EP0915954A1 - Composition de detergence - Google Patents

Composition de detergence

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Publication number
EP0915954A1
EP0915954A1 EP97936179A EP97936179A EP0915954A1 EP 0915954 A1 EP0915954 A1 EP 0915954A1 EP 97936179 A EP97936179 A EP 97936179A EP 97936179 A EP97936179 A EP 97936179A EP 0915954 A1 EP0915954 A1 EP 0915954A1
Authority
EP
European Patent Office
Prior art keywords
acid
source
die
detergent composition
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97936179A
Other languages
German (de)
English (en)
Other versions
EP0915954A4 (fr
Inventor
Robin Gibson Hall
Christian Leo Marie Vermote
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0915954A1 publication Critical patent/EP0915954A1/fr
Publication of EP0915954A4 publication Critical patent/EP0915954A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof

Definitions

  • the present invention relates to a detergent composition which is suitable for use in laundry and dish washing methods.
  • the present invention also relates to a process for preparing these detergent powders.
  • phosphate builders which have generally been replaced with zeolite (crystalline aluminosilicate).
  • Detergents containing zeolite builders have been found to be poorer dispensers than detergents containing phosphate builders.
  • EP-A-0 578 871 describes a process which seeks to make a high bulk density detergent composition which dissolves rapidly and dispenses effectively.
  • the process involves formulating a base powder with a particle size distribution between 150 microns and 1700 microns in combination with additional filler ingredients whereby at least 20% by weight of the filler particles is less than 150 microns.
  • the filler particles include salts of citrate, sulphate, (bi-)carbonate and silicates.
  • WO95/14767 relates to the poor dispensing of high density, non-spray-dried detergent powders, and discloses the use of a citric acid salt which has a Rosin Rammler particle size of less than 800 microns.
  • WO94/28098 discloses a non-spray-dried detergent powder comprising a combination of an ethoxylated primary C8-18 alcohol, an alkali metal aluminosilicate builder and 5 to 40 wt% of a water-soluble salt of a citric acid.
  • EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a detergent. Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the percarbonate bleach.
  • EP-A-0 639 639 contains a similar disclosure in this respect.
  • effervescence to improve the dispersibility of granular materials has been used extensively in pharmaceutical preparations.
  • the use of this simple effervescent system has also been described for improving the dispersibility of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2, 184,946.
  • US-A-4,414,130 discloses the use of a readily disintegratable builder particle with a zeolite-based detergent. It also discloses the use of an effervescence material to improve the dissolving and dissolution of the particles.
  • Sodium carbonate or sodium bicarbonate may be combined with the zeolite binder mix and the balance of the detergent may include citric acid, monosodium phosphate, boric acid or other suitable acidifying material, preferably encapsulated or agglomerated with bicarbonate, for reaction with it to generate carbon dioxide.
  • WO92/18596 discloses that improved solubility/dispersion for granular detergents can be achieved by admixing sodium carbonate and citric acid in a specified weight ratio of from 2: 1 to 15:1.
  • EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of 350 to 1500 microns.
  • US-A-5,114,647 discloses a sanitizing composition in compressed form comprising an laklai metal carbonate, an aliphatic carboxylic acid and an alkali metal chloroisocyanurate to aid disintegration.
  • JP-A- 1024900 discloses a detergent comtaining a water-soluble carbonate powder and a solid acid powder in a bag made of a film of a water-soluble polymer.
  • EP-A-0 333 223 relates to a bathing preparation containing (a) fumaric acid, (b) a carbonate, (c) carboxymethyl cellulose, or an alkali metal slat thereof, and (d) not less than 0.02% by weight and less than 0.1% by weight, based on fumaric acid, of a nonionic surface active agent having an HLB of 7 or more.
  • citric acid results in a reduction in alkalinity.
  • Such an alkaline pH promotes cleaning, stain removal and soil suspension, there is therefore need to minimize the level of citric acid used.
  • citric acid is a relatively expensive ingredient which further reinforces the need to keep the level of citric acid very low.
  • the present invention allows low levels of the acid to be satisfactorily used in the detergent composition. More particularly, the present invention specifies more weight effective acids which provide dispensing benefits to detergents, particularly granular detergents.
  • a detergent composition comprising a detergent surfactant, a dicarboxylic acid source and an alkaline source wherein said dicarboxylic acid source and alkaline source are capable of reacting together to produce a gas; said dicarboxylic acid source has an effervescence optimum index (EOI) of ⁇ 4.00, where
  • MW molecular weight of the dicarboxylic acid of the acid source
  • hydrophobicity index ratio of the number of carbon atoms in the chemical formula of the dicarboxylic acid of the acid source : number of oxygen atoms in the chemical formula of the dicarboxylic acid of the acid source;
  • pKai is the logarithm of the reciprocal of the dissociation constant of one of the carboxylic acid groups;
  • pKa 2 is the logarithm of the reciprocal of the dissociation constant of the second carboxylic acid group; and
  • pKa's > 10.20 are not taken into consideration; and the mole ratio of the dicarboxylic acid source to the alkaline source is between 0.005
  • the detergent composition does not contain an alkali metal chloroisocyanurate.
  • organic acid materials which meet the defined criteria of the present invention provide improved dispensing.
  • the addition of the acid source in accordance with the crtieria of the present invention and an alkaline source to a detergent composition improves the solubility and/or dispersion of the detergent in the laundering solution and eliminates or reduces the problems of solid detergent particles remaining in the washing machine and on washed clothes. It is believed that the acid reacts rapidly with the alkali in the laundering solution to release the gas. This helps disperse the detergent and minimize the formation of insoluble clumps.
  • the present invention includes a granular detergent composition.
  • Such compositions comprise a base composition containing one or more surfactant, and preferably a builder material.
  • the base composition may be prepared by spray-drying and dry- mixing/agglomeration.
  • the base composition may also comprise the alkaline source.
  • the paniculate acid source and/or alkaline source may be added as separate components to the detergent base composition, preferably in a granular form.
  • ingredients of the present invention including optional ingredients, and processes for making the detergents, are described in detail below.
  • This ingredient is preferably present in an amount of from 1 %, preferably to 90%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight of the detergent composition.
  • the detergent is selected from anionics, nonionics, zwitterionics, ampholytics, amphoteric, cationics and mixtures thereof.
  • the surfactant is anionic, nonionic or a mixture thereof.
  • the additional surfactant is preferably present at a level of from 0.1 % to 50%, more preferably from 1 % to 40%, most preferably from 5% to 30% by weight of the total surfactant present.
  • ampholytic, amphoteric and zwitterionic surfactants are generally used in combiantion with one or more anionic and/or nonionic surfactants.
  • the surfactant system may include an anionic surfactant.
  • anionic surfactants useful for detersive purposes are suitable. 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 surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alk l succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C , ⁇ -C , g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C, 4 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.
  • Anionic sulfate surfactant 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 j - C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 1 o-C 1 g alkyl sulfates, more preferably the C 1 ⁇ -C ⁇ 5 branched chain alkyl sulfates and the C]2-Ci4 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cio-C is 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 11 -C 18, most preferably C j ⁇ -C j 5 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 alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C.5-C22 primary or secondary alkane sulfonates, C ⁇ -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 CH2C00"M + wherein R is a Cg to C ⁇ $ alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj -CHR2-O) x -R3 wherein R is a C6 to C ⁇ % alkyl group, x is from 1 to 25, Rj 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 d e 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- 1 -undecanoic acid, 2-ethyl- 1 -decanoic acid, 2-propyl- 1 - nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R* is a C- -C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R* is a C- -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.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • Nonionic alkoxylated alcohol surfactant can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • 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.
  • Particularly preferred 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.
  • Nonionic polvhvdroxy fatty acid amide surfactant Nonionic polvhvdroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C- 7 alkyl or alkenyl, most preferably straight-chain C ⁇ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R ⁇ CON(R ⁇ )2 wherein R*> is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R is selected from the group consisting of hydrogen, C1-C4 alkyl, C ⁇ - C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • alkylpolysaccharides for use herein are 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 2 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.
  • 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 N ⁇ (R5)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 C IO-CJ S alkyl dimethylamine oxide, and C J O-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 hereof. 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 C6-C18 hydrocarbyl group, each R* is typically C1-C3 alkyl, and R 2 is a C--C5 hydrocarbyl group.
  • Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the lO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-Cj6, preferably Cg-C ⁇ Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the surfactant system may include a cationic ester surfactant. That is. a preferably water dispersible compound having surfactant properties comprising at least one ester (ie - 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.
  • Preferred water dispersible cationic ester surfactants are the choline esters having the formula:
  • Rj is a C ⁇ ⁇ -C ⁇ g linear or branched alkyl chain.
  • the cationic ester surfactant is hydroly sable under the conditions of a laundry wash method.
  • the alkalinity system is present in the detergent composition such that it has the capacity to react with the source of acidity to produce a gas.
  • this g.as is carbon dioxide, and therefore the alkali is a carbonate, or a suitable derivative thereof.
  • the detergent composition of the present invention preferably contains from about 2% to about 75%, preferably from about 5% to about 60%, most preferably from about 10% to about 30% by weight of the alkali source.
  • the agglomerate preferably contains from about 10% to about 60% of the alkali source.
  • the alkalinity source is a carbonate.
  • preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine 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 alkalinity source may also include other components, such as a silicate.
  • Suitable silicates include d e water soluble sodium silicates with an Si ⁇ 2: Na2 ⁇ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred.
  • the silicates may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an Si ⁇ 2: Na2 ⁇ ratio of 2.0 is the most preferred silicate.
  • Alkali metal persilicates are also suitable sources of silicate herein.
  • Preferred crystalline layered silicates for use herein have the general formula NaMSi x O 2 ⁇ +l .yH 2 O
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is ⁇ -Na2Si2 ⁇ 5, available from Hoechst AG as NaSKS-6.
  • the dicarboxylic acid source is present in the detergent composition such that the it is capable of reacting with the source of alkali to produce a gas.
  • the dicarboxylic acid source an effervescence optimum index (EOI) of ⁇ 4.00, where
  • M W molecular weight of the dicarboxylic acid of the acid source
  • hydrophobicity index the ratio of the number of carbon atoms in the chemical formula of the dicarboxylic acid of die acid source : number of oxygen atoms in the chemical formula of the dicarboxylic acid of the acid source;
  • pKai is the logarithm of the reciprocal of the dissociation constant of one of the carboxylic acid groups;
  • pKa is the logarithm of the reciprocal of the dissociation constant of the second carboxylic acid group; and
  • pKa's > 10.20 are not taken into consideration.
  • the EOI is ⁇ 3.40, more preferably ⁇ 3.10, even more preferably ⁇ 2.80.
  • the EOI is ⁇ 2.40.
  • the acid source is fumaric acid, malic acid, maleic acid, tartaric acid, malonic acid, or a derivative thereof.
  • Tartaric acid or a derivative thereof is especially preferred.
  • Preferred derivatives include salts and esters.
  • the source of acidity is preferably present at a level of about to about 15% by weight of the composition. Preferably up to about 10%, more preferably up to about 7% by weight. As previously mentioned it is advantageous to use as little of the source of acidity as possible, we have found that the present invention allows the use of levels as low as about 0.25% to about 5%. In a preferred embodiment of the present invention the source of acidity is present in the range of about 1% to about 3%, most preferably about 3% by weight of the composition.
  • the mole ratio of the dicarboxylic acid source to the alkaline source is between 0.005 : 1 and 2.00 : 1. In a preferred embodiment the mole ratio is between 0.008 : 1 and 1 : 1. In a more preferred embodiment, the mole ratio is between 0.01 : 1 and 0.07 : 1.
  • the molecular weight of funaric acid is 116.1 and diat of sodium carbonate is 106.
  • the detergent compositions of the invention may also contain additional detergent components.
  • additional detergent components selected from additional surfactants, bleaches, builders, organic polymeric compounds, enzymes, suds suppressers, lime soap dispersants, soil suspension and anti- redeposition agents and corrosion inhibitors.
  • the detergent compositions of the present invention preferably contain a water-soluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include die 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, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include die water soluble salts of lactic acid, glycolic acid and edier derivatives thereof.
  • Polycarboxylates containing two carboxy groups include d e 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 d e sulfinyl carboxylates.
  • Polycarboxylates 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.
  • Polycarboxylates containing sulfo substituents include die 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 die 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 polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the detergent compositions of die present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of largely water insoluble builders include die 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; die 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. Synd etic 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 die formula Na 6 [(A!O 2 )86(SiO2)l06]- 276 H 2 O.
  • a preferred feature of detergent compositions of die invention is an organic peroxyacid bleaching system.
  • d e 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 die precursor widi a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of die compositions.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate .and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
  • Sodium perborate is a preferred perhydrate salt and can be in d e form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is .another inorganic perhydrate salt of use in the detergent compositions herein.
  • 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 d e 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 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 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 9 " M , -SO M , -N (R ) ⁇ X ⁇ and
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, mediylsulfate or acetate anion.
  • 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 die N- ,N,N ⁇ Nl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • Odier preferred 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 suitable herein, including diose of the following general formulae:
  • R 1 is an alkyl group widi from 1 to 14 carbon atoms
  • R 2 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.
  • Amide substituted bleach activator compounds of mis type are described in EP-A-0170386.
  • 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 die benzoylation products of sorbitol, glucose, and all saccharides widi benzoylating agents, and d ose of the imide type including N-benzoyl succinimide, tetrabenzoyl ediylene diamine and die 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 widi 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 die 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 diereof, 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 die ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of die N-acylated caprolactam class include me trialkyl ammonium methylene 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 organic peroxyacid bleaching system 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 die following general formulae:
  • R* is an alkyl, aryl or alkaryl group widi from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing 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 diis 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.
  • compositions optionally contain a transition metal containing bleach catalyst.
  • a transition metal containing bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(memylenephosphonic acid) and water-soluble salts thereof.
  • ethylenediaminetetraacetic acid ethylenediaminetetra(memylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include die manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(Cl ⁇ 4)2, Mn 1 4(u-O)6( 1 ,4,7- triazacyclononane)4-(Cl ⁇ 4)2, Mn IU Mn IV 4(u-O) ⁇ (u-OAc)2-( 1 ,4,7-trimethyl- 1 ,4,7- triazacyclononane)2-(Cl ⁇ 4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272.
  • ligands suitable for use herein include 1 ,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, l,2,4,7-tetramethyl-l,4,7-triazacyclononane, and mixtures thereof.
  • bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,1 14,606, is a water-soluble complex of manganese (III), and/or (IV) widi a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Odier examples include binuclear Mn complexed wid tetra-N-dentate and bi-N-dentate ligands, including N4Mn ⁇ (u-O)2Mn IV N4) + and [Bipy2Mn ⁇ (u-O)2Mn Iv bipy2]-(Cl ⁇ 4)3.
  • bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,71 1,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support widi manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,1 19,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866, 191
  • the detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components 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.
  • Preferred among d e above species are diediylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
  • Odier suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as emylenediaminotetracetic acid, ethylenetri.amine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyed ⁇ yl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymed yl N-2-hydroxypropyl-3- sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.
  • Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under die tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, d ose sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred .amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under die tradename Rapidase by Gist-Brocades, and iose sold under die tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance widi the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing su * ain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning d e gene from Humicola lanuginosa and expressing die gene in Aspergillus orvza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A S, Bagsvaerd, Denmark, under die trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where mey may act such as to bind die paniculate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
  • Organic polymeric compound is typically incorporated in die detergent compositions of die invention 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.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which die polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more man two carbon atoms.
  • Die polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more man two carbon atoms.
  • Examples of such salts are polyacrylates of MWt 2000-5000 and dieir copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid 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, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in die detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymeric compounds are d e polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of die 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 die foaming or sudsing produced by a solution of a detergent composition, particularly in die presence of agitation of mat solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general diroughout die industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include die monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include die alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 -C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
  • silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under d e tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a C 1 g-C 18 ed oxylated alcohol widi a degree of etiioxylation of from 5 to 50, preferably 8 to 15 , at a level of from 5% to 80%, preferably 10% to 70%, by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • the detergent compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric 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, polyvinylpyrrolidonepolymers or combinations thereof.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -0-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein d e nitrogen of die N- O group can be attached or wherein the nitrogen of die N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to die polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of die N-O group forms part of the R- group.
  • Preferred polyamine N-oxides are diose wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives diereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to die polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has die desired water- solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K- 15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having die structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyed ⁇ yl
  • R2 is selected from N-2-bis-hydroxyemyl, N-2-hydroxyed ⁇ yl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ is anilino
  • R2 is N-2-bis-hydroxyed ⁇ yl and M is a cation such as sodium
  • die brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyed ⁇ yl- N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • me brightener is 4,4 , -bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under die tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Cationic fabric softening agents can also be incorporated into compositions in accordance widi the present invention.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A- 1 514 276 and EP-B-0 01 1 340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
  • compositions of die invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions preferably have a pH measured as a 1 % solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0.
  • compositions in accordance widi d e invention can take a variety of physical forms including granular, tablet, bar and liquid forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum wi i the soiled fabric load.
  • the mean particle size of me base composition of granular compositions in accordance with the invention should preferably be such that no more tiiat 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • 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 Tyler sieves. The weight fractions tiiereby 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.
  • the bulk density of granular detergent compositions in accordance widi die present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided widi a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below d e funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled widi powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is tiien weighed and the value obtained for the weight of powder doubled to provide a bulk density in g litre. Replicate measurements are made as required.
  • the composition is preferably soluble in cold or cool water, i.e. the composition readily dissolves/disperses in water at a temperature between about 0°C and 32.2°C, preferably between about 1.6°C and 10°C.
  • the surfactant system herein is preferably present in granular compositions in the form of surfactant agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • the most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits.
  • Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 821 1 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).
  • a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 821 1 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstras
  • a high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is typically used.
  • the paste may be pumped into die agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • the detergent composition has a density of greater tiian about 600 g/1 and is in die form of powder or a granulate containing more man about 5% by weight of die alkali source, preferably (bicarbonate or percarbonate.
  • die alkali source preferably (bicarbonate or percarbonate.
  • the alkali material is either dry-added or delivered via agglomerates.
  • the addition of acid source(up to 10%) may be introduced into the product as a dry-add, or via a separate particle.
  • Machine laundry methods herein typically comprise treating soiled laundry widi an aqueous wash solution in a washing machine having dissolved or dispensed tiierein 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 40g 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.
  • a dispensing device is employed in the washing metiiod.
  • the dispensing device is charged widi the detergent product, and is used to introduce the product directly into the drum of die washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in die washing method.
  • the dispensing device containing die detergent product is placed inside the drum.
  • water is introduced into the drum and die drum periodically rotates.
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as die drum rotates and also as a result of its contact with the wash water.
  • die device may possess a number of openings through which the product may pass.
  • die device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product.
  • die detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of die washing machine at tiiis stage of the wash cycle.
  • 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 die composition of die 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 published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use widi granular laundry products which are of a type commonly know as the "granulette”.
  • Another preferred dispensing device for use widi the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
  • Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070.
  • the latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, die orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of die washing medium flows through the orifice into the bag, dissolves the product, and die solution then passes outwardly through d e orifice into the washing medium.
  • the support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, diis arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
  • 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 published Patent Application No. 0018678.
  • it may be formed of a water-insoluble syntiietic polymeric material provided wid an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 001 1502, and 001 1968.
  • 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.
  • any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates.
  • a preferred packaging execution is described in European Application No. 94921505.7.
  • An especially preferred container is a double bag.
  • Preferably any container is water-insoluble.
  • a Hotpoint automatic washing machine was employed, and a 2 minute 20°C cycle selected. 150 g of detergent dispensed via me dispenser drawer was used. The water flow rate into d e machine was set at 2.0 1/minute.
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Silicate Amorphous Sodium Silicate Si ⁇ 2:Na2 ⁇ ; 2.0 ratio
  • MA/AA Copolymer of 1 :4 maleic/acrylic acid average molecular weight about 70,000.
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • TAED Tetraacetylethylenediamine DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under die
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
  • C is a phosphorus-containing detergent composition
  • D is a zeolite-containing detergent composition
  • E is a compact detergent composition

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Cette composition de détergence comprend un tensioactif détergent une source d'acide dicarboxylique ainsi qu'une source alcaline, et elle est caractérisée en ce que la source d'acide dicarboxylique et la source alcaline peuvent réagir ensemble afin de produire un gaz. La source d'acide dicarboxylique présente un indice optimal d'effervescence (EOI) ≤ 4,00, cet indice répondant à la formule: EOI = (MW x HI) x (10,2-pKa1)-1 x (10,2-pKa¿2)?-1, dans laquelle MW représente la masse moléculaire de l'acide dicarboxylique de la source acide, HI représente l'indice d'hydrophobie, lequel correspond au rapport du nombre d'atomes de carbones de la formule chimique de l'acide dicarboxylique de la source acide sur le nombre d'atomes d'oxygène de la formule chimique de cet acide dicarboxylique, pKa¿1? représente le logarithme de la valeur inverse de la constante de dissociation de l'un des groupes de l'acide carboxylique, pKa2 représente le logarithme de la réciproque de la valeur inverse de dissociation du second groupe de l'acide carboxylique, les pKa ≥ à 10,20 n'étant pas pris en considération, et le rapport molaire source d'acide dicarboxylique/source alcaline se situe entre 0,005/1 et 2,00/1, à la condition que la composition de détergence ne contienne pas un chloro-isocyanurate de métal alcalin.
EP97936179A 1996-07-31 1997-07-23 Composition de detergence Withdrawn EP0915954A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9616112 1996-07-31
GB9616112A GB2315762A (en) 1996-07-31 1996-07-31 Detergent composition comprising a dicarboxylic acid source and an alkaline source
PCT/US1997/012896 WO1998004667A1 (fr) 1996-07-31 1997-07-23 Composition de detergence

Publications (2)

Publication Number Publication Date
EP0915954A1 true EP0915954A1 (fr) 1999-05-19
EP0915954A4 EP0915954A4 (fr) 2000-03-22

Family

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EP97936179A Withdrawn EP0915954A4 (fr) 1996-07-31 1997-07-23 Composition de detergence

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EP (1) EP0915954A4 (fr)
JP (1) JPH11514041A (fr)
AR (1) AR008116A1 (fr)
AU (1) AU3891397A (fr)
BR (1) BR9710638A (fr)
CA (1) CA2261944A1 (fr)
CZ (1) CZ29999A3 (fr)
GB (1) GB2315762A (fr)
HU (1) HUP9904366A3 (fr)
MA (1) MA24283A1 (fr)
NO (1) NO990410L (fr)
TR (1) TR199900175T2 (fr)
WO (1) WO1998004667A1 (fr)
ZA (1) ZA976672B (fr)

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Publication number Priority date Publication date Assignee Title
EP0872544A1 (fr) * 1997-04-14 1998-10-21 The Procter & Gamble Company Granules secs effervescents et les compositions granulaires les contenant
GB2355721A (en) * 1999-10-28 2001-05-02 Procter & Gamble Detergent compositions
GB2355722A (en) * 1999-10-28 2001-05-02 Procter & Gamble Detergent compositions and methods for cleaning
DE60120668T3 (de) * 2000-04-14 2010-05-20 Reckitt Benckiser N.V. Wasserenthärter in form eines brausepulvers
JP2010043210A (ja) * 2008-08-15 2010-02-25 Ai Media Kk 起泡性洗浄組成物
JP2013213184A (ja) * 2012-03-09 2013-10-17 Kao Corp 粉末洗浄剤組成物
JP2013213185A (ja) * 2012-03-09 2013-10-17 Kao Corp 粉末洗浄剤組成物

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FR1142255A (fr) * 1955-03-02 1957-09-16 Fettchemie Procédé pour la fabrication de produits de lavage pour linge fin et gros
US4252664A (en) * 1978-10-30 1981-02-24 Colgate-Palmolive Company Effervescent granules
CH659082A5 (en) * 1984-04-09 1986-12-31 Ciba Geigy Ag Detergent powder additives in the form of speckles
EP0752466A1 (fr) * 1995-07-05 1997-01-08 The Procter & Gamble Company Compositions détergentes non-aqueuses contenant un système effervescent

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US4180467A (en) * 1971-10-07 1979-12-25 Colgate-Palmolive Company Stable denture soak product
US3976601A (en) * 1974-06-24 1976-08-24 Johnson & Johnson Water soluble lubricant for tabletting compositions
US4115293A (en) * 1975-10-06 1978-09-19 E. I. Du Pont De Nemours And Company Denture cleanser
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AT358147B (de) * 1976-12-03 1980-08-25 Gergely Gerhard Reinigungsmaterial
GB2000177B (en) * 1977-06-27 1982-01-20 Akzo Nv Detergent compositions
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CA1231026A (fr) * 1984-01-17 1988-01-05 Yvon J. Nedonchelle Detergent liquide
US4619710A (en) * 1984-04-20 1986-10-28 Badger Pharmacal, Inc. Disposer cleaner
JPS6230198A (ja) * 1985-07-31 1987-02-09 ライオン株式会社 タブレツト洗剤
JPS6424900A (en) * 1987-07-21 1989-01-26 Sanki Shokuhin Kk Packed detergent
CA1329134C (fr) * 1988-03-17 1994-05-03 Yuji Ichii Preparation de bain
JPH02151696A (ja) * 1988-12-03 1990-06-11 Lion Corp 発泡型台所用粉体洗浄剤組成物
JPH04214884A (ja) * 1990-06-11 1992-08-05 Denka Seiyaku Kk 貴金属及び宝飾品の洗浄剤
JPH07278598A (ja) * 1994-04-05 1995-10-24 Pias Arise Kk トイレ用防臭洗浄剤

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Publication number Priority date Publication date Assignee Title
FR1142255A (fr) * 1955-03-02 1957-09-16 Fettchemie Procédé pour la fabrication de produits de lavage pour linge fin et gros
US4252664A (en) * 1978-10-30 1981-02-24 Colgate-Palmolive Company Effervescent granules
CH659082A5 (en) * 1984-04-09 1986-12-31 Ciba Geigy Ag Detergent powder additives in the form of speckles
EP0752466A1 (fr) * 1995-07-05 1997-01-08 The Procter & Gamble Company Compositions détergentes non-aqueuses contenant un système effervescent

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See also references of WO9804667A1 *

Also Published As

Publication number Publication date
EP0915954A4 (fr) 2000-03-22
BR9710638A (pt) 1999-08-17
JPH11514041A (ja) 1999-11-30
AU3891397A (en) 1998-02-20
CZ29999A3 (cs) 1999-07-14
NO990410D0 (no) 1999-01-28
HUP9904366A2 (hu) 2000-04-28
GB2315762A (en) 1998-02-11
GB9616112D0 (en) 1996-09-11
NO990410L (no) 1999-03-31
TR199900175T2 (xx) 1999-05-21
AR008116A1 (es) 1999-12-09
ZA976672B (en) 1998-02-11
WO1998004667A1 (fr) 1998-02-05
HUP9904366A3 (en) 2001-11-28
CA2261944A1 (fr) 1998-02-05
MA24283A1 (fr) 1998-04-01

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