WO2000039274A1 - Compositions de nettoyage - Google Patents

Compositions de nettoyage Download PDF

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Publication number
WO2000039274A1
WO2000039274A1 PCT/US1999/029552 US9929552W WO0039274A1 WO 2000039274 A1 WO2000039274 A1 WO 2000039274A1 US 9929552 W US9929552 W US 9929552W WO 0039274 A1 WO0039274 A1 WO 0039274A1
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Prior art keywords
tue
particle
alkyl
acid
surfactant
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PCT/US1999/029552
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English (en)
Inventor
Tiffany Alice Hensman
Peter Gerard Gray
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The Procter & Gamble Company
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Priority to AU21789/00A priority Critical patent/AU2178900A/en
Publication of WO2000039274A1 publication Critical patent/WO2000039274A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing 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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated

Definitions

  • the present invention relates to solid cleaning compositions which comp ⁇ se particles containing an anionic surfactant and specific nonionic surfactant which have improved dispensing properties whilst having good cleaning properties.
  • Detergent compositions traditionally employ nonionic surfactants, in particular ethoxylated alcohol surfactants having an ethylene number of from about 2 to 50 These surfactants are often liquids When formulating solid detergent compositions, these liquid nonionic surfactants are often sprayed onto the particles of the detergent, thus coating the particles with the nonionic ethoxylated alcohols.
  • nonionic surfactants in particular ethoxylated alcohol surfactants having an ethylene number of from about 2 to 50
  • Anionic surfactants can also have a tendency to form gels upon contact with water.
  • the inventors have found that these gelling problems are even more apparent when the detergent composes both these nonionic ethoxylated alcohol surfactants and anionic surfactants, more than one would expect from the gelling of the nonionic surfactant or the anionic surfactant on its own. Therefore, there is also a need to improve the improve the delivery to the washing water of compositions containing anionic surfactants and to reduce the problem related to the incorporation of nonionic alkoxylated alcohol surfactants
  • the inventors have found that the amount of nonionic alkoxylated alcohol surfactant can be reduced, even to 0%, when these specific amide surfactants are used, and that this results in reduced gelling of the particles, reduced caking of the particles, reduced 'bleeding' of detergent ingredients and an improved handling of the products, improved flowability of the product and at the same time improved dispensing of the product, whilst still excellent cleaning performance is achieved.
  • nonionic alkoxylated alcohol surfactants have a tendency to loose performance under hard water conditions.
  • the inventors have surprisingly found that the nonionic polyalkoxylated amide surfactants remain a satisfactory surfactant performance under hard water conditions. This allows simplification of the builder system employed in the detergents or the reduction of the level of builders incorporated in the detergents.
  • the inventors have found that the specific nonionic polyalkoxy fatty acid amides can easily be combined with an effervescence source, which further improves the dispensing.
  • the present invention provides a detergent composition comprising a particle containing intimately mixed
  • R ⁇ is a C ⁇ 2 -C 18 alkyl or alkenyl group
  • R 2 is a C 2 -C 4 alkyl ene group
  • R is a - C 4 alkyl group or preferably hydrogen
  • R is a C ⁇ -C 4 alkyl group or preferably hydrogen
  • n is a number from 3 to 12;
  • the level of nonionic alkoxylated alcohol surfactant when present is from 0% to 20% by weight of the particle.
  • the invention provides a detergent composition
  • a detergent composition comprising a particle containing, a) a spray-on component containing of from 0.1 % to 50% by weight of the particle of a nonionic alkoxylated fatty acid amide of the formula:
  • Ri is a C ⁇ 2 -Cj 8 alkyl or alkenyl group
  • R 2 is a C 2 -C alkyl ene group
  • R 3 is a C ⁇ - C 4 alkyl group or preferably hydrogen
  • R is a C ⁇ -C alkyl group or preferably hydrogen
  • n is a number from 3 to 12;
  • the spray-on component is sprayed onto the particle core; provided that the level of nonionic alkoxylated alcohol surfactant when present, is from 0% to 20% by weight of the particle.
  • compositions comprises at least two anionic surfactants.
  • the detergent composition comprises an effervescence system, preferably comprised in the particle described herein.
  • the composition of the invention has a reduced sensitivity to water hardness and may thus employ reduced levels of builder.
  • the detergent compositions herein preferably comprise a builder system up to 60%> by weight, more preferably up to 50% or even up to 40% by weight and smaller levels may be preferred, for example up to 35%> or even 30%o by weight.
  • the detergent composition further comprises one or more enzymes, brighteners, perfumes or dyes or mixtures thereof.
  • the invention also relates to the use of a nonionic alkoxylated fatty acid amide surfactant in detergent particles containing an anionic surfactant for improvement of the dispensing of the detergent composition comprising the particles, preferably also comprising an enzyme, dye, brightener, perfume or mixtures thereof.
  • compositions herein are preferably in the form of granules, pastilles, extrudates or tablets.
  • the compositions are laundry or dish washing detergent composition.
  • the detergent compositions of the invention have an improved dispensing of the detergent composition as a whole. This includes for the purpose of the invention, that the composition or components thereof have a reduced gelling upon contact with water, in particular upon contact with small amounts of water at the beginning of the wash, such as in the dispensing drawer or in the interior of the washing machine; have an improved dispensing from the dispensing drawer or from a dispensing device; and/or have an improved dissolution into the wash water.
  • the particle of the composition of the invention comprises the alkoxylated fatty acid amide and the anionic and/ or additional nonionic surfactant intimately mixed with one another.
  • 'intimately mixed' means for the purpose of the invention that components of the particle are substantially homogeneously divided in the particle, and 'intimate mixture' should be interpreted accordingly.
  • the particle or particle core may have any form and can be made by any known method involving the mixing of the surfactants, which can be part of a granulation process, including spray-drying process, spherisation process, extrusion process, pastillation processes and in particular agglomeration processes, or be part of a tabletting process or flaking process, as described herein.
  • the particle or particle core may preferably be made by agglomerating the components with one another, optionally in the presence of an additional liquid or additional powder material, such as inorganic salts, silicates, aluminosilicates, organic acids or salts.
  • an additional liquid or additional powder material such as inorganic salts, silicates, aluminosilicates, organic acids or salts.
  • the particle or particle core is prepared by a process whereby any sold component are melted and mixed with any liquid component, in general the alkoxylated fatty acid amides, whereafter any additional powdered components can be dispersed with this liquid/ melted mixture.
  • the resulting mixture may optionally be agglomerated to obtain an homogeneously mixture.
  • the mixture is then solidified to form the particle, preferably by solidifying the melt by reducing the process temperature.
  • the alkoxylated fatty acid amide is comprised in a spray-on component, which is sprayed onto the particle core comprising an anionic surfactant and/ or an additional nonionic surfactant, by any spray-on method known in the art.
  • the particle core is preferably an agglomerate, a spray-dried particle or an extrudate.
  • the particle is substantially anhydrous.
  • substantially anhydrous means that no more than 5% by weight of free moisture is present, preferably no more than 4%, even more preferably no more than 3% and most preferably no more than 2% or even 1% by weight.
  • the free moisture content as used herein can be determined by placing 5 grams of the particles in a petri dish and placing this petri dish in a convection oven at 50°C for 2 hours, and subsequently measuring the weight loss, due to water evaporation.
  • the particle preferably has a weight average particle size of from 150 microns to 2000 microns, or it may be preferred to be from 200 microns to 1600 microns, more preferably from 400 microns to 1400 microns, as measured by use of Tyler sieves.
  • the particle preferably has a density of from 400gr/litre to 1500gr/litre, preferably from 450gr/litre to 1200gr/litre or even from 550gr/litre to 900gr/litre.
  • compositions, the particle and the particle core preferably comprise additional ingredients, as described hereinafter.
  • additional ingredients as described hereinafter.
  • levels of incorporation thereof will depend on the application of the particle or the compositions herein and the physical form of the particle and the compositions.
  • additional components it may be preferred that the nonionic alkoxylated fatty acid amide and the anionic and/ or nonionic surfactant are premixed prior to admixing any additional ingredients.
  • the particle is present as a separate granule in the composition.
  • the composition is in the form of a tablet or coarse granules, droplets or pastilles which then comprise the particle of the invention intimately mixed with the optional additional ingredients.
  • compositions preferably comprise additional particles which do not comprising the alkoxylated fatty acid amide.
  • the particle is preferably present at a level of from 0.5% to 80% by weight, more preferably from 1% to 50% by weight, even more preferably from 5% to 35% by weight of the composition.
  • the level of nonionic alkoxylated fatty acid amide surfactant is preferably from 0.5%> to 30% by weight of the composition or particle, preferably from 1.0% to 20%> by weight of the particle or composition, or more preferably from 1.5% to 15% by weight of the composition or from 3%> to 16% by weight of the particle.
  • the level of the other nonionic surfactant or anionic surfactant or mixtures thereof is preferably from 1.0%> to 80%> by weight of the composition or particle, preferably from 2% to 60%) by weight of the particle or from 3% to 50%> by weight of the composition, or even from 5% to 35% by weight of the composition or from 10%> to 50%) by weight of the particle.
  • the level of any nonionic alkoxylated alcohol surfactant is from 0%> to 20%) by weight of the particle and preferably also from 0% to 20%> by weight of the composition, more preferably from 0% to 10%, or even 6%> by weight of the particle or the composition. It may even be preferred that no nonionic polyalkoxylated alcohol surfactant is present in the particle, or in the composition.
  • This ratio of alkoxylated fatty acid amide to the total of the anionic and/ or nonionic surfactant is preferably from 2:1 to 1 :40, preferably from 1:1 to 1 :30, or even from 1 :5 to 1:25.
  • the alkoxylated fatty acid amide herein comprises preferably a compound of the formula
  • Ri is a C ⁇ 2 -C ⁇ 8 alkyl or alkenyl group
  • R 2 is a C 2 -C alkylene group
  • R 3 is a hydrogen or a C ⁇ -C alkyl group
  • R is a -C 4 alkyl group or hydrogen
  • n is a number from 3 to 12.
  • Preferred alkoxylated fatty acid amides have a Ri being a C ] -C] 4 or a C 16 -C ⁇ 8 alkyl group, R being a propylene or more preferably ethylene, n being from 5 to 10 or even 9, more preferably 5 to 7, most preferably 5, being methyl or more preferably hydrogen, R being preferably hydrogen, or optionally an ethyl group.
  • composition of the invention and the particle thereof comprises an anionic surfactant.
  • the ratio of the nonionic surfactant to the anionic surfactants is from 1 :10 to 10:1, preferably from 1 :4 to 5:1.
  • composition and the particle herein s an anionic surfactant.
  • anionic surfactants useful for detersive purposes can be comprised herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.
  • the anionic surfactant of the particle comprises at least an anionic sulfate or a sulphonate surfactant, as described herein. It may be preferred that the anionic surfactant in the particle comprises both sulfonate and sulfate surfactants. It may however also be preferred that the aionic surfactant of the particle consist essentially of anionic sulfate surfactant or anionic sulphonate surfactant.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(C ⁇ -
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary lO" i8 alkyl sulfates, more preferably the Cj ⁇ -C ⁇ branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 1 1 - Ci g, most preferably Cj 1 -C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, in particular ⁇ -methyl ester sulphonates, Cg-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a Cg to Cj g alkyl group, x is from 1 to 25, R ⁇ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • Suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • Rl is a C 1 -C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, ,-,-C, R monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C, . diesters), N-acyl sarcosinates.
  • 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 tallow oil. Additional ingredients
  • the particle herein and the detergent compositions of the invention preferably comprise additional ingredients.
  • additional components and levels of incorporation thereof will depend on the physical form of the composition or particle and the precise nature of the washing operation for which it is to be used.
  • compositions of the invention preferably contain one or more additional detergent components selected from effervescence sources, additional surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti- redeposition agents soil releasing agents, perfumes, dyes, dyed speckles, brighteners, photobleaching agents and additional corrosion inhibitors.
  • additional detergent components selected from effervescence sources, additional surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti- redeposition agents soil releasing agents, perfumes, dyes, dyed speckles, brighteners, photobleaching agents and additional corrosion inhibitors.
  • the composition comprises one or more brighteners, enzymes, perfume, dye or mixtures thereof. They may be comprised in the particle herein and/ or they may be incorporated in the composition comprised in a different particle.
  • the brightener, perfume and/ or dye are sprayed onto the particle.
  • the polyalkoxylated fatty acid amide may be mixed with the brightener, perfume and/ or dye and then sprayed onto the particle core to obtain the particle described herein above.
  • compositions and/ or the particle herein preferably comprises an effervescence source.
  • the effervescence source comprises an alkali source and an acid source, capable of reacting with one another in the presence of water to produce a gas, preferably carbon dioxide.
  • the alkali source is preferably a carbonate source.
  • preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fme calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Alkali metal percarbonate salts are also suitable sources of carbonate species and are described in more detail in the section 'inorganic perhydrate salts' herein.
  • the acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof.
  • the acid source may be a mono-, bi- or tri-protonic acid.
  • Preferred derivatives include a salt or ester of the acid.
  • the source of acidity is preferably non-hygroscopic, which can improve storage stability. However, a monohydrate acidic source can be useful herein.
  • Organic acids and their derivatives are preferred.
  • the acid is preferably water-soluble. Suitable acids include citric, glutaric, tartaric acid, succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid, maleic acid, malic acid or fumaric acid are especially preferred.
  • the acid source is preferably present at a level from 1% to 12%, even more preferably from 1%) to 1%, most preferably from 2% to 5% by weight of the composition.
  • the effervescence source may comprise anhydrous perborate, preferably stabilised with a coating agent or a diluent.
  • the effervescence source may preferably be intimately mixed with intimate mixture herein, in particular when comprised in a separate particle, prior to addition of the intimate mixture or particle thereof to the composition.
  • Preferred hereby may be that the effervescence source is an intimate mixture of maleic acid or citric acid or fumaric acid, but preferably of malic acid with a carbonate source and preferably also a bicarbonate source.
  • the effervescence source is then comprised in the particle containing the intimate mixture at a level of from 3% to 40% by weight of the particle, more preferably at a level of from 4%o to 30% or even from 5% to 25% by weight of the particle.
  • the dye which may be used herein can be a dye stuff or an aqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the particles, preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight, as described above.
  • the dye also comprising other ingredients such as organic binder materials.
  • the dyestuff can be any suitable dyestuff.
  • suitable dyestuffs include El 04 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), El 31 - food blue 5 (patent blue V), Ultra Marine blue (trade name), El 33 - food blue 2 (brilliant blue FCF), El 40 - natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine).
  • Preferred dyestuffs may be Monastral Blue BV paste (trade name) and or Pigmasol Green (trade name).
  • compositions in accord with the invention or the particles thereof may contain one or more surfactants selected from certain nonionic surfactants, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • the particle or detergent may also comprise nonionic alkylpolysaccharide surfactants, such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • nonionic alkylpolysaccharide surfactants such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula:
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • the particle herein and the compositions herein may comprise alkoxylated alcohol surfactants, preferably only up to 10%, or even 5% or even 2% by weight of the composition or particle.
  • alkoxylated alcohol surfactants commonly employed in detergent compositions can be reduced, even to 0%, in the compositions of the invention, containing the polyalkoxylated fatty acid amide surfactants.
  • the nonionic polyalkoxylated or alkoxylated alcohol surfactants are selected from the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Typical are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR4) X NO( .5)2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R-> is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are alkyl dimethylamine oxide, and CIQ-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2COO ⁇ wherein R is a Cg-C ⁇ g hydrocarbyl group, each R* is typically C1-C3 alkyl, and R ⁇ is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the lO-18 acylamidopropane (or ethane) dimethyl (or di ethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein. Cationic Surfactants
  • Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono C -
  • N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • cationic ester surfactants Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • cationic mono-alkoxylated amine surfactant preferably of the general formula I:
  • Ri is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms;
  • R ⁇ and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R ⁇ and R are methyl groups;
  • R ⁇ is selected from hydrogen (preferred), methyl and ethyl;
  • X' is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and
  • p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
  • Particularly preferred ApR ⁇ groups are — CH 2 CH 2 OH, — CH 2 CH 2 CH 2 OH, — CH 2 CH(CH 3 )OH and —
  • R 1 groups are linear alkyl groups.
  • Linear Ri groups having from 8 to 14 carbon atoms are preferred.
  • Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
  • Rl is CJQ- I S hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably CJQ and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2 ⁇ ] and
  • the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%>, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
  • the cationic bis-alkoxylated amine surfactant preferably has the general formula II:
  • R* is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about
  • R ⁇ is an alkyl group containing from one to three carbon atoms, preferably methyl; R ⁇ and R ⁇ can vary independently and are selected from hydrogen
  • methyl and ethyl X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -
  • CH2CH2O- propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • Rl is CjQ-Cig hydrocarbyl and mixtures thereof, preferably C ⁇ Q, C ⁇ 2 > Cl4 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • Rl is CIQ- I S hydrocarbyl, preferably CjO' ⁇ alkyl, independently p is 1 to about 3 and q is 1 to about 3, R ⁇ is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • compositions are a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • a preferred feature of the composition is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic- peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • part of the precursor compound or all of the precursor compound is comprised in the particle described herein, comprising the polyalkoxylated fatty acid amide surfactant.
  • compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20%) by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to
  • R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or
  • R , and Y is H or a solubilizing group. Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO., M , -CO 2 M , -SO . M , -N (R ) ,X and
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl Percarboxylic Acid Bleach Precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
  • TAED Tetraacetyl ethylene diamine
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • amide substituted alkyl peroxyacid precursor compounds are amide substituted alkyl peroxyacid precursor compounds. It is believed that the polyalkoxylated fatty acid amide surfactant interacts with the amide precursor in such a manner that the precursor is dissolved or dispensed more sufficiently.
  • Suitable amide substituted alkyl peroxyacid precursors herein including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • this class of agents include the precursors or the acids such as (6-hexylamino)-6-oxo-caproic acid(6-octylamino)-6-oxo-caproic acid, (6- nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the salt of metachloro perbenzoic acid, 4- nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid, or precursors thereof, in particularly having a benzene sulphonate leaving group.
  • Such bleaching agents are disclosed in U.S. 4,483,781, U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 and EP 0,170,386
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a " perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methyl ene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1%> to 15% by weight, more preferably from 1%> to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R s an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group contaimng from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
  • the composition can contain a transition metal containing bleach catalyst.
  • compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1%> to 80%) by weight, preferably from 10%> to 60% by weight, most preferably from 15% to 40%) by weight of the composition.
  • the detergent compositions of the invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60% > , more preferably from 5% to 50%), more preferably from 8% to 40.
  • the phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • the most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
  • Zeolite X has the formula Nagg
  • Another preferred builder can be an crystalline layered silicate material, preferably of the formula Na 2 Si 2 O 5 , preferably as sold by Clariant under the trade name SKS-
  • the crystalline layered silicate material is present at a level of from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
  • compositions preferably contain as an optional component a heavy metal ion sequestrant, which act to sequester (chelate) heavy metal ions.
  • a heavy metal ion sequestrant which act to sequester (chelate) heavy metal ions.
  • These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5%) to 5% by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • compositions may comprise one or more enzymes.
  • Preferred additional enzymatic materials include the commercially available enzymes.
  • Said enzymes include enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, puUulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
  • a preferred combination of additional enzymes in a composition according to the present invention comprises a mixture of conventional applicable enzymes such as lipase, protease, amylase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • Suitable enzymes are exemplified in US Patents 3,519,570 and 3,533,139.
  • Suitable proteases are the subtilisins which are obtained from particular strains of R. subtilis and B. licheniformis (subtilisin BPN and BPN').
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo".
  • proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
  • Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A” herein.
  • Protease C is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C.
  • protease from Bacillus sp. NCLMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • One or a mixture of proteolytic enzymes may be incorporated in the compositions of the present invention, generally at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
  • the lipolytic enzyme component is generally present at levels of from 0.00005% to 2% of active enzyme by weight of the detergent composition, preferably 0.001% to 1% by weight, most preferably from 0.0002%> to 0.05% by weight active enzyme in the detergent composition.
  • Suitable lipolytic enzymes for use in the present invention include those produced by micro-organisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable Upases include those which show a positive immunological cross-section with the antibody of the lipase produced by the microorganism Pseudomonas Hisorescent LAM 1057. This lipase is available from Amano Pharmaceutical Co.
  • Amano-P Lipase P
  • Other suitable commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • lipases such as Ml Lipase ⁇ - and Lipomax ⁇ - (Gist-Brocades) and
  • Lipolase ⁇ - and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use in the present invention.
  • Another preferred lipase for use in the present invention is D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa. Most preferably the Humicola lanuginosa strain DSM 4106 is used.
  • D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 in wUich the native lipase ex Humicola lanuginosa has the aspartic acid (D) residue at position 96 changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • D96L the standard LU assay may be used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07).
  • a substrate for D96L was prepared by emulsifying glycerine tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity is assayed at pH 7 using pH stat. method.
  • compositions may also contain one or a mixture of more than one amylase enzyme ( ⁇ and/or ⁇ ).
  • amylase enzyme ⁇ and/or ⁇
  • WO94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo).
  • amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
  • Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and
  • Termamyl®, Ban® ,Fungamyl® and Duramyl® all available from Novo Nordisk A/S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other preferred amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • amylolytic enzymes if present are generally incorporated in the compositions at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024%) to 0.048% pure enzyme by weight of the composition.
  • compositions of the invention may additionally incorporate one or more cellulase enzymes.
  • Suitable cellulases include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CENU (Cellulose Viscosity Unit).
  • CENU Cellulose Viscosity Unit
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
  • suitable cellulases are the EGUI cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.
  • Peroxidase enzymes may also be inco ⁇ orated into the compositions herein.
  • Peroxidasis are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo- peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
  • Preferred enhancers are substituted phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10- phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said cellulases and/or peroxidases are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Said additional enzymes when present, are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • the additional enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • organic polymeric compound any polymeric organic compound commonly used as dispersants, anti-redeposition or soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
  • Such an organic polymeric compound is generally incorporated in the compositions at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
  • Suitable polymers are disclosed in GB-A-1, 596,756.
  • Examples of such salts are polyacrylic acid or polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • Polymaleates or polymaleic acid polymers and salts thereof are also suitable examples.
  • Polyamino compounds useful herein include those derived from aspartic acid including polyaspartic acid and such as those disclosed in EP-A-305282, EP-A-305283 and EP-A- 351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, aspartic acid and vinyl alcohol or acetate, particularly those having an average molecular weight of from 1,000 to 30,000, preferably 3,000 to 10,000, are also suitable for inco ⁇ oration into the compositions of the present invention.
  • organic polymeric compounds suitable for inco ⁇ oration in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose.
  • Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000 to 10000, more particularly 2000 to 8000 and most preferably about 4000.
  • composition herein may comprise water-soluble cationic ethoxylated amine compounds with particulate soil/clay-soil removal and/or anti-redeposition properties.
  • cationic compounds are described in more detail in EP-B-111965, US 4659802 and US 4664848. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or triamines.
  • These compounds where present in the composition are generally present in an amount of from 0.01 to 30% by weight, preferably 0.05 to 10% by weight.
  • the cleaning composition require low-sudsing, and that thus inco ⁇ oration of suds suppressant for foam control are desirable. They are preferably present in amounts no greater than 2.5% and most preferably in amounts no greater than 1.5% or even no greater than 0.5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • compositions herein may also comprise from 0.01%> to 10 %, preferably from 0.05%> to 0.5%) by weight of additional polymeric compounds, not comprised in the photo- bleaching agnet of the compositions of the invention, which act as dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • compositions herein may optionally contain from about 0.005%) to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophihc optical brighteners useful herein include those having the structural formula:
  • Rj 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, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ 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-UNP A-GX by Ciba- Geigy Co ⁇ oration. Tinopal-UNP A-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R is N-2-hydroxyethyl-N-2-methylamino and
  • 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 Co ⁇ oration.
  • R ⁇ is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-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 Co ⁇ oration.
  • SRA polymeric soil release agents
  • compositions typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric or polymeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other SRA's include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093,
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • compositions of the invention include perfumes, colours and filler salts, including speckles, with sodium sulfate being a preferred filler salt.
  • the cleaning compositions are operative within a wide range of wash pHs (e.g. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pH, i.e. an initial pH of from about 7.0 to about 10.5 at a concentration of from about 0.1 to about 2% by weight in water at 20°C.
  • Near neutral wash pH formulations are better for enzyme stability and for preventing stains from setting.
  • the wash pH is preferably from about 7.0 to about 10.5, more preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.
  • Preferred near neutral wash pH detergent formulations are disclosed to European Patent Application 83.200688.6, filed May 16, 1983, J.H.M. Wertz and P.C.E. Goffinet.
  • Highly preferred cleaning compositions of this type also preferably contain from about 2 to about 10%) by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes and brighteners, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein inco ⁇ orated by reference).
  • compositions in accordance with the invention and the cleaning compositions herein can take a variety of physical forms including solid forms sucU as granular, tablet, flake, pastille and bar and liquid forms.
  • Liquids may be aqueous or non-aqueous and may be in tUe form of a gel, however, preferred are solid forms.
  • the cleaning compositions may be pre-treatment compositions or may be conventional washing detergents. It may be preferred that the cleaning compositions are particularly granular detergent compositions , preferably the so-called concentrated ,adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • Such granular detergent compositions or components thereof in accordance with the present invention can be made via a variety of methods, including spray-drying, dry- mixing, extrusion, agglomerating and granulation.
  • the bleaching compositions herein can be added to the other components of the cleaning compositions as a dry-add, mixed with the other component and agglomerated, extruded and/ or spray-dried.
  • the bleaching agent and the photo-bleaching agent may be premixed prior to addition to the other ingredients of the cleaning composition or the bleaching composition; the bleaching composition may also be pre-mixed with one or more of the additional ingredients of the cleaning composition, prior to further addition of the remaining ingredients.
  • compositions can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
  • the mean particle size of the components of granular compositions in accordance with the invention is such that no more than 15% of the particles are greater than 1.8mm in diameter and not more than 15% of the particles are less than 0.25mm in diameter.
  • the composition comprises particles of mean particle size at least 0.8 mm, more preferably at least 1.0 mm and most preferably from 1.0, or 1.5 to 2.5 mm. Most preferably at least 95% of the particles will have such a mean particle size.
  • Such particles are preferably prepared by an extrusion process.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • Compacted solid detergents may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Dosage is dependent upon the particular conditions such as water hardness and degree of soiling of the soiled laundry.
  • the detergent composition may be dispensed for example, from the drawer dispenser of a washing machine or may be sprinkled over the soiled laundry placed in the machine.
  • a dispensing device is employed in the washing method.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A- 0288345 and EP-A-0288346.
  • An article by J.Bland also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette”.
  • Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European publicationsUed Patent Application No. 0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • Nai2( l () 2Si ⁇ 2)i2-27H2 ⁇ having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • Citric acid Anhydrous citric acid
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Silicate Amo ⁇ hous sodium silicate (SiO2:Na2O 2.0:1)
  • Protease Proteolytic enzyme having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
  • Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
  • Amylase II Amylolytic enzyme as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0%> by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase
  • Lipolytic enzyme having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 Sodium perborate tetrahydrate of nominal formula
  • NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate
  • TAED Tetraacetylethylenediamine DTPA
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate
  • PEO Polyethylene oxide with an average molecular weight of TEPAE TetraetUylenepentaamine etUoxylate
  • PVI Polyvinyl imidosole with an average molecular weight of
  • PVP Polyvinylpyrolidone polymer witU an average molecular weight of 60,000
  • PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000
  • PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • Opacifier Water based monostyrene latex mixture, sold by BASF
  • Particle 1 agglomerate containing, by weight 20% EFAA 1, 20% C 245 AS, 30% zeolite A, 20% sodium carbonate and 10% citric acid (anhydrous)
  • Particle 2 agglomerate containing, by weight 20% EFAA 2, 40% LAS, 40% SKS-6 Example 1
  • TUe following formulations are examples of compositions in accordance witU tUe invention, wUicU may be in tUe form of granules or in tUe form of a tablet.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne une composition de détergent, qui nettoie avec d'excellents résultats et dont la dispersion ou la dissolution est améliorée. Cette composition comprend une particule contenant un amide d'acide gras alcoxylé non ionique de formule (I). Dans cette formule R1 représente un alkyle en C12-C18 ou un groupe alkényle, R2 représente un groupe alkylène en C2-C4, R3 représente un hydrogène ou un groupe alkyle en C1-C4, R4 représente un groupe alkyle en C1-C4 ou un hydrogène et n est un nombre allant de 3 à 12. Cette composition comprend aussi un tensioactif anionique sous réserve que le niveau de tensioactif alcoolique alcoxylé non ionique s'il est présent, soit compris entre 0 % et 20 % en poids de la particule. Ce tensioactif non ionique et cet amide d'acide gras alcoxylé non ionique peuvent être mélangés intimement ou ledit amide d'acide gras alcoxylé non ionique est projeté sur un noyau de particule contenant le tensioactif anionique.
PCT/US1999/029552 1998-12-24 1999-12-13 Compositions de nettoyage WO2000039274A1 (fr)

Priority Applications (1)

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AU21789/00A AU2178900A (en) 1998-12-24 1999-12-13 Cleaning compositions

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GB9828482A GB2345065A (en) 1998-12-24 1998-12-24 Cleaning compositions

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006020789A1 (fr) * 2004-08-11 2006-02-23 The Procter & Gamble Company Composition detergente solide pour blanchisserie, hautement hydrosoluble, formant une liqueur de lavage limpide par dissolution dans l'eau
WO2018077649A1 (fr) * 2016-10-26 2018-05-03 Basf Se Compositions détergentes sans phosphate et leurs applications

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0714569D0 (en) * 2007-07-26 2007-09-05 Innospec Ltd Composition
CN106367215A (zh) * 2016-08-19 2017-02-01 广东泰强化工实业有限公司 一种气雾多功能清洗剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4194986A (en) * 1977-02-02 1980-03-25 Union Generale De Savonnerie Powdered or flaked washing compositions adapted to automatic laundry machines
EP0264615A1 (fr) * 1986-09-22 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Agent de lavage ayant une teneur réduite en phosphate contenant d'acide gras d'amides-N alcoxylé
WO1995007333A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Particules detergentes contenant des tensioactifs anioniques et des amides d'acides gras n-alkoxy ou n-aryloxy
WO1998046714A1 (fr) * 1997-04-14 1998-10-22 The Procter & Gamble Company Particule detergente

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2236538A (en) * 1989-10-06 1991-04-10 Unilever Plc Detergent compositions
GB2315768A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4194986A (en) * 1977-02-02 1980-03-25 Union Generale De Savonnerie Powdered or flaked washing compositions adapted to automatic laundry machines
EP0264615A1 (fr) * 1986-09-22 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Agent de lavage ayant une teneur réduite en phosphate contenant d'acide gras d'amides-N alcoxylé
WO1995007333A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Particules detergentes contenant des tensioactifs anioniques et des amides d'acides gras n-alkoxy ou n-aryloxy
WO1998046714A1 (fr) * 1997-04-14 1998-10-22 The Procter & Gamble Company Particule detergente

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006020789A1 (fr) * 2004-08-11 2006-02-23 The Procter & Gamble Company Composition detergente solide pour blanchisserie, hautement hydrosoluble, formant une liqueur de lavage limpide par dissolution dans l'eau
US7605116B2 (en) 2004-08-11 2009-10-20 The Procter & Gamble Company Highly water-soluble solid laundry detergent composition that forms a clear wash liquor upon dissolution in water
WO2018077649A1 (fr) * 2016-10-26 2018-05-03 Basf Se Compositions détergentes sans phosphate et leurs applications

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GB2345065A (en) 2000-06-28
GB9828482D0 (en) 1999-02-17

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