WO1999015617A1 - Compositions de blanchiment - Google Patents

Compositions de blanchiment Download PDF

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Publication number
WO1999015617A1
WO1999015617A1 PCT/IB1998/001346 IB9801346W WO9915617A1 WO 1999015617 A1 WO1999015617 A1 WO 1999015617A1 IB 9801346 W IB9801346 W IB 9801346W WO 9915617 A1 WO9915617 A1 WO 9915617A1
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WIPO (PCT)
Prior art keywords
composition
fabrics
bleaching
acid
weight
Prior art date
Application number
PCT/IB1998/001346
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English (en)
Inventor
Oreste Todini
Andrea Agostini
Giovanni Grande
Original Assignee
The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PL98339379A priority Critical patent/PL339379A1/xx
Priority to EP98938858A priority patent/EP1017779A1/fr
Priority to AU87448/98A priority patent/AU8744898A/en
Publication of WO1999015617A1 publication Critical patent/WO1999015617A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—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
    • C11D3/395—Bleaching agents
    • C11D3/3951—Bleaching agents combined with specific additives
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to the bleaching of fabrics, including hand and machine laundry methods, with liquid hypohalite bleach-containing compositions.
  • Bleaching compositions are well-known in the art. Amongst the different bleaching compositions available, those relying on bleaching by hypohalite bleaches such as hypochlorite are often preferred, mainly for performance reasons, especially at lower temperature.
  • hypohalite bleach-containing compositions especially when it is desired to have good stain removal performance on the fabrics treated therewith on top of the fabric whiteness performance. This is even more a problem when aged compositions are used, i.e. when the compositions are used in a laundry application after prolonged periods of storage after their manufacturing.
  • the resulting composition generally shows a poor chemical stability upon ageing of the composition, resulting in low stain removal performance of the composition when used in any laundry application after prolonged periods of storage. Indeed, upon prolonged storage periods the surfactants may be decomposed by the hypohalite bleach present in such a liquid hypohalite bleach-based composition, and thus may lose their stain removal potential. This surfactant decomposition can be accelerated by product exposure at high temperature or by raw material impurities.
  • the liquid bleaching composition used to bleach fabrics comprises a hypohalite bleach, a surfactant and a stabilising agent selected from the group consisting of a radical scavenger, a chelating agent and a mixture thereof.
  • a stabilising agent selected from the group consisting of a radical scavenger, a chelating agent and a mixture thereof.
  • a liquid hypohalite bleach-containing composition comprising a surfactant, of such a stabilising agent, provides improved surfactant stability in said composition upon prolonged periods of storage.
  • a further advantage of the processes of bleaching fabrics according to the present invention is that they are suitable for the bleaching 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.
  • synthetic fibers may be bleached according to the present invention despite a standing prejudice against the use of hypohalite bleaches, especially hypochlorite bleaches, on synthetic fibers, as evidenced by warning on labels of commercially available hypochlorite bleaches and clothes.
  • the compositions used according to the bleaching processes of the present invention are not only safe to the fabrics perse bleached therewith but also to the fabrics colours.
  • liquid bleaching compositions used according to the present invention may be contacted to the fabrics to bleach, in diluted conditions, e.g. when used as a detergent additive or alone as a laundry detergent composition, and/or in neat condition, e.g. when used as a liquid pretreater (spotter).
  • diluted conditions e.g. when used as a detergent additive or alone as a laundry detergent composition
  • neat condition e.g. when used as a liquid pretreater (spotter).
  • EP-A-668 345 discloses hypochlorite-containing compositions comprising a source of strong alkalinity, a pH buffering means (silicate/carbonate) and radical scavengers. Surfactants are disclosed as optional ingredients without mentioning any, nor levels thereof.
  • European co-pending application number 97870041.7 discloses bleaching compositions comprising a hypohalite bleach, a pH buffering means and an effective amount of an anionic surfactant. Radical scavengers and chelating agents are mentioned as optional ingredients without specifying any, nor levels thereof.
  • European co-pending applications numbers 96870088.0 and 96870128.4 discloses hypochlohte-based compositions with surfactants and optionally radical scavengers. Chelants are mentioned as optional ingredients without specifying any, nor levels thereof. No laundry application is disclosed.
  • EP-A-317 066 discloses thickened aqueous cleaning compositions comprising an active cleaning ingredient (hypochlorite, acids, bases (NaoH, carbonate, silicate)), a quaternary ammonium compound, and an organic counterion (e.g. benzoic acid). No laundry application is disclosed.
  • an active cleaning ingredient hyperochlorite, acids, bases (NaoH, carbonate, silicate)
  • a quaternary ammonium compound e.g. benzoic acid
  • US 5384 061 discloses thickened compositions comprising hypochlorite, a cross-linked polycarboxylate polymer, phytic acid, a radical scavenging rheology stabilizing agent, an alkaline buffering agent to provide said composition with a pH above 10.
  • Various surfactants are disclosed. No laundry application is disclosed.
  • the present invention encompasses a process of bleaching fabrics which comprises the steps of:
  • a liquid bleaching composition comprising a hypohalite bleach, from 0.1 % to 20% by weight of the total composition of a surfactant and from 0.001 % to 10% by weight of a stabilising agent selected from the group consisting of radical scavenger, chelating agent and mixture thereof, in its diluted or neat form, allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, and then rinsing said fabrics with water.
  • compositions used in the present invention further comprise a pH buffering component.
  • a pH buffering component in the compositions herein further contributes to the effective whiteness performance of these compositions as well as to their fabric safety, when used to bleach fabrics.
  • the pH buffering component allows to control the alcalinity 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 (wate ⁇ composition)).
  • This buffering action of the pH buffering component reduces the conversion of hypochlorite into hypochlorous acid, one of the species which are most responsible for fabric yellowing and/or fabric damage.
  • the present invention further encompasses the use, in a liquid hypohalite bleach-containing composition comprising a surfactant, of a stabilizing agent selected from the group consisting of radical scavenger, chelating agent and mixture thereof, for effective stain removal performance of said composition upon ageing of the composition.
  • the present invention encompasses a process of bleaching fabrics with a bleaching composition as described herein after.
  • fabrics any types of fabrics including for example clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like.
  • the process of bleaching fabrics herein is suitable for both natural fabrics and synthetic fabrics.
  • natural fabrics it is meant fabrics made of cotton, viscose, linene, silk and/or wood.
  • synthetic fabrics it is meant those made of synthetic fibers like polymeric fibers (polyamide, polyester, lycra® and elasthane®), and those made of both natural and synthetic fibers.
  • the process of bleaching fabrics according to the present invention comprises the steps of contacting said fabrics with a liquid bleaching composition comprising a hypohalite bleach, a surfactant (0.1 %-20%) and a stabilizing agent as defined herein after (0.001 %-10%).
  • a liquid bleaching composition comprising a hypohalite bleach, a surfactant (0.1 %-20%) and a stabilizing agent as defined herein after (0.001 %-10%).
  • the compositions used in the process of bleaching fabrics herein are liquid hypochlorite-containing compositions that may further comprise a pH buffering component as defined hereinafter.
  • Said process of bleaching according to the present invention delivers effective stain removal performance upon ageing of the compositions.
  • liquid compositions according to the present invention are contacted to fabrics in their 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 process of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a liquid bleaching composition as described herein, 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 in 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 process according to the present invention allows to bleach fabrics and optionally to wash fabrics with a detergent composition comprising at least one surface active agent before the step of contacting said fabrics with the liquid bleaching composition as described herein and/or in the step where said fabrics are contacted with the bleaching composition and/or after the step where said fabrics are contacted with the bleaching composition and before the rinsing step, and/or after the rinsing step.
  • the process of bleaching fabrics comprises the step of contacting fabrics with a liquid bleaching composition as described herein after, in its neat form, of 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 and then rinsing said fabrics in 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 said fabrics have been bleached.
  • 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 present invention provides a process of bleaching fabrics wherein liquid hypohalite bleach-containing compositions are applied neat onto a fabric to bleach, despite a standing prejudice against using hypochlorite-containing compositions neat on fabrics.
  • the bleaching pre-treatment operation may also be followed by the diluted bleaching process as described herein before either in bucket (hand operation) or in a washing machine.
  • the temperatures at which the bleaching process herein is performed do have an influence on the stain removal performance delivered. More specifically, an increased temperature accelerates the bleaching process, i.e. diminishes the time required to bleach a given soil.
  • the bleaching solutions occurring in the bleaching processes according to the present invention where the bleaching compositions herein are used in their diluted form have a temperature of from 4°C to 60°C, preferably from 10°C to 50°C and most preferably from 20°C to 40°C.
  • compositions for use in these bleaching processes are in liquid form.
  • these compositions are in liquid 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.
  • 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.
  • the preferred hypohalite bleaches among the above described 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, more preferably the alkali metal sodium hypochlorite.
  • the liquid compositions used according to the present invention comprise said hypohalite bleach such that the content of active halide in the composition is of 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.
  • the surfactant is the surfactant
  • An essential component of the invention is a surfactant or mixture thereof.
  • Said surfactant is present in the compositions used according to the present invention in amounts of from 0.1% to 20% by weight of the total composition, preferably of from 0.1% to 15%, more preferably from 1 % to 10% and most preferably from 2% to 8%.
  • Surfactants for use herein include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. Naturally, for the purpose of the invention, the surfactants have to be stable to the hypohalite bleach. Surfactants are essential ingredients herein as they deliver the desired stain removal performance on the fabrics bleached.
  • Suitable anionic surfactants for use herein include water-soluble salts or acids of the formula ROSO3M wherein R preferably is a C4-C24 hydrocarbyl, preferably linear or branched alkyl having a C -C20 alkyl component, more preferably a Cs-Cis 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 C4-C24 hydrocar
  • Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO3M wherein R is a linear or branched alkyl group having a C4-C24 alkyl component, preferably a C8-C20 linear or branched alkyl, more preferably C10-C18 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 a linear or branched alkyl group having a C4-C24 alkyl component, preferably a C8-C20 linear or branched alkyl, more preferably C10-C18 linear or branched alkyl
  • A is an
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12- 18 alkyl polyethoxylate (1.0) sulfate, C-
  • anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C4-C24 linear alkylbenzenesulfonates, C ⁇ - C22 primary or secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C4-C24 linear alkylbenzenesulfonates C ⁇ - C22 primary or secondary alkanesulfonates
  • C8-C24 olefinsulfonates C8
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as Ci4_ ⁇ i6 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 ⁇ i2- ⁇
  • 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 3,929,676, 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:
  • 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 amino-acid 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 for use herein include C12 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 C14 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).
  • C12 acyl sarcosinate is commercially available, for example, as Hamposyl L-30® supplied by Hampshire.
  • C14 acyl sarcosinate is commercially available, for example, as Hamposyl M-30® supplied by Hampshire.
  • compositions for use in the bleaching process of the present invention comprise at least an anionic surfactant, especially an alkylbenzenesulphonate, alkylsulphate, alkyl alkoxy (preferably ethoxy) sulphate and/or alkylethoxycarboxylate with an alkyl chain containing from 4 to 24 carbon atoms, preferably from 8 to 18, most preferably from 8 to 16.
  • anionic surfactants have been found to provide good stain removal performance as well as to improve the whiteness to fabrics which are treated according to the process herein, with a bleaching composition comprising them.
  • the whitening effect i.e. the yellowing-prevention effect
  • the whitening effect can be determined by both visual and instrumental grading.
  • Visually the difference in yellowing between items treated with different compositions can be determined by a team of expert panellists. Instrumentally, the assessment can be determined with the help of Colorimeters such as Ganz Griesser® instruments (e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500) or a ZEISS ELREPHO® or others which are available for instance from Hunterlab® or Gardner®.
  • Ganz Griesser® instruments e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500
  • ZEISS ELREPHO® ZEISS ELREPHO® or others which are available for instance from Hunterlab® or Gardner®.
  • the surfactant system used is an anionic surfactant system, namely alkyl alkoxy (preferably ethoxy) sulphate like alkyl (ethoxy) 3 sulphate alone or together with a co-surfactant, preferably a C4-C18 alkyl sulphate and/or a C8-C1 ⁇ alkyl or aryl sulphonate like C8-C18 benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
  • alkyl alkoxy preferably ethoxy
  • a co-surfactant preferably a C4-C18 alkyl sulphate and/or a C8-C1 ⁇ alkyl or aryl sulphonate like C8-C18 benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
  • the presence of said alkyl (ethoxy) 3 sulphate alone or together with a cosurfactant provides the desired viscosity to the compositions suitable for use according to the process of bleaching of the present invenion, and delivers excellent stain removal properties to said compositions when used in any laundry application herein.
  • compositions suitable for use herein 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 the following viscosity parameter : angle :1°58, gap : 60, diameter : 4.0 cm and iner :63.60 at a temperature of 25°C and a shear rate of 30 1/sec.
  • anionic surfactants and other surfactants especially zwitterionic surfactants like betaine surfactants are also suitable herein.
  • 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 :
  • the polyethylene oxide condensates of alkyl phenols e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 20 carbon atoms in either a straight chain or branched chain configuration, preferably from 8 to 12 carbon atoms, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, and nonane; (ii) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. Examples are compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5000 to about 11000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000;
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Particularly suitable nonionic surfactants for use herein are capped nonionic ethoxylated surfactants according to the formula:
  • is a C ⁇ -C-
  • R2 is a C2-C10 linear or branched alkyl group, preferably a C4 group;
  • R3 is a C-
  • 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:
  • 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:
  • A is phosphorus or sulfur atom
  • R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons
  • 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 : R 2
  • 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 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 - CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2-, and mixtures thereof
  • each R 4 is selected from the group consisting of C1-C4 alkyl, benzyl ring structures formed by joining the two R 4 groups, and hydrogen when y is not 0
  • R ⁇ is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18
  • each y is from 0 to about 10 and the sum of the y values is from 0 to about 15
  • X is any compatible anion.
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I):
  • R1 is a short chainlength alkyl (C6-C10) y is 2-4, preferably 3.
  • R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula II,
  • X " is a counterion, preferably a halide, e.g. chloride or methylsulfate.
  • R6 is C- ⁇ -C4 and z is 1 or 2.
  • Preferred quat ammonium surfactants are those as defined in formula I whereby
  • is C ⁇ , C ⁇
  • o or mixtures thereof, x o,
  • R 4, R5 CH 3 .
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds having the formula :
  • R-j is CQ-C ⁇ Q alkyl
  • each of R2, R3 and R4 is independently C1-C4 alkyl, benzyl, and -(C2H4Q) X H where x has a value from 2 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • is C-12-C15 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 R2R3 and R4 are methyl and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; C-
  • the stabilising agent is the stabilising agent
  • An essential component of the invention is a stabilising agent being a radical scavenger, a chelating agent or a mixture thereof.
  • the stabilizing agents have to be stable to the hypohalite bleach.
  • the stabilising agent is a radical scavenger or a mixture thereof alone, or together with a chelating agent or a mixture thereof.
  • Suitable radical scavengers for use herein include aromatic radical scavengers comprising an unsaturated ring system of from 3 to 20 carbon atoms, preferably of from 3 to 18 and more preferably of from 5 to 14 and having a double bond set comprising a total of 4n+2 electrons, wherein n is an integer of from 0 to 4, preferably of from 1 to 3.
  • aromatic radical scavengers include benzene derivatives, naphthalene derivatives, annulene derivatives, cyclopentadiene derivatives, cyclopropene derivatives and the like, especially aryl carboxylates and/or aryl sulfonates.
  • Particularly suitable radical scavengers (aryl carboxylates, aryl sulphonate and derivatives thereof) for use in the present invention have one of the following formulas:
  • each X, Y, and Z are -H, -COO-M+, -CI, -Br, -SO3-M + , -NO2, - OCH3, or a Ci to C ⁇ o primary and secondary alkyl groups and M is H or an alkali metal, or mixtures thereof.
  • these components include pyromellitic acid, i.e. where X, Y and Z are -COO-H + ; hemimellitic acid, trimellitic acid, i.e. where X and Y are -COO-H + and Z is H.
  • radical scavengers are phthalic acid; sulfophthalic acid; other mono-substituted phthalic acids; di-substituted benzoic acids; alkyl-, chloro-, bromo-, sulfo-, nitro- or alkoxy- benzoic acids, i.e. where Y and Z are -H and X is a C-
  • radical scavengers useful in the present invention are benzoic acid, methoxy benzoic acid, toluic acid, 4-toluene sulfonic acid, 3-nitro benzoic acid, 2 n- octyl benzoic acid, 2 n-octyl sulfonic acid, anisic acid or mixtures thereof. Most preferred herein are benzoic acid and/or methoxy benzoic acid and/or 3-nitrobenzoic acid.
  • radical scavengers described above are the acidic form of the species, i.e. M is H. It is intended that the present invention also covers the salt derivatives of these species, i.e. M is an alkali metal, preferably sodium or potassium. In fact, since the pH of the compositions of the present invention is in the alkaline range, the radical scavengers of the present invention exist primarily as the ionized salt in the aqueous composition herein.
  • the anhydrous derivatives of certain species described herein above can also be used in the present invention, e.g. pyromellitic dianhydride, phthalic anhydride, sulphthalic anhydride and the like.
  • Suitable chelating agents for use herein 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.
  • 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 for use herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP).
  • DTPMP diethylene triamine penta methylene phosphonate
  • HEDP ethane 1-hydroxy diphosphonate
  • 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
  • the reaction can be repeated with any of the reactive OH groups, and phosphate ingredients are obtained which can be - linear or branched polyphosphates of structure
  • the phosphate compound contains both cycles and branched chain, and can be referred to as an ultraphosphate.
  • M is a counterion, preferably an alkali metal
  • 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 a chelating agent particularly suitable for use herein, is a hexa-phosphohc 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 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, 1967, 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 tripolyphosphate, sodium pyrophosphate, phytic acid, and mixtures thereof. Indeed, these chelating agents when present in the bleaching compositions used to bleach fabrics herein have been found to further participate to the excellent stain removal performance delivered by these compositions upon ageing of the compositions.
  • compositions for use herein comprise from 0.01% to 10% by weight of the total composition of a stabilising agent, or mixtures thereof, preferably from 0.01% to ⁇ % by weight, more preferably from 0.1 % to 5%, and most preferably from 0.2% to 3%.
  • the present invention is based on the finding that the addition of a stabilizing agent, preferably a radical scavenger alone or together with a chelating agent, in a liquid bleaching composition comprising a hypohalite bleach and a surfactant results in effective stain removal performance of the aged composition when used in any laundry application.
  • a stabilizing agent preferably a radical scavenger alone or together with a chelating agent
  • the stain removal performance delivered on fabrics bleached with an aged composition according to the present invention is improved, as compared to the stain removal performance delivered by the same composition, but without such a stabilizing agent as mentioned herein before in the same aged condition.
  • the present invention allows to maintain excellent stain removal performance after prolonged periods of storage time, as compared to the same composition but without said stabilizing agent.
  • the stain removal performance upon ageing of the composition in the process of bleaching according to the present invention can be measured by comparison to the same bleaching process wherein the composition used is free of said stabilizing agent (e.g. after 3 months of storage at ambient temperature (around 25°C) after the manufacturing of these compositions).
  • the stain removal performance can be determined by visual grading on a scale of for example four grades. This test can be conducted on commercially available stained items (e.g. from WFK Germany or EMPA Switzerland) or on realistic soiled items.
  • the pH of the liquid compositions used according to the present invention is typically from 12 to 14 measured at 25°C.
  • the liquid compositions for use according to the processes of bleaching 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 the hypohalite bleach mentioned hereinbefore and optionally the pH buffering component when present, which are alkalis. However, in addition to these components, a strong source of alkalinity may also optionally be used.
  • 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 used according to the present invention the presence of a pH buffering component is not compulsory, but is highly preferred.
  • 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.
  • the 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.
  • Liquid bleaching compositions for use herein will typically 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.
  • the compositions according to the invention may comprise other optional components such as organic or inorganic alkalis, builders, thickening agents, polymers, pigments, dyes, solvents, perfumes, brighteners and mixtures thereof.
  • any brighteners known to those skilled in the art may be used herein including both hydrophobic and hydrophilic brigtheners and mixtures thereof.
  • the brightener has to be stable to the hypohalite bleach.
  • the brighteners may be desired herein to further enhance the whiteness performance of the compositions herein.
  • Brighteners are compounds which have the ability to fluorescent by absorbing ultraviolet wave-lengths of light and re-emitting visible light. Brighteners, also referred to as fluorescent whitening agent (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 agent
  • 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, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6- membered-ring heterocycles, 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.
  • 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; Artie White CC® and Artie White CWD®; the 2-(4-styryl-phenyl)-2H-naptho[1 ,2- djtriazoles; 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-diethyl- amino coumarin; 1 ,2-bis(-benzimidazol-2-yl)ethylene; 1 ,3-diphenyl- pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[1 ,2- djoxazole; 2-(stilbene-4-yl)-2H-naphtho[1 ,2-d]triazole, 3-phenyl-7-
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • is anilino
  • R2 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.
  • is anilino
  • R2 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.
  • is anilino
  • R2 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.
  • 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.
  • compositions used according to the present invention comprise up to 1.0% by weight of the total composition of a brightener or a mixture thereof, preferably from 0.005% to 0.5%, more preferably from 0.005% to 0.3% and most preferably from 0.00 ⁇ % to 0.1%.
  • a brightener or a mixture thereof may both be solubilized or suspended in the hypohalite bleach-containing 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-186366.
  • 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.
  • liquid compositions for use herein 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.
  • hydrophobic brigthener may be suspended by means of a specific suspending agent, like polymers and/or colloidal particulate silicate.
  • 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 for herein is a polymer. That polymer, has surprisingly been found to also reduce the yellowing of the fabrics treated therewith, i.e. improve whiteness, as well as improve fabric safety. Naturally, for the purpose of the invention, the polymer has to be stable to the hypohalite bleach.
  • Suitable polymers for use are polymers comprising 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.
  • Preferred commercially available polymers are the polyacrylate polymers, especially the Norasol® polyacrylate polymers and more preferred are the polyacrylate polymer Norasol® 41 ON (MW 10,000) and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 764 (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 764 (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 % by weight, more preferably from 0.001 % to 0.5% by weight, most preferably from 0.005% to 0.2% by weight of the liquid composition.
  • Tinopal PLC® is bis(sulfobenzenfuranyl)biphenyl available from Ciba Geigy.
  • Na C12-C14 E3S is an alkyl C12-C14 (ethoxy) 3 sulphate commercially available from Rhone Poulenc and Albright & Wilson.
  • Benzoic acid is commercially available from Elf Atochem, Enichem, or
  • Methoxy benzoate is available from Aid rich.
  • Norasol 440N® is a polyacrylate polymer modified with phosphonic groups (MW 4000) from Norso Haas.
  • Betaine ** is lauryl dimethyl aminebetaine available from Albright & Wilson.
  • Nonionic surfactant*** is Plurafac® available from BASF.
  • compositions deliver excellent stain removal performance on various stain including greasy stains, enzymatic stains and/or bleachable stains when used in a laundry application in their neat or diluted form, e.g. 200 times their weight of water, after prolonged periods of storage time, e.g., after 3 months of storage at ambient temperature (25°C) after having been prepared.

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Abstract

La présente invention concerne des procédés de blanchiment de textiles, consistant à mettre ces textiles en contact avec une composition de blanchiment liquide, laquelle comprend un agent de blanchiment à l'hypohalite, un tensioactif représentant 0,1 à 20 % en poids du poids de la composition, et un agent de stabilisation représentant 0,001 à 10 % en poids du poids de la composition et choisi dans le groupe constitué par un piégeur de radicaux, un agent de chélation, ou un mélange de ceux-ci, sous forme diluée ou pure. Cette composition est avantageuse, car elle permet d'enlever efficacement les tâches, même après une longue période de stockage de la composition, lors d'une utilisation de celle-ci dans une quelconque opération de blanchissage.
PCT/IB1998/001346 1997-09-19 1998-08-28 Compositions de blanchiment WO1999015617A1 (fr)

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PL98339379A PL339379A1 (en) 1997-09-19 1998-08-28 Bleaching compositions
EP98938858A EP1017779A1 (fr) 1997-09-19 1998-08-28 Compositions de blanchiment
AU87448/98A AU8744898A (en) 1997-09-19 1998-08-28 Bleaching compositions

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EP97870140A EP0905225B1 (fr) 1997-09-19 1997-09-19 Procédés pour le blanchissage du linge

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DE102005041436A1 (de) * 2005-08-31 2007-03-01 Henkel Kgaa Flüssiges hypohalogenithaltiges Bleichmittel
EP1865050A1 (fr) * 2006-06-08 2007-12-12 The Procter & Gamble Company Compositions de blanchiment

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EP1069178A1 (fr) * 1999-07-12 2001-01-17 The Procter & Gamble Company Stabilisant de blanchiment pour un dispositif pour détacher
CA2409393C (fr) * 2000-06-19 2007-04-10 The Procter & Gamble Company Stabilisateur de blanchiment pour applicateur detachant
DE102005062008B3 (de) 2005-12-22 2007-08-30 Henkel Kgaa Geruchsreduktion hypochlorithaltiger Mittel
DE102005063177A1 (de) * 2005-12-30 2007-07-05 Henkel Kgaa Erhöhung der Stabilität hypochlorihaltiger Waschmittel
EP1835016A1 (fr) * 2006-03-17 2007-09-19 The Procter and Gamble Company Procédé de blanchiment du linge
EP1837395A3 (fr) * 2006-03-17 2007-10-03 The Procter and Gamble Company Procédé de blanchiment du linge
WO2007107898A2 (fr) * 2006-03-17 2007-09-27 The Procter & Gamble Company Procede de blanchiment de tissu
US20160168780A1 (en) * 2014-12-16 2016-06-16 Washing Systems, Llc Process to produce hygienically clean textile

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DE102005041436A1 (de) * 2005-08-31 2007-03-01 Henkel Kgaa Flüssiges hypohalogenithaltiges Bleichmittel
EP1865050A1 (fr) * 2006-06-08 2007-12-12 The Procter & Gamble Company Compositions de blanchiment
WO2007141734A1 (fr) * 2006-06-08 2007-12-13 The Procter & Gamble Company Compositions de blanchiment
US7875583B2 (en) 2006-06-08 2011-01-25 The Procter & Gamble Company Bleaching compositions

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Publication number Publication date
EP1017779A1 (fr) 2000-07-12
CO5040135A1 (es) 2001-05-29
EP0905225B1 (fr) 2006-11-08
DE69736927D1 (de) 2006-12-21
ATE344832T1 (de) 2006-11-15
ES2276418T3 (es) 2007-06-16
TR200001431T2 (tr) 2002-09-23
AR016654A1 (es) 2001-07-25
PE114799A1 (es) 1999-12-03
MA24803A1 (fr) 1999-12-31
EP0905225A1 (fr) 1999-03-31
PL339379A1 (en) 2000-12-18
AU8744898A (en) 1999-04-12
ZA988578B (en) 1999-03-19

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