WO1999015618A1 - Compositions de blanchiment epaissies et stables - Google Patents

Compositions de blanchiment epaissies et stables Download PDF

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Publication number
WO1999015618A1
WO1999015618A1 PCT/IB1998/001348 IB9801348W WO9915618A1 WO 1999015618 A1 WO1999015618 A1 WO 1999015618A1 IB 9801348 W IB9801348 W IB 9801348W WO 9915618 A1 WO9915618 A1 WO 9915618A1
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composition
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acid
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PCT/IB1998/001348
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English (en)
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Oreste Todini
Andrea Agostini
Giovanni Grande
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU87449/98A priority Critical patent/AU8744998A/en
Priority to PL98339380A priority patent/PL339380A1/xx
Priority to EP98938860A priority patent/EP1017780A1/fr
Publication of WO1999015618A1 publication Critical patent/WO1999015618A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to liquid thickened bleaching compositions, in particular to liquid thickened hypochlorite bleaching compositions, which can be used to bleach various surfaces including but not limited to, hard- surfaces likes walls, tiles, floors, glass, bathrooms surfaces, kitchen surfaces, toilet bowls, dishes as well as fabrics, clothes, carpets and the like.
  • Thickened bleaching compositions are well-known in the art. Amongst the different thickened bleaching compositions available, those relying on bleaching by hypohalite bleaches such as hypochlorite are often preferred, mainly for performance reasons.
  • viscosity will be build up by a so called 'self thickening surfactant or surfactant system' as opposed to using a thickener for that specific purpose.
  • thickeners such as gums have at least one drawback that they affect the formula cost, while providing only one benefit, which is thickening. They do not participate to the actual cleaning of the surface and therefore represent "inert" materials. Also, some thickeners are detrimental to the physical stability of the liquid compositions they are formulated in.
  • liquid thickened bleaching compositions based on hypohalite bleach with the help of a viscosifying surfactant which on top of its viscosifying properties also delivers good cleaning performance, i.e. good stain removal performance on a variety of stains including greasy stains and/or enzymatic stains and the like. More particularly, there is a need to liquid thickened bleaching compositions based on hypohalite bleach and a viscosifying surfactant that are Theologically stable upon ageing of the compositions, i.e. for prolonged periods of storage after their manufacturing.
  • the resulting composition when it is desired to incorporate a viscosifying surfactant in a liquid hypohalite bleach-based composition, the resulting composition generally shows a poor rheological stability, upon ageing of the composition, resulting in lowering of the viscosity of the composition upon prolonged periods of storage.
  • the viscosifying surfactants may be decomposed by the hypohalite bleach present in such a liquid hypohalite bleach-based composition, and thus may lose their viscosifying potential.
  • This surfactant decomposition can be accelerated by product exposure at high temperature or by raw material impurities like presence of metal ions.
  • It is therefore an object of the invention to provide a stable liquid thickened hypohalite bleach-containing composition comprising a viscosifying surfactant, said composition being Theologically stable upon ageing of the composition.
  • a liquid bleaching composition comprising a hypohalite bleach, a pH buffering means, an alkyl (alkoxy) 2-4 sulphate, optionally a co-surfactant and a stabilising agent (0.01 %-10%) being either a radical scavenger, a chelating agent or a mixture thereof.
  • a stabilising agent preferably a radical scavenger alone or together with a chelating agent
  • a liquid bleaching composition comprising a hypohalite bleach, an alkyl (alkoxy) 2-4 sulphate, and optionally a co-surfactant
  • compositions of the invention are also chemically stable upon ageing of the compositions.
  • Another advantage of the compositions of the present invention is that they deliver effective bleaching performance, more particularly effective whiteness performance when used in any laundry application, as well as effective stain removal performance on various stains including greasy stains like lipstick, make up, sebum, oil (mineral and vegetable), mayonnaise, eggs and the like and/or enzymatic stains like grass, cocoa, blood and the like, even upon ageing of the composition.
  • a stabilising agent in the liquid hypohalite bleach- containing compositions of the present invention that delivers these benefits upon ageing of these compositions.
  • compositions of the invention are suitable for the bleaching of different types of surfaces including hard-surfaces like floors, walls, tills, glass, kitchen surfaces, bathrooms surfaces, toilet bowls and/or dishes and the like as well as fabrics. More particularly, the compositions of the present invention are suitable for bleaching any type of fabrics including natural fabrics (e.g., fabrics made of cotton, viscose, linen, silk and wool), synthetic fabrics such as those made of polymeric fibers of synthetic origin as well as those made of both natural and synthetic fibers.
  • natural fabrics e.g., fabrics made of cotton, viscose, linen, silk and wool
  • synthetic fabrics such as those made of polymeric fibers of synthetic origin as well as those made of both natural and synthetic fibers.
  • compositions of the present invention may be used on synthetic fibers despite a standing prejudice against the use of hypohalite bleaches, especially hypochlorite bleaches, on synthetic fibers, as evidenced by warning on labels of commercially available hypochlorite bleaches and clothes.
  • the compositions of the present invention are not only safe to the fabrics perse bleached therewith but also to the fabrics colours.
  • a further advantage of the liquid bleaching compositions of the present invention is that said bleaching compositions are suitable for various laundry bleaching applications both when used in diluted conditions, e.g. as a detergent additive or a fully formulated laundry detergent composition, and when used in neat condition, e.g. as a liquid pretreater (spotter).
  • European co-pending applications number 96870088.0 and 96870128.4 disclose hypochlorite-based compositions with surfactants like alkyl ethoxy sulphates and optionally radical scavengers. Chelants are mentioned as optional ingredients without specifying any, nor levels thereof. No pH buffering means are disclosed.
  • compositions based on hypochlorite and alkyl alkoxy sulphate see for instance EP-447 261 , EP-340 371 or WO 93/08247.
  • a stabilising agent like a radical scavenger and/or a chelating agent in said compositions, let alone that it improves the rheological stability of the compositions upon ageing.
  • the present invention is a liquid thickened bleaching composition
  • a liquid thickened bleaching composition comprising
  • hypohalite bleach - an alkyl (alkoxy) n sulphate, wherein n is from 2 to 4
  • a stabilising agent selected from the group consisting of a radical scavenger, a chelating agent and a mixture thereof.
  • the present invention further encompasses the use, in a liquid bleaching composition comprising a hypohalite bleach, an alkyl (alkoxy) 2-4 sulphate, and optionally a co-surfactant, of a stabilising agent selected from the group consisting of a radical scavenger, a chelating agent and a mixture thereof, for improving the rheological stability of the composition upon ageing.
  • the present invention also encompasses a process of bleaching a surface (including fabrics, hard-surfaces and/or dishes) where said surface is contacted with a bleaching composition according to the present invention, in its neat or diluted form.
  • Liquid bleaching compositions are:
  • compositions according to the present invention are in liquid form.
  • the compositions of the invention are in liquid aqueous form. More preferably, they comprise water in an amount of from 60% to 98% by weight, more preferably of from 80% to 97% and most preferably of from 85% to 97% by weight of the total aqueous liquid bleaching composition.
  • compositions according to the present invention are thickened compositions, thus they typically have a viscosity of from 10 cps to 2000 cps, when measured with a rheometer, for example a Carri-med CSL2- 100®, at the following viscosity parameters : angle : 1°58, gap : 60, diameter : 4.0 cm, iner : 63.60, temperature of 25°C and a shear rate of 30 1/sec, preferably from 25 cps to 1500 cps, and more preferably from 50 cps to 1200 cps.
  • a rheometer for example a Carri-med CSL2- 100®
  • Hypohalite bleaches may be provided by a variety of sources, including bleaches that are oxidative bleaches and subsequently lead to the formation of positive halide ions as well as bleaches that are organic based sources of halides such as chloroisocyanurates.
  • Suitable hypohalite bleaches for use herein include the alkali metal and alkaline earth metal hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N- chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
  • the preferred hypohalite bleaches among the above described are the alkali metal and/or alkaline earth metal hypochlorites selected from the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites, and mixtures thereof, more preferably the alkali metal sodium hypochlorite.
  • the liquid compositions according to the present invention comprise said hypohalite bleach or mixture thereof such that the content of active halide in the composition is of from 0.1% to 20% by weight, more preferably from 0.25% to 8% by weight, most preferably from 0.5% to 6% by weight of the composition.
  • alkyl alkoxyka sulphates
  • An essential component of the invention is an alkyl (alkoxy) n sulphate, wherein n is from 2 to 4, or a mixture thereof.
  • Suitable alkyl (alkoxy) 2- sulphate surfactants for use herein are water- soluble salts or acids of the formula :
  • - R is a substituted or unsubstituted C4-C24 linear or branched alkyl group having a C4-C24 alkyl component, preferably a C8-C20 linear or branched alkyl, more preferably C-8-C-
  • - A is an ethoxy or propoxy unit
  • - n is from 2 to 4, preferably 2 or 3 and more preferably 3, - and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
  • ammonium or substituted-ammonium cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
  • Alkyl (ethoxy)2 sulfates and alkyl (ethoxy)3 sulfates are preferred herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Sodium C12/C14 E3 sulphate may be for example commercially available from Albright & Wilson under the name EMPICOL ESC3®.
  • Sodium C12/C14 E2 sulphate may be for example commercially available from Rhone Poulenc under the name Rhodapex ES-2®.
  • the liquid compositions according to the present invention comprise said alkyl (alkoxy) 2-4 sulphate in amount of from 0.1 % to 20% by weight, more preferably from 0.5% to 15%, even more preferably from 2% to 10% by weight, most preferably from 3% to 8% by weight of the composition.
  • alkyl (alkoxy) 2-4 sulphate preferably an alkyl (ethoxy)2-4 sulphate
  • the liquid compositions of the present invention may further comprise a co- surfactant or a mixture thereof as a desirable optional ingredient to regulate the viscosity of the compositions herein.
  • the co- surfactants for use herein have the properties to modify the initial viscosity provided by the presence of the alkyl (alkoxy) 2-4 sulphate in the compositions of the present invention, i.e. to lower or higher the viscosity provided by the sole presence of such alkyl (alkoxy) 2-4 sulphate as a viscosifying surfactant, in the compositions herein.
  • such a co-surfactant will be chosen depending on the initial viscosity desired for the compositions of the present invention.
  • the presence of the co- surfactants in the bleaching compositions according to the present invention further contributes to deliver effective stain removal performance and/or whiteness performance to fabrics treated therewith.
  • compositions according to the present invention comprise said co-surfactant in amounts of from 0.01 % to 10% by weight of the total composition, preferably of from 0.1 % to 5% and more preferably of from 1% to 2.5%.
  • Suitable co-surfactants for use herein are typically selected from the group consisting of alkyl sulphates, alkyl aryl sulphonates, alkyl alkoxy sulphates with 1 or more than 4 alkoxylated units, zwitterionic surfactants like betaine surfactants, cationic surfactants like alkyl trimethylammonium halogenides and mixture thereof.
  • Suitable alkyl sulphates for use in the compositions herein include water- soluble salts or acids of the formula ROSO3M wherein R preferably is a C4- C24 hydrocarbyl, preferably linear or branched alkyl having a C6-C20 a'kyl component, more preferably a CQ- C ⁇ 8 linear or branched alkyl, most preferably a CQ- C ⁇
  • alkyl alkoxy sulphates for use herein are water-soluble salts or acids of the formula RO(A) m SO3M wherein R is a substituted or unsubstituted C4- C24 linear or branched alkyl group having a C4-C24 alkyl component, preferably a C8-C20 linear or branched alkyl, more preferably C-10-C18 linear or branched alkyl, most preferably C10-C16 linear or branched alkyl, A is an ethoxy or propoxy unit, m is 1 or above 4, typically between about 5 and about 30, more preferably between about 5 and about 15, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is a substituted or unsubstituted C4- C24 linear or branched alkyl group having a C4-
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12- 18 alkyl polyethoxylate( ⁇ ) sulfate, C-
  • Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO3M wherein R is an aryl, preferably a benzyl, substituted by a C4-C20 linear or branched saturated or unsaturated alkyl group, preferably a C12-C-18 al group and more preferably a C14-C16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) 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 mixture
  • 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 sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • R2 is hydrogen, C ⁇ -CQ alkyl, hydroxy alkyl or other substituted C ⁇ -CQ alkyl group;
  • R3 is C ⁇
  • R4 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;
  • X is the hydrophilic group which is a carboxylate or sulfonate group.
  • 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-l 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. However, the hydrophobic group R ⁇
  • 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 D 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 D )2) moiety.
  • Preferred R2 is hydrogen, or a C1-C3 alkyl and more preferably methyl.
  • Preferred R3 is a C1-C4 carboxylic acid group or C1-C4 sulfonate group, or a C-1-C3 alkyl and more preferably methyl.
  • Preferred R4 is (CH2) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
  • 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 C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
  • C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
  • betaine is Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
  • Suitable cationic surfactants are alkyl trimethylammonium halogenides and those surfactants having the formula:
  • R2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain
  • each R3 is selected from the group consisting of - CH 2 CH 2 -, -CH 2 CH(CH3)-, -CH2CH 2 CH 2 -, and mixtures thereof
  • each R4 is selected from the group consisting of C1-C4 alkyl, benzyl ring structures formed by joining the two R4 groups, and hydrogen when y is not 0
  • R ⁇ is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R 5 is not more than about 18
  • each y is from 0 to about 10 and the sum of the y values is from 0 to about 15
  • X is any compatible anion.
  • Most preferred cationics are linear or branched C8-C20 trimethyl ammonium chlorides.
  • a pH buffering component is another essential component for the compositions of the invention.
  • the pH buffering component ensures that the pH of the composition is buffered to a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5 after the composition has been diluted into 1 to 500 times its weight of water.
  • Suitable pH buffering components for use herein are selected from the group consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, boron salts, phosphates, stannates, alluminates and mixtures thereof.
  • the preferred alkali metal salts for use herein are sodium and potassium.
  • Suitable boron salts or mixtures thereof for use herein include alkali metal salts of borates and alkyl borates and mixtures thereof.
  • Examples of boron salts include boric acid, alkali metal salts of metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and alkyl borate containing from 1 to 12 carbon atoms, preferably from 1 to 4.
  • Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate.
  • Particularly preferred boron salts herein are the alkali metal salts of metaborate, such as sodium metaborate, potassium metaborate, and the alkali metal salts of borate, such as sodium borate, or mixtures thereof.
  • Boron salts like sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica Larderello under the name sodium metaborate and Borax®.
  • pH buffering components are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures thereof.
  • the raw materials involved in the preparation of hypohalite bleaches usually contain by-products, e.g calcium carbonate resulting in an amount of up to 0.4% by weight of by-product within the hypohalite composition. However, at such amount, the by-product will not have the buffering action defined above.
  • Liquid bleaching compositions herein will contain an amount of pH buffering component of from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight, and more preferably in an amount of from 0.6% to 3% by weight of the composition.
  • An essential component of the invention is a stabilising agent being a radical scavenger, a chelating agent or a mixture thereof.
  • the stabilizing agents have to be stable to the hypohalite bleach.
  • the stabilising agent is a radical scavenger or a mixture thereof alone, or together with a chelating agent or a mixture thereof.
  • Suitable radical scavengers for use herein include aromatic radical scavengers comprising an unsaturated ring system of from 3 to 20 carbon atoms, preferably of from 3 to 18 and more preferably of from 5 to 14 and having a double bond set comprising a total of 4n+2 electrons, wherein n is an integer of from 0 to 4, preferably of from 1 to 3.
  • aromatic radical scavengers include benzene derivatives, naphthalene derivatives, annulene derivatives, cyclopentadiene derivatives, cyclopropene derivatives and the like, especially aryl carboxylates and/or aryl sulfonates.
  • radical scavengers aryl carboxylates, aryl sulphonate and derivatives thereof
  • aryl carboxylates, aryl sulphonate and derivatives thereof have one of the following formulas:
  • each X, Y, and Z are -H, -COO-M+, -Cl, -Br, -SO3-M + , -NO2, - OCH3, or a C-
  • these components include pyromellitic acid, i.e. where X, Y and Z are -COO-H + ; hemimellitic acid, trimellitic acid, i.e. where X and Y are -COO-H + and Z is H.
  • radical scavengers are phthalic acid; sulfophthalic acid; other mono-substituted phthalic acids; di-substituted benzoic acids; alkyl-, chloro-, bromo-, sulfo-, nitro- and alkoxy- benzoic acids, i.e. where Y and Z are -H and X is a C ⁇
  • radical scavengers useful in the present invention are benzoic acid, toluic acid, 4-toluene sulfonic acid, 3-nitro benzoic acid, 2 n-octyl benzoic acid, 2 n-octyl sulfonic acid, anisic acid or mixtures thereof Most preferred herein are benzoic acid, methoxy benzoic acid and/or 3-nitrobenzoic acid.
  • radical scavengers described above are the acidic form of the species, i.e. M is H. It is intended that the present invention also covers the salt derivatives of these species, i.e. M is an alkali metal, preferably sodium or potassium. In fact, since the pH of the compositions of the present invention is in the alkaline range, the radical scavengers of the present invention exist primarily as the ionized salt in the aqueous composition herein.
  • the anhydrous derivatives of certain species described herein above can also be used in the present invention, e.g. pyromellitic dianhydride, phthalic anhydride, sulphthalic anhydride and the like.
  • Suitable chelating agents for use herein may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, phosphate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
  • Suitable phosphonate chelating agents 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).
  • DTPMP diethylene triamine penta methylene phosphonate
  • HEDP ethane 1 -hydroxy diphosphonate
  • Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
  • Suitable phosphate chelating agents are as following: Phosphonic acid can be condensed in the reaction
  • the reaction can be repeated with any of the reactive OH groups, and phosphate ingredients are obtained which can be - linear or branched polyphosphates of structure
  • M is a counterion, preferably alkali metal
  • the phosphate compound contains both cycles and branched chain, and can be referred to as an ultraphosphate.
  • M is a counterion, preferably an alkali metal
  • phosphate ingredients are suitable for use herein, and preferred are linear phosphate ingredients (i.e. R is M) where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)), most preferably where n is 2.
  • R linear phosphate ingredients
  • n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)
  • STPP tripolyphosphate
  • M is Sodium
  • Phytic acid which is a chelating agent particularly suitable for use herein, is a hexa-phosphoric acid that occurs naturally in the seeds of many cereal grains, generally in the form of the insoluble calcium-magnesium salt. It may also be derived from corn steep liquor. Commercial grade phytic acid is commercially available from J.T.Baker Co., e.g. as a 40% aqueous solution. It is intended that the present invention covers the acidic form of phytic acid as well as alkali metal salt derivatives thereof, particularly sodium or potassium salts thereof. Sodium phytate is available from Jonas Chemical Co (Brooklyn, N.Y.).
  • the phytic acid component exists primarily as the ionized salt in the liquid compositions herein even if it is added in its acidic form. Mixtures of such salts of phytic acid are also covered.
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • N,N'- disuccinic acids especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
  • Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Particularly preferred chelating agents for use herein are phosphate chelating agents like sodium tripolyphosphate, sodium pyrophosphate, phytic acid, and mixtures thereof.
  • compositions according to the present invention comprise from 0.01 % to 10% by weight of the total composition of a stabilising agent, or mixtures thereof, preferably from 0.01 % to 8% by weight, more preferably from 0.1 % to 5%, and most preferably from 0.2% to 3%.
  • Alkyl (alkoxy) sulphates as used in the bleaching compositions of the present invention are vulnerable to bleach-initiated degradation and result in a loss of rheology that can be unacceptable for most applications.
  • a certain small percentage of chlorine bleach ingredient is present in solution in the form of free radicals, i.e. molecular fragments having one or more unpaired electrons.
  • These radicals although short lived, are highly reactive and may initiate the degradation of alkyl (alkoxy) sulphate surfactants present in a bleaching composition, via propagation mechanism. It is believed that alkyl (alkoxy) sulphates are subject to this degradation because of the presence of alkoxy groups that are oxidizable sites.
  • a stabilising agent especially a radical scavenger alone or together with a chelating agent, increases the rheological stability of the compositions of the present invention.
  • compositions of the present invention do not loose more than 30% initial viscosity after 10 days at 50°C, preferably not more than 20%.
  • the radical scavenger react with the free radicals present and prevent them from reacting/oxidising the alkyl (alkoxy) 2-4 sulphates.
  • the chelating agents present bind metal ion impurities (e.g., copper, iron, manganese and the like) present in the compositions (e.g. as by product of the raw material) and thus prevent them from attacking the hypochlorite bleach thereby limiting the generation of free radicals, that would otherwise be generated in presence of such metal ions impurities.
  • adding the chelating agents on top of the radical scavengers further contribute to deliver excellent rheological stability upon ageing of the compositions.
  • the liquid bleaching compositions of the present invention are also chemically stable.
  • chemically stable it is meant that the hypohalite bleaching compositions of the present invention do not undergo more than 25% loss of available chlorine after 5 days of storage at 50°C ⁇ 0.5°C, preferably not more than 20%.
  • the % loss of available chlorine may be measured using the method described, for instance, in “Analyses des Eaux et Extraits de Javel” by "La perhaps syndicalerati de L'eau de Javel et des building connexes", pages 9-10 (1984). Said method consists in measuring the available chlorine in the fresh compositions, i.e. just after they are made, and in the same compositions after 5 days at 50°C.
  • the whitening performance delivered on fabrics bleached with an aged composition according to the present invention is improved, as compared to the whitening performance delivered by the same composition but without any stabilising agent as mentioned herein before in the same aged condition.
  • the present invention allows to maintain excellent whitening performance after prolonged periods of storage time, as compared to the same composition but without said stabilising agent.
  • the whitening effect, i.e. the yellowing-prevention effect, of the present invention upon ageing of the composition can be evaluated by comparing the composition according to the present invention to the same composition without the stabilising agent upon ageing of the compositions.
  • the degree of yellowing can be determined by both visual and instrumental grading. Visually, the difference in yellowing between items treated with different compositions can be determined by a team of expert panellists. Instrumentally, the assessment can be determined with the help of Colorimeters such as Ganz Griesser® instruments (e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500) or a ZEISS ELREPHO® or others which are available for instance from Hunterlab® or Gardner®.
  • Ganz Griesser® instruments e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500
  • ZEISS ELREPHO® ZEISS ELREPHO® or others which are available for instance from Hunterlab® or Gardner®.
  • the stain removal performance of the present invention upon ageing of the composition can be evaluated by comparing the compositions according to the present invention to the same compositions without the stabilising agent upon ageing of the compositions.
  • the stain removal performance can be determined on different stains like greasy stains and/or enzymatic stains visually.
  • the presence of the stabilising agents may also contribute to reduce tensile strength loss of fabrics and/or colour damage, especially in a laundry pretreatment application.
  • Fabric safety may be evaluated by different test methods including the degree of polymerisation test method according to UNI (Ente Nazionale Italiano di Unificazione) official method UNI 8282-Determinazione della viscosita intrinseca in soluée di cuprietilendiammina (CED).
  • the pH of the liquid compositions according to the present invention is typically from 12 to 14 measured at 25°C.
  • the liquid compositions of the invention have a pH of from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5, when diluted into 1 to 500 times its weight of water. It is in this alkaline range that the optimum stability and performance of the hypohalite as well as fabric whiteness and/or safety are obtained.
  • the pH range is suitably provided by the pH buffering component and the hypohalite bleach mentioned hereinbefore, which are alkalis. However, in addition to these components, a strong source of alkalinity may also optionally be used.
  • Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such as sodium and/or potassium oxide.
  • a preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide. Typical levels of such caustic alkalis, when present, are of from 0.1 % to 1.5% by weight, preferably from 0.5% to 1.5% by weight of the composition.
  • composition according to the invention may comprise other optional components such as other bleach-stable surfactants, organic or inorganic alkalis, builders, thickening agents, polymers, pigments, dyes, solvents, perfumes, brighteners, and mixtures thereof.
  • other optional components such as other bleach-stable surfactants, organic or inorganic alkalis, builders, thickening agents, polymers, pigments, dyes, solvents, perfumes, brighteners, and mixtures thereof.
  • the liquid compositions of the present invention may further comprise another surfactant or a mixture thereof on top of the alkyl (alkoxy) 2-4 sulphate and optional co-surfactant mentioned herein before.
  • Said other surfactants may be present in the compositions according to the present invention in amounts up to 30% by weight of the total composition, preferably of from 0.1 % to 20% and more preferably of from 1 % to 10%.
  • Surfactants for use herein include other anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof as long as they do not affect the viscosity and rheological properties of the compositions according to the present invention.
  • the additional surfactants have to be stable to the hypohalite bleach.
  • compositions herein is a polymer. That polymer, has surprisingly been found to also reduce the yellowing of the fabrics treated therewith, i.e. improve whiteness, as well as improve fabric safety. Naturally, for the purpose of the invention, the polymer has to be stable to the hypohalite bleach.
  • Suitable polymers for use are polymers comprising monomeric units selected from the group consisting of unsaturated carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids and mixtures thereof. Co-polymerisation of the above monomeric units among them or with other co-monomers such as styrenesulfonic acid is also suitable.
  • Preferred examples of such polymers are the polymers and co-polymers of monomeric units selected from the group consisting of acrylic acid, maleic acid, vinylsulphonic acid and mixtures thereof. Also suitable for use herein are the above mentioned polymers and co-polymers which are modified in order to contain other functional groups such as aminophosphonic and/or phosphonic units. More preferred polymers are selected from the group consisting of polyacrylate polymers, co-polymers of acrylic and maleic acid, co-polymers of styrene sulphonic acid and maleic acid, and mixtures thereof, preferably modified with aminophosphonic and/or phosphonic groups.
  • the molecular weight for these polymers and co-polymers is preferably below 100,000, most preferably between 500 and 50,000. Most suitable polymers and co-polymers for use herein will be soluble in an amount up to 0.1 % by weight, in an aqueous composition comprising 5% by weight of sodium hypochlorite with its pH adjusted to 13 with sodium hydroxide.
  • polyacrylate polymers sold under the tradename Good-Rite® from BF Goodrich, Acrysol® from Rohm & Haas, Sokalan® from BASF, Norasol® from Norso Haas.
  • co-polymers of styrene sulphonic acid and maleic acid commercially available under the tradename Versaflex® from National Starch such as Versaflex 157, as well as Acumer® terpolymers from Rohm and Haas, in particular Acumer® 3100.
  • Preferred commercially available polymers are the polyacrylate polymers, especially the Norasol® polyacrylate polymers and more preferred are the polyacrylate polymer Norasol® 41 ON (MW 10,000) and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000).
  • a preferred polymer for use herein is a polyacrylate polymer modified with phosphonic groups commercially available under the tradename Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000) from Norso-Haas.
  • Polymers herein are preferably present in low amounts, i.e. in amounts of up to 10% by weight, preferably up to 1 %, more preferably from 0.001 % to 0.5% by weight, most preferably from 0.005% to 0.2% by weight of the liquid composition.
  • compositions according to the present invention may also comprise a brightener or a mixture thereof as an optional ingredient.
  • the brightener has to be stable to the hypohalite bleach.
  • the brighteners may be desired herein to further enhance the whiteness performance of the compositions herein.
  • Brighteners are compounds which have the ability to fluorescent by absorbing ultraviolet wave-lengths of light and re-emitting visible light. Brighteners, also referred to as fluorescent whitening agent (FWA), have been extensively described in the art, see for instance EP-A-0 265 041 , EP- A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening agents" by A.K. Sarkar, published by MERROW, especially page 71-72.
  • FWA fluorescent whitening agent
  • optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6- membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical brighteners which may also be used in the present invention include naphthlimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE® series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal-UNPA®, Tinopal CBS® and Tinopal 5BM® available from Ciba-Geigy; Artie White CC® and Artie White CWD®; the 2-(4-styryl-phenyl)-2H-naptho[1 ,2- djtriazoles; 4,4'-bis(1 ,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • brighteners useful herein include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(-benzimidazol-2-yl)ethylene; 1 ,3-diphenyl- pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[1 ,2- djoxazole; 2-(stilbene-4-yl)-2H-naphtho[1 ,2-d]triazole, 3-phenyl-7-
  • optical brighteners useful in the present invention are those having the structural formula:
  • is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA- GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba- Geigy Corporation.
  • is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine- 2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • substituted stilbene 2,2'-disulfonic acid derivatives also include 4-4'- bis (2-2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy under the trade name Brightener 49® or other hydrophilic brighteners like for example Brightener 3® or Brightener 47®, also commercially available from Ciba-Geigy.
  • brighteners useful in the present invention include the polycyclic oxazole derivatives such as benzo-oxazole derivatives, or mixtures thereof and particularly preferred herein the benzo- oxazole derivatives.
  • An example of such a brightener is benzoxazole,2,2'- (thiophenaldyi)bis having the following formula C18H10N2O2S, commercially available from Ciba-Geigy under the trade name Tinopal SOP ®.
  • This brightener is almost insoluble in water, i.e. it has a solubility being lower than 1 gram per liter.
  • Another example of such a brightener is bis(sulfobenzofuranyl)biphenyl, commercially available from Ciba-Geigy under the trade name Tinopal PLC®.
  • compositions according to the present invention comprise up to 1.0% by weight of the total composition of a brightener or a mixture thereof, preferably from 0.005% to 0.5%, more preferably from 0.005% to 0.3% and most preferably from 0.008% to 0.1 %.
  • the liquid bleaching composition of the present invention needs to be contacted with the surface to treat.
  • surfaces any inanimate surface.
  • inanimate surfaces include, but are not limited to, hard-surfaces typically found in houses like kitchens, bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs and the like, as well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets.
  • Inanimate surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
  • treating a surface it is meant herein bleaching and/or disinfecting said surfaces as the compositions of the present invention comprise a hypohalite bleach and cleaning, i.e. removing various types of stains from the surfaces, as said compositions comprise an alkyl (alkoxy) 2-4 sulphate and optionally a co-surfactant.
  • the present invention also encompasses a process of treating (e.g. bleaching) a fabric, as the inanimate surface.
  • a 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 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 bleaching composition, as defined herein, is added on top of a wash liquor formed by dissolution or dispersion of a typical laundry detergent. 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 processes of treating surfaces fabrics according to the present invention, especially fabrics, delivers effective whiteness performance and/or effective stain removal performance upon ageing of the compositions.
  • compositions according to the present invention are preferably contacted to fabrics in a liquid form. Indeed, by "in a liquid form”, it is meant herein the liquid compositions according to the present invention per se in neat or diluted form.
  • compositions according to the present invention are typically used in diluted form in a laundry operation.
  • in diluted form it is meant herein that the compositions for the bleaching of fabrics according to the present invention may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by other means such as in a washing machine.
  • Said compositions can be diluted up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times.
  • the process of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted together with the bleaching of said fabrics by contacting said fabrics at the same time with a bleaching composition according to the present invention and said detergent composition, or said washing may be conducted before or after that said fabrics have been bleached.
  • said process according to the present invention allows to bleach fabrics and optionally to wash fabrics with a detergent composition comprising at least one surface active agent before the step of contacting said fabrics with 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 process of bleaching fabrics comprises the step of contacting fabrics with a liquid bleaching composition according to the present invention, in its neat form, of allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes and then rinsing said fabrics with water.
  • the washing may be conducted before or after that said fabrics have been bleached.
  • the level of hypohalite bleach is from 0.01 % to 5%, preferably from 0.1 % to 3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1 %.
  • the present invention provides liquid hypohalite bleach-containing compositions that may be applied neat onto a fabric to bleach, despite a standing prejudice against using hypochlorite-containing compositions neat on fabrics.
  • the bleaching pre-treatment operation may also be followed by the diluted bleaching process as described herein before either in bucket (hand operation) or in a washing machine.
  • the present invention also encompasses a process of treating a hard-surface, as the inanimate surface.
  • a composition as defined herein, is contacted with the hard-surfaces to be treated.
  • 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.
  • composition as defined herein, may be applied to the surface to be treated in its neat form or in its diluted form typically up to 200 times their weight of water, preferably into 80 to 2 times their weight of water, and more preferably 60 to 2 times.
  • compositions of the present invention are easy to rinse and provide good shine characteristics on the treated surfaces.
  • hard-surfaces any hard-surfaces as mentioned herein before as well as dishes.
  • Na C 12 -C 14 E3S is an alkyl C 12 14 (ethoxy)3 sulphate commercially available from Rhone Poulenc and Albright & Wilson.
  • Na C 12 -C1 E2S is an alkyl C12 14 (ethoxy)2 sulphate commercially available from Rhone Poulenc.
  • Na C 12 -C 14 E1S is an alkyl C 12/14 (ethoxy)1 sulphate commercially available from Rhone Poulenc.
  • NaC 8 S is sodium C 8 alkyl sulphate.
  • Betaine is lauryl dimethyl amine betaine from Albright & Wilson.
  • LAS is sodium paraffin benzene sulphonate from Albright & Wilson.
  • compositions above are Theologically stable upon prolonged periods of storage, e.g. they do not undergo more than 30% loss of initial viscosity after 10 days of storage at 50°C.
  • compositions deliver effective stain removal performance as well as effective whiteness performance when used in a laundry application in their neat or diluted form, e.g. 200 times their weight of water, after prolonged periods of storage, e.g., after 3 months of storage at room temperature (25°C) after their manufacturing.
  • compositions also deliver effective cleaning performance when used in any household cleaning application.

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Abstract

La présente invention concerne des compositions liquides, épaissies et contenant un agent de blanchiment à l'hypohalite, un tampon de pH, un sulfate d'alkyle(alcoxy)2-4, éventuellement un co-tensioactif ainsi qu'un agent de stabilisation. Ces compositions possèdent une excellente stabilité rhéologique même après une longue période de stockage.
PCT/IB1998/001348 1997-09-19 1998-08-28 Compositions de blanchiment epaissies et stables WO1999015618A1 (fr)

Priority Applications (3)

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AU87449/98A AU8744998A (en) 1997-09-19 1998-08-28 Stabled thickened bleaching compositions
PL98339380A PL339380A1 (en) 1997-09-19 1998-08-28 Stably thickened bleaching compositions
EP98938860A EP1017780A1 (fr) 1997-09-19 1998-08-28 Compositions de blanchiment epaissies et stables

Applications Claiming Priority (2)

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EP97870138A EP0905223B2 (fr) 1997-09-19 1997-09-19 Compositions de blanchiment auto-épaississantes
EP97870138.1 1997-09-19

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EP0942064A1 (fr) * 1998-03-09 1999-09-15 The Procter & Gamble Company Compositions liquides de blanchiment à base d'hypohalite
GB9818131D0 (en) * 1998-08-19 1998-10-14 Jeyes Group Plc Liquid bleaching compositions
EP1069178A1 (fr) * 1999-07-12 2001-01-17 The Procter & Gamble Company Stabilisant de blanchiment pour un dispositif pour détacher
CA2409393C (fr) 2000-06-19 2007-04-10 The Procter & Gamble Company Stabilisateur de blanchiment pour applicateur detachant
DE102005062008B3 (de) 2005-12-22 2007-08-30 Henkel Kgaa Geruchsreduktion hypochlorithaltiger Mittel
DE102005063065A1 (de) * 2005-12-29 2007-07-12 Henkel Kgaa Korrosionsinhibierung flüssiger hypochlorithaltiger Reinigungsmittel
DE102005063177A1 (de) 2005-12-30 2007-07-05 Henkel Kgaa Erhöhung der Stabilität hypochlorihaltiger Waschmittel

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US3954675A (en) * 1972-06-01 1976-05-04 Colgate-Palmolive Company Heavy duty oxidizing bleach stable liquid laundry detergent
EP0144166A2 (fr) * 1983-11-11 1985-06-12 The Procter & Gamble Company Compositions détergentes
US5034150A (en) * 1989-05-03 1991-07-23 The Clorox Company Thickened hypochlorite bleach solution and method of use
WO1993008247A1 (fr) * 1991-10-22 1993-04-29 The Clorox Company Compositions de nettoyage aqueuses epaissies et procedes d'utilisation desdites compositions
US5705467A (en) * 1991-10-22 1998-01-06 Choy; Clement K. Thickened aqueous cleaning compositions and methods of use

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Publication number Priority date Publication date Assignee Title
ES2007221A6 (es) † 1988-05-05 1989-06-01 Henkel Iberica Composicion blanqueante a base de hipocloritos alcalinos y procedimiento para su obtencion.
WO1993021298A1 (fr) † 1992-04-13 1993-10-28 The Procter & Gamble Company Procede de preparation de compositions detergentes liquides thixotropes
DE4333100C1 (de) * 1993-09-29 1994-10-06 Henkel Kgaa Bleich- und Desinfektionsmittel

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US3954675A (en) * 1972-06-01 1976-05-04 Colgate-Palmolive Company Heavy duty oxidizing bleach stable liquid laundry detergent
EP0144166A2 (fr) * 1983-11-11 1985-06-12 The Procter & Gamble Company Compositions détergentes
US5034150A (en) * 1989-05-03 1991-07-23 The Clorox Company Thickened hypochlorite bleach solution and method of use
WO1993008247A1 (fr) * 1991-10-22 1993-04-29 The Clorox Company Compositions de nettoyage aqueuses epaissies et procedes d'utilisation desdites compositions
US5279758A (en) * 1991-10-22 1994-01-18 The Clorox Company Thickened aqueous cleaning compositions
US5705467A (en) * 1991-10-22 1998-01-06 Choy; Clement K. Thickened aqueous cleaning compositions and methods of use

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TR200001430T2 (tr) 2002-08-21
EP1017780A1 (fr) 2000-07-12
EP1015545A1 (fr) 2000-07-05
ATE237673T1 (de) 2003-05-15
ZA988581B (en) 1999-02-19
PL339382A1 (en) 2000-12-18
MA24801A1 (fr) 1999-12-31
DE69737652D1 (de) 2007-06-06
PE114899A1 (es) 1999-12-07
CO5040179A1 (es) 2001-05-29
DE69813426D1 (de) 2003-05-22
ES2195305T3 (es) 2003-12-01
PL339380A1 (en) 2000-12-18
CO5031314A1 (es) 2001-04-27
ES2285726T3 (es) 2007-11-16
ATE360679T1 (de) 2007-05-15
WO1999014305A1 (fr) 1999-03-25
TR200001429T2 (tr) 2001-03-21
AU9320598A (en) 1999-04-05
ES2285726T5 (es) 2011-09-05
EP0905223A1 (fr) 1999-03-31
EP0905223B2 (fr) 2011-04-06
EP0905223B1 (fr) 2007-04-25
AU8744998A (en) 1999-04-12
ZA988580B (en) 1999-03-19
AR016929A1 (es) 2001-08-01

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