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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
• • 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
  • C11D17/065—High-density particulate detergent compositions

Definitions

• the invention relates to the use of a specific detergent component in detergent compositions for improvement ofthe dispensing ofthe product or components thereof.
• agglomerates of crystalline layered silicate comprising high levels of water are disclosed in WO92/07932 (Procter & Gamble), which however describes aluminosilicates to be more preferred huilder ingredients than crystalline layered silicates.
• EP425804 discloses particles comprising high levels of aluminosilicate, surfactant and crystalline layered silicates. These agglomerates known in the art are often exactly those ingredients which are found to cause dispensing problems in detergents.
• Another problem associated with detergent products is that certain ingredients are not water-soluble and have a tendency to deposit on fabrics or in the washing machine, forming undesirable residues.
• the inventors have now found that when the surfactants are intimately mixed with a specific amount of crystalline layered silicate builder material, preferably by agglomeration, prior to addition to the detergent formulation, these problems are ameliorated. It has been found that the levels of crystalline layered silicate and surfactant which are intimately mixed are essential for ameliorating these problems, for example intimate mixtures comprising more than about 60% surfactant do not dispense satisfactory.
• the invention provides a method for improving the dispensing of a detergent composition or component thereof, comprising a surfactant and other detergent components, by providing a detergent composition comprising an intimate mixture of the surfactant component and a crystalline layered silicate.
• the invention also relates to the use ofthe intimate mixture obtainable by intimately mixing a surfactant and a crystallise layered silicate in a detergent composition, comprising a surfactant and other detergent components, for improving the dispensing ofthe detergent component.
• the intimate mixture preferably comprises less than 10%) or even less than 5% or even less than 3% by weight of free moisture.
• the surfactant preferably comprises an anionic surfactant, in particular a sulphonate surfactant.
• the detergent composition is preferably a solid dish washing detergent composition or laundry detergent composition.
• an improvement ofthe dispensing of a detergent composition is achieved.
• the dispensing ofthe detergent composition or component thereof in the wash water including from a dispensing drawer of a washing machine or a dispensing device, is improved compared to detergent compositions which comprise the anionic surfactant not intimately mixed with a crystalline layered silicate.
• the improvement in the dispensing may also include an improvement ofthe dissolution of a detergent composition or component thereof in the washing water, including the washing water in the dispensing drawer and the washing water in the interior ofthe washing machine, compared to detergent compositions which comprise the anionic surfactant not intimately mixed with an crystalline layered silicate.
• the improvement ofthe dispensing ofthe detergent composition or component thereof may also include a reduction of deposition of residues ofthe detergent composition or components thereof on fabrics in the wash or on the washing machine, compared to detergent compositions which comprise the anionic surfactant not intimately mixed with an crystalline layered silicate.
• the improvement ofthe dispensing ofthe detergent composition or component thereof may also include a reduction ofthe gelling ofthe detergent composition or component upon contact with water, in particularly at the beginning ofthe washing process, in particular the initial contact with water ofthe detergent composition in a dispensing drawer of a washing machine or in the interior ofthe washing machine, compositions which comprise the anionic surfactant not intimately mixed with an crystalline layered silicate.
• the intimate mixture When used herein, 'intimate mixture' means for the purpose ofthe invention that components ofthe mixture are substantially homogeneously distributed in the mixture, preferably being in the form of a particle. Intimately mixing or mixed should be interpreted accordingly.
• the intimate mixture can be obtained by any process involving the mixing ofthe components, which can be part of a tableting process, extrusion process and granulation, including spray-drying and agglomeration processes.
• the intimately mixing step is preferably done by agglomerating the surfactant and the crystalline layered silicate. This may be done by any conventional agglomeration process.
• the intimate mixture preferably comprises the crystalline layered silicate material at a level of from 90%> to 35%>, more preferably from 80%> to 40%, or even from 70% to 45% or even 50% by weight ofthe mixture.
• the weight ratio ofthe crystalline layered silicate to the surfactant in the intimate mixture is from 4:5 to 7:3, more preferably from 1 :1 to 2:1, most preferably from 5:4 to 3:2.
• the intimate mixture comprises the surfactant at a level of from 10% to 55% or more preferably from 20% to 55%, or even 30% to 45% by weight ofthe mixture.
• the intimate mixture in particular the agglomerated particle, comprises less than 10% or even less than 5% or most preferably less than 3% by weight ofthe intimate mixture of free moisture.
• the free moisture content as used herein, can be determined by placing 5 grams ofthe intimate mixture 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 intimate mixture may also comprise additional ingredients, for example in amounts of from 0% to 25%, generally up to 20% or even 15% by weight ofthe intimate mixture.
• additional ingredients for example in amounts of from 0% to 25%, generally up to 20% or even 15% by weight ofthe intimate mixture.
• the precise nature of these additional ingredients, and levels of incorporation thereof will depend on the application ofthe component or compositions and the physical form ofthe components and the compositions.
• the intimate mixture preferably comprises less than 15% or even less than 10% or even 5% or even 0% by weight ofthe mixture of aluminosilicates. If the intimate mixture is in the form of an agglomerate, any aluminosilictaes present is preferably in the form of dusted unto the agglomerate.
• the intimate mixture preferably comprises less than 15%, or even less than 10% or even less than 5% or even 0% of nonionic surfactants.
• the intimate mixture comprises polymeric binder material. Hereby, it is preferred to use as little binder material as possible. It may be preferred that the intimate mixture comprises less than 25%, preferably less than 10%, more preferably less than 5% by weight, most preferably 0% by weight of ethylene oxide polymers.
• the intimate mixture herein is mixed with the other components ofthe detergent composition.
• the intimate mixture may thus be present in the form of a separate particle, or the intimate mixture may be agglomerated with other ingredients or may be sprayed or dusted with other ingredients.
• the particle When in the form of a separate particle, the particle preferably has a weight average particle size by weight similar to the weight average particle size ofthe other components ofthe detergent composition.
• the particle preferably has a weight average particle size of from 150 microns to 1500 microns, or more preferably 80% by weight ofthe particles has a particle size of more than 300 microns (80% by weight on Tyler sieve mesh 48) and less than 10% by weight ofthe particles has a particle size of more than 1180 microns or even 710 microns (on Tyler mesh sieve24).
• the density of intimate mixture when present in a separate particle, is from 380g/litre to 1500gr/litre, or more preferably from 500 g/litre to 1200 g/litre, more preferably from 550 g/litre to 900g/litre.
• compositions ofthe invention contain one or more surfactants, whereof at least a part is intimately mixed with the crystalline layered silicate material.
• the surfactant may comprise any surfactant known in the art, selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. It should be understood that for the purpose ofthe invention the detergent composition may comprise surfactant which is not present in the intimate mixture with the crystalline layered silicate, but present in the other detergent components.
• the surfactant in the intimate is an anionic surfactant, preferably an anionic sulphonate surfactant, preferably an alkyl sulphonate surfactant, as described herein. More preferably, the anionic surfactant is from 50% to 100% or even from 60% to 100% or even from 75% to 100% by weight ofthe surfactant in the intimate mixture.
• the intimate mixture comprises as surfactant, only anionic surfactant or even only anionic sulphonate surfactant.
• nonionic surfactants when present, the level thereof is up to 15% by weight ofthe mixture, or even less than 10% or even 5% by weight, or it may be preferred that no nonionic surfactant is present.
• compositions and the intimate mixtures in accord with the present invention preferably comprise an anionic surfactant.
• anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) ofthe anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
• Anionic sulfate and sulfonate surfactants are preferred.
• surfactants systems comprising a sulfonate, preferably a linear or branched alkyl benzene sulfonate, as described herein, preferably combined with a cationic surfactants as described herein.
• 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, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
• 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 sulphonate surfactants are anionic sulphonate surfactants.
• Particularly suitable for use herein include the salts of C5-C20 linear or branched alkylbenzene sulphonates, but also may be used alkyl ester sulphonates, Cg-C22 primary or secondary alkane sulphonates, C ⁇ -C24 olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, and any mixtures thereof. Most preferred are C 9 -C 14 linear alkyl benzene sulphonates.
• 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 j -C4 alkyl) and -N-(Cj-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 Q-C 18 alkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ 5 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 C1 1 -C ⁇ g, most preferably Cj ⁇ -C ⁇ 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 ofthe invention employs mixtures ofthe preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
• 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-(CHR ⁇ -CHR2-O)-R3 wherein R is a Cg to Ci 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 ofthe water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-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.
• Suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
• RI CH2 COOM wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R! is a C1-C4 alkyl group and M is an alkali metal ion.
• Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
• R, Rl, and R ⁇ are each independently selected from hydrogen and C1-C3 alkyl (preferably methyl), provided R, Rl, and R ⁇ are not all hydrogen and, when z is 0, at least R or Rl is not hydrogen;
• w is an integer from 0 to 13;
• x is an integer from 0 to 13;
• y is an integer from 0 to 13;
• z is an integer from 0 to 13; and
• w + ⁇ + y + z is from 7 to 13.
• mid-chain branched surfactant compounds ofthe surfactant system certain points of branching (e.g., the location along the chain ofthe R, Rl, and/or R ⁇ moieties in the above formula) are preferred over other points of branching along the backbone ofthe surfactant.
• the formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A* 5 moieties useful according to the present invention.
• mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants. It should be understood that for the purpose ofthe invention, it may be preferred that the surfactant system comprises a mixture of two or more mid-chain branched primary alkyl sulfate or sulphonate surfactants.
• Preferred mid-chain branched primary alkyl_sulfate surfactants are ofthe formula
• These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms.
• the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5.
• the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.
• R, Rl, and R ⁇ are each independently selected from hydrogen and C1-C3 alkyl group (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R ⁇ , and R ⁇ are not all hydrogen. Further, when z is 1, at least R or R ⁇ is not hydrogen.
• M is hydrogen or a salt forming cation depending upon the method of synthesis.
• salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula
• R3 R6— -R4 R5 wherein R ⁇ , R4, R5 an d R6 ⁇ g independently hydrogen, C1-C22 alkylene, C4-C22 branched alkylene, Cj-Cg alkanol, C1 -C22 alkenylene, C4-C22 branched alkenylene, and mixtures thereof.
• Preferred cations are ammonium (R ⁇ , R4, R5 and
• R6 equal hydrogen
• the monoalkanol ammonium compounds ofthe present invention have R3 equal to C ⁇ -Cg alkanol, R4, R5 and R ⁇ equal to hydrogen
• dialkanol ammonium compounds ofthe present invention have R ⁇ and R ⁇ equal to Cj-Cg alkanol, R ⁇ and R ⁇ equal to hydrogen
• trialkanol ammonium compounds ofthe present invention have R ⁇ , R ⁇ and R ⁇ equal to Cj-Cg alkanol, R ⁇ equal to hydrogen.
• Preferred alkanol ammonium salts ofthe present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas: H3N + CH 2 CH 2 OH, H2N + (CH 2 CH 2 OH)2, HN + (CH 2 CH 2 OH)3 .
• Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium.
• a preferred mid-chain branched primary alkyl sulfate surfactant is, a C 16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and having 1, 2, or 3 branching units (i.e., R, R and/or R ⁇ ) of in total 3 carbon atoms, (whereby thus the total number of carbon atoms is at least 16).
• Preferred branching units can be one propyl branching unit or three methyl branching units.
• Another preferred surfactant system ofthe present invention have one or more branched primary alkyl sulfates having the formula
• the surfactant system comprises at least 20% by weight ofthe system, more preferably at least 60% by weight , even more preferably at least 90% by weight ofthe system, of a mid chain branched primary alkyl sulfates, preferably having Rl and R ⁇ independently hydrogen or methyl, provided Rl and R ⁇ are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 15 to 17, more preferably from 16-17.
• preferred surfactant systems are those, which comprise at least about 20%), more preferably at least 60%>, even more preferably at least 905 by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula:
• Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5- methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11 -methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5 -methyl hexadecanol sulfate, 6-methyl hexa
• Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2,5- methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2, 8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2, 10-methyl tetradecanol sulfate, 2,11 -methyl tetradecanol sulfate, 2, 12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl penta
• M is preferably sodium.
• branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
• 2,10-dimethylpentadecylsulfate having the formula wherein M is preferably sodium.
• any alkoxylated nonionic surfactants are suitable herein.
• the ethoxylated and propoxylated nonionic surfactants are preferred.
• Preferred alkoxylated surfactants can be selected from the classes ofthe 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 surfactant can be present in the detergent compositions. It may be preferred that the level of ethoxylated nonionic surfactants in the intimate mixture are below 10%) by weight ofthe mixture, preferably even 5%> by weight.
• 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 ofthe 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.
• Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONRlZ 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 ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-
• C31 hydrocarbyl preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Ci 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 preferably will be derived from a reducing sugar in a reductive animation reaction; more preferably Z is a glycityl.
• 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, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
• Suitable 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:
• R2 ⁇ (C n H 2n O)t(glycosyl) x
• R2 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
• 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 CIQ-CJ S alkyl dimethylamine oxide, and CI Q-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 C6-C] 8 hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2 is a C1 -C5 hydrocarbyl group.
• Preferred betaines are C ⁇ . ⁇ dimethyl-ammonio hexanoate and the C ⁇ o_ ⁇ acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
• Complex betaine surfactants are also suitable for use herein.
• Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants.
• the quaternary ammonium surfactant is a mono Cg-Cjg, preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining
• 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.
• ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
• the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
• spacer groups having, for example, -O-O- (i.e.
• spacer groups having, for example - CH2-O- CH2- and -CH2-NH-CH2- linkages are included.
• the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
• cationic mono-alkoxylated amine surfactant preferably of the general formula I:
• Rl 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
• 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 4 groups are — CH 2 CH 2 OH, — CH2CH 2 CH 2 OH, — CH CH(CH 3 )OH and— CH(CH 3 )CH 2 OH, with — CH 2 CH 2 OH being particularly preferred.
• Preferred Rl groups are linear alkyl groups. Linear Rl groups having from 8 to 14 carbon atoms are preferred.
• Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are ofthe formula
• Rl is C ⁇ Q-CI S hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably CJ Q and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
• compounds ofthe foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3 ⁇ ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
• EO ethoxy
• i-Pr isopropoxy units
• Pr n-propoxy units
• the levels ofthe cationic mono-alkoxylated amine surfactants used in detergent compositions ofthe 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 ofthe composition.
• the cationic bis-alkoxylated amine surfactant preferably has the general formula II:
• Rl 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 14 carbon atoms;
• R2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
• R ⁇ and R can vary independently and are selected from hydrogen (preferred), 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 CI Q-CJ S hydrocarbyl and mixtures thereof, preferably CI Q, C12, C14 alkyl and mixtures thereof.
• X is any convenient anion to provide charge balance, preferably chloride.
• Rl is derived from (coconut) Cl2"Cl4 alkyl fraction fatty acids, R2 is methyl and ApR ⁇ and A'qR 4 are each monoethoxy.
• Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
• Rl is Ci Q-CI 8 hydrocarbyl, preferably CJ Q-C H alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C ⁇ -C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
• the preferred crystalline layered silicate herein have the general formula
• 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 has a value of 2, 3 or 4 and is preferably 2.
• M is preferably H, K orNa or mixtures thereof, preferably Na.
• the most preferred material is -Na2Si2 ⁇ 5 j ⁇ .
• the crystalline layered silicate material, in particular ofthe formula Na2Si2 ⁇ 5 may optionally comprise other elements such as B, P, S, for example obtained by processes as described in EP 578986-B.
• the crystalline layered silicate is a coarse material having an weight average particle size above 150 microns, as measurable by sieving on Tyler sieves, or fine material of weight average particle size below 20 microns, Malvern Instruments SB.OC light scattering equipment.
• At least 95%> or even 98% or even 100% by weight ofthe crystalline layered silicate has a particle size of less than 102 microns or more preferably less than 88.2 microns or even less than 65.6 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns or even from 17.3 to 42.1 microns, as measured with a Malvern Instruments SB.OC light scattering equipment.
• the weight average particle when the weight average particle is from 16.0 to 48.8 microns, at least 90%by weight ofthe particle has a particle size of from 17.3 to 88.2 and when the weight average particle is from 17.3 to 42.1 microns, at least 90% by weight ofthe particle has a particle size of from 23.3 to 76.0, as measured with a Malvern Instruments SB.OC light scattering equipment, according to the Malvern Instruments users manual.
• the crystalline layered silicate is ground material, preferably obtained by grinding in an air jet mill or ceramic ball mill coarse crystalline layered silicate material.
• compositions in accord with the invention and also the intimate mixture herein may contain additional detergent components.
• additional detergent components The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or the intimate mixture, and the precise nature ofthe washing operation for which it is to be used.
• compositions ofthe invention preferably contain one or more additional detergent components selected from bleaches, bleach catalysts, alkalinity systems, additional builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
• additional detergent components selected from bleaches, bleach catalysts, alkalinity systems, additional builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
• a preferred additional components ofthe compositions or intimate mixtures herein is 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 2Na2C ⁇ 3-3H2 ⁇ 2, 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 ofthe composition or intimate mixtures herein is an organic peroxyacid bleaching system.
• the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
• the production ofthe 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, such as the perborate bleach ofthe claimed invention.
• 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.
• 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 ofthe 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 ofthe 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 14 carbon atoms
• R 3 is an alkyl chain containing from 1 to 8 carbon atoms
• R 4 is H or R 3
• Y is H or a solubilizing group.
• Any of R 1 , R3 and R 4 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 3 " M + , -CO 2 " M + , -SO 4 " M + , -N + (R 3 ) 4 X "
• M is an alkyl chain containing from 1 to 4 carbon atoms
• M is a cation which provides solubility to the bleach activator
• X is an anion which provides solubility to the bleach activator.
• 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 form percarboxylic acids on perhydrolysis.
• Preferred precursors of this type provide peracetic acid on perhydrolysis.
• Preferred alkyl percarboxylic precursor compounds ofthe imide type include the N-
• TAED Tetraacetyl ethylene diamine
• the TAED is preferably not present in the agglomerated particle ofthe 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.
• iso-NOBS sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate
• NOBS nonanoyloxybenzene sulfonate
• ABS sodium acetoxybenzene sulfonate
• pentaacetyl glucose pentaacetyl glucose
• Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those ofthe 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.
• Amide substituted bleach activator compounds of this 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 the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those ofthe 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 ofthe ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
• Preferred cationic peroxyacid precursors ofthe N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
• precursor compounds ofthe benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
• R 1 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 ofthe composition.
• a preferred class of organic peroxyacid compounds are the amide substituted compounds ofthe following general formulae:
• Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
• R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
• R5 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.
• Other organic peroxyacids include 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.
• One suitable type of bleach catalyst is a catalyst system comprising a transition 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(methylenephosphonic acid) and water-soluble salts thereof.
• a transition 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
• a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
• bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnI ⁇ 2( u "C)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)2, MnH ⁇ u- O) i (u-O Ac)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(ClO4)2, MnI V 4(u- O)6(l,4,7-triazacyclononane)4-(ClO4)2, MnIIlMnI V 4(u-O)i(u-OAc)2-(l,4,7- trimethyl-l,4,7-triazacyclononane)2-(Cl ⁇ 4)3, and mixtures thereof.
• ligands suitable for use herein include 1 ,5,9-trimethyl-l ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7-triazacyclononane, and mixtures thereof.
• the bleach catalysts useful herein may also be selected as appropriate for the present invention.
• suitable 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 is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
• Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
• U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
• Said ligands are ofthe formula:
• Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
• said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
• substituents such as alkyl, aryl, alkoxy, halide, and nitro.
• Particularly preferred is the ligand 2,2'-bispyridylamine.
• Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes.
• Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2Cl ⁇ 4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
• binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands include [Bipy2MnIH(u-
• bleach catalysts are described, for example, in European patent application, publication 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. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)
• the bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein.
• catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal ofthe stain or stains of interest from the target substrate.
• the test conditions will vary, depending on the type of washing appliance used and the habits ofthe user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance ofthe bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted.
• compositions and processes herein can be adjusted to provide on the order of at least one part per ten million ofthe active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor.
• the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3- 5 fold may be required under U.S. conditions to achieve the same results.
• compositions or the intimate mixtures herein may 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 ofthe composition.
• the detergent compositions ofthe invention may comprise phosphate-containing builder material, preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate, present at a level of from 0.5% to 60%), more preferably from 5% to 50%, more preferably from 8%> to 40. It may be preferred that the composiitons are free of phosphate-containing builder material.
• 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. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447.
• 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 ofthe 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 ofthe 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. It may be preferred that the polymeric or oligomeric polycarboxylates are present at levels of less than 5%, preferably less than 3%> or even less than 2% or even 0% by weight ofthe compositions.
• compositions or intimate mixtures herein may contain an insoluble builder compound, but preferably only present at a level of from 0% to 25% by weight, most preferably from 0% to 15% weight ofthe composition, or even 0% to 10% by weight ofthe 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 Na86 [(Al ⁇ 2)86(Si ⁇ 2)l06]- 276 H 2 O.
• Zeolite MAP is zeolite MAP builder.
• Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate ofthe zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
• zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
• the zeolite MAP detergent builder has a particle size, expressed as a d5 ⁇ value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
• the d50 value indicates that 50%> by weight ofthe particles have a diameter smaller than that figure.
• the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5 values are disclosed in EP 384070A.
• Heavy metal ion sequestrant are also useful additional ingredients herein.
• 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 10%, preferably from 0.1 %> to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight ofthe 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 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, 1,1 hydroxy ethane diphosphonic acid and 1,1 hydroxy ethane dimethylene phosphonic acid.
• Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
• Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl 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-carboxymethyl 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-l,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.
• diethylenetriamine pentacetic acid ethylenediamine- N,N'-disuccinic acid (EDDS) and 1,1 hydroxy ethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
• EDDS ethylenediamine- N,N'-disuccinic acid
• 1,1 hydroxy ethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
• Another preferred ingredient useful herein is one or more additional enzymes.
• Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, 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 the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those 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 ofthe 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 the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S.
• Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
• Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight ofthe 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 ofthe compositions.
• the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces 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 the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the 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 ofthe compositions herein or the intimate mixtures herein, where they may act such as to bind the intimate mixture components together.
• organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as binder, dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any ofthe high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quatemised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
• Organic polymeric compound is typically incorporated in the detergent compositions ofthe invention at a level of from 0.01% to 30%>, preferably from 0.1%> to 15%), most preferably from 0.5% to 10% by weight ofthe compositions.
• organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
• Polymers ofthe latter type are disclosed in GB-A-1, 596,756.
• Examples of such salts are 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.
• 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.
• Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
• organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
• Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
• Another organic compound which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
• X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
• a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
• Other dispersants/ anti-redeposition agents for use herein are described in EP-B- 011965 and US 4,659,802 and US 4,664,848.
• the detergent compositions ofthe invention when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%), preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight ofthe 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.
• 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 throughout the 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 the 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 the 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 Ci -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 ofthe 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
• an inert carrier fluid compound most preferably comprising a C ⁇ g-C ⁇ ethoxylated alcohol with a degree of ethoxylation 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.
• suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.
• 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, whereby these polymers can be cross-linked polymers.
• 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 the structural formula:
• R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxy ethyl;
• R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino; and 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-UNPA-GX by Ciba-Geigy Co ⁇ oration.
• Tinopal-CBS-X and 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- 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 are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
• SRA Polymeric soil release agents, hereinafter "SRA" can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01%) to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, ofthe compositions.
• Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
• Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
• esters may be made using additional monomers capable of being inco ⁇ orated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
• Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric 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.
• ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
• DMT dimethyl terephthalate
• PG ,2-propylene glycol
• SRA's include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
• Gosselink et al. for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
• SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
• Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; 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.
• 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.
• SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals ofthe polymer through an ester ofthe isolated carboxylic acid of trimellitic anhydride rather than by opening ofthe anhydride linkage.
• Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
• Other classes include: (III) anionic terephthalate- based SRA's ofthe urethane-linked variety, see U.S. 4,201,824, Violland et al.;
• compositions ofthe invention include perfumes, speckles, colours or dyes, filler salts, with sodium sulfate being a preferred filler salt.
• composition ofthe invention can be made via a variety of methods, including dry-mixing, agglomerating, compaction, or spray-drying ofthe various compounds comprised in the detergent component, or mixtures of these techniques.
• compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular or tablet forms.
• compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
• Detergent compositions herein in particular laundry detergents, preferably have a bulk density of from 280 g/litre to 200 g/litre, or preferably from 300 g/litre or even 350g/litre or 420g/litre to 2000g/litre or more preferably to 1500g/litre or 100 g/litre or even to 700g/litre.
• 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 ofthe 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.
• the composition may also be formulated such that it is suitable for hard-surface cleaning or hand washing or for pre-treatment or soaking of soiled and stained fabrics.
• Nai2(AlO2SiO2)i2- 7H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
• NaSKS-6 Crystalline layered silicate of formula ⁇ - Na2Si2 ⁇ 5 NaSKS-6 (II) Crystalline layered silicate of formula ⁇ - Na2Si2 ⁇ 5 0 f weight average particle size of 18 microns and at least 90% by weight of particle size of below 65.6 microns
• 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
• 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
• Lipase (1) 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
• DOBA Decanoyl oxybenzoic acid
• 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 50,000
• PVNO Poly vinylpyridine N-oxide polymer with an average molecular weight of 50,000
• SRP 1 Anionically end capped poly esters
• SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
• PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
• compositions in accordance with the invention which may be in the form of granules or in the form of a tablet.

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• 1998
  • 1998-07-08 GB GB9814687A patent/GB2339203A/en not_active Withdrawn
• 1999
  • 1999-07-08 CA CA002331359A patent/CA2331359C/fr not_active Expired - Fee Related
  • 1999-07-08 DE DE69923066T patent/DE69923066T2/de not_active Expired - Lifetime
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  • 1999-07-08 EP EP99933732A patent/EP1095129B1/fr not_active Expired - Lifetime
  • 1999-07-08 WO PCT/US1999/015310 patent/WO2000002993A1/fr active IP Right Grant
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