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EP0984059A1 - Compositions de blanchiment - Google Patents

Compositions de blanchiment Download PDF

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Publication number
EP0984059A1
EP0984059A1 EP98870185A EP98870185A EP0984059A1 EP 0984059 A1 EP0984059 A1 EP 0984059A1 EP 98870185 A EP98870185 A EP 98870185A EP 98870185 A EP98870185 A EP 98870185A EP 0984059 A1 EP0984059 A1 EP 0984059A1
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Prior art keywords
alkyl
present
compositions
composition
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EP98870185A
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German (de)
English (en)
Inventor
Oreste Todini (Nmn)
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP98870185A priority Critical patent/EP0984059A1/fr
Priority to US09/786,076 priority patent/US6506718B1/en
Priority to PCT/US1999/020127 priority patent/WO2000012668A1/fr
Priority to CA002340253A priority patent/CA2340253A1/fr
Publication of EP0984059A1 publication Critical patent/EP0984059A1/fr
Priority to US10/301,169 priority patent/US6649583B2/en
Withdrawn legal-status Critical Current

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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 bleaching compositions, in particular to hypochlorite bleaching compositions, suitable for use in various laundry applications including hand and machine laundry methods.
  • Bleaching compositions are well-known in the art. Amongst the different bleaching compositions available, those relying on bleaching by hypohalite bleaches such as hypochlorite are often preferred, mainly for performance reasons, especially at lower temperature.
  • hypohalite bleaches are known to be aggressive bleaching agents that may potentially facilitate the decomposition of other components of a bleaching composition.
  • the Applicant has found that this is particularly true of alkyl ethoxy sulphates which are often preferred anionic surfactants of hypohalite bleach-containing compositions.
  • EP 243 685 and EP 181 212 both describe compositions comprising alkyl ethoxy sulphate having an average of from 1 to 3 and less than 6 moles of ethoxy groups respectively. However neither document describe compositions comprising hypohalite bleach.
  • EP 580 245 describes a composition comprising alky ethoxy sulphate having from 1 to 11 moles of ethoxy groups and optionally on oxygen-releasing bleach.
  • the object of the present invention is to provide a hypohalite-containing composition comprising an alkyl ethoxy sulphate that is stable and provides improved soil removal benefits.
  • the present invention provides a liquid bleaching composition
  • a liquid bleaching composition comprising a hypohalite bleach and an alkyl ethoxy sulphate having an average of 2 or less moles of ethoxy groups.
  • Liquid bleaching compositions :
  • 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.
  • 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 alkali metal sodium hypochlorite.
  • the liquid compositions according to the present invention comprise said hypohalite bleach such that the content of active halide in the composition is from 0.1% to 20% by weight, more preferably from 0.25% to 8% by weight, most preferably from 0.5% to 6% by weight of the composition.
  • the second essential component of the composition of the present invention is an alky ethoxy sulphate.
  • the alkyl ethoxy sulphate is preferably a water-soluble salt or acid of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 6 -C 30 linear or branched alkyl group, preferably a C 10 -C 20 linear or branched alkyl, more preferably C 12 -C 18 , most preferably C 12 -C 14 linear or branched alkyl group, A is an ethoxy unit, m is 2 or less, more preferably between 0.05 and 2, most preferably 0.05 1 moles, and M is H or a cation which can be, for example, a metal cation, preferably an alkali or alkaline earth metal, (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 6
  • 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.
  • alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • alkyl ethoxy sulphates are selected from the group consisting of C 12 -C 14 ethoxy sulfate.
  • the most preferred alkyl ethoxy sulfate is the sodium salt of lauryl ethoxy (1) sulfate or C 12 H 25 OCH 2 CH 2 OSO 3 Na.
  • compositions of the present invention provide improved soil removal fabric whiteness and storage stability versus identical compositions, not comprising an alkyl ethoxy sulfate having 2 or less moles of ethoxy groups.
  • compositions of the present invention exhibit improved stability versus identical compositions comprising the alkyl ethoxy sulfate with a higher degree of ethoxylation, i.e. greater than 2. It is believed that this stability benefit is achieved because, as the Applicant has found, it is the ethoxy groups of alkyl ethoxy sulfate that are sensitive to hypohalite bleach. Thus, the Applicant has found that by lowering the number of moles of ethoxy groups of 2 or less, the stability of the surfactant and the composition can be improved without adversely affecting solubility of the surfactant.
  • compositions according to the present invention have a viscosity between 0 cps and 2000 cps, preferably between 50 cps and 1100 cps.
  • the viscosity of the composition can be further modified by addition of a co-surfactant. Where present the ratio of alkyl ethoxy sulfate and a co-surfactant will determine the actual viscosity.
  • Viscosity is measured with a rheometer like carri-med CSL2-100® at the following viscosity parameters : angle : 1°58, gap: 60, diameter: 4.0 cm, iner : 63.60 at a temperature of 25°C and a shear rate of 30 1/sec.
  • the bleaching composition may also comprise one or more optional components.
  • Optional components may be selected from brightener, radical scavenger, chelating agent, pH buffering agent, co-surfactant and polymers.
  • An optional component of the invention is a brightener. Any brighteners known to those skilled in the art may be used herein including both hydrophobic and hydrophilic brighteners and mixtures thereof.
  • Brighteners are compounds which have the ability to fluorescence by absorbing ultraviolet wave-lengths of light and re-emitting visible light. Brighteners, also referred to as fluorescent whitening agents (FWA), have been extensively described in the art, see for instance EP-A-0 265 041, EP-A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening agents" by A.K. Sarkar, published by MERROW, especially page 71-72.
  • FWA fluorescent whitening agents
  • optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanine, dibenzothiophene-5,5-dioxide, azole, 5- and 6-membered-ring heterocycle, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical brighteners which may also be used in the present invention include naphthlimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof. Particularly preferred brighteners for use herein are the derivatives of stilbene and mixtures thereof.
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE® series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal-UNPA®, Tinopal CBS® and Tinopal 5BM® available from Ciba-Geigy; Artic White CC® and Artic White CWD®; the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • An other optional component of the invention is a radical scavenger.
  • the radical scavengers have to be stable to the hypohalite bleach.
  • 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 for use in the present invention have one of the following formulas: wherein each X, Y, and Z are -H, -COO-M + , -Cl, -Br, -SO 3 -M + , -NO 2 , -OCH 3 , or a C 1 to C 10 primary and secondary alkyl groups and M is H or an alkali metal, or mixtures thereof.
  • these components include pyromellitic acid, i.e. where X, Y and Z are -COO-H + ; hemimellitic acid, trimellitic acid, i.e.
  • 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 1 to C 10 primary and secondary alkyl groups, -Cl, -Br, -SO 3 -H + , -NO 2 , and -OCH 3 respectively and substituted sulfonic acids.
  • radical scavengers useful in the present invention are benzoic acid, methoxy benzoic acid, 3-nitrobenzoic acid, 4-toluene sulfonic acid, 2 n-octyl benzoic acid, 2 n-octyl sulfonic acid, anisic acid or salts thereof or mixtures thereof.
  • Highly preferred examples of radical scavengers herein are benzoic acid and/or methoxy benzoic acid and/or 3-nitro benzoic 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.
  • radical scavenger may be present at a level of from 0.001% to 10% by weight of the total composition of a radical scavenger, preferably from 0.01 % to 8%, more preferably from 0.1 % to 6% and most preferably from 0.2% to 4%.
  • a chelating agent is an optional but preferred component.
  • the chelating agents have to be stable to the hypohalite bleach.
  • Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, phosphate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'-disuccinic acids, or mixtures thereof.
  • Chelating agents may be desired in the compositions of the present invention, preferably phosphate chelating agents like phytic acid, as they further contribute to the benefit delivered by the radical scavengers herein by further improving the stability of the brighteners, thus delivering effective whiteness performance in any laundry application upon ageing of the compositions, i.e. after prolonged periods of storage.
  • the present invention encompasses the use, in a hypohalite bleaching composition comprising a brightener, of a chelating agent, for improved brightener stability in said composition as well as the use, in a hypohalite bleaching composition comprising a brightener, of a chelating agent, for effective whiteness performance upon ageing of the composition.
  • the presence of chelating agents may also contribute to reduce tensile strength loss of fabrics and/or colour damage, especially in a laundry pretreatment 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 hypohalite bleach.
  • 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 viscosità intrinseca in soluée di cuprietilendiammina (CED).
  • UNI Ente Nazionale Italiano di Unificacade
  • CED cuprietilendiammina
  • Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
  • Suitable phosphate chelating agents are as following: Phosphonic acid can be condensed in the reaction :
  • reaction can be repeated with any of the reactive OH groups, and phosphate ingredients are obtained which can be
  • phosphate ingredients are suitable for use herein, and preferred are linear phosphate ingredients (i.e. R is M) where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)), most preferably where n is 2.
  • R linear phosphate ingredients
  • n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)
  • STPP tripolyphosphate
  • M is Sodium
  • Phytic acid which is particularly suitable for use herein, is a hexa-phosphoric acid that occurs naturally in the seeds of many cereal grains, generally in the form of the insoluble calcium-magnesium salt. It may also be derived from corn steep liquor. Commercial grade phytic acid is commercially available from J.T.Baker Co., e.g. as a 40% aqueous solution. It is intended that the present invention covers the acidic form of phytic acid as well as alkali metal salt derivatives thereof, particularly sodium or potassium salts thereof. Sodium phytate is available from Jonas Chemical Co (Brooklyn, N.Y.).
  • the phytic acid component exists primarily as the ionized salt in the liquid compositions herein even if it is added in its acidic form. Mixtures of such salts of phytic acid are also covered.
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • Ethylenediamine N,N'-disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
  • Ethylenediamine N,N'-disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Particularly preferred chelating agents for use herein are phosphate chelating agents like sodium pyrophosphate, sodium tripolyphosphate, phytic acid, and mixtures thereof.
  • compositions according to the present invention comprise up to 10% by weight of the total composition of a chelating agent, or mixtures thereof, preferably from 0.01% to 5% by weight, more preferably from 0.05% to 2% and most preferably from 0.1% to 1.5%.
  • the liquid compositions of the present invention have a pH of preferably from 8 to 14, more preferably from 9 to 14, most preferably from 10 to 13.
  • the pH of the diluted solution is preferably from 7.5 to 13, more preferably from 8 to 12, most preferably from 8.5 to 11.5. It is in this alkaline range that the optimum stability and performance of the hypohalite, as well as fabric whiteness and/or safety are obtained.
  • the pH range is suitably provided by the hypohalite bleach mentioned hereinbefore and optionally the pH buffering component when present, which are alkalis. However, in addition to these components, a strong source of alkalinity may also optionally be used.
  • Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such as sodium and/or potassium oxide.
  • a preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide. Typical levels of such caustic alkalis, when present, are of from 0.1% to 1.5% by weight, preferably from 0.5% to 1.5% by weight of the composition.
  • compositions of the present invention the presence of a pH buffering component is not compulsory, but is highly preferred.
  • the pH buffering component ensures that the pH of the composition and diluted solution are buffered to pH range described above.
  • 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 preferably contain an amount of pH buffering component of from 0.5% to 9% by weight, more preferably from 0.5% to 5% by weight, and most preferably in an amount of from 0.6% to 3% by weight of the composition.
  • composition according to the invention may comprise other optional components such as bleach-stable surfactants, organic or inorganic alkalis, builders, thickening agents, polymers, pigments, dyes, solvents, perfumes, and mixtures thereof.
  • the liquid compositions of the present invention may further comprise a co-surfactant or a mixture thereof as an optional ingredient.
  • Said co-surfactants may be present in the compositions according to the present invention in amounts of preferably from 0.1% to 50% by weight of the total composition, more preferably of from 0.1 % to 40% and most preferably of from 1% to 30%.
  • Surfactants suitable for use herein as co-surfactants include additional anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
  • Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably linear or branched alkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 linear or branched alkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • R preferably is a
  • alkyl propoxylated sulfates preferably having from 0.5 to 30, more preferably 0.5 to 5 moles of propoxy groups.
  • anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary or secondary alkanesulfonates, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 9 -C 20 linear alkylbenzenesulfonates C 8 -C 22 primary or secondary alkanesulfonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • acyl sarcosinate or mixtures thereof, in its acid and/or salt form preferably long chain acyl sarcosinates having the following formula: wherein M is hydrogen or a cationic moiety and wherein R is an alkyl group of from 11 to 15 carbon atoms, preferably of from 11 to 13 carbon atoms.
  • M are hydrogen and alkali metal salts, especially sodium and potassium.
  • Said acyl sarcosinate surfactants are derived from natural fatty acids and the 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 nonionic surfactants for use herein include a class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohol) or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • suitable nonionic synthetic surfactants include :
  • nonionic surfactants for use herein are capped nonionic ethoxylated surfactants according to the formula: R 1 (OR 2 ) n OR 3
  • surfactants are commercially available from BASF under the trade name Plurafac®, from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
  • Preferred capped nonionic ethoxylated surfactant of the above formula are those commercially available under the tradename Genapol® L 2.5 NR from Hoechst, and Symperonic® LF/CS 1100 from ICI.
  • Suitable nonionic surfactants for use herein include the amine oxides corresponding to the formula: R R' R'' N ⁇ O wherein R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons, and wherein R' and R'' are, each, independently, an alkyl group containing 1 to 6 carbon atoms.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • the preferred amine oxides are those in which the primary alkyl group has a straight chain in at least most of the molecules, generally at least 70%, preferably at least 90% of the molecules, and the amine oxides which are especially preferred are those in which R contains 10-18 carbons and R' and R'' are both methyl.
  • Exemplary of the preferred amine oxides are the N-hexyldimethylamine oxide, N-octyldimethylamine oxide, N-decyldimethylamine oxide, N-dodecyl dimethylamine oxide, N-tetradecyldimethylamine oxide, N-hexadecyl dimethylamine oxide, N-octadecyldimethylamine oxide, N-eicosyldimethylamine oxide, N-docosyldimethylamine oxide, N-tetracosyl dimethylamine oxide, the corresponding amine oxides in which one or both of the methyl groups are replaced with ethyl or 2-hydroxyethyl groups and mixtures thereof.
  • a most preferred amine oxide for use herein is N-decyldimethylamine oxide.
  • Suitable nonionic surfactants for the purpose of the invention are the phosphine or sulfoxide surfactants of formula : R R' R'' A ⁇ O wherein A is phosphorus or sulfur atom, R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons, and wherein R' and R'' are, each, independently selected from methyl, ethyl and 2-hydroxyethyl.
  • the arrow in the formula is a conventional representation of a semi-polar bond.
  • Suitable zwitterionic detergents for use herein comprise the betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
  • Some common examples of these detergents are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
  • Preferred zwitterionic detergent compounds have the formula : wherein R1 is an alkyl radical containing from 8 to 22 carbon atoms, R2 and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chain containing from 1 to 3 carbon atoms, X is selected from the group consisting of hydrogen and a hydroxyl radical, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 radicals is from 14 to 24 carbon atoms.
  • Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378, said patents being incorporated herein by reference. Additional synthetic detergents and listings of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980, incorporated herein by reference.
  • Cationic surfactants suitable for use in compositions of the present invention are those having a long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula: [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X - wherein R 2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, benzyl ring structures formed by joining the two R 4 groups, and hydrogen when y is not 0; R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I):
  • Preferred quat ammonium surfactants are those as defined in formula I whereby
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R 3 R 4 N + X - wherein R 1 is C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is independently C 1 -C 4 alkyl, benzyl, and -(C 2 H 40 ) x H where x has a value from 2 to 5, and X is an anion. Not more than one of R 2 , R 3 or R 4 should be benzyl.
  • the preferred alkyl chain length for R 1 is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R 2 R 3 and R 4 are methyl and the anion X may be selected from halide, methosulphate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are :
  • compositions herein is a polymer. 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® 410N (MW 10,000) and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000).
  • a preferred polymer for use herein is a polyacrylate polymer modified with phosphonic groups commercially available under the tradename Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 754 (MW 4000) from Norso-Haas.
  • Polymers herein are preferably present in low amounts, i.e. in amounts of up to 10%, preferably up to 1%, more preferably up to 0.5% by weight, even more preferably from 0.001% to 0.3% by weight, and most preferably from 0.005% to 0.2% by weight of the liquid composition.
  • Particularly preferred surfaces to be bleached with the compositions herein are fabrics including for example clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets.
  • the present invention further encompasses a method of bleaching fabrics which comprises the step of contacting said fabrics with a bleaching composition according to the present invention.
  • the compositions used in said method of bleaching fabrics are liquid hypochlorite-containing compositions that may further comprise a chelating agent and/or a pH buffering component as defined hereinbefore. Said method according to the present invention delivers effective whiteness performance upon ageing of the compositions.
  • compositions according to the present invention are 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 method of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted together with the bleaching of said fabrics by contacting said fabrics at the same time with a bleaching composition according to the present invention and said detergent composition, or said washing may be conducted before or after that said fabrics have been bleached.
  • said method 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 method 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. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted before or after that said fabrics have been bleached.
  • the level of hypohalite bleach is from 0.01 % to 5%, preferably from 0.1% to 3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1%.
  • the present invention provides 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 method as described herein before either in bucket (hand operation) or in a washing machine.
  • compositions exemplified above exhibit effective whiteness performance when used to bleach fabrics both in neat or diluted conditions (e.g. at a dilution of 200 (typical dilution)) after 3 months of storage at room temperature (e.g. about 25°C) after their manufacturing.

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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EP98870185A 1998-09-01 1998-09-01 Compositions de blanchiment Withdrawn EP0984059A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP98870185A EP0984059A1 (fr) 1998-09-01 1998-09-01 Compositions de blanchiment
US09/786,076 US6506718B1 (en) 1998-09-01 1999-09-01 Bleaching compositions
PCT/US1999/020127 WO2000012668A1 (fr) 1998-09-01 1999-09-01 Compositions de blanchiment
CA002340253A CA2340253A1 (fr) 1998-09-01 1999-09-01 Compositions de blanchiment
US10/301,169 US6649583B2 (en) 1998-09-01 2002-11-21 Bleaching compositions

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EP98870185A EP0984059A1 (fr) 1998-09-01 1998-09-01 Compositions de blanchiment

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IL146449A0 (en) * 2001-11-12 2002-07-25 Lycored Natural Prod Ind Ltd Method and pharmaceutical preparations for reducing the activity of cells

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Publication number Priority date Publication date Assignee Title
US3560389A (en) * 1966-08-11 1971-02-02 Cyclo Chemicals Ltd Liquid detergent bleach composition
US3929661A (en) * 1973-12-11 1975-12-30 Kao Corp Liquid detergent bleaching composition
US4388204A (en) * 1982-03-23 1983-06-14 The Drackett Company Thickened alkali metal hypochlorite compositions
US4588514A (en) * 1983-09-23 1986-05-13 Lever Brothers Company Liquid thickened bleaching composition
EP0340371A2 (fr) * 1988-05-05 1989-11-08 Henkel Iberica, S.A. Composition de blanchiment à base d'hypochlorite alcalin et procédé pour sa préparation
US5034150A (en) * 1989-05-03 1991-07-23 The Clorox Company Thickened hypochlorite bleach solution and method of use
US5279758A (en) * 1991-10-22 1994-01-18 The Clorox Company Thickened aqueous cleaning compositions
JPH10204495A (ja) * 1997-01-28 1998-08-04 Kao Corp 硬質表面用漂白剤組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0903403B1 (fr) * 1997-09-19 2003-04-16 The Procter & Gamble Company Compositions de blanchiment stables
DE69827758D1 (de) * 1998-01-16 2004-12-30 Procter & Gamble Stabile gefärbte verdickte Bleichmittelzusammensetzungen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3560389A (en) * 1966-08-11 1971-02-02 Cyclo Chemicals Ltd Liquid detergent bleach composition
US3929661A (en) * 1973-12-11 1975-12-30 Kao Corp Liquid detergent bleaching composition
US4388204A (en) * 1982-03-23 1983-06-14 The Drackett Company Thickened alkali metal hypochlorite compositions
US4588514A (en) * 1983-09-23 1986-05-13 Lever Brothers Company Liquid thickened bleaching composition
EP0340371A2 (fr) * 1988-05-05 1989-11-08 Henkel Iberica, S.A. Composition de blanchiment à base d'hypochlorite alcalin et procédé pour sa préparation
US5034150A (en) * 1989-05-03 1991-07-23 The Clorox Company Thickened hypochlorite bleach solution and method of use
US5279758A (en) * 1991-10-22 1994-01-18 The Clorox Company Thickened aqueous cleaning compositions
JPH10204495A (ja) * 1997-01-28 1998-08-04 Kao Corp 硬質表面用漂白剤組成物

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Title
DATABASE WPI Section Ch Week 9841, Derwent World Patents Index; Class A97, AN 98-477069, XP002091017 *

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CA2340253A1 (fr) 2000-03-09

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