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EP1001011B2 - Composition de blanchiment comprenant acide benzoique alkoxylé - Google Patents

Composition de blanchiment comprenant acide benzoique alkoxylé Download PDF

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Publication number
EP1001011B2
EP1001011B2 EP99870211A EP99870211A EP1001011B2 EP 1001011 B2 EP1001011 B2 EP 1001011B2 EP 99870211 A EP99870211 A EP 99870211A EP 99870211 A EP99870211 A EP 99870211A EP 1001011 B2 EP1001011 B2 EP 1001011B2
Authority
EP
European Patent Office
Prior art keywords
bleaching composition
bleaching
alkyl
acid
salt
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
EP99870211A
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German (de)
English (en)
Other versions
EP1001011A2 (fr
EP1001011A3 (fr
EP1001011B1 (fr
Inventor
Valerio Del Duca
Carlo Ricci
Stefano Giunti
Luca Sarcinelli
Milena Leone
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27239782&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1001011(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP98870263A external-priority patent/EP1001010B1/fr
Priority to ES99870211T priority Critical patent/ES2270572T5/es
Priority to EP99870211A priority patent/EP1001011B2/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to PCT/US1999/026605 priority patent/WO2000027972A1/fr
Priority to AU18168/00A priority patent/AU1816800A/en
Priority to CO99070900A priority patent/CO5210994A1/es
Priority to TR2001/01308T priority patent/TR200101308T2/xx
Publication of EP1001011A2 publication Critical patent/EP1001011A2/fr
Publication of EP1001011A3 publication Critical patent/EP1001011A3/fr
Priority to MA26186A priority patent/MA25309A1/fr
Publication of EP1001011B1 publication Critical patent/EP1001011B1/fr
Application granted granted Critical
Publication of EP1001011B2 publication Critical patent/EP1001011B2/fr
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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—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
    • 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
    • C11D3/37—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to bleaching compositions, which can be used to treat various surfaces including, but not limited to, fabrics, clothes, and carpets as well as hard-surfaces like walls, tiles, floors, glass, bathrooms surfaces, kitchen surfaces, toilet bowls and dishes.
  • Bleach-containing compositions for treating various surfaces e.g., fabrics and carpets are well known in the art.
  • Peroxygen bleach-containing compositions have been extensively described in the art, especially in laundry applications as laundry detergents, laundry additives or laundry pretreaters, and in carpet treatment applications.
  • peroxygen bleach-containing compositions in laundry and/or carpet treatment applications to boost the removal of dried on (encrusted) stains/soils and "problem" stains, such as grease, coffee, tea, grass, mud/clay-containing soils, which are otherwise particularly difficult to remove.
  • peroxygen bleaches are considered as being safer to fabrics/carpets, specifically to coloured fabrics/carpets, compared to other bleaches, as for example hypohalite bleaches.
  • peroxygen bleach-containing bleaching compositions have the inconvenience of being less stable compared to bleaching compositions based on other bleaches.
  • peroxygen bleach-containing compositions a major problem associated with such peroxygen bleach-containing compositions, is their tendency to be unstable, especially upon storage, and more especially under conditions of elevated temperature. More particularly, it is believed that the peroxygen bleach ("oxidising agent") present in such bleaching composition can decompose resulting in a reduction of the concentration of oxidising agent over time (“loss of available oxygen"). Loss of available oxygen in such compositions consequently leads to the reduction of the cleaning and whitening performance of the compositions.
  • Bleaching compositions can be formulated comprising a radical scavenger in addition to the peroxygen bleach. It is believed that radical scavengers act as a bleach stabilizer in such bleaching compositions. Examples of such compositions known in the art, include bleaching compositions used to treat fabrics and/or hard-surfaces and comprising a peroxygen bleach and a radical scavenger, as e.g., butyl hydroxy toluene (BHT) and the like ( EP-A-0 791 362 , EP-A-0 842 604 , EP-A-0 842 606 and EP-A-0 843 001 ) or carpet treatment compositions comprising a peroxygen bleach and a radical scavenger, e.g., n-propyl gallate or butyl hydroxy toluene (BHT) ( EP-A-0 906 950 ).
  • BHT butyl hydroxy toluene
  • carpet treatment compositions comprising a per
  • the stability of the peroxygen bleach in said bleaching compositions immediately after the manufacture of said bleaching composition (“immediate chemical stability") and the stability of the peroxygen bleach in said bleaching compositions upon prolonged periods of storage (“upon storage”) may still be further improved.
  • a bleaching composition comprising a peroxygen bleach and a di- or tri-alkoxylated benzoic acid, as defined in claim 1.
  • the bleaching compositions as described herein also provide excellent bleaching performance.
  • compositions of the present invention provide excellent bleaching performance when used in any laundry application (“fabric treatment applications”), e.g., as a laundry detergent, a laundry additive and/or a laundry pretreater, and in carpet treatment applications.
  • fabric treatment applications e.g., as a laundry detergent, a laundry additive and/or a laundry pretreater, and in carpet treatment applications.
  • a further advantage of the bleaching compositions according to the present invention is that they are able to perform in a variety of conditions, i.e., in hard and soft water as well as when used neat or diluted.
  • bleaching compositions of the present invention are also suitable for the bleaching of different types of surfaces including hard-surfaces like floors, walls, tiles, glass, kitchen surfaces, bathrooms surfaces, toilet bowls and/or dishes, in addition to the above mentioned fabric and carpet treatment applications.
  • the bleaching compositions of the present invention are suitable for bleaching any type of fabrics/carpets including natural fabrics/carpets (e.g., fabrics/carpets made of cotton, viscose, linen, silk and wool), synthetic fabrics/carpets, such as those made of polymeric fibers of synthetic origin, as well as those made of both natural and synthetic fibers.
  • the present invention encompasses a bleaching composition
  • a bleaching composition comprising a peroxygen bleach and a di- or tri-alkoxylated benzoic acid or a salt thereof, as defined in claim 1.
  • the present invention further encompasses processes of treating a surface, e.g., a fabric or a carpet, with a bleaching composition as defined herein.
  • the bleaching composition is a mixture of:
  • the bleaching compositions according to the present invention may be formulated either as solids or liquids.
  • liquids it is meant to include conventional liquids, gels and pastes.
  • solids it is meant herein granules, tablets and/or powders.
  • Solids are preferably applied onto the fabrics/carpets to be treated in combination with, preferably dissolved in, an appropriate solvent, typically water.
  • the bleaching compositions are preferably, but not necessarily formulated as aqueous compositions.
  • Liquid bleaching compositions are preferred herein for convenience of use.
  • Preferred liquid bleaching compositions of the present invention are aqueous and therefore, preferably may comprise water, more preferably may comprise water in an amount of from 60% to 98%, even more preferably of from 80% to 97% and most preferably 85% to 97% by weight of the total composition.
  • the pH of the liquid bleaching compositions herein, as is measured at 25°C, preferably is at least, with increasing preference in the order given, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5.
  • the pH of the liquid bleaching compositions herein, as is measured at 25°C preferably is no more than, with increasing preference in the order given, 9, 8.5, 8, 7.5, 7, 6.5, 6 or 5.5.
  • Solid bleaching compositions or liquid bleaching compositions herein have a pH measured at 25°C, preferably of at least, with increasing preference in the order given, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, when diluted into 1 to 500 times its weight of water.
  • solid bleaching compositions or liquid bleaching compositions herein have a pH measured at 25°C, preferably of no more than, with increasing preference in the order given, 12, 11.5, 11, 10.5, 10, 9.5, 9, 8.5 or 8, when diluted into 1 to 500 times its weight of water.
  • liquid compositions according to the present invention are formulated in the neutral to the acidic pH range. It is within this neutral to acidic pH range that the optimum chemical stability and bleaching and/or cleaning performance of the peroxygen bleach as well as fabric/carpet yellowing-prevention and/or safety are obtained.
  • compositions herein may further comprise an acid or a base to adjust the pH as appropriate.
  • Preferred acids herein are organic or inorganic acids or mixtures thereof.
  • Preferred organic acids are acetic acid, citric acid or a mixture thereof.
  • Preferred inorganic acids are sulfuric acid, phosphoric acid or a mixture thereof.
  • a particularly preferred acid to be used herein is an inorganic acid and most preferred is sulfuric acid.
  • Typical levels of such acids when present, are of from 0.01 % to 3.0%, preferably from 0.05% to 2.0% and more preferably from 0.1% to 1.0% by weight of the total composition.
  • bases to be used herein can be organic or inorganic bases.
  • Suitable bases for use herein 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 or mixtures thereof.
  • a preferred base is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide.
  • Suitable bases include ammonia, ammonium carbonate and hydrogen carbonate.
  • Typical levels of such bases when present, are of from 0.01% to 1.0%, preferably from 0.05% to 0.8% and more preferably from 0.1% to 0.5% by weight of the total composition.
  • the bleaching compositions according to the present invention comprise a peroxygen bleach.
  • Suitable peroxygen bleaches to be used herein are selected from the group consisting of: hydrogen peroxide; water soluble sources of hydrogen peroxide; organic or inorganic peracids; hydroperoxides; diacyl peroxides; and mixtures thereof.
  • a hydrogen peroxide source refers to any compound that produces perhydroxyl ions on contact with water.
  • Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, perborates and persilicates and mixtures thereof.
  • Suitable diacyl peroxides for use herein include aliphatic, aromatic and aliphatic-aromatic diacyl peroxides, and mixtures thereof.
  • Suitable aliphatic diacyl peroxides for use herein are dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, or mixtures thereof.
  • a suitable aromatic diacyl peroxide for use herein is for example benzoyl peroxide.
  • a suitable aliphatic-aromatic diacyl peroxide for use herein is for example lauroyl benzoyl peroxide.
  • Suitable organic or inorganic peracids for use herein include : persulphates such as monopersulfate; peroxyacids such as diperoxydodecandioic acid (DPDA); magnesium perphthalic acid; perlauric acid; phthaloyl amidoperoxy caproic acid (PAP); perbenzoic and alkylperbenzoic acids; and mixtures thereof.
  • persulphates such as monopersulfate
  • peroxyacids such as diperoxydodecandioic acid (DPDA); magnesium perphthalic acid; perlauric acid; phthaloyl amidoperoxy caproic acid (PAP); perbenzoic and alkylperbenzoic acids; and mixtures thereof.
  • DPDA diperoxydodecandioic acid
  • PAP phthaloyl amidoperoxy caproic acid
  • perbenzoic and alkylperbenzoic acids and mixtures thereof.
  • 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 and mixtures thereof.
  • Such hydroperoxides have the advantage of being particularly safe to fabrics and color while delivering excellent bleaching performance when used in any laundry application.
  • such hydroperoxides have the advantage of being particularly safe to carpets and carpet dyes whilst delivering excellent bleaching performance when used in carpet treatment applications.
  • a preferred peroxygen bleach herein is selected from the group consisting of : hydrogen peroxide; water soluble sources of hydrogen peroxide; organic or inorganic peracids; hydroperoxides; and diacyl peroxides; and mixtures thereof.
  • a more preferred peroxygen bleach herein is selected from the group consisting of hydrogen peroxide, water soluble sources of hydrogen peroxide and diacyl peroxides and mixtures thereof.
  • An even more preferred peroxygen bleach herein is selected from the group consisting of hydrogen peroxide, water soluble sources of hydrogen peroxide, aliphatic diacyl peroxides, aromatic diacyl peroxides and aliphatic-aromatic diacyl peroxides and mixtures thereof.
  • the most preferred peroxygen bleach herein is hydrogen peroxide, water soluble sources of hydrogen peroxide or mixtures thereof.
  • the bleaching composition herein may comprise from 0.01% to 30%, preferably from 0.05% to 20%, more preferably from 0.1% to 15%, even more preferably from 0.15% to 10%, and most preferably from 0.2% to 10% by weight of the total composition of said peroxygen bleach.
  • peroxygen bleaches are chosen herein as oxidising agents over other oxidising agents, as for example hypohalite bleaches, as they are considered as being safer to fabrics/carpets, specifically to coloured fabrics/carpets.
  • bleachable stains any soils or stains containing ingredients sensitive to bleach that can be found on any carpet, e.g., coffee or tea.
  • compositions according to the present invention comprise an alkoxylated benzoic acid or a salt thereof.
  • the alkoxylated benzoic acid or the salt thereof has the general formula : wherein : M is hydrogen, a cation or a cationic moiety.
  • M is selected from the group consisting of hydrogen, alkali metal ions and alkaline earth metal ions. More preferably, M is selected from the group consisting of hydrogen, sodium and potassium. Even more preferably, M is hydrogen.
  • the alkoxylated benzoic acid or the salt thereof is a dialkoxy benzoic acid or a salt thereof, wherein in the above general formula : the substituent of the benzene ring X is selected from -H; the substituent of the benzene ring Y is -OR'; R' is independently selected from C 1 to C 20 linear or branched alkyl chains, preferably R' is independently selected from C 1 to C 5 linear or branched alkyl chains, more preferably R' is -CH 3 .
  • said alkoxylated benzoic acid or the salt thereof is a trialkoxy benzoic acid or a salt thereof, wherein in the above general formula : the substituents of the benzene ring Y and X are -OR'; R' is independently selected from C 1 to C 20 linear or branched alkyl chains, preferably R' is independently selected from C 1 to C 5 linear or branched alkyl chains, more preferably R' is -CH 3 .
  • Said alkoxylated benzoic acid or a salt thereof is selected from the group consisting of : a dialkoxy benzoic acid, or a salt thereof; a trialkoxy benzoic acid, or a salt thereof; and a mixture thereof. Even more preferably, said alkoxylated benzoic acid or a salt thereof, is a trimethoxy benzoic acid or a salt thereof.
  • said alkoxylated benzoic acid or the salt thereof is a trimethoxy benzoic acid or a salt thereof (TMBA), wherein in the above general formula : the substituents of the benzene ring Y and X are -OR'; R' is -CH 3 and; M is hydrogen, a cation or a cationic moiety.
  • TMBA trimethoxy benzoic acid or a salt thereof
  • said alkoxylated benzoic acid or the salt thereof is selected from the group consisting of 3,4,5,- trimethoxy benzoic acid, a salt thereof, 2,3,4-trimethoxy benzoic acid, a salt thereof, 2,4,5- trimethoxy benzoic acid, a salt thereof and a mixture thereof. More preferably, said alkoxylated benzoic acid or the salt thereof is 3,4,5,- trimethoxy benzoic acid or a salt thereof. Even more preferably, said alkoxylated benzoic acid or the salt thereof is 3,4,5,- trimethoxy benzoic acid.
  • Suitable trimethoxy benzoic acids or salts thereof are commercially available from Aldrich and Merck.
  • the bleaching composition according to the present invention may comprise from 0.001 % to 5%, preferably from 0.005% to 2.5% and more preferably from 0.01% to 1.0% by weight of the total composition of said alkoxylated benzoic acid or a salt thereof.
  • a di- or tri-alkoxylated benzoic acid or a salt thereof preferably a trialkoxy benzoic acid or a salt thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA)
  • acts as a radical scavenger in the bleaching composition according to the present invention thereby not only stabilizing the peroxygen bleach in said bleaching composition immediately after the manufacture of said bleaching composition ("immediate chemical stability benefit") but also stabilizing the peroxygen bleach in said bleaching composition upon storage (“chemical stability upon storage benefit”).
  • a di- or tri-alkoxylated benzoic acid or a salt thereof preferably a trialkoxy benzoic acid or a salt thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA)
  • TMBA trimethoxy benzoic acid or a salt thereof
  • the radicals formed are more reactive and better oxidising species than the parent, accelerating the decomposition kinetics of the peroxygen bleach and its reaction or interaction with the other ingredients, when present in the composition.
  • the result of such reactions is the decomposition of the peroxygen bleach and the other ingredients, when present.
  • decomposition thereof can be initiated by one electron processes, resulting in the loss or decrease of viscosity upon storage.
  • Di- or tri-alkoxylated benzoic acids or salts thereof preferably trialkoxy benzoic acids or salts thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA) have been found to exhibit an excellent performance in reduction, slowing down or complete suppression of said one electron oxidation chemistry reactions, particularly in peroxygen bleach-containing compositions.
  • TMBA trimethoxy benzoic acid or a salt thereof
  • the "immediate chemical stability" and/or “the chemical stability upon storage” of the peroxygen bleach in the bleaching composition according to the present invention and/or the other actives ingredients therein (where present) is improved when a di- or tri-alkoxylated benzoic acid or a salt thereof, preferably a trialkoxy benzoic acid or a salt thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA), is present versus when it is not or when another radical scavenger, as e.g., butyl hydroxy toluene (BHT) and n-propyl gallate is present.
  • TMBA trimethoxy benzoic acid or a salt thereof
  • immediate chemical stability it is meant herein, that the peroxygen bleach in bleaching compositions is stable immediately after the manufacture of said bleaching composition.
  • chemical stability upon storage it is meant herein, that the peroxygen bleach in bleaching compositions remains stable over a period of storage of 3 months at 25 °C. Thus, in practice this means that a bleaching composition remains sufficiently stable throughout the use by the consumer.
  • the immediate chemical stability and chemical stability upon storage of the peroxygen bleach in a bleaching composition may be evaluated by measuring the concentration of available oxygen (often abbreviated to AvO2) immediately after and at given storage times after having manufactured the composition.
  • concentration of available oxygen (often abbreviated to AvO2)
  • the % loss of available oxygen and/or the concentration of remaining available oxygen can be measured by chemical titration methods known in the art, such as the iodometric method, thiosulphatimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the choice of the appropriate method are described for example in "Hydrogen Peroxide", W. C. Schumb, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.
  • the chemical stability upon storage of the compositions according to the present invention may alternatively be assessed in the laboratory using a rapid ageing test ("RAT").
  • the RAT involves measuring the level of available oxygen in the fresh bleaching composition just after it is made and in the same composition after 7 days at 50°C.
  • AvO2 25% loss of available oxygen
  • the compositions of the present invention typically do not undergo more than 25% loss of available oxygen (AvO2) at 50°C ⁇ 0.5°C after 7 days of storage as compared to the level of available oxygen of the fresh compositions. More preferably not more than 20% loss of available oxygen at 50°C ⁇ 0.5°C after 7 days of storage.
  • certain radical scavengers other than a di- or tri-alkoxylated benzoic acids or salts thereof, preferably other than trialkoxy benzoic acids or salts thereof, more preferably other than trimethoxy benzoic acid or a salt thereof (TMBA), as for example BHT, are themselves not completely chemically stable in bleaching compositions. Indeed, BHT can be present in a dimeric form in bleaching composition comprising a peroxygen bleach.
  • this dimeric form of BHT is formed by the interaction or reaction of BHT with radicals originating from the decomposition pathway of the peroxygen bleach and/or metal ions present in said bleaching compositions, especially when said BHT-containing bleaching composition is exposed to UV radiation (e.g., sunlight).
  • the BHT dimer has a yellow color and therefore can lead to fabric and/or carpet yellowing when a bleaching composition comprising BHT is used to treat said fabric and/or carpet.
  • the fabric and/or carpet yellowing effect is due to the deposition of said BHT dimer formed during the storage of said bleaching composition and/or formed in-situ (on the fabric/carpet) during the treatment of said fabric and/or carpet with said bleaching composition.
  • the bleaching composition itself may turn yellow or at least get a yellowish color tone due to the presence of said yellow colored BHT dimer in said bleaching composition.
  • the fabric/carpet yellowing and/or the bleaching composition yellowing may be observed when said fabric/carpet treated with a bleaching composition comprising BHT and/or said bleaching composition comprising BHT is exposed to light, for example direct sunlight, a UV lamp or the like, for a prolonged time, e.g., three to four hours.
  • di- or tri-alkoxylated benzoic acids or salts thereof preferably trialkoxy benzoic acids or salts thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA), itself are “substantially color stable", in bleaching composition as described herein.
  • substantially color stable it is meant herein that substantially no coloured derivatives of di- or tri-alkoxylated benzoic acids or salts thereof, preferably trialkoxy benzoic acids or salts thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA), are formed in the bleaching composition according to the present invention.
  • TMBA trimethoxy benzoic acid or a salt thereof
  • a bleaching composition comprising an alkoxylated benzoic acid or a salt thereof, preferably a trialkoxy benzoic acid or a salt thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA)
  • TMBA trimethoxy benzoic acid or a salt thereof
  • the present invention encompasses the use of a di- or tri-alkoxylated benzoic acid or a salt thereof, preferably a trialkoxy benzoic acid or a salt thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA), in a bleaching composition comprising a peroxygen bleach whereby a fabric and/or carpet yellowing prevention benefit and/or a bleaching composition yellowing prevention benefit is provided.
  • TMBA trimethoxy benzoic acid or a salt thereof
  • the yellowing of a fabric and/or a carpet when a bleaching composition is used to treat said fabric and/or carpet (“fabric and/or carpet yellowing") and/or the yellowing of the bleaching composition itself (“bleaching composition yellowing”) can be assessed by visual grading.
  • the visual grading may be performed by a group of expert panelists using panel score units (PSU).
  • PSU panel score units
  • To asses the fabric and/or carpet yellowing prevention benefit of a given bleaching composition a PSU-scale ranging from 0, meaning no noticeable difference in yellowing of a treated fabric/carpet versus an untreated fabric/carpet, to 4, meaning a clearly noticeable difference in yellowing of a treated fabric/carpet versus an untreated fabric/carpet, can be applied.
  • compositions according to the present invention may comprise as a highly preferred, but optional ingredient a thickener.
  • compositions of the present invention may have a viscosity of 1 cps or greater, more preferably of from 5 to 5000 cps, and still more preferably of from 10 to 2500 cps when measured with a CSL 2 100® Rheometer at 20°C with a 4 cm spindle (linear increment from 10 to 100 dyne/cm 2 in 2 minutes).
  • the bleaching compositions according to the present invention may comprise from 0.001% to 10%, preferably from 0.05% to 5% and more preferably from 0.1 % to 1.0 % by weight of the total composition of a thickener.
  • the thickener is selected from the group consisting of : any suitable natural polymers and derivatives thereof, preferably polysaccharide polymers; vinyl-, carboxyvinyl-, crosslinked and non-crosslinked carboxylic-, preferably acrylic-, methacrylic- maleic-, and acryloamido-polymers; fatty acid esters; silicates; idantoinic resins; pirogenic oxides; and mixtures thereof. More preferably, the thickener is a polysaccharide polymer, acrylic- or acryloamido-polymer or a mixture thereof. Even more preferably, the thickener is a polysaccharide polymer or a mixture thereof. Most preferably, the thickener is xanthan gum.
  • Suitable polysaccharide polymers for use herein include cellulose, substituted cellulose materials like carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan gum and naturally occurring polysaccharide polymers like xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof, or mixtures thereof.
  • xanthan gum and derivatives thereof are xanthan gum and derivatives thereof.
  • Xanthan gum and derivatives thereof may be commercially available for instance from Kelco under the trade name Keltrol RD®, Kelzan S®, Kelzan ASX® or Kelzan T®.
  • Other suitable Xanthan gum are commercially available by Rhone Poulenc under the trade name Rhodopol T® and Rhodigel X747®.
  • Succinoglycan gum for use herein is commercially available by Rhone Poulenc under the trade name Rheozan ®.
  • compositions herein are thickened, meaning that the compositions have an increased viscosity
  • the presence of a di- or tri-alkoxylated benzoic acid or a salt thereof, preferably a trialkoxy benzoic acid or a salt thereof, more preferably trimethoxy benzoic acid or a salt thereof (TMBA) increases the rheological stability of the bleaching compositions according to the present invention upon storage.
  • the rheological stability upon storage of the compositions according to the present invention may be assessed in the laboratory using a rapid ageing test ("RAT").
  • the RAT involves measuring the % loss of viscosity by comparing the viscosity of the fresh thickened bleaching composition ("initial viscosity") after it is made with the viscosity of the same compositions after 2 days at 50°C.
  • initial viscosity the viscosity of the fresh thickened bleaching composition
  • the compositions of the present invention typically do not undergo more than 60% loss of viscosity at 50°C ⁇ 0.5°C after 2 days of storage as compared to the initial viscosity of the fresh compositions. More preferably not more than 50% loss of viscosity at 50°C ⁇ 0.5°C after 2 days of storage.
  • compositions according to the present invention may comprise as a highly preferred but optional ingredient a surfactant.
  • compositions of the present invention may further comprise a surfactant including nonionic surfactants, zwitterionic surfactants, anionic surfactants, cationic surfactants and/or amphoteric surfactants.
  • a surfactant including nonionic surfactants, zwitterionic surfactants, anionic surfactants, cationic surfactants and/or amphoteric surfactants.
  • compositions according to the present invention may comprise from 0.01% to 30%, preferably from 0.1% to 25 % and more preferably from 0.5% to 20% by weight of the total composition of a surfactant.
  • Suitable nonionic surfactants include alkoxylated nonionic surfactants.
  • Preferred alkoxylated nonionic surfactants herein are ethoxylated nonionic surfactants according to the formula RO-(C 2 H 4 O) n H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 alkyl benzene chain, and wherein n is from 0 to 20, preferably from 1 to 15 and, more preferably from 2 to 15 and most preferably from 2 to 12.
  • the preferred R chains for use herein are the C 8 to C 22 alkyl chains.
  • Propoxylated nonionic surfactants and ethoxy/propoxylated ones may also be used herein instead of the ethoxylated nonionic surfactants as defined herein above or together with said surfactants
  • Preferred ethoxylated nonionic surfactants are substantially linear ethoxylated nonionic surfactants according to the above formula.
  • linear it is meant herein that the fatty alcohols used as a basis of the nonionic surfactant (raw material) at least 90%, preferably at least 95%, more preferably at least 97%, and most preferably 100% by weight of the total amount of fatty alcohols of linear (i.e., straight chain) fatty alcohols.
  • Suitable substantially linear ethoxylated nonionic surfactants for use herein are Marlipal® 24-7 (R is a mixture of linear C 12 and C 14 alkyl chains, n is 7), Marlipal® 24-4 (R is a mixture of linear C 12 and C 14 alkyl chains, n is 4), Marlipal® 24-3 (R is a mixture of linear C 12 and C 14 alkyl chains, n is 3), Marlipal® 24-2 (R is a mixture of linear C 12 and C 14 alkyl chains, n is 2), or mixtures thereof.
  • These Marlipal® surfactants are commercially available from Condea.
  • Preferred ethoxylated nonionic surfactants are according to the formula above and have an HLB (hydrophilic-lipophilic balance) below 16, preferably below 15, and more preferably below 14. Those ethoxylated nonionic surfactants have been found to provide good grease cutting properties.
  • Dobanol® 91-2.5 or Lutensol® TO3, or Lutensol® AO3, or Tergitol® 25L3, or Dobanol® 23-3, or Dobanol® 23-2, or Dobanol® 45-7, Dobanol® 91-8, or Dobanol® 91-10, or Dobanol® 91-12, or mixtures thereof.
  • Dobanol® surfactants are commercially available from SHELL.
  • Lutensol® surfactants are commercially available from BASF and these Tergitol® surfactants are commercially available from UNION CARBIDE.
  • Suitable chemical processes for preparing the alkoxylated nonionic surfactants for use herein include condensation of corresponding alcohols with alkylene oxide, in the desired proportions. Such processes are well known to the man skilled in the art and have been extensively described in the art.
  • compositions herein may desirably comprise one of those ethoxylated nonionic surfactants or a mixture of those ethoxylated nonionic surfactants having different HLBs (hydrophilic-lipophilic balance).
  • the compositions herein comprise an ethoxylated nonionic surfactant according to the above formula and having an HLB up to 10 (i.e., a so called hydrophobic ethoxylated nonionic surfactant), preferably below 10, more preferably below 9, and an ethoxylated nonionic surfactant according to the above formula and having an HLB above 10 to 16 (i.e., a so called hydrophilic ethoxylated nonionic surfactant), preferably from 11 to 14.
  • compositions of the present invention typically comprise from 0.01% to 15% by weight of the total composition of said hydrophobic ethoxylated nonionic surfactant, preferably from 0.5% to 10% and from 0.01% to 15% by weight of said hydrophilic ethoxylated nonionic surfactant, preferably from 0.5% to 10%.
  • Such mixtures of ethoxylated nonionic surfactants with different HLBs may be desired as they allow optimum grease cleaning removal performance on a broader range of greasy soils having different hydrophobic/hydrophilic characters.
  • Suitable nonionic surfactants to be used herein include polyhydroxy fatty acid amide surfactants, or mixtures thereof, according to the formula: R2 - C(O) - N(R 1 )-Z, wherein R 1 is H, or C 1 -C 4 alkyl, C 1- C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5- C 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is C 1- C 4 alkyl, more preferably C 1 or C 2 alkyl and most preferably methyl
  • R 2 is a straight chain C 7- C 19 alkyl or alkenyl, preferably a straight chain C 9- C 18 alkyl or alkenyl, more preferably a straight chain C 11- C 18 alkyl or alkenyl, and most preferably a straight chain C 11- C 14 alkyl or alkenyl, or mixtures thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n-1 -CH 2 OH, -CH 2 -(CHOH) 2- (CHOR')(CHOH)-CH 2 OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly CH 2 -(CHOH) 4 -CH 2 OH.
  • R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R 2 - C(O) - N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide and the like.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl and 1-deoxymaltotriotityl.
  • Suitable polyhydroxy fatty acid amide surfactants to be used herein may be commercially available under the trade name HOE® from Hoechst.
  • polyhydroxy fatty acid amide surfactants are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • compositions containing polyhydroxy fatty acid amides are disclosed for example in GB patent specification 809,060 , published February 18, 1959, by Thomas Hedley & Co., Ltd., US patent 2,965,576, issued December 20, 1960 to E.R. Wilson, US patent 2,703,798 , Anthony M. Schwartz, issued March 8, 1955, US patent 1,985,424, issued December 25, 1934 to Piggott and WO92/06070 .
  • Suitable zwitterionic betaine surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
  • the typical anionic hydrophilic groups are carboxylates and sulphonates, although other groups like sulfates, phosphonates, and the like can be used.
  • a generic formula for the zwitterionic betaine surfactant to be used herein is : R 1 -N + (R 2 )(R 3 )R 4 X - wherein R 1 is a hydrophobic group; R 2 is hydrogen, C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group; R 3 is C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group which can also be joined to R 2 to form ring structures with the N, or a C 1 -C 6 sulphonate group; R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group, which is a carboxylate or sulphonate group.
  • R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more preferably from 10 to 16. These simple alkyl groups are preferred for cost and stability reasons.
  • the hydrophobic group R 1 can also be an amido radical of the formula R a -C(O)-NH-(C(R b ) 2 ) m , wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18, more preferably up to 16, R b is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R b ) 2 ) moiety.
  • Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
  • Preferred R 3 is C 1 -C 4 sulphonate group, or a C 1 -C 3 alkyl and more preferably methyl.
  • Preferred R 4 is (CH 2 ) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
  • betaine/sulphobetaine Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275 , 2,702,279 and 2,255,082 .
  • alkyldimethyl betaines examples include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
  • coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
  • Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
  • amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine or C 10 -C 14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
  • C 10 -C 14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
  • betaine Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H 2 C-HA®.
  • Suitable anionic surfactants to be used 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 an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, 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).
  • 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 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxy
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • 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
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate (C 12- C 18 E(1.0)SM), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate (C 12- C 18 E(2.25)SM), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12- C 18 E(3.0)SM), and C 12 -C 18 alkyl polyethoxylate (
  • Suitable anionic surfactants for use herein are sulphonated anionic surfactants.
  • Suitable sulphonated anionic surfactants for use herein include alkyl sulphonates, alkyl aryl sulphonates, naphthalene sulphonates, alkyl alkoxylated sulphonates, C 6 -C 20 alkyl alkoxylated linear or branched diphenyl oxide disulphonates, or mixtures thereof.
  • Suitable alkyl sulphonates for use herein include water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 8 -C 18 alkyl group and more preferably a C 14 -C 17 alkyl group, 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.
  • R is a C 6 -C 20 linear or branched
  • Suitable alkyl aryl sulphonates for use herein include water-soluble salts or acids of the formula RSO 3 M wherein R is an aryl, preferably a benzyl, substituted by a C 6 -C 20 linear or branched saturated or unsaturated alkyl group, preferably a C 8 -C 18 alkyl group and more preferably a C 10 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium 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,
  • Particularly suitable linear alkyl sulphonates include C 14 -C 17 paraffin sulphonate like Hostapur ® SAS commercially available from Hoechst.
  • An example of commercially available alkyl aryl sulphonate is Lauryl aryl sulphonate from Su.Ma..
  • Particularly preferred alkyl aryl sulphonates are alkyl benzene sulphonates commercially available under trade name Nansa® available from Albright&Wilson.
  • linear alkyl sulphonate it is meant herein a non-substituted alkyl sulphonate wherein the alkyl chain comprises from 6 to 20 carbon atoms, preferably from 8 to 18 carbon atoms, and more preferably from 14 to 17 carbon atoms, and wherein this alkyl chain is sulphonated at one terminus.
  • Suitable alkoxylated sulphonate surfactants for use herein are according to the formula R(A) m SO 3 M wherein R is an unsubstituted C 6 -C 20 alkyl, hydroxyalkyl or alkyl aryl group, having a linear or branched C 6 -C 20 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy or butoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 6 -C 20 alkyl, hydroxyalkyl or alkyl aryl group, having a linear
  • Alkyl ethoxylated sulphonates, alkyl butoxylated sulphonates as well as alkyl propoxylated sulphonates 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.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulphonate (C 12 -C 18 E(1.0) SO 3 M), C 12 -C 18 alkyl polyethoxylate (2.25) sulphonate (C 12 -C 18 E(2.25) SO 3 M), C 12 -C 18 alkyl polyethoxylate (3.0) sulphonate (C 12 -C 18 E(3.0) SO 3 M), and C 12 -C 18 alkyl polyethoxylate (4.0) sulphonate (C 12 -C 18 E(4.0) SO 3 M), wherein M is conveniently selected from sodium and potassium.
  • Particularly suitable alkoxylated sulphonates include alkyl aryl polyether sulphonate like Triton X-200® commercially available from Union Carbide.
  • Suitable C 6 -C 20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate surfactants for use herein are according to the following formula: wherein R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and X+ is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium.
  • R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group
  • X+ is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium.
  • Particularly suitable C 6 -C 20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate surfactants to be used herein are the C 12 branched di phenyl oxide disulphonic acid and C 16 linear di phenyl oxide disulphonate sodium salt respectively commercially available by DOW under the trade name Dowfax 2A1® and Dowfax 8390®.
  • anionic surfactants suitable herein include sulfosuccinate surfactants, alkyl carboxylate surfactants, sulfosuccinamate surfactants and sulfosuccinamide surfactants.
  • Suitable sulfosuccinate surfactants are according to the formula : wherein : R 1 is hydrogen or a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group; R 2 is a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group; and M is hydrogen or a cationic moiety, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium or ammonium or substituted ammonium (e.g., methyl
  • Such sulfosuccinate surfactants are commercially available under the tradenames Aerosol® from Cytec, Anionyx® from Stepan, Arylene® from Hart, Setacin® from Zschimmer & Schwarz, Mackanate® from McIntyre and Monawet® from Mona Industries.
  • Suitable sulfosuccinamate surfactants for use herein are according to the formula wherein R 1 and R 2 each independently represent a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium 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.
  • an alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium 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
  • Suitable sulfosuccinamide surfactants for use herein are according to the formula wherein R 1 and R 2 each independently represent a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) 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 thereo.f
  • alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
  • 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 qua
  • Suitable alkyl carboxylate surfactants for use herein are according to the formula RCO 2 M wherein : R represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20, preferably 8 to 18, more preferably 10 to 16, carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium 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.
  • an alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium 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
  • 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, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulphonates such as C 14-16 methyl ester sulphonates; acyl glycerol sulphonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH 2 CH 2 O) k CH 2 COO-M + wherein R is a C 8 -C 22 alkyl,
  • 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.
  • acyl sarcosinate 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. Preferred 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 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 amphoteric surfactants to be used herein include amine oxides having the following formula R 1 R 2 R 3 NO wherein each of R 1 , R 2 and R 3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chains of from 1 to 30 carbon atoms.
  • Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R 1 R 2 R 3 NO wherein R 1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R 2 and R 3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups.
  • R1 may be a saturated substituted or unsubstituted linear or branched hydrocarbon chain.
  • Suitable amine oxides for use herein are for instance natural blend C 8 -C 10 amine oxides as well as C 12 -C 16 amine oxides commercially available from Hoechst.
  • said bleaching compositions according to the present invention comprise a nonionic surfactant or a zwitterionic betaine surfactant or a mixture thereof.
  • said compositions comprise a sulphonated anionic surfactant. More preferably said composition further comprises a second surfactant selected from the group consisting of nonionic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.
  • said bleaching compositions according to the present invention comprise a sarcosinate surfactant, an alkyl sulphonate surfactant, an alkyl sulphate surfactant, or a zwitterionic betaine surfactant and mixtures thereof, and more preferably an alkyl sarcosinate surfactant.
  • said compositions comprise a sulfosuccinate surfactant More preferably, said compositions comprise a mixture of a sulfosuccinate surfactant and a second anionic surfactant. Most preferably, said compositions comprise a mixture of a sulfosuccinate surfactant and a sulphate surfactant.
  • the bleaching compositions herein may further comprise a variety of other optional ingredients such as builders, chelating agents, stabilisers, bleach activators, soil suspenders, soil suspending polyamine polymers, polymeric soil release agents, foam reducing systems or agents, catalysts, dye transfer agents, brighteners, perfumes, hydrotropes, solvents, pigments and dyes.
  • optional ingredients such as builders, chelating agents, stabilisers, bleach activators, soil suspenders, soil suspending polyamine polymers, polymeric soil release agents, foam reducing systems or agents, catalysts, dye transfer agents, brighteners, perfumes, hydrotropes, solvents, pigments and dyes.
  • the bleaching compositions of the present invention may further comprise one or more builders and/or a modified polycarboxylate co-builder.
  • Suitable builders are selected from the group consisting of : organic acids and salts thereof; polycarboxylates; and mixtures thereof.
  • said builders have a calcium chelating constant (pKCa) of at least 3.
  • pKCa calcium chelating constant
  • the value of a builder or a mixture thereof is measured using an 0.1M NH 4 Cl-NH 4 OH buffer (pH 10 at 25°C) and a 0.1% solution of said builder or mixture thereof with a standard calcium ion electrode.
  • builders are organic acids like citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, monosuccinic acid, disuccinic acid, oxydisuccinic acid, carboxymethyl oxysuccinic acid, diglycolic acid, carboxymethyl tartronate, ditartronate and other organic acid or mixtures thereof.
  • Suitable salts of organic acids include alkaline, preferably sodium or potassium, alkaline earth metal, ammonium or alkanolamine salts.
  • Such organic acids and the salts thereof are commercially available from Jungbunzlaur, Haarman & Reimen, Sigma-Aldrich or Fluka.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt or "overbased". When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • Useful polycarboxylates include homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid.
  • polycarboxylate builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polyacetic acids such as nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid
  • Suitable polycarboxylates are commercially available from Rohm & Haas under the trade name Norasol® or Acusol®.
  • Preferred builders herein are selected from the group consisting of : citric acid; tartaric acid; tartrate monosuccinate; tartrate disuccinate; lactic acid; oxalic acid; and malic acid; and mixtures thereof. Even more preferred builders herein are selected from the group consisting of : citric acid; tartaric acid; tartrate monosuccinate; tartrate disuccinate; and malic acid; and mixtures thereof. The most preferred builders herein are selected from the group consisting of : citric acid; tartaric acid; tartrate monosuccinate; and tartrate disuccinate; and mixtures thereof.
  • the bleaching compositions herein may comprise up to 40%, preferably from 0.01% to 25%, more preferably from 0.1% to 15%, and most preferably from 0.5% to 10% by weight of the total composition of said builder.
  • compositions of the present invention may further comprise a modified polycarboxylate co-builder.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • modified polycarboxylate it is meant herein that at least at one end of the polycarboxylate compound, i.e., the polycarboxylate chain, said compound is modified by a functional group, e.g., a phosphono group.
  • Preferred modified polycarboxylate co-builders are polycarboxylates with phosphono end groups.
  • phosphono end group it is meant herein a phosphono functional group according to the formula : wherein each M is independently H or a cation, preferably both M are H.
  • Suitable polycarboxylates with phosphono end groups are copolymers of acrylic acid and maleic acid having a phosphono end group and homopolymers of acrylic acid having a phosphono end group.
  • a preferred modified polycarboxylate is a copolymer of acrylic acid and maleic acid with a phosphonic/phosphono end group according to the general formula : having an average molecular weight of from 1000 to 100000, preferably an average molecular weight of from 1000 to 20000, more preferably an average molecular weight of from 1000 to 10000, and most preferably an average molecular weight of from 1500 to 5000; wherein n is from 10 mol% to 90 mol%, preferably 80 mol% and m is from 10 mol% to 90 mol%, preferably 20 mol%.
  • an example of a suitable modified polycarboxylate is a copolymer of acrylic acid and maleic acid (80/20) with a phosphonic/phosphono end group according to the formula : wherein n is 80 mol% and m is 20 mol%; having an average molecular weight of 2000.
  • Such modified polycarboxylate are available from Rohm & Haas under the trade name Acusol 425®, Acusol 420® or Acusol 470®.
  • the bleaching compositions herein may comprise up to 40%, preferably from 0.01% to 25%, more preferably from 0.1% to 15%, and most preferably from 0.5% to 5% by weight of the total composition of said modified polycarboxylate co-builder.
  • the bleaching compositions of the present invention may comprise a chelating agent as a preferred optional ingredient.
  • 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, amino carboxylate chelating agents, other carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
  • a chelating agent may be desired in the compositions of the present invention as it allows to increase the ionic strength of the compositions herein and thus their stain removal and bleaching performance on various surfaces.
  • the presence of chelating agents may also contribute to reduce the tensile strength loss of fabrics and/or color damage, especially in a laundry through the wash application. Indeed, the chelating agents inactivate the metal ions present on the surface of the fabrics and/or in the cleaning compositions (neat or diluted) that otherwise would contribute to the radical decomposition of the peroxygen bleach.
  • Suitable phosphonate chelating agents to be used 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®.
  • 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 acid is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
  • R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO 2 , -C(O)R', and - SO 2 R''; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R'' is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R 5 , R 6 , R 7 , and R 8 are independently selected from the group consisting of -H and alkyl.
  • Particularly preferred chelating agents to be used herein are amino aminotri(methylene phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic acid, and mixtures thereof.
  • the bleaching compositions according to the present invention may comprise up to 5%, preferably from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5% by weight of the total composition of a chelating agent.
  • the bleaching compositions according to the present invention may further comprise a solvent.
  • Preferred solvents herein include hydrophobic solvents, hydrophilic solvents and mixtures hereof.
  • hydrophilic index molecular weight of the hydrophilic part of the solvent total molecular weight of the solvent * 100
  • hydrophilic part of a given solvent it is meant herein all the groups O, CO, OH, of a given solvent.
  • molecular weight of the hydrophilic part of a solvent it is meant herein the total molecular weight of all the hydrophilic parts of a given solvent.
  • hydrophilic solvents to be used herein have a hydrophilic index of more than 18, preferably more than 25, and more preferably more than 30, and the hydrophobic solvents to the used herein have a hydrophilic index of less than 18, preferably less than 17 and more preferably 16 or less.
  • Suitable hydrophobic solvents to be used herein include paraffins, terpenes or terpene derivatives, as well as alkoxylated aliphatic or aromatic alcohols, aliphatic or aromatic alcohols, glycols or alkoxylated glycols, and mixtures thereof, all these solvents have a hydrophilic index of less than 18.
  • Suitable terpenes are mono-and bicyclic monoterpenes, especially those of the hydrocarbon class, which include the terpinenes, terpinolenes, limonenes and pinenes and mixtures thereof. Highly preferred materials of this type are d-limonene, dipentene, alpha-pinene and/or beta-pinene.
  • pinene is commercially available form SCM Glidco (Jacksonville) under the name Alpha Pinene P&F®.
  • Terpene derivatives such as alcohols, aldehydes, esters, and ketones which have a hydrophilic index of less than 18 can also be used herein.
  • Such materials are commercially available as, for example, the ⁇ and ⁇ isomers of terpineol and linalool.
  • paraffins hydrophilic index of 0
  • paraffins hydrophilic index of 0
  • octane octane
  • Octane is commercially available for example from BASF.
  • Suitable hydrophobic alkoxylated aliphatic or aromatic alcohols to be used herein are according to the formula R-(A) n -OH wherein R is a linear or branched saturated or unsaturated alkyl group, or alkyl substituted or non-alkyl substituted aryl group of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms, wherein A is an alkoxy group preferably an butoxy, propoxy and/or ethoxy group, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable hydrophobic aliphatic or aromatic alcohols to be used herein are according to the formula R-OH wherein R is a linear or branched saturated or unsaturated alkyl group, or alkyl substituted or non-alkyl substituted aryl group of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms.
  • Suitable hydrophobic glycols to be used herein are according to the formula HO-CR 1 R 2 -OH wherein R 1 and R 2 are independently H or a C 2 -C 10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic hydrocarbon chain.
  • Suitable hydrophobic alkoxylated glycols to be used herein are according to the formula R-(A) n -R 1 -OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms, wherein R 1 is H or a linear saturated or unsaturated alkyl of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms, and A is an alkoxy group preferably an ethoxy, methoxy, and/or propoxy group and n is from 1 to 5, preferably 1 to 2.
  • hydrophobic solvents to be used herein include d-limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol, or mixtures thereof.
  • Suitable hydrophilic solvents to be used herein include alkoxylated aliphatic or aromatic alcohols, aliphatic or aromatic alcohols, glycols or alkoxylated glycols, and mixtures thereof, all these solvents having a hydrophilic index of more than 18.
  • Suitable hydrophilic alkoxylated aliphatic or aromatic alcohols to be used herein are according to the formula R-(A) n -OH wherein R is a linear or branched saturated or unsaturated alkyl group, or alkyl substituted or non-alkyl substituted aryl group of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms, wherein A is an alkoxy group preferably a butoxy, propoxy and/or ethoxy group, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable hydrophilic aliphatic or aromatic alcohols to be used herein are according to the formula R-OH wherein R is a linear or branched saturated or unsaturated alkyl group, or alkyl substituted or non-alkyl substituted aryl group of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms.
  • Suitable hydrophilic glycols to be used herein are according to the formula HO-CR 1 R 2 -OH wherein R 1 and R 2 are independently H or a C 2 -C 10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic hydrocarbon chain.
  • Suitable hydrophilic alkoxylated glycols to be used herein are according to the formula R-(A) n -R 1 -OH wherein R is H, OH, a linear saturated or unsaturated alkyl group of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms, wherein R 1 is H or a linear saturated or unsaturated alkyl group of from 1 to 20, preferably from 2 to 15 and more preferably from 2 to 10 carbon atoms, and A is an alkoxy group preferably an ethoxy, methoxy, and/or propoxy group and n is from 1 to 5, preferably 1 to 2.
  • the bleaching compositions according to the present invention may comprise up to 30%, preferably from 0.01% to 15%, more preferably from 0.1 % to 10%, and most preferably from 0.5% to 5% by weight of the total composition of a solvent.
  • compositions herein comprise a mixture of a hydrophobic solvent and a hydrophilic solvent
  • weight ratio of said hydrophobic solvent to said hydrophilic is from 1:20 to 1:1, more preferably from 1: 14 to 1: 2.
  • Solvents when present, contribute to the excellent stain removal performance of the bleaching compositions as described herein.
  • the bleaching compositions according to the present invention may further comprise a foam reducing agent or a foam reducing system.
  • foam reducing agents known to those skilled in the art are suitable for use herein.
  • a foam reducing system comprising a fatty acid together with a capped alkoxylated nonionic surfactant as defined herein after and/or silicone is used.
  • the bleaching compositions herein may comprise from 1.10 -4 % to 10%, preferably from 1.10 -3 % to 5% and more preferably from 1 ⁇ 10 -2 % to 5% by weight of the total composition of a fatty acid.
  • the bleaching compositions herein may comprise from 1 ⁇ 10 -3 % to 20%, preferably from 1 ⁇ 10 -2 % to 10% and more preferably from 5 ⁇ 10 -2 % to 5% by weight of the total composition of a capped alkoxylated nonionic surfactant as defined herein.
  • the bleaching compositions herein may comprise from 1 ⁇ 10 -5 % to 5%, preferably from 1 ⁇ 10 -5 % to 1% and more preferably from 1 ⁇ 10 -4 % to 0.5% by weight of the total composition of a silicone.
  • Suitable fatty acids for use herein are the alkali salts of a C 8 -C 24 fatty acid.
  • Such alkali salts include the metal fully saturated salts like sodium, potassium and/or lithium salts as well as the ammonium and/or alkylammonium salts of fatty acids, preferably the sodium salt.
  • Preferred fatty acids for use herein contain from 8 to 22, preferably from 8 to 20 and more preferably from 8 to 18 carbon atoms.
  • Suitable fatty acids may be selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures of fatty acids suitably hardened, derived from natural sources such as plant or animal esters (e.g., palm oil, coconut oil, soybean oil, castor oil, tallow, ground oil, whale and fish oils and/or babassu oil.
  • plant or animal esters e.g., palm oil, coconut oil, soybean oil, castor oil, tallow, ground oil, whale and fish oils and/or babassu oil.
  • coconut Fatty Acid is commercially available from UNICHEMA under the name PRIFAC 5900®.
  • Suitable capped alkoxylated nonionic surfactants for use herein are according to the formula: R 1 (O-CH 2 -CH 2 ) n -(OR 2 ) m -O-R 3 wherein R 1 is a C 8 -C 24 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably R 1 is a C 8 -C 18 alkyl or alkenyl group, more preferably a C 10 -C 15 alkyl or alkenyl group, even more preferably a C 10 -C 15 alkyl group; wherein R 2 is a C 1 -C 10 linear or branched alkyl group, preferably a C 2 -C 10 linear or branched alkyl group, preferably a C 3 group; wherein R 3 is a C 1 -C 10 alkyl or alkenyl group, preferably a C 1 -C 5 alkyl group, more preferably methyl; and wherein n
  • 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 alkoxylated surfactants of the above formula are those commercially available under the tradename Genapol® L 2.5 NR from Hoechst, and Plurafac® from BASF.
  • Suitable silicones for use herein include any silicone and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the silicone is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier. Alternatively, the silicone can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • silicone has become a generic term which encompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types. Indeed, silicone compounds have been extensively described in the art, see for instance US 4 076 648 , US 4 021 365 , US 4 749 740 , US 4 983 316 , EP 150 872 , EP 217 501 and EP 499 364 .
  • the silicone compounds disclosed therein are suitable in the context of the present invention.
  • the silicone compounds can be described as siloxanes having the general structure : wherein n is from 20 to 2000, and where each R independently can be an alkyl or an aryl radical.
  • Preferred polydiorganosiloxanes are polydimethylsiloxanes having trimethylsilyl end blocking units and having a viscosity at 25°C of from 5 x 10 -5 m 2 /s to 0.1 m 2 /s, i.e., a value of n in the range 40 to 1500. These are preferred because of their ready availability and their relatively low cost.
  • a preferred type of silicone compounds useful in the compositions herein comprises a mixture of an alkylated siloxane of the type herein above disclosed and solid silica.
  • the solid silica can be a fumed silica, a precipitated silica or a silica made by the gel formation technique.
  • the silica particles can be rendered hydrophobic by treating them with diakylsilyl groups and/or trialkylsilane groups either bonded directly onto the silica or by means of silicone resin.
  • a preferred silicone compound comprises a hydrophobic silanated, most preferably trimethylsilanated silica having a particle size in the range from 10 mm to 20 mm and a specific surface area above 50 m 2 /g.
  • Silicone compounds employed in the compositions according to the present invention suitably have an amount of silica in the range of 1 to 30% (more preferably 2.0 to 15%) by weight of the total weight of the silicone compounds resulting in silicone compounds having an average viscosity in the range of from 2 x 10 -4 m 2 /s to 1m 2 /s.
  • Preferred silicone compounds may have a viscosity in the range of from 5 x 10 -3 m 2 /s to 0.1 m 2 /s.
  • Particularly suitable are silicone compounds with a viscosity of 2 x 10 -2 m 2 /s or 4.5 x 10 -2 m 2 /s.
  • Suitable silicone compounds for use herein are commercially available from various companies including Rhone Poulenc, Fueller and Dow Corning.
  • Examples of silicone compounds for use herein are Silicone DB® 100 and Silicone Emulsion 2-3597® both commercially available from Dow Corning.
  • silicone compound is disclosed in Bartollota et al. U.S. Patent 3 933 672 .
  • Other particularly useful silicone compounds are the self-emulsifying silicone compounds, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544®, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil®.
  • the bleaching compositions according to the present invention may further comprise an antioxidant.
  • the bleaching compositions herein may comprise up to 10%, preferably from 0.002% to 5%, more preferably from 0.005% to 2%, and most preferably from 0.01% to 1% by weight of the total composition of an antioxidant.
  • Suitable antioxidants to be used herein include organic acids like citric acid, ascorbic acid, tartaric acid, adipic acid and sorbic acid, or amines like lecithin, or aminoacids like glutamine, methionine and cysteine, or esters like ascorbil palmitate, ascorbil stearate and triethylcitrate, or mixtures thereof.
  • Preferred antioxidants for use herein are citric acid, ascorbic acid, ascorbil palmitate, lecithin or mixtures thereof.
  • the compositions of the present invention may comprise a bleach activator.
  • bleach activator it is meant herein a compound which reacts with hydrogen peroxide to form a peracid.
  • the peracid thus formed constitutes the activated bleach.
  • Suitable bleach activators to be used herein include those belonging to the class of esters, amides, imides, or anhydrides. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523 .
  • Suitable examples of such compounds to be used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS).
  • TAED tetracetyl ethylene diamine
  • NOBS n-nonanoyloxybenzenesulphonate
  • N-acyl caprolactams selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam or mixtures thereof.
  • a particular family of bleach activators of interest was disclosed in EP 624 154 , and particularly preferred in that family is acetyl triethyl citrate (ATC).
  • Acetyl triethyl citrate has the advantage that it is environmental-friendly as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the product upon storage and it is an efficient bleach activator. Finally, it provides good building capacity to the composition.
  • the bleaching compositions according to the present invention may comprise from 0.01% to 20%, preferably from 1% to 10%, and more preferably from 3% to 7% by weight of the total composition of said bleach activator.
  • the bleaching compositions according to the present invention may further comprise a sulphonated hydrotrope.
  • alkyl aryl sulphonates or alkyl aryl sulphonic acids are used.
  • Preferred alkyl aryl sulphonates include sodium, potassium, calcium and ammonium xylene sulphonates, sodium, potassium, calcium and ammonium toluene sulphonates, sodium, potassium, calcium and ammonium cumene sulphonates, sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulphonates and mixtures thereof.
  • Preferred alkyl aryl sulphonic acids include xylenesulphonic acid, toluenesulphonic acid, cumenesulphonic acid, substituted or unsubstituted naphthalenesulphonic acid and mixtures thereof. More preferably, xylenesulphonic acid or p-toluene sulphonate or mixtures thereof are used.
  • the bleaching compositions herein comprise from 0.01 % to 20% by weight of the total composition of a sulphonated hydrotrope, preferably from 0.05% to 10% and more preferably from 0.1% to 5%.
  • the bleaching composition of the present invention is used by applying the bleaching composition, preferably in a liquid form, to the fabric to be treated.
  • a liquid form it is meant herein, the liquid compositions according to the present invention per se in neat or diluted form, as well as the granular or powder compositions or tablets according to the present invention that have been diluted with an appropriate solvent, typically water, before use, i.e., before being contacted to said fabrics.
  • 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 may be used at a dilution level of up to 1500:1 (solvent:composition), preferably from 5:1 to 1000:1 and more preferably from 10:1 to 700:1 (solvent:composition).
  • liquid bleaching compositions are applied directly onto the fabrics to be treated without undergoing any dilution, i.e., the liquid compositions herein are applied onto the fabrics as described herein.
  • Fabrics to be treated herein include, but are not limited to, clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags and/or tents.
  • treating a fabric it is meant herein cleaning said and/or bleaching/disinfecting said fabric.
  • a bleaching composition according to the present invention is contacted with the fabrics to be treated.
  • pretreatment mode where a liquid bleaching composition, as defined herein, is applied neat onto said fabrics before the fabrics are rinsed, or washed, then rinsed, or in a "soaking mode” where a liquid or solid bleaching composition, as defined herein, is first diluted in an aqueous bath and the fabrics are immersed and soaked in the bath, before they are rinsed, or in a "through-the-wash mode", where a liquid or solid bleaching composition, as defined herein, is added in addition to a wash liquor formed by dissolution or dispersion of a typical laundry detergent, preferably in a washing machine. It is also essential in both cases, that the fabrics be rinsed after they have been contacted with said composition, before said composition has completely dried off.
  • the process of bleaching fabrics according to the present invention preferably comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, 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, the washing of said fabrics with a detergent composition comprising at least one surface active agent may be conducted before the step of contacting said fabrics with said bleaching composition and/or in the step where said fabrics are contacted with said 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 bleaching composition may be used in dilute or neat form. Where it is used diluted, the bleaching composition should remain in contact with the fabric for typically 1 to 60 minutes, preferably 5 to 30 minutes. Whereas, when the bleaching composition is used in its neat form, it should remain in contact with the fabric for a much shorter time, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes.
  • the bleaching pretreatment operation may also be followed by the diluted bleaching process as described above either in bucket (hand operation) or in a washing machine.
  • the present invention also encompasses a process of treating a hard-surface.
  • the hard-surfaces to be treated is contacted with a composition, as defined herein.
  • the present invention also encompasses a process of treating a hard-surface with a composition, as defined herein, wherein said process comprises the step of applying said composition to said hard-surface, preferably only soiled portions thereof, and optionally rinsing said hard-surface.
  • the composition in the process of treating hard-surfaces according to the present invention may be applied to the surface to be treated in its neat form or in its diluted form.
  • the composition is preferably diluted with up to 200 times its weight of water, preferably 80 to 2 times its weight of water, and more preferably 60 to 2 times its weight of water.
  • compositions of the present invention are easy to rinse and provide good shine characteristics on the treated surfaces.
  • compositions herein can be packaged in a variety of containers including conventional bottles, bottles equipped with roll-on, sponge, brusher, sprayers, pouches, sachets, boxes,
  • the present invention encompasses a process of treating a carpet comprising the application of a bleaching composition according to the present invention onto said carpet.
  • a bleaching composition according to the present invention onto said carpet.
  • said bleaching composition is applied in its liquid form onto said carpet using a spraying device.
  • composition is applied onto said carpet using an electrical spraying device.
  • said process comprises the steps of applying a liquid bleaching composition according to the present invention to the surface of the carpet and leaving said composition to substantially dry on the carpet. More preferably, said process of treating a carpet further comprises the step of removing said composition, even more preferably, said process of treating a carpet further comprises the step of removing said composition in combination with soil particles.
  • said process comprises the steps of applying a liquid bleaching composition according to the present invention to parts, preferably heavily soiled parts, of the carpet, mechanically agitating the composition with an implement into the soiled parts of the carpet layer and leaving said composition to substantially dry on the carpet. More preferably said process of treating a carpet further comprises the step of removing said composition, even more preferably said process of treating a carpet further comprises the step of removing said composition in combination with soil particles.
  • Any number of implements may be used to provide said mechanical agitation, including brushes, paper towels, a cleaning glove and a human finger. Said mechanical agitation allows the liquid composition to better penetrate into the carpet fibers and thus improves the chemical cleaning action of said composition. In addition, said contact loosens the dirt particles forming the stain.
  • a liquid bleaching composition according to the present invention is applied onto the carpet using a spraying device.
  • Said spraying device is preferably a container that has at least one aperture through which the composition is dispensed to produce a spray of droplets.
  • Such a spraying device may comprise a means for delivering the composition by a pump ("pump spray dispenser") or may be operated by any source of pressurised gas such as an aerosol-can or a pressurizer.
  • Pump spray dispensers may be manually or electrically, preferably electrically, operated. Said pump spray dispensers are particularly preferable if a large area is to be treated and/or if a high amount of product has to be applied onto a heavily stained area (“spot”) of the carpet as they facilitate the ease of use by the consumer. Said pump spray dispensers ensure uniform coverage of the area to be treated.
  • Preferred spraying devices herein are manually or electrically operated pump spray dispensers. More preferred spraying devices herein are electrically operated pump spray dispensers.
  • Typical manually operated pump spray dispensers include push button operated or trigger operated pump spray dispenser.
  • a preferred electrically operated pump spray dispensers herein is a container wherein the means for delivering the composition comprises an electrically driven pump and a spray arm.
  • Said spray arm is either extended or extendible and has at least one aperture so that in operation, the composition is pumped by said electrically driven pump from the container, through the spray arm to the aperture from which it is dispensed.
  • the spray arm communicates with the container by means of a flexible connector.
  • the spray arm may have at least one aperture located along its length. The spray arm makes it easier to control where the composition is sprayed, thereby increasing the accuracy with which the composition is applied.
  • the electrically driven pump may be, for example, a gear pump, an impeller pump, a piston pump, a screw pump, a peristaltic pump, a diaphragm pump, or any other miniature pump.
  • the electrically driven pump for use herein is a gear pump with a typical speed between 6000 rpm and 12000 rpm.
  • the electrically driven pump is driven by a means which typically produces a torque of between 1 and 20 mN.m such as an electric motor.
  • the electric motor must in turn be provided with a power source.
  • the power source may be either mains electricity (optionally via transformer), or it may be a throw-away battery or rechargeable battery.
  • the spray arm may be rigidly extended. However such a spray arm can be difficult to store, and the spray arm is preferably extensible either by means of telescopic or foldable configuration.
  • the composition is applied onto the carpet in the form of a spray of droplets having a particle size distribution with a mean diameter D(v,0.9) of less than 1500 microns, preferably less than 1000 microns, more preferably of less than 750 microns, even more preferably less than 500 microns, and most preferably from 350 microns to 10 microns.
  • mean diameter D(v,0.9) of less than 1500 microns for a droplet size distribution it is meant that 90% of the spray of droplets dispensed (expressed in volume unit) has a droplet diameter of less than 1500 microns.
  • a D(v,0.9) of less than 1500 microns indicates that 90% of the total sprayed volume is dispensed with droplets whose diameter is less than 1500 microns.
  • a suitable test equipment is the Malvem Mastersizer S LongBed® with 1000 mm lens and a maximum particle size range of 3475 microns.
  • the Malvern Mastersizer S LongBed® provides a 21 cm opening (between its lenses) to accommodate spray flow. In all readings at the Malvern®, the lens surface must remain free of spray contamination. In the present setup procedure, the distance from the aperture of the spray dispenser to the laser was fixed at 8 cm, this to minimize lens contamination. At 8 cm distance, the spray was directed to the laser beam to place the laser center to the spray cone. At least three readings have to be made for each composition sprayed to determine the particle size distribution of the spray of droplets.
  • the electrically operated spraying devices to be used in the test according to the present invention is preferably a battery-operated system. If such a battery-operated system is used, a “Full charge test” is being performed. By “Full charge test” it is meant herein, that the current was held consistent by connecting the battery-operated spray dispenser to a 3.9 voltage direct current (vdc) from an external power supply, this ensures a constant spray force.
  • vdc voltage direct current
  • Any container adapted to deliver a spray of droplets as defined herein is suitable for use herein.
  • Several modifications can be made to the conventional, single aperture, spray head to ensure that a spray of such droplets as required herein is formed.
  • compositions for the treating of carpets according to the present invention applied will depend on the severity of the stain or soil. In the case of stubborn stains more than one application may be required to ensure complete removal of the stain.
  • the area to be treated by applying the compositions according to the present invention may be of any size. Indeed, parts of the carpets, a complete section and/or the whole carpet may be treated with the composition for treating of a carpet according to the present invention.
  • the liquid bleaching composition according to the present invention applied to the carpet is left to substantially dry.
  • the composition is left to dry on the carpet for less than 2 hours, preferably less than 1 hour, more preferably less than 40 minutes, even more preferably from 1 to 30 minutes and most preferably from 1 to 20 minutes.
  • the step of leaving said composition to dry onto the carpet can either be an “active drying step” or a “passive drying step”.
  • active drying step it is meant herein, performing an additional action to facilitate the evaporation of the volatile ingredients of the liquid composition as disclosed herein, preferably by heating the carpet and/or the liquid composition applied thereon, preferably heating by means of application of hot air, infrared radiation and the like.
  • passive drying step it is meant herein, evaporation of the volatile ingredients of the liquid composition as disclosed herein without performing further action.
  • substantially dry it is meant herein the stage where at least 40%, preferably at least 60% of the initial amount of composition dispensed onto the carpet is lost due to evaporation.
  • normal temperature conditions it is meant herein, from 15° C to 25° C, preferably from 20° C to 25° C.
  • normal humidity conditions it is meant herein, from 40 %RH (%-relative humidity) to 80 %RH, preferably from 50 %RH to 65 %RH.
  • said composition may be left to substantially dry until said composition combined with dirt forms substantially dry residues.
  • said composition more preferably said substantially dry residues, are then removed from the carpet.
  • said substantially dry residues are removed mechanically, as e.g., by brushing, sweeping beating, and/or by vacuum cleaning. This may be carried out with the help of any commercially available vacuum cleaner like for instance a standard Hoover® 1300W vacuuming machine.
  • the bleaching compositions herein may be used for the removal of stains and soils as well as of odors from carpets or hard wearing textiles and fabrics, e.g., upholstery.
  • the compositions according to the present invention may be used to hygienise, disinfect and/or exterminate microinsects from carpets or hard wearing textiles and fabrics, e.g., upholstery, rugs, curtains.
  • compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • the following Examples are meant to exemplify compositions used in a process according to the present invention but are not necessarily used to limit or otherwise define the scope of the present invention.
  • the compositions VI, VII and X to XVI are comparative example compositions.
  • Dobanol® 23-3 is a C 12 -C 13 EO3 nonionic surfactant commercially available from SHELL.
  • Dobanol® 45-7 is a C 14 -C 15 EO7 nonionic surfactant commercially available from SHELL.
  • Dobanol® 91-8 is a C 9 -C 11 EO8 nonionic surfactant commercially available from SHELL.
  • Dobanol® 91-10 is a C 9 -C 11 EO10 nonionic surfactant commercially available from SHELL.
  • Marlipal® 24-4 is a linear C 12 -C 14 EO4 nonionic surfactant commercially available from Condea
  • Marlipal® 24-7 is a linear C 12 -C 14 EO7 nonionic surfactant commercially available from Condea Alkyl betaine is Lauryl di-methyl betaine commercially available by Hoechst under the trade name GENAGEN.LAB® Hydrogen Peroxide is commercially available from Ausimont.
  • Norasol SP02N® is a polycarboxylate builder commercially available from Rohm & Haas.
  • Acusol 425® is a modified polycarboxylate co-builder commercially available from Rohm & Haas.
  • Capped Alcohol is PLURAFAC LF231® commercially available from BASF 3,4,5-TMBA is 3,4,5-trimethoxy benzoic acid commercially available from Aldrich.
  • m-MBA is m-methoxy benzoic acid commercially available from Aldrich.

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Claims (20)

  1. Composition de blanchiment comprenant un agent de blanchiment peroxygène et un acide benzoïque alcoxylé ou un sel de celui-ci, dans laquelle ledit acide benzoïque alcoxylé ou sel de celui-ci est de formule générale :
    Figure imgb0017
     dans laquelle ledit acide benzoïque alcoxylé est un acide dialcoxybenzoïque ou un sel de celui-ci, dans laquelle : le substituant du cycle benzène X est -H, le substituant du cycle benzène Y est -OR' ; R' est indépendamment choisi parmi des chaînes alkyle linéaires ou ramifiées en C1 à C20 ; et M est un hydrogène, un fragment cationique ou un cation ou, dans laquelle ledit acide benzoïque alcoxylé est un acide trialcoxybenzoïque ou un sel de celui-ci ;dans laquelle : les substituants du cycle benzène Y et X sont -OR' ; R' est indépendamment choisi parmi des chaînes alkyle linéaires ou ramifiées en C1 à C20 ; et M est un hydrogène, un fragment cationique ou un cation.
  2. Composition de blanchiment selon la revendication 1, dans laquelle ledit agent de blanchiment peroxygène est choisi dans le groupe constitué de : peroxyde d'hydrogène ; sources hydrosolubles de peroxyde d'hydrogène ; peracides organiques ou inorganiques ; hydroperoxydes ; et peroxydes de diacyle ; et leurs mélanges.
  3. Composition de blanchiment selon la revendication 1, dans laquelle dans la formule générale : les substituants du cycle benzène X et Y sont -OR' ; R' est - CH3 ; et M est un hydrogène, un fragment cationique ou un cation.
  4. Composition de blanchiment selon l'une quelconque des revendications précédentes, dans laquelle ledit acide benzoïque alcoxylé ou un sel de celui-ci est de l'acide 3,4,5,- triméthoxy benzoïque ou un sel de celui-ci.
  5. Composition de blanchiment selon l'une quelconque des revendications précédentes, sous sa forme liquide, où ladite composition de blanchiment liquide ainsi a un pH, mesuré à 25 °C, de pas plus de 9.
  6. Composition de blanchiment selon l'une quelconque des revendications précédentes, sous sa forme liquide ou solide, où ladite composition de blanchiment liquide et/ou solide, lorsqu'elle est diluée dans 1 à 500 fois son poids d'eau, a un pH, mesuré à 25 °C, de pas plus de 12.
  7. Composition de blanchiment selon l'une quelconque des revendications précédentes, où ladite composition de blanchiment comprend, en outre, un épaississant.
  8. Composition de blanchiment selon la revendication 7, dans laquelle ledit épaississant est choisi dans le groupe constitué de : polymères polysaccharidiques ; polymères vinyl-, carboxyvinyl-, carboxylique- réticulés et non-réticulés, et acryloamido- ; esters d'acide gras ; silicates ; résines idantoiniques ; oxydes pyrogéniques ; et leurs mélanges.
  9. Composition de blanchiment selon l'une quelconque des revendications 7 ou 8, dans laquelle ledit épaississant est de la gomme de xanthane.
  10. Composition de blanchiment selon l'une quelconque des revendications précédentes, sous sa forme liquide, où ladite composition de blanchiment a une viscosité de 1 cP ou plus, plus préférablement allant de 5 à 5000 cP, et encore plus préférablement allant de 10 à 2500cP lorsqu'on mesure avec un rhéomètre CSL2 100® à 20 °C avec un mobile cylindrique de 4 cm (incrément linéaire de 1 à 10 Pa (10 à 100 dyne/cm2) en 2 minutes).
  11. Composition de blanchiment selon l'une quelconque des revendications précédentes, où ladite composition de blanchiment comprend, en outre, un agent tensioactif, de préférence un agent tensioactif choisi parmi le groupe constitué d'agents tensioactifs non ioniques, d'agents tensioactifs zwittérioniques de bétaïne, d'agents tensioactifs anioniques sulfonés, d'agents tensioactifs sarcosinate, d'agents tensioactifs alkyl sulfate, d'agents tensioactifs sulfosuccinate et leurs mélanges.
  12. Procédé de traitement des tissus qui comprend l'étape de mise en contact desdits tissus avec une composition de blanchiment selon l'une quelconque des revendications précédentes, sous sa forme diluée à un taux de dilution avec de l'eau jusqu'à 1500 fois.
  13. Procédé de traitement des tissus selon la revendication 12, qui comprend, en outre, les étapes supplémentaires consistant à :
    - laisser lesdits tissus en contact avec ladite composition de blanchiment pendant un laps de temps suffisant pour blanchir lesdits tissus,
    - puis rincer lesdits tissus dans l'eau pour éliminer ladite composition de blanchiment.
  14. Procédé selon l'une quelconque des revendications 12 ou 13, dans lequel lesdits tissus sont lavés avec une composition détergente comprenant au moins un agent tensioactif avant et/ou pendant la mise en contact avec la composition de blanchiment et/ou après le rinçage lorsque ladite composition de blanchiment a été éliminée.
  15. Procédé de traitement d'un tissu, qui comprend l'étape consistant à mettre en contact ledit tissu avec une composition de blanchiment sous sa forme liquide selon l'une quelconque des revendications 1 à 11, sous sa forme pure, à laisser ledit tissu en contact avec ladite composition de blanchiment pendant un laps de temps suffisant pour blanchir ledit tissu, puis à rincer ledit tissu dans l'eau pour éliminer ladite composition de blanchiment.
  16. Procédé selon la revendication 15, dans lequel ledit tissu est lavé avec une composition détergente comprenant au moins un agent tensioactif avant l'étape de mise en contact dudit tissu avec ladite composition de blanchiment et/ou pendant l'étape de mise en contact dudit tissu avec ladite composition de blanchiment et/ou après l'étape de rinçage dans laquelle ladite composition de blanchiment a été éliminée.
  17. Procédé de traitement d'un tapis, comprenant l'application d'une composition de blanchiment selon l'une quelconque des revendications 1 à 11 sur ledit tapis.
  18. Procédé de traitement d'un tapis selon la revendication 17, dans lequel ladite composition de blanchiment est appliquée sous sa forme liquide sur ledit tapis en utilisant un dispositif de pulvérisation.
  19. Utilisation d'un acide benzoïque alcoxylé selon la revendication 1 ou un sel de celui-ci dans une composition de blanchiment comprenant un agent de blanchiment peroxygène, selon laquelle un effet bénéfique de stabilité chimique immédiate et/ou un effet bénéfique de stabilité chimique lors du stockage sont fournis.
  20. Utilisation d'un acide benzoïque alcoxylé selon la revendication 1 ou un sel de celui-ci dans une composition de blanchiment comprenant un agent de blanchiment peroxygène et un épaississant, selon laquelle un effet bénéfique de stabilité rhéologique lors du stockage est fourni.
EP99870211A 1998-11-10 1999-10-14 Composition de blanchiment comprenant acide benzoique alkoxylé Expired - Lifetime EP1001011B2 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
ES99870211T ES2270572T5 (es) 1998-11-10 1999-10-14 Composicion blanqueadora que comprende un acido benzoico alcoxilado.
EP99870211A EP1001011B2 (fr) 1998-11-11 1999-10-14 Composition de blanchiment comprenant acide benzoique alkoxylé
PCT/US1999/026605 WO2000027972A1 (fr) 1998-11-10 1999-11-10 Composition de blanchiment comprenant un acide benzoique alcoxyle
AU18168/00A AU1816800A (en) 1998-11-10 1999-11-10 Bleaching composition comprising an alkoxylated benzoic acid
CO99070900A CO5210994A1 (es) 1998-11-11 1999-11-10 Composiciones blanqueadoras que comprenden un acido benzoico alcoxilado
TR2001/01308T TR200101308T2 (tr) 1998-11-11 1999-11-10 Bir alkoksile benzoik asiti içeren ağartma bileşimi
MA26186A MA25309A1 (fr) 1998-11-11 2001-05-09 Composition de blanchiment comprenant un acide benzo¤que alcoxyle

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP98870247 1998-11-10
EP98870247 1998-11-11
EP98870263A EP1001010B1 (fr) 1998-11-10 1998-12-02 Compositions de blanchiment
EP98870263 1998-12-02
EP99870211A EP1001011B2 (fr) 1998-11-11 1999-10-14 Composition de blanchiment comprenant acide benzoique alkoxylé

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EP1001011A2 EP1001011A2 (fr) 2000-05-17
EP1001011A3 EP1001011A3 (fr) 2000-08-09
EP1001011B1 EP1001011B1 (fr) 2006-08-02
EP1001011B2 true EP1001011B2 (fr) 2010-06-23

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AU (1) AU1816800A (fr)
CO (1) CO5210994A1 (fr)
MA (1) MA25309A1 (fr)
TR (1) TR200101308T2 (fr)
WO (1) WO2000027972A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11330819B2 (en) 2018-12-28 2022-05-17 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19904230A1 (de) * 1999-02-04 2000-08-10 Henkel Kgaa Verwendung von phosphonsäure-modifizierten Polyacrylaten als Sequestriermittel
GB0001233D0 (en) * 2000-01-19 2000-03-08 Procter & Gamble Hair colouring compositions
WO2002074273A1 (fr) * 2001-03-20 2002-09-26 The Procter & Gamble Company Compositions oxydantes comprenant un agent chelatant et un agent revitalisant et procedes de traitement des cheveux
US7179302B2 (en) 2001-03-20 2007-02-20 The Procter & Gamble Company Oxidative treatment of hair with reduced hair damage
WO2002074271A1 (fr) * 2001-03-20 2002-09-26 The Procter & Gamble Company Traitement capillaire oxydant a sensibilisation reduite
US7186275B2 (en) 2001-03-20 2007-03-06 The Procter & Gamble Company Compositions suitable for the treatment of hair comprising chelants and methods for reducing oxidative hair damage
GB2386068A (en) * 2001-03-20 2003-09-10 Procter & Gamble Oxidative treatment of hair with reduced hair damage
JP3851273B2 (ja) * 2001-03-20 2006-11-29 ザ プロクター アンド ギャンブル カンパニー キレート剤を含む毛髪処理に適当な組成物及び毛髪の酸化損傷を低減する方法
GB2379214A (en) * 2001-09-04 2003-03-05 Reckitt Benckiser Nv Thickened aqueous compositions
US7906473B2 (en) * 2002-09-13 2011-03-15 Bissell Homecare, Inc. Manual spray cleaner
ES2321497T3 (es) * 2003-03-28 2009-06-08 THE PROCTER & GAMBLE COMPANY Composicion de blanqueo que comprende acido trimetoxibenzoico o una sal del mismo.
US7390775B2 (en) * 2005-03-07 2008-06-24 S.C. Johnson & Son, Inc. Thickened bleach compositions comprising an amine oxide and anionic polymer
EP1860176A1 (fr) * 2006-05-22 2007-11-28 Akzo Nobel N.V. Composition aqueuse contenant du péroxyde d'hydrogène et son utilisation pour le nettoyage des surfaces
ES2371690T3 (es) * 2008-04-25 2012-01-09 The Procter & Gamble Company Composición de blanqueo coloreada.
EA022063B1 (ru) * 2009-09-02 2015-10-30 Юнилевер Нв Жидкая композиция для обработки ткани, способ ее получения и способ стирки ткани с ее использованием
GB201019988D0 (en) * 2010-11-25 2011-01-05 Reckitt Benckiser Nv Composition

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62195100A (ja) † 1986-02-20 1987-08-27 ライオン株式会社 漂白性組成物
EP0668345A1 (fr) † 1994-02-22 1995-08-23 The Procter & Gamble Company Compositions de blanchiment d'hypochlorite
EP0751214A1 (fr) † 1995-06-30 1997-01-02 The Procter & Gamble Company Compositions de blanchiment stables contenant des agents de blanchiment péroxydés
EP0776966A1 (fr) † 1995-12-02 1997-06-04 The Procter & Gamble Company Compositions de blanchiment liquides, emballées dans un atomiseur, et procédé pour la prétraitement des tissus avec celles-ci
EP0794245A1 (fr) † 1996-03-04 1997-09-10 The Procter & Gamble Company Procédé de prétraitement pour le lavage du ligne et compositions de blanchiment
US5759439A (en) † 1996-06-14 1998-06-02 The Procter & Gamble Company Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics
EP0903403A1 (fr) † 1997-09-19 1999-03-24 The Procter & Gamble Company Compositions de blanchiment stables
EP0905224A1 (fr) † 1997-09-19 1999-03-31 The Procter & Gamble Company Compositions de blanchiment
WO1999028427A1 (fr) † 1997-12-04 1999-06-10 The B.F. Goodrich Company Compositions de blanchiment epaissies
EP0931829A1 (fr) † 1998-01-16 1999-07-28 The Procter & Gamble Company Compositions de blanchiment stables colorées et épaisses

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69027423T2 (de) * 1989-09-11 1997-02-06 Kao Corp Bleichzusammensetzung
BR9306242A (pt) * 1992-04-13 1998-06-23 Procter & Gamble Processo para preparaçao de composiçoes detergentes líquidas tixotrópicas

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62195100A (ja) † 1986-02-20 1987-08-27 ライオン株式会社 漂白性組成物
EP0668345A1 (fr) † 1994-02-22 1995-08-23 The Procter & Gamble Company Compositions de blanchiment d'hypochlorite
EP0751214A1 (fr) † 1995-06-30 1997-01-02 The Procter & Gamble Company Compositions de blanchiment stables contenant des agents de blanchiment péroxydés
EP0776966A1 (fr) † 1995-12-02 1997-06-04 The Procter & Gamble Company Compositions de blanchiment liquides, emballées dans un atomiseur, et procédé pour la prétraitement des tissus avec celles-ci
EP0794245A1 (fr) † 1996-03-04 1997-09-10 The Procter & Gamble Company Procédé de prétraitement pour le lavage du ligne et compositions de blanchiment
US5759439A (en) † 1996-06-14 1998-06-02 The Procter & Gamble Company Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics
EP0903403A1 (fr) † 1997-09-19 1999-03-24 The Procter & Gamble Company Compositions de blanchiment stables
EP0905224A1 (fr) † 1997-09-19 1999-03-31 The Procter & Gamble Company Compositions de blanchiment
WO1999028427A1 (fr) † 1997-12-04 1999-06-10 The B.F. Goodrich Company Compositions de blanchiment epaissies
EP0931829A1 (fr) † 1998-01-16 1999-07-28 The Procter & Gamble Company Compositions de blanchiment stables colorées et épaisses

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11330819B2 (en) 2018-12-28 2022-05-17 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
US11758906B2 (en) 2018-12-28 2023-09-19 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
US11871744B2 (en) 2018-12-28 2024-01-16 Diversey, Inc. Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same

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AU1816800A (en) 2000-05-29
CO5210994A1 (es) 2002-10-30
WO2000027972A1 (fr) 2000-05-18
TR200101308T2 (tr) 2001-10-22
EP1001011A2 (fr) 2000-05-17
EP1001011A3 (fr) 2000-08-09
EP1001011B1 (fr) 2006-08-02
MA25309A1 (fr) 2001-12-31

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