. This brightener is almost insoluble in water, i.e. it has a solubility being lower than 1 gram per liter.
  • Another example of such a brightener is bis(sulfobenzofuranyl)biphenyl, commercially available from Ciba-Geigy under the trade name Tinopal PLC®.
  • hydrophobic brighteners any brightener whose solubility in water is lower than 10 grams per liter at 25°C.
  • solubility of a given compound, it is to be understood herein the amount of said compound solubilized in deionized water at 25°C.
  • a compound having a solubility being lower than 10 grams per liter means that when less than 10 grams of said given compound is incorporated in deionized water at 25°C said compound is entirely dissolved in said water, i.e. a clear and stable solution is obtained.
  • incorporating 10 grams per liter or more of said given compound in water will result in a precipitation of said compound in said medium.
  • hydrophilic brighteners it is to be understood herein any brightener whose solubility in water is higher or equal to 10 grams per liter at 25°C.
  • brightener is incorporated at a level of from 0.001% to 1.0%, preferably from 0.005% to 0.5%, more preferably from 0.005% to 0.3% and most preferably from 0.008% to 0.1%, by weight of the composition.
  • hydrophobic brighteners are present in the compositions herein they may both be solubilized or suspended in the compositions of the present invention.
  • Such brighteners solubilisation can be for example achieved by means of a surfactant or a mixture thereof as described herein after.
  • Various surfactants may be used for this purpose like C8-C20 alkyl aryl sulphonates as described for example in U.S. Patent 4, 623,476 or amine oxides as described for example in EP-A-186386.
  • Preferred surfactants also called "co-surfactants" to solubilise and/or suspend such a hydrophobic brightener are anionic surfactants including alkyl sulphates or alkylalkoxy sulphates having from 4 to 30 carbon atoms in the alkyl chain, or alkylethoxycarboxylates having from 6 to 30 carbon atoms in the alkyl chain such as Akyposoft® 100 NV from Chemy or Sandosan LNCS from Sandoz. Preferred are C12-C14 alkyethoxysulphates.
  • Such co-surfactants herein should be used in amounts required to solubilize the hydrophobic brightener in need thereof.
  • the liquid compositions of the present inventions are prepared in a process wherein the hydrophobic brightener and the co-surfactant are first mixed to form a premix, before the premix is then mixed with the remainder of the composition which has been separately prepared.
  • the hydrophobic brightener may be suspended by means of a specific suspending agent, like polymers and/or colloidal particulate silicate. Any polymers known to those skilled in the art as having suspending properties are suitable for use herein including those described for example in EP-A-206718.
  • compositions of the present invention the presence of a chelating agent in addition to radical scavenger is not compulsory, but is highly preferred.
  • compositions of the present invention further contributes to the brightener stability upon prolonged periods of storage, and thus to the effective whiteness performance of these compositions upon ageing.
  • Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, phosphate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
  • Chelating agents may be desired in the compositions of the present invention, preferably phosphate chelating agents like phytic acid, as they further contribute to the benefit delivered by the radical scavengers herein by further improving the stability of the brighteners, thus delivering effective whiteness performance in any laundry application upon ageing of the compositions, i.e. after prolonged periods of storage.
  • Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
  • 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 phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
  • Suitable phosphate chelating agents are as following: Phosphonic acid can be condensed in the reaction :
  • reaction can be repeated with any of the reactive OH groups, and phosphate ingredients are obtained which can be
  • phosphate ingredients are suitable for use herein, and preferred are linear phosphate ingredients (i.e. R is M) where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)), most preferably where n is 2.
  • R linear phosphate ingredients
  • n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)
  • STPP tripolyphosphate
  • M is Sodium
  • Phytic acid which is particularly suitable for use herein, is a hexa-phosphoric acid that occurs naturally in the seeds of many cereal grains, generally in the form of the insoluble calcium-magnesium salt. It may also be derived from corn steep liquor. Commercial grade phytic acid is commercially available from J.T.Baker Co., e.g. as a 40% aqueous solution. It is intended that the present invention covers the acidic form of phytic acid as well as alkali metal salt derivatives thereof, particularly sodium or potassium salts thereof. Sodium phytate is available from Jonas Chemical Co (Brooklyn, N.Y.).
  • the phytic acid component exists primarily as the ionized salt in the liquid compositions herein even if it is added in its acidic form. Mixtures of such salts of phytic acid are also covered.
  • 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.
  • Particularly preferred chelating agents for use herein are phosphate chelating agents like sodium pyrophosphate, sodium tripolyphosphate, phytic acid, and mixtures thereof.
  • compositions according to the present invention comprise up to 10%, preferably from 0.01% to 5% by weight, more preferably from 0.05% to 2% and most preferably from 0.1% to 1.5% by weight of the composition.
  • the pH of the liquid compositions according to the present invention is typically from 12 to 14 measured at 25°C.
  • the liquid compositions of the invention have a pH of from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5, when diluted into 1 to 500 times its weight of water. It is in this alkaline range that the optimum stability and performance of the hypohalite as well as fabric whiteness and/or safety are obtained.
  • the pH range is suitably provided by a buffering component.
  • Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such as sodium and/or potassium oxide.
  • a preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide. Typical levels of such caustic alkalis, when present, are of from 0.1% to 1.5% by weight, preferably from 0.5% to 1.5% by weight of the composition.
  • compositions of the present invention the presence of a pH buffering component is not compulsory, but is preferred.
  • the presence of a pH buffering component in the compositions of the present invention further contributes to the effective whiteness performance of these compositions as well as to the fabric safety.
  • the pH buffering component allows to control the alkalinity in the bleaching solution, i.e. maintain the pH of the bleaching solution at a pH of at least 7.5, preferably at least 8.5, and more preferably at least 9.5 for a longer period of time starting from the moment at which the dilution is completed (e.g. when the bleaching composition of the present invention is diluted in the bleaching solution at a dilution level of 200:1 (water:composition)).
  • the pH buffering component may also contribute to brightener stability, where present, and thus to the effective whiteness performance of the compositions herein.
  • the pH buffering component ensures that the pH of the composition is buffered to a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5 after the composition has been diluted into 1 to 500 times its weight of water.
  • Suitable pH buffering components for use herein are selected from the group consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, boron salts, phosphates, stannates, alluminates and mixtures thereof. More preferably alkali metal salts of carbonate, silicate and borateThe preferred alkali metal salts for use herein are sodium and potassium.
  • Suitable boron salts or mixtures thereof for use herein include alkali metal salts of borates and alkyl borates and mixtures thereof.
  • Examples of boron salts include boric acid, alkali metal salts of metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and alkyl borate containing from 1 to 12 carbon atoms, preferably from 1 to 4.
  • Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate.
  • Particularly preferred boron salts herein are the alkali metal salts of metaborate, such as sodium metaborate, potassium metaborate, and the alkali metal salts of borate, such as sodium borate, or mixtures thereof.
  • Boron salts like sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica Larderello under the name sodium metaborate and Borax®.
  • pH buffering components are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures thereof.
  • the raw materials involved in the preparation of hypohalite bleaches usually contain by-products, e.g. calcium carbonate resulting in an amount of up to 0.4% by weight of by-product within the hypohalite composition. However, at such amount, the by-product will not have the buffering action defined above.
  • by-products e.g. calcium carbonate resulting in an amount of up to 0.4% by weight of by-product within the hypohalite composition.
  • the by-product will not have the buffering action defined above.
  • Liquid bleaching compositions herein will contain an amount of pH buffering component of from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight, and more preferably in an amount of from 0.6% to 3% by weight of the composition.
  • composition according to the invention may comprise other optional components such as bleach-stable surfactants, organic or inorganic alkalis, builders, thickening agents, polymers, pigments, dyes, solvents, perfumes, and mixtures thereof.
  • the liquid compositions of the present invention may comprise a surfactant as a desirable optional ingredient.
  • Said surfactants may be present in the compositions according to the present invention in amounts of from 0.1% to 50%, preferably from 0.1% to 40% and more preferably from 1% to 30% by weight of the composition.
  • Surfactants suitable for use herein include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
  • the surfactant is selected from the group consisting of alkyl sulphate, alkyl ether sulphate and mixtures thereof.
  • Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably linear or branched alkyl having a C 10 -C 20 alkyl component, more preferably a C 12 - C 18 linear or branched alkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • R preferably is a
  • Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 6 -C 24 linear or branched alkyl group having a C 6 -C 24 alkyl component, preferably a C 10 -C 20 linear or branched alkyl, more preferably C 12 -C 18 linear or branched alkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 30, more preferably between about 0.5 and about 5, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 6 -C 24 linear or branched alkyl group having a C 6 -C 24 alkyl component, preferably a C 10 -C 20 linear or
  • 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 C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0) sulfate, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25) sulfate, C 12 -C 18 alkyl polyethoxylate (3.0) sulfate, C 12 -C 18 E(3.0) sulfate, and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, C 12 -C 18 E(4.0) sulfate, wherein the counterion is conveniently selected from sodium and potassium.
  • the surfactant system used is an anionic surfactant system, namely alkyl alkoxy (preferably ethoxy) sulphate alone for example alkyl (ethoxy) 3 sulphate or in combination with a co-surfactant, preferably a C2-C10 alkyl sulphate and/or a C8-C22 alkyl or aryl sulphonate like C8-C22 benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
  • a co-surfactant preferably a C2-C10 alkyl sulphate and/or a C8-C22 alkyl or aryl sulphonate like C8-C22 benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
  • a co-surfactant preferably a C2-C10 alkyl sulphate and/or a
  • compositions according to the present invention have a viscosity between 25 cps and 1500 cps, preferably between 50 cps and 1100 cps, depending from the ratio between AE 3 S and the co-surfactant, when measured with a rheometer like carri-med CSL2-100® at the following viscosity parameters : angle : 1°58, gap : 60, diameter : 4.0 cm, iner : 63.60 at a temperature of 25°C and a shear rate of 30 1/sec.
  • 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 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary or secondary alkanesulfonates, C 8 -C 24 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 9 -C 20 linear alkylbenzenesulfonates C 8 -C 22 primary or secondary alkanesulfonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 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 C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as
  • 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).
  • acyl sarcosinate or mixtures thereof, in its acid and/or salt form preferably long chain acyl sarcosinates having the following formula: wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of from 11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms.
  • M are hydrogen and alkali metal salts, especially sodium and potassium.
  • Said acyl sarcosinate surfactants are derived from natural fatty acids and the aminoacid sarcosine (N-methyl glycine). They are suitable to be used as aqueous solution of their salt or in their acidic form as powder. Being derivatives of natural fatty acids, said acyl sarcosinates are rapidly and completely biodegradable and have good skin compatibility.
  • suitable long chain acyl sarcosinates to be used herein include C 12 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 11 carbon atoms) and C 14 acyl sarcosinate (i.e., an acyl sarcosinate according to the above formula wherein M is hydrogen and R is an alkyl group of 13 carbon atoms).
  • C 12 acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied by Hampshire.
  • C 14 acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied by Hampshire.
  • Suitable nonionic surfactants for use herein include a class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohol) or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • suitable nonionic synthetic surfactants include:
  • nonionic surfactants for use herein are capped nonionic ethoxylated surfactants according to the formula: R 1 (OR 2 ) n OR 3 wherein R 1 is a C 8 -C 18 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably, R 1 is a C 10 -C 15 alkyl or alkenyl group, more preferably a C 10 -C 15 alkyl group; R 2 is a C 2 -C 10 linear or branched alkyl group, preferably a C 4 group; R 3 is a C 1 -C 10 alkyl or alkenyl group, preferably a C 1 -C 5 alkyl group, and n is an integer ranging in the range of from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof.
  • surfactants are commercially available from BASF under the trade name Plurafac®, from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
  • Preferred capped nonionic ethoxylated surfactant of the above formula are those commercially available under the tradename Genapol® L 2.5 NR from Hoechst, and Symperonic® LF/CS 1100 from ICI.
  • Suitable nonionic surfactants for use herein include the amine oxides corresponding to the formula: RR'R"N ⁇ O wherein R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons, and wherein R' and R" are, each, independently, an alkyl group containing 1 to 6 carbon atoms.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • the preferred amine oxides are those in which the primary alkyl group has a straight chain in at least most of the molecules, generally at least 70%, preferably at least 90% of the molecules, and the amine oxides which are especially preferred are those in which R contains 10-18 carbons and R' and R" are both methyl.
  • Exemplary of the preferred amine oxides are the N-hexyldimethylamine oxide, N-octyldimethylamine oxide, N-decyldimethylamine oxide, N-dodecyl dimethylamine oxide, N-tetradecyldimethylamine oxide, N-hexadecyl dimethylamine oxide, N-octadecyldimethylamine oxide, N-eicosyldimethylamine oxide, N-docosyldimethylamine oxide, N-tetracosyl dimethylamine oxide, the corresponding amine oxides in which one or both of the methyl groups are replaced with ethyl or 2-hydroxyethyl groups and mixtures thereof.
  • a most preferred amine oxide for use herein is N-decyldimethylamine oxide.
  • Suitable nonionic surfactants for the purpose of the invention are the phosphine or sulfoxide surfactants of formula : R R' R" A ⁇ O wherein A is phosphorus or sulfur atom, R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons, and wherein R' and R" are, each, independently selected from methyl, ethyl and 2-hydroxyethyl.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • Suitable zwitterionic detergents for use herein comprise the betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
  • Some common examples of these detergents are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
  • Preferred zwitterionic detergent compounds have the formula wherein R1 is an alkyl radical containing from 8 to 22 carbon atoms, R2 and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chain containing from 1 to 3 carbon atoms, X is selected from the group consisting of hydrogen and a hydroxyl radical, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 radicals is from 14 to 24 carbon atoms.
  • Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378, said patents being incorporated herein by reference. Additional synthetic detergents and listings of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980, incorporated herein by reference.
  • Cationic surfactants suitable for use in compositions of the present invention are those having a long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula: [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X - wherein R 2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, benzyl ring structures formed by joining the two R 4 groups, and hydrogen when y is not 0; R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I): whereby
  • Preferred quat ammonium surfactants are those as defined in formula I whereby
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R 3 R 4 N + X - wherein R 1 is C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is independently C 1 -C 4 alkyl, benzyl, and -(C 2 H 40 ) X H where x has a value from 2 to 5, and X is an anion. Not more than one of R 2 , R 3 or R 4 should be benzyl.
  • the preferred alkyl chain length for R 1 is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R 2 R 3 and R 4 are methyl and the anion X may be selected from halide, methosulphate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are :
  • compositions herein is a polymer.
  • Suitable polymers for use herein comprise monomeric units selected from the group consisting of unsaturated carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids and mixtures thereof. Co-polymerisation of the above monomeric units among them or with other co-monomers such as styrenesulfonic acid is also suitable.
  • Preferred examples of such polymers are the polymers and co-polymers of monomeric units selected from the group consisting of acrylic acid, maleic acid, vinylsulphonic acid and mixtures thereof. Also suitable for use herein are the above mentioned polymers and co-polymers which are modified in order to contain other functional groups such as aminophosphonic and/or phosphonic units. More preferred polymers are selected from the group consisting of polyacrylate polymers, co-polymers of acrylic and maleic acid, co-polymers of styrene sulphonic acid and maleic acid, and mixtures thereof, preferably modified with aminophosphonic and/or phosphonic groups.
  • the molecular weight for these polymers and co-polymers is preferably below 100,000, most preferably between 500 and 50,000. Most suitable polymers and co-polymers for use herein will be soluble in an amount up to 0.1% by weight, in an aqueous composition comprising 5% by weight of sodium hypochlorite with its pH adjusted to 13 with sodium hydroxide.
  • polyacrylate polymers sold under the tradename Good-Rite® from BF Goodrich, Acrysol® from Rohm & Haas, Sokalan® from BASF, Norasol® from Norso Haas.
  • co-polymers of styrene sulphonic acid and maleic acid commercially available under the tradename Versaflex® from National Starch such as Versaflex 157, as well as Acumer® terpolymers from Rohm and Haas, in particular Acumer® 3100.
  • Preferred commercially available polymers are the polyacrylate polymers, especially the Norasol® polyacrylate polymers and more preferred are the polyacrylate polymer Norasol® 410N (MW 10,000) and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000).
  • a preferred polymer for use herein is a polyacrylate polymer modified with phosphonic groups commercially available under the tradename Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000) from Norso-Haas.
  • Polymers herein are preferably present in low amounts, i.e. in amounts of up to 10%, preferably up to 1%, more preferably up to 0.5% by weight, even more preferably from 0.001% to 0.3% by weight, and most preferably from 0.005% to 0.2% by weight of the composition.
  • Particularly preferred surfaces to be bleached with the compositions herein are fabrics including for example clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets.
  • the present invention further encompasses a method of bleaching fabrics which comprises the step of contacting said fabrics with a bleaching composition according to the present invention.
  • the compositions used in said method of bleaching fabrics are liquid hypochlorite-containing compositions that may further comprise a chelating agent and/or a pH buffering component as defined hereinbefore. Said method according to the present invention delivers effective whiteness performance upon ageing of the compositions.
  • compositions according to the present invention are applied to fabrics in a liquid form. Indeed, by "in a liquid form”, it is meant herein the liquid compositions according to the present invention per se in neat or diluted form.
  • compositions according to the present invention are typically used in diluted form in a laundry operation.
  • in diluted form it is meant herein that the compositions for the bleaching of fabrics according to the present invention may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by other means such as in a washing machine.
  • Said compositions can be diluted up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times.
  • the method of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted together with the bleaching of said fabrics by contacting said fabrics at the same time with a bleaching composition according to the present invention and said detergent composition, or said washing may be conducted before or after that said fabrics have been bleached.
  • the method of bleaching fabrics comprises the step of contacting fabrics with a liquid bleaching composition according to the present invention, in its neat form, and allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes before rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted before or after that the fabrics have been bleached with the composition herein.
  • the level of hypohalite bleach is from 0.01% to 5%, preferably from 0.1% to 3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1%.
  • the bleaching pre-treatment operation may also be followed by the diluted bleaching method as described herein before either in bucket (hand operation) or in a washing machine.

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  • Cosmetics (AREA)

Claims (7)

  1. Flüssige Reinigungszusammensetzung, umfassend ein Oxidationsmittel und einen Radikalfänger, gewählt aus der Gruppe, bestehend aus 2,3,4,5-Tetramethoxybenzoesäure; 2,3,4,5,6-Pentamethoxybenzoesäure; Polystyrol; Styrol:Maleinsäure-Copolymer; Styrol:Acrylsäure-Copolymer; Styrol:Ethylenglykol-Pfropfpolymere; Poly(ethylenglykol)-ditoluolsulfonat; Polyhydroxystyrol; Polymethylstyrol; Polystyroldivinylbenzol; Polyvinylphenol; und Mischungen hiervon.
  2. Zusammensetzung nach mindestens einem vorangehenden Anspruch, wobei das Oxidationsmittel ein Hypohalogenit-, vorzugsweise Hyprochlorit-Bleichmittel ist.
  3. Zusammensetzung nach mindestens einem vorangehenden Anspruch, umfassend weiterhin auf Aufheller.
  4. Zusammensetzung nach mindestens einem vorangehenden Anspruch, umfassend zusätzlich ein Tensid, gewählt aus der Gruppe, bestehend aus anionischen, nichtionischen, kationischen, amphoteren, zwitterionischen Tensiden und Mischungen hiervon.
  5. Zusammensetzung nach Anspruch 4, umfassend ein anionisches Tensid, gewählt aus Alkylsulfat, Alkylethersulfat und Mischungen hiervon.
  6. Zusammensetzung nach mindestens einem vorangehenden Anspruch, in verdickter flüssiger, vorzugsweise wässriger Form.
  7. Verwendung einer Verbindung, gewählt aus der Gruppe, bestehend aus 2,3,4,5-Tetramethoxybenzoesäure; 2,3,4,5,6-Pentamethoxybenzoesäure; Polystyrol; Styrol:Maleinsäure-Copolymer; Styrol:Acrylsäure-Copolymer; Styrol:Ethylenglykol-Pfropfpolymere; Poly(ethylenglykol)-ditoluolsulfonat; Polyhydroxystyrol; Polymethylstyrol; Polystyroldivinylbenzol; Polyvinylphenol; und Mischungen hiervon als Radikalfänger.
EP98870263A 1998-11-10 1998-12-02 Bleichmittelzusammensetzungen Expired - Lifetime EP1001010B1 (de)

Priority Applications (17)

Application Number Priority Date Filing Date Title
AT98870263T ATE239779T1 (de) 1998-11-11 1998-12-02 Bleichmittelzusammensetzungen
EP98870263A EP1001010B1 (de) 1998-11-10 1998-12-02 Bleichmittelzusammensetzungen
ES98870263T ES2195306T3 (es) 1998-11-11 1998-12-02 Composiciones de blanqueo.
DE69814398T DE69814398D1 (de) 1998-11-11 1998-12-02 Bleichmittelzusammensetzungen
AT99870211T ATE335068T1 (de) 1998-11-11 1999-10-14 Bleichmittelzusammensetzung enthaltende alkoxyliertenbenzoesäure
EP99870211A EP1001011B2 (de) 1998-11-11 1999-10-14 Bleichmittelzusammensetzung enthaltende Alkoxyliertenbenzoesäure
ES99870211T ES2270572T5 (es) 1998-11-10 1999-10-14 Composicion blanqueadora que comprende un acido benzoico alcoxilado.
DE69932580T DE69932580T3 (de) 1998-11-10 1999-10-14 Bleichmittelzusammensetzung enthaltende Alkoxyliertenbenzoesäure
US09/831,192 US6894015B1 (en) 1998-11-11 1999-11-10 Bleaching compositions
CO99070900A CO5210994A1 (es) 1998-11-11 1999-11-10 Composiciones blanqueadoras que comprenden un acido benzoico alcoxilado
CO99070882A CO5221050A1 (es) 1998-11-11 1999-11-10 Composicion limpiadora que comprende un depurados de radicales, para limpieza eficaz y estabilidad mejorada en almacenamiento
AU18165/00A AU1816500A (en) 1998-11-10 1999-11-10 Bleaching compositions
PCT/US1999/026605 WO2000027972A1 (en) 1998-11-10 1999-11-10 Bleaching composition comprising an alkoxylated benzoic acid
TR2001/01308T TR200101308T2 (tr) 1998-11-11 1999-11-10 Bir alkoksile benzoik asiti içeren ağartma bileşimi
AU18168/00A AU1816800A (en) 1998-11-10 1999-11-10 Bleaching composition comprising an alkoxylated benzoic acid
PCT/US1999/026588 WO2000027978A1 (en) 1998-11-10 1999-11-10 Bleaching compositions
MA26186A MA25309A1 (fr) 1998-11-11 2001-05-09 Composition de blanchiment comprenant un acide benzo¤que alcoxyle

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP98870247 1998-11-10
EP98870247 1998-11-11
EP98870263A EP1001010B1 (de) 1998-11-10 1998-12-02 Bleichmittelzusammensetzungen

Publications (2)

Publication Number Publication Date
EP1001010A1 EP1001010A1 (de) 2000-05-17
EP1001010B1 true EP1001010B1 (de) 2003-05-07

Family

ID=26152302

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98870263A Expired - Lifetime EP1001010B1 (de) 1998-11-10 1998-12-02 Bleichmittelzusammensetzungen

Country Status (7)

Country Link
EP (1) EP1001010B1 (de)
AT (2) ATE239779T1 (de)
AU (1) AU1816500A (de)
CO (1) CO5221050A1 (de)
DE (2) DE69814398D1 (de)
ES (2) ES2195306T3 (de)
WO (1) WO2000027978A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7390775B2 (en) 2005-03-07 2008-06-24 S.C. Johnson & Son, Inc. Thickened bleach compositions comprising an amine oxide and anionic polymer
US10258554B2 (en) 2010-01-29 2019-04-16 Colgate-Palmolive Company Fluoride free and anionic surfactant free dentifrice having a high micro efficacy

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1462564B1 (de) * 2003-03-28 2009-01-21 The Procter & Gamble Company Trimethoxybenzoesäure oder ihre Salze enthaltende Bleichmittelzusammensetzung
DE102005062008B3 (de) 2005-12-22 2007-08-30 Henkel Kgaa Geruchsreduktion hypochlorithaltiger Mittel
DE102005063181A1 (de) * 2005-12-30 2007-07-05 Henkel Kgaa Erhöhung der Stabilität hypochlorithaltiger Waschmittel
DE102005063177A1 (de) * 2005-12-30 2007-07-05 Henkel Kgaa Erhöhung der Stabilität hypochlorihaltiger Waschmittel
ES2727924T3 (es) * 2006-06-08 2019-10-21 Procter & Gamble Composiciones decolorantes
DE102006055669A1 (de) 2006-11-23 2008-07-17 Henkel Kgaa Enzymzubereitung mit trägergebundenen Antioxidationsmitteln
PT2112218E (pt) * 2008-04-25 2011-10-24 Procter & Gamble Composição de branqueamento colorida
DE102009028891A1 (de) 2009-08-26 2011-03-03 Henkel Ag & Co. Kgaa Verbesserte Waschleistung durch Radikalfänger
DE102009028892A1 (de) 2009-08-26 2011-03-03 Henkel Ag & Co. Kgaa Verbesserte Waschleistung durch Polymere mit aromatischen Gruppen
WO2016207691A1 (en) 2015-06-22 2016-12-29 Fater S.P.A. Stable bleaching composition

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Publication number Priority date Publication date Assignee Title
US5135675A (en) * 1989-07-13 1992-08-04 Lever Brothers Company, Divison Of Conopco, Inc. Machine dishwashing compositions comprising organic clay and sulfonated polystyrene polymer or copolymer as thickening agents
GB2271119A (en) * 1992-09-16 1994-04-06 Kao Corp Color liquid cleaning and bleaching composition
EP0824146A1 (de) * 1996-08-12 1998-02-18 The Procter & Gamble Company Bleichmittelzusammensetzungen
WO1999035227A1 (en) * 1998-01-12 1999-07-15 The Procter & Gamble Company Acidic aqueous cleaning compositions

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EP0636169A1 (de) * 1992-04-13 1995-02-01 The Procter & Gamble Company Verfahren zur herstellung thixotroper flüssiger waschmittelzusammensetzungen
CA2126383C (en) * 1993-07-15 1999-01-12 Rodney M. Wise Stable thickened liquid or gel cleaning composition containing bleach
US5384061A (en) * 1993-12-23 1995-01-24 The Procter & Gamble Co. Stable thickened aqueous cleaning composition containing a chlorine bleach and phytic acid
EP0668345B1 (de) * 1994-02-22 2001-12-12 The Procter & Gamble Company Hypochloritbleichmittelzusammensetzungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5135675A (en) * 1989-07-13 1992-08-04 Lever Brothers Company, Divison Of Conopco, Inc. Machine dishwashing compositions comprising organic clay and sulfonated polystyrene polymer or copolymer as thickening agents
GB2271119A (en) * 1992-09-16 1994-04-06 Kao Corp Color liquid cleaning and bleaching composition
EP0824146A1 (de) * 1996-08-12 1998-02-18 The Procter & Gamble Company Bleichmittelzusammensetzungen
WO1999035227A1 (en) * 1998-01-12 1999-07-15 The Procter & Gamble Company Acidic aqueous cleaning compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7390775B2 (en) 2005-03-07 2008-06-24 S.C. Johnson & Son, Inc. Thickened bleach compositions comprising an amine oxide and anionic polymer
US10258554B2 (en) 2010-01-29 2019-04-16 Colgate-Palmolive Company Fluoride free and anionic surfactant free dentifrice having a high micro efficacy

Also Published As

Publication number Publication date
ATE239779T1 (de) 2003-05-15
CO5221050A1 (es) 2002-11-28
DE69932580D1 (de) 2006-09-14
DE69932580T2 (de) 2007-07-19
ES2270572T3 (es) 2007-04-01
ES2270572T5 (es) 2010-11-22
DE69814398D1 (de) 2003-06-12
ATE335068T1 (de) 2006-08-15
DE69932580T3 (de) 2011-01-05
EP1001010A1 (de) 2000-05-17
WO2000027978A1 (en) 2000-05-18
AU1816500A (en) 2000-05-29
ES2195306T3 (es) 2003-12-01

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