WO1998011185A1 - Composition de detergent - Google Patents

Composition de detergent Download PDF

Info

Publication number
WO1998011185A1
WO1998011185A1 PCT/US1997/015977 US9715977W WO9811185A1 WO 1998011185 A1 WO1998011185 A1 WO 1998011185A1 US 9715977 W US9715977 W US 9715977W WO 9811185 A1 WO9811185 A1 WO 9811185A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
acid
preferred
automatic dishwashing
dishwashing detergent
Prior art date
Application number
PCT/US1997/015977
Other languages
English (en)
Inventor
Graeme Duncan Cruickshank
Lynda Anne Speed
Michael Mcdonnell
Original Assignee
The Procter & Gamble Company
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
Priority claimed from GB9716317A external-priority patent/GB2327948A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP97940976A priority Critical patent/EP0925341A1/fr
Priority to BR9712817-1A priority patent/BR9712817A/pt
Priority to AU42638/97A priority patent/AU4263897A/en
Priority to JP10513803A priority patent/JP2000502750A/ja
Priority to CA002264916A priority patent/CA2264916A1/fr
Publication of WO1998011185A1 publication Critical patent/WO1998011185A1/fr

Links

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
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising at least one high cloud point nonionic surfactant and an amount of water-soluble salt to provide conductivity in deionised water measured at 25°C of greater than 3 milli Siemens/cm.
  • Detergent compositions generally comprise at least one detergent surfactant.
  • Surfactants can be selected from anionic, nonionic, cationic, zwitterionic or amphoteric. Surfactants are known to provide two distinct functions defined by the cloud point of the particular surfactant. Above the cloud point of the surfactant, the surfactant tends to become increasingly insoluble and provides a suds suppression function, whereas below the cloud point, the surfactant tends to be soluble, providing a cleaning function. The majority of commonly available surfactants are generally used below their cloud points providing cleaning benefits but also produce suds. Since suds reduce the cleaning action of the automatic dishwasher use of these surfactants is undesirable in automatic dishwashers. Generally, surfactants selected for use in automatic dishwashing are low-sudsing nonionic surfactants.
  • Low-sudsing nonionic surfactants generally have low cloud points and are therefore generally above their cloud points, providing a suds suppression function, in use in the dishwasher.
  • surfactants above their cloud point generally provide only limited cleaning benefits, for example spot reduction benefits. Attempts at making use of higher cloud point nonionic surfactants that provide a cleaning function have typically failed due to the unacceptable sudsing of such surfactants.
  • the Applicant has found that a nonionic surfactant having a high cloud point can be incorporated into an automatic dishwashing detergent composition.
  • the cleaning performance of the high cloud point surfactant is further improved, especially on cleaning greasy soils (e.g., lipstick) when the conductivity of the wash water of the dishwasher is greater than 3 milli Siemens/cm (measured at 25°C).
  • the automatic dishwashing detergent composition additionally comprises a suds suppresser and/or more particularly a low cloud point nonionic surfactant.
  • an automatic dishwashing detergent composition comprising: a) one or more high cloud point nonionic surfactants having a cloud point of greater than 40°C; and b) an amount of water-soluble salt to provide conductivity in deionised water measured at 25°C of greater than 3 milli Siemens/cm.
  • High cloud point nonionic surfactants useful in the present invention are present at levels of from 0.1% to 15% of the composition. In general, bleach-stable surfactants are preferred.
  • the nonionic surfactant of the present invention has a high cloud point.
  • Cloud point is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the “cloud point” (See Kirk Othmer's Encyclopedia of Chemical Technology, 3 rd Ed. Vol.22 pp. 360-379,”Surfactants and Detersive Systems”).
  • high cloud point nonionic has a cloud point of greater than 40°C, preferably greater than 50°C, and more preferably greater than 60°C.
  • the nonionic surfactant comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • Suitable high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • the high cloud point nonionic surfactant additionally has a hydrophile-lipophile balance ("HLB"; see Kirk Othmer hereinbefore) value within the range of from 9 to 15, preferably 1 1 to 15.
  • HLB hydrophile-lipophile balance
  • Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • high cloud point nonionic surfactant is derived from a straight or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon atoms (Cg-C20 alcohol), including secondary alcohols and branched chain primary alcohols.
  • high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/C1 1 or Cl 1/C15 branched alcohol ethoxylates, condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of alcohol.
  • ethoxylated nonionic surfactants have a narrow ethoxylate distribution relative to the average.
  • Nonionic surfactants can optionally contain propylene oxide in an amount up to 15% by weight.
  • Other preferred nonionic surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference.
  • Suitable water-soluble salts include any known water-soluble salt commonly available and suitable for incorporation into an automatic dishwashing detergent composition. Preferred water-soluble salts dissolve in water, preferably at temperature less than
  • the water-soluble salt dissolves at ambient temperature.
  • the water-soluble salt is present in an amount such that when dissolved in deionised water it provides conductivity in deionised water measured at 25°C of greater than 3 milli Siemens/cm, preferably greater than 4 milli Siemens/cm, most preferably greater than 4.5 milli Siemens/cm.
  • Preferred water-soluble salts incorporated into the detergent composition of the present invention include those that readily dissociate in water.
  • Preferred salts include those which provide multi valent dissociated ions, for example the salts of sulphate, nitrate or perborate, however salts that provide dissociated ions with single valency (eg. chloride) may also be used.
  • Preferred salts are those which remain dissociated in water providing sustained conductivity, for example water soluble sulphate salts. However, salts that dissociate but then re-associate with the same and/or other ions to form the same and/or other salts, thus providing only transient conductivity, may also be used.
  • water-soluble salts are used such that a combination of a number of water- soluble salts provide conductivity greater than 3 milli Siemens/cm, preferably greater than 4 milli Siemens/cm, most preferably greater than 4.5 milli Siemens/cm.
  • conductivity was measured using a Jenway 4020 conductivity meter calibrated against a standard sample of known conductivity; for example a 0.01 M solution of potassium chloride provides conductivity of 1.413 milli Siemens/cm.
  • a solution comprising 4g of detergent composition in 1 litre of deionised water was prepared.
  • the solution was continuously stirred at a constant rate to aid dissolution of the detergent composition.
  • 60ml samples of the solution are removed at intervals and the conductivity measured using the Jenway 4020 conductivity meter.
  • a highly preferred water-soluble salt is a water-soluble sulphate salt.
  • the water-soluble sulphate salt is present at a level of from 0.1% to 40%, more preferably from 1% to 30%, most preferably from 5% to 25% by weight of the compositions.
  • the water-soluble sulphate salt may be essentially any sulphate salt with any suitable counter cation.
  • Preferred salts are selected from the sulphates of the alkali and alkaline earth metals, particularly sodium sulphate.
  • Another preferred water-soluble salt is a water-soluble silicate salt.
  • the water-soluble silicate salt is an alkali or alkaline earth metal silicate.
  • a preferred alkali metal silicate is sodium silicate having an Si ⁇ 2:Na2 ⁇ ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0.
  • Sodium silicate is preferably present at a level of less th.an 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight of Si ⁇ 2-
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • Alkali metal silicate whilst providing conductivity in the wash water will also provide alkalinity.
  • Alkalinity is also preferably provided by the presence of sodium metasilicate. Where present the sodium metasilicate is present at a level of at least 8/11185 7
  • Sodium metasilicate has a nominal Si ⁇ 2 : Na2 ⁇ ratio of 1.0.
  • the weight ratio of said sodium silicate to said sodium metasilicate, measured as Si ⁇ 2, is preferably from 50: 1 to 5:4, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.
  • water-soluble salts include salts of bleaching agents, for example the salts of oxygen-releasing or chloride bleaching agents.
  • Preferred water-soluble include those of perborate and chloride bleaching agents. These and other suitable bleaching agents are described in more detail hereafter.
  • Particularly preferred components of the detergent composition are compounds for . reducing or suppressing the formation of suds. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • suds suppressers are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppresser of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppresser 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.
  • the detergent compositions herein may also contain non-surfactant suds suppressers.
  • non-surfactant suds suppressers include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cj 8-C40 ketones (e.g., stearone), etc.
  • Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to 8/11185 8
  • 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, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, .and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than HO C (atmospheric pressure).
  • hydrocarbons preferably having a melting point below 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions.
  • Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic. aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (0-13)3 SiOj/2 units of S-O2 units in a ratio of from (CH3)3 SiOj/2 units and to Si ⁇ 2 units of from about 0.6:1 to about 1.2:1 ; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1 ,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1 ,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200PEG 300.
  • Preferred is a weight ratio of between about 1 :1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene glycol opolymer of polyethylene-polypropylene glycol.
  • the detergent composition additionally comprises a low cloud point nonionic surfactant sud suppressor.
  • a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30°C, preferably less than 20°C, and most preferably less than 10°C.
  • Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO EO/PO) reverse block polymers.
  • low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, described in WO 94/22800, published October 13, 1994 by Olin Corporation) and ether-capped poly(oxyalkylated) alcohol surfactants described in more detail later.
  • ethoxylated-propoxylated alcohol e.g., Olin Corporation's Poly-Tergent® SLF18
  • epoxy-capped poly(oxyalkylated) alcohols e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, described in WO 94/22800, published October 13, 1994 by Olin Corporation
  • ether-capped poly(oxyalkylated) alcohol surfactants described in more detail later.
  • Low cloud point nonionic surfactants may comprise a polyoxyethylene, polyoxypropylene block polymeric compound.
  • Block polyoxyethylene- polyoxypropylene polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane .and ethylenedieunine as initiator reactive hydrogen compound.
  • Certain of the block polymer surfactant compounds designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention.
  • Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants are typically useful herein as low cloud point nonionic surfactants.
  • the detergent composition of the present invention comprises a low cloud point as well as a high cloud point surfactant the surfactants are combined in a weight ratio preferably within the range of from 10:1 to 1 :10.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075, 1 18 and EP 150,872.
  • the secondary alcohols include the C -C ⁇ alkyl alcohols having a Cj-Cjg chain.
  • a preferred alcohol is 2- butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the tradem.ark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5: 1.
  • suds should not form to the extent that they either overflow the washing machine or negatively affect the washing mechanism of the dishwasher.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an .amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry or dishwashing detergents for use in automatic laundry or dishwashing machines.
  • compositions herein will generally comprise from 0% to 10% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to 5%, by weight, of the detergent composition.
  • from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any optional materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used.
  • the low cloud point nonionic surfactant suds suppressors are typically used at 0.1%-15% by weight of the finished compositions
  • the detergent composition described herein is prepared by conventional methods, in that particulate components are premixed in a suitable mixer and liquid components are applied to, preferably sprayed onto the premix to form the detergent composition.
  • Particulate components may be prepared by any known method for example spray drying granulation or agglomeration.
  • Suitable mixers may be batch or continuous mixers and include, but are not limited to pan, rotary drum and vertical blender types.
  • the detergent composition described herein may include a variety of different ingredients including builder compounds, additional surfactants, enzymes, bleaching agents, alkalinity sources, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • builder compounds additional surfactants, enzymes, bleaching agents, alkalinity sources, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • Highly preferred components of the detergent composition as described earlier include a builder compound, a surfactant, an enzyme and a bleaching agent.
  • the detergent compositions of the present invention preferably contain a 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.
  • the salt may also provide conductivity in the wash water.
  • builder compounds include salts of polycarboxylates, carbonates, bicarbonates, borates, phosphates.
  • 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, carbonates, bicarbonates, 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 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 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 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-pro ⁇ ane 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.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4, 5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5- tetr.ahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particul.arly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50°C, especially less than about 40°C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
  • Highly preferred builder compounds for use in the present invention are water- soluble phosphate builders.
  • 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 polymerisation ranges from about 6 to 21 , and salts of phytic acid.
  • 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.
  • compositions of the present invention may contain a partially soluble or insoluble builder compound.
  • Partially soluble and insoluble builder compounds are particularly suitable for use in detegent compositions prepared for use in laundry cleaning methods.
  • Examples of partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A-0164514, DE-A- 3417649 and DE-A-3742043. Preferred are the crystalline layered sodium silicates of general formula
  • Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so called ⁇ -layered structure, as described in EP 0 164514 and EP 0 293640. Methods for preparation of crystalline layered silicates of this type 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.
  • the most preferred crystalline layered sodium silicate compound has the formula ⁇ - Na2Si2 ⁇ 5 , known as NaSKS-6 (trade name), available from Hoechst AG.
  • the crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water- soluble ionisable material as described in PCT Patent Application No. WO92/18594.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.
  • aluminosilicates examples include the sodium aluminosilicates.
  • Suitable aluminosilicates include the aluminosilicate zeolites having 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. 98/11185 1 6
  • 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.
  • a preferred method of synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14(2), 1 10-116), in which the author describes a method of preparing colloidal aluminosilicate zeolites.
  • the colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles are of size greater than l ⁇ m in diameter and not more than 5% of particles are of size less then 0.05 ⁇ m in diameter.
  • the aluminosilicate zeolite particles have an average particle size diameter of between 0.01 ⁇ m and l ⁇ m, more preferably between 0.05 ⁇ m and 0.9 ⁇ m, most preferably between 0.1 ⁇ m and 0.6 ⁇ m.
  • Zeolite A has the formula
  • Zeolite X has the formula Nagg
  • Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
  • colloidal aluminosilicate zeolites especially colloidal zeolite A, provide enhanced builder performance in terms of providing improved stain removal.
  • Enhanced builder performance is also seen in terms of reduced fabric encrustation and improved fabric whiteness maintenance; problems believed to be associated with poorly built detergent compositions.
  • mixed aluminosilicate zeolite detergent compositions comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium ion sequestration performance versus an equal weight of commercially available zeolite A.
  • Another surprising finding is that mixed aluminosilicate zeolite detergent compositions, described above, provide improved magnesium ion sequestration performance versus an equal weight of commercially available zeolite A.
  • the detergent composition of the present invention may comprise an additional surfactant.
  • Suitable surfactants are selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • Automatic dishwashing machine products should be low foaming in character, thus the foaming of the surfactant system for use in dishwashing methods is preferably suppressed.
  • the total surfactant is typically present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of the compositions.
  • nonionic surfactants useful for detersive purposes can be included in the compositions.
  • Preferred, non-limiting classes of useful nonionic surfactants are listed below.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene 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 1 o
  • a suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula:
  • Rj is a linear or branched, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms
  • R2 is a linear or branched aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms
  • x is an integer having an average value of from 0.5 to about 1.5, more preferably about 1
  • y is an integer having a value of at least about 15, more preferably at least about 20.
  • the surfactant of formula I at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2].
  • Suitable surfactants of formula I are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.
  • Preferred surfactants for use herein include ether-capped poly(oxyalkylated) alcohols having the formula:
  • Rl .and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms;
  • R ⁇ is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms;
  • x is an integer having an average value from 1 to 30, wherein when x is 2 or greater R ⁇ may be the same or different and k and j are integers having an average value of from 1 to 12, and more preferably 1 to 5.
  • Ri .and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred.
  • H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms is most preferred for R ⁇ .
  • x is an integer having an average value of from 1 to 20, more preferably from 6 to 15.
  • R ⁇ when, in the preferred embodiments, and x is greater than 2, R ⁇ may be the same or different. That is, R- > may vary between any of the alklyeneoxy units as described above. For instance, if x is 3, R ⁇ may be be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) .and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO).
  • the integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, mulitple (EO) units and a much small number of (PO) units.
  • Particularly preferred surfactants as described above include those that have a low cloud point of less than 20°C. These low cloud point surfactants may then be employed in conjunction with a high cloud point surfactant as described in detail below for superior grease cleaning benefits.
  • ether-capped poly(oxyalkylated) alcohol surfactants are those wherein k is 1 and j is 1 so that the surfactants have the formula:
  • R* , R 2 and R 3 are defined as above and x is an integer with an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18.
  • Most preferred are surfactants wherein R and R 2 range from 9 to 14, R 3 is H forming ethyleneoxy and x ranges from 6 to 15.
  • the ether-capped poly(oxyalkylated) alcohol surfactants comprise three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap.
  • the alkyl ether end cap and the alcohol serve as a hydrophobic, oil- soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.
  • These surfactants exhibit significant improvements in spotting and filming characteristics and removal of greasy soils, when used in conjunction with high cloud point surfactants, relative to conventional surfactants.
  • the ether-capped poly(oxyalkylene) alcohol surfactants of the present invention may be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Examples of methods of preparing the ether- capped poly(oxyalkylated) alcohol surfactants are described below:
  • a C' 2/14 fatty alcohol (100.00 g, 0.515 mol.) and tin (IV) chloride (0.58 g, 2.23 mmol, available from Aldrich) are combined in a 500 mL three-necked round- bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 °C. Epichlorhydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise so as to keep the temperature between 60-65 °C. After stirring an additional hour at 60 °C, the mixture is cooled to room temperature.
  • the mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) while being stirred mechanically. After addition is completed, the mixture is heated to 90 °C for 1.5 h, cooled, .and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 mL), dried over MgSO-j, filtered, and concentrated. Distillation of the oil at 100-120 °C (0.1 mm Hg) providing the glycidyl ether as an oil.
  • the ethoxylated Cg-Cj fatty alcohols and C ⁇ -C ig mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the Cio-C jg ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C ⁇ -C j ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • Examples of compounds of this type include certain of the commercially-available Pluronic ⁇ M surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • 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, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, ,-,-C, monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cr--Cr j 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 include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinate
  • 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-C ⁇ 7 acyl-N-(C ⁇ -C4 alkyl) and -N-(C ⁇ -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 Cjo-Cj alkyl sulfates, more preferably the Cj ⁇ -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 C 1 Q-C 1 g 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 Ci j -C j , most preferably Cj j-Cj5 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 surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, C6-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 Cj g 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
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l -undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl- 1 -nonanoic acid, 2-butyl- 1 -octanoic acid and 2-pentyl- 1 -heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (Ri) CH2 COOM, wherein R is a C5-C ⁇ 7 linear or branched alkyl or alkenyl group, 8/11185 25
  • Ri 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.
  • 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(OR 4 ) X N0(R5)2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 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 R5 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 Cjo-Cjg alkyl dimethylamine oxide, .and C] -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 + R 2 COO" wherein R is a Cg-Cj hydrocarbyl group, each R* is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are Cj 2- 18 dimethyl-.ammonio hexanoate and the C J Q-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C -C ⁇ g, preferably C ⁇ -C ⁇ Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the detergent compositions described herein may comprise an enzyme.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, Iigninases, pullulanases, tannases, pentosanases, malanases, ⁇ - glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
  • a preferred combination is a cleaning composition having cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit).
  • CEVU Cellulose Viscosity Unit
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which disctose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • O ⁇ ier suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, .an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
  • suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) .are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.
  • Said cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
  • Preferred enhancers are substitued phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable upases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • Other suitable commercial lipases include Amano-CES, Upases ex Chromobacter viscosum, 8/11185 29
  • Upases ex Pseudomonas gladioli.
  • Upases such as MI Lipase ⁇ an( ⁇ Lipomax ⁇ (Gist-Brocades) and Lipolase ⁇ and Lipolase Ultra ⁇ (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely Upases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • the Upases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN').
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist- Brocades.
  • Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein “Protease B”, and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called “Protease A” herein.
  • Suitable is what is called herein "Protease C”, which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine 8/11185 30
  • Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes
  • proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.
  • protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor a . re described in WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • the proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
  • Amylases can be included for removal of carbohydrate-based stains.
  • WO94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676.456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
  • ⁇ -amylases examples are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability .and a higher activity level are described in WO95/35382.
  • amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned. 98/11185 32
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques.
  • Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971. Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • a highly preferred component of the detergent composition is a bleaching agent.
  • Suitable bleaching agents include chlorine and oxygen-releasing bleaching agents.
  • the oxygen-releasing bleaching agent contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • 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.
  • compositions in accord with the invention preferably include a hydrogen peroxide source, as an oxygen-releasing bleach.
  • Suitable hydrogen peroxide sources include the inorganic perhydrate salts.
  • the inorganic perhydrate salts are normally incorporated in the form of the 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 the 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.
  • Sodium perborate can be in the 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 for inclusion in compositions in accordance with the invention.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise.
  • the percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material providing in product stability comprises sodium silicate of S.O2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1 , preferably 1.8: 1 to 2.4: 1 , and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of Si ⁇ 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating.
  • Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the 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 perhydrolysis 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 10% by weight, most preferably from 1.5% to 5% by weight of the 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, 1 147871, 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 stabilise 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 is an alkyl chain containing from 1 to 8 carbon atoms, R is
  • R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group.
  • Any ofR 1, R 3 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 ammonium groups.
  • M is a cation which provides solubility to the bleach activator and 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, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
  • Perbenzoic acid precursor compounds of the imide type include 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 and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. 8/11185 38
  • perbenzoic acid precursors include the benzoyl diacyi peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
  • Suitable N-acylated lactam perbenzoic acid precursors have the formula:
  • n is from 0 to 8, preferably from 0 to 2
  • R is a benzoyl group.
  • Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
  • Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (i.e.; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
  • a preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • R' is an aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an arylene, or 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 and L can be essentially any leaving group.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R ⁇ may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for ex-ample, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R* and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type re described in EP-A-0170386.
  • 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 ammonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or .an amide substituted alkyl peroxyacid precursor as described hereinafter
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl .ammonium substituted .alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, .and monobenzoyltetr-aacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl .ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • N-acylated caprolactam class examples include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12, particularly from 1 to 5.
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N ⁇ N ⁇ 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. Tetr.aacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetr.aacetyl ethylene diamine
  • alkyl percarboxylic acid precur-sors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:
  • R* is an alkyl group with 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.
  • R* preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R* may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. .Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R* and R 5 should not contain more than 18 carbon atoms in total.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Benzoxazin Organic Peroxyacid Precursors
  • 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, arylalkyl, and wherein R , R-,, R 4 , and R ⁇ may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR ⁇ (wherein R fi is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed 8/11185 44
  • organic peroxyacid typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R* is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 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.
  • R preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R' may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • org.anic peroxyacids include diacyi and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • DibenzoyI peroxide is a preferred organic peroxyacid herein.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N- phthaloylaminoperoxicaproic acid are also suitable herein.
  • compositions comprising a bleach described herein may additionally contain a metal containing bleach catalyst as a preferred component.
  • a metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt-containing bleach catalyst.
  • a suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestr ⁇ mt having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephos ⁇ honic acid) and water-soluble salts thereof.
  • a heavy metal cation of defined bleach catalytic activity such as copper, iron cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminium cations
  • a sequestr ⁇ mt having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephos ⁇ honic acid) and water-soluble salts thereof.
  • Preferred types of 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 Mn ⁇ 2 (u-O)3( * ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(PF6)2, Mn ⁇ u-O) 1 (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Cl ⁇ 4)2,
  • ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, 1,2,4,7-tetramethyl- 1 ,4,7- triazacyclononane, and mixtures thereof.
  • bleach catalysts useful in the compositions 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- 1,4,7- triazacyclononane)(OCH3)3.(PFg).
  • 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. 5.1 14,61 1 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cycIic ligand. Said ligands are of the 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), trisdipyridyI.amine-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.
  • Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N- dentate ligands, including N4Mn ⁇ "(u-O)2 n ⁇ N4) + and [Bipy2Mn ⁇ (u- O) 2 MnIVbipy 2 ]-(ClO4)3.
  • the bleach-catalyzing manganese complexes of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxy 1 and nitrogen atoms of the ligand with the manganese cation.
  • the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+III), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in 98/11185 7
  • the aqueous bleaching media Whatever the form of the active Mn ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stains such as tea, ketchup, coffee, wine, juice, and the like.
  • 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.
  • Preferred cobalt catalysts of this type have the formula:
  • the preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Y y , and especially [Co(NH3)5Cl]Cl2.
  • T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF>5 ⁇ , BF4", B(Ph)4", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof.
  • T can be protonated if more than one anionic group exists in T, e.g., HPO4 2* , HCO3", H2PO4 " , etc.
  • T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).
  • anionic surfactants e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.
  • anionic polymers e.g., polyacrylates, polymethacrylates, etc.
  • the M moieties include, but .are not limited to, for example, F", SO4' , NCS", SCN-, S2O3- 2 , NH3, PO4 3 -, and carboxylates (which preferably are mono-carboxylates, but more than one carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety may be protonated or in its salt form).
  • carboxylates which preferably are mono-carboxylates, but more than one carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety may be protonated or in its salt form).
  • M can be protonated if more than one anionic group exists in M (e.g., HPO4 2 ", HCO3", H2PO4", HOC(O)CH2C(O)O-, etc.)
  • Preferred M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
  • R is preferably selected from the group consisting of hydrogen and C 1 -C30 (preferably C ] -C ⁇ g) unsubstituted and substituted alkyl, C - C30 (preferably Cg-Cjg) unsubstituted and substituted aryl, and C3-C30 (preferably C5-Cjg) unsubstituted .and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR'3, -NR'4 + , - C(O)OR', -OR', -C(O)NR'2, wherein R' is selected from the group consisting of hydrogen and Cj-Cg moieties.
  • Such substituted R therefore include the moieties -(CH2)n »H and -(CH2) n NR'4 + , wherein n is .an integer from 1 to about 16, preferably from about 2 to about 10, and most preferably from about 2 to about 5.
  • M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C 12 alkyl, and benzyl. Most preferred R is methyl.
  • Preferred carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.
  • the B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine).
  • carboxylates e.g., oxalate, malonate, malic, succinate, maleate
  • picolinic acid e.g., glycine, alanine, beta-alanine, phenylalanine.
  • Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94.
  • cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH 3 )5OAc](OAc)2; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH3) 5 OAc](SO 4 ); [Co(NH 3 ) 5 OAc](BF4)2; and [Co(NH 3 ) 5 OAc](NO3)2 (herein "PAC").
  • catalysts may be coprocessed with adjunct materials so as to reduce the color impact if desired for the aesthetics of the product, or to be included in enzyme-containing particles as exemplified hereinafter, or the compositions may be manufactured to contain catalyst "speckles".
  • Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from 20 to 50; preferred hydrocarbons are saturated and/or branched; preferred hydrocarbon oil selected from predominantly branched C25.45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 : 10 to 2: 1 , preferably from 1 :5 to 1 : 1.
  • a preferrred hydrocarbon oil is paraffin.
  • a paraffin oil meeting the characteristics as outlined above, having a ratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WTNOG 70.
  • compositions of the may contain a water-soluble bismuth compound, preferably present at a level of from 0.005% to 20%, more preferably from 0.01% to 5%, most preferably from 0.1% to 1% by weight of the compositions.
  • the water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion.
  • Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate.
  • Bismuth acetate and citrate are preferred salts with an organic counter anion.
  • Bismuth salts are preferred components of the detergent compositions described herein, in that they may additionally provide conductivity.
  • compositions of the present invention may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen- containing corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • Organic silver coating agents are described in PCT Publication No. WO94/16047 and copending European application No. EP-A-690122.
  • Nitrogen-containing corrosion inhibitor compounds are disclosed in copending European Application no. EP-A-634,478.
  • Mn(II) compounds for use in corrosion inhibition are described in copending European Application No. EP-A-672 749.
  • Organic silver coating agent may be incorporated at a level of from 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition.
  • the functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied.
  • the silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.
  • Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly- carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain.
  • monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and ⁇ , ⁇ '- dihydroxyisobutyric acid.
  • suitable polycarboxylic acids include: n- butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
  • the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • glycerol esters are also highly preferred. These are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above.
  • fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl proprionate.
  • Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.
  • Glycerol monostearate glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
  • Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.
  • Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
  • Waxes including microcrystalline waxes are suitable organic silver coating agents herein.
  • Preferred waxes have a melting point in the range from about 35°C to about 110°C and comprise generally from 12 to 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
  • Alginates and gelatin are suitable organic silver coating agents herein.
  • Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C12-C20 methyla . mmonium halides are also suitable.
  • organic silver coating agents include certain polymeric materials.
  • perfume materials particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.
  • Polymeric soil release agents can also be used as an organic silver coating agent.
  • Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1 -C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly( vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cj-Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., Cj-Cg vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end- capped oligomeric esters of U.S.
  • Patent 4,721,580 issued January 26, 1988 to Gosselink
  • block polyester oligomeric compounds of U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink.
  • Other polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-eth,anesulfonate.
  • a preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predominantly branched C25-45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 :10 to 2: 1, preferably from 1 :5 to 1 :1.
  • Nitrogen-Containing Corrosion Inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139, 279 and British Patent GB-A- 1,137,741 , which also discloses a method for making imidazole compounds.
  • nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Rj, R3, R4 and R5 where R ⁇ is .any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of C ⁇ -C o alkyl or hydroxyl, .and R4 is any of H, NH2 or NO2.
  • nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, l-phenyl-5-mercapto-l ,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, .aminotetrazole and indazole.
  • Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulphate or diammonium hydrogen citrate are also suitable.
  • the compositions may contain an Mn(II) corrosion inhibitor compound.
  • the Mn(II) compound is preferably incorporated at a level of from 0.005% to 5% by weight, more preferably from 0.01% to 1%, most preferably from 0.02% to 0.4% by weight of the compositions.
  • the Mn(II) compound is incorporated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.
  • the Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride.
  • the Mn(II) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.
  • the Mn(II) compound may be a salt or complex of an organic ligand.
  • the organic ligand is a heavy metal ion sequestrant.
  • the organic ligand is a crystal growth inhibitor.
  • additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated Cj ⁇ -C20 fat y acids, or their salts, especially aluminium tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa- decane and other anti-oxidants such as betahydroxytoluene (BHT) axe also suitable.
  • BHT betahydroxytoluene
  • Copolymers of butadiene and maleic acid particularly those supplied under the trade reference no. 07787 by Polysciences Inc have been found to be of particular utility as corrosion inhibitor compounds.
  • the level of available oxygen in the present compositions is preferably controlled; the level of available oxygen should hence preferably be in the range from 0.3% to 2.5%, preferably from 0.5% to 1.7%, more preferably from 0.6% to 1.5%, most preferably from 0.7% to 1.2%, measured according to the method described hereunder.
  • the rate of release of available oxygen is preferably also controlled; the rate of release of available oxygen from the compositions herein preferably should be such that, when using the method described hereinafter, the available oxygen is not completely released from the composition until after 3.5 minutes, preferably the available oxygen is released in a time interval of from 3.5 minutes to 10.0 minutes, more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0 minutes to 8.5 minutes.
  • a beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrer speed is selected to ensure that the product is evenly dispersed through the solution.
  • the detergent composition typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler
  • the detergent composition is added and simultaneously a stop clock is started.
  • the temperature control should be adjusted so as to maintain a constant temperature of 20°C throughout the experiment.
  • Samples are taken from the detergent solution at 2 minute time intervals for 20 minutes, starting after 1 minute, and are titrated by the "titration procedure" described below to determine the level of available oxygen at each point.
  • AvO level is plotted versus time to determine the maximum level of AvO, and the rate of release of AvO
  • a means may be provided for controlling the rate of release of oxygen bleach to the wash solution.
  • Means for controlling the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution.
  • Such means could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.
  • Suitable controlled release means can include coating any suitable component with a coating designed to provide the controlled release.
  • the coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.
  • the coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1 :99 to 1 :2, preferably from 1 :49 to 1 :9.
  • Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
  • Other suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.
  • a preferred coating material particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of Si ⁇ 2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of S-O2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating.
  • Suitable binders include the C10- 20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10 ⁇ preferably 100 ⁇ to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents.
  • polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C ⁇ 0-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C ⁇ 0-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include die C10-C20 mono- and diglycerol ethers and also the C10-C2O fatty acids.
  • Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.
  • One method for applying the coating material involves agglomeration.
  • Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
  • Suitable means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compression, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.
  • particle size Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.
  • Additional protocols for providing the means of controlled release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved.
  • 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.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 : 1.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • the detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, inco ⁇ orated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.
  • a crystal growth inhibitor component preferably an organodiphosphonic acid component
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C i -C4 diphosphonic acid, more preferably a C diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1 -hydroxy- 1 , 1 -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • a C diphosphonic acid such as ethylene diphosphonic acid, or most preferably ethane 1 -hydroxy- 1 , 1 -diphosphonic acid (HEDP)
  • HEDP ethane 1 -hydroxy- 1 , 1 -diphosphonic acid
  • Preferred enzyme-containing compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01 % to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • Organic polymeric compounds may be added as preferred components of the compositions in accord with the invention.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.
  • Organic polymeric compound is typically inco ⁇ orated in the detergent compositions of the 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 the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1 ,596,756.
  • salts are polyacrylates of molecular weight 2000- 10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CR j (CO- O-R3)]- wherein at least one of the substituents R ⁇ , R2 or R3, preferably R or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R ⁇ or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • R ⁇ is methyl
  • R2 is hydrogen (i.e. a methacrylic acid monomer).
  • the most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80%) by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.
  • 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.
  • compositions of the invention may contain a lime soap dispersant compound, preferably present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or .amine salts of fatty acids by calcium or magnesium ions.
  • Preferred lime soap disperant compounds are disclosed in PCT Application No. WO93/08877.
  • 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.
  • compositions of the invention include perfumes, colours .and filler salts, with sodium sulfate being a preferred filler salt.
  • the detergent compositions used in the present invention are preferably not formulated to have an unduly high pH, in preference having a pH measured as a 1% solution in distilled water of from 8.0 to 12.5, more preferably from 9.0 to 1 1.8, most preferably from 9.5 to 11.5.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a detergent composition in accord with the invention.
  • an effective .amount of the detergent composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods. Examples
  • Silicate Amo ⁇ hous Sodium Silicate (SiO2:Na2O ratio 1.6-
  • TAED Tetraacetyl ethylene diamine HEDP Ethane 1 -hydroxy- 1,1 -diphosphonic acid DETPMP Diethyltriamine penta (methylene) phosphonate, marketed by monsanto under the tradename Dequest
  • tablet detergent composition examples Q to V in accord with the present invention were prepared by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm 2 using a standard 12 head rotary press:

Abstract

On décrit une composition de détergent de lavage automatique de vaisselle comprenant un tensio-actif non ionique à point de trouble élevé et une quantité de sel soluble dans l'eau pour assurer la conductivité dans de l'eau désionisée à une température de 25° et à plus de 3 milli Siemens/cm.
PCT/US1997/015977 1996-09-11 1997-09-10 Composition de detergent WO1998011185A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP97940976A EP0925341A1 (fr) 1996-09-11 1997-09-10 Composition de detergent
BR9712817-1A BR9712817A (pt) 1996-09-11 1997-09-10 Composição detergente
AU42638/97A AU4263897A (en) 1996-09-11 1997-09-10 Detergent composition
JP10513803A JP2000502750A (ja) 1996-09-11 1997-09-10 洗剤組成物
CA002264916A CA2264916A1 (fr) 1996-09-11 1997-09-10 Composition de detergent

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US2472696P 1996-09-11 1996-09-11
US60/024,726 1996-09-11
US3126596P 1996-11-15 1996-11-15
US60/031,265 1996-11-15
GB9716317A GB2327948A (en) 1997-08-02 1997-08-02 Dish-washer detergent composition containing a high cloud point surfactant
GB9716317.4 1997-08-02

Publications (1)

Publication Number Publication Date
WO1998011185A1 true WO1998011185A1 (fr) 1998-03-19

Family

ID=27268960

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/015977 WO1998011185A1 (fr) 1996-09-11 1997-09-10 Composition de detergent

Country Status (7)

Country Link
EP (1) EP0925341A1 (fr)
JP (1) JP2000502750A (fr)
AU (1) AU4263897A (fr)
BR (1) BR9712817A (fr)
CA (1) CA2264916A1 (fr)
TR (1) TR199901131T2 (fr)
WO (1) WO1998011185A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999006466A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO1999006468A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Procede utile pour preparer des tensioactifs a base d'alcool poly(alcoxyle) a coiffe d'ether
WO1999006467A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO2000027516A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
WO2001048133A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co.Kg Detergent solide
WO2001048134A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Corps moules d"agents de lavage et de nettoyage presentant des proprietes de decomposition ameliorees
WO2001048131A2 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Granulats de tensioactifs presentant une plus grande vitesse de dissolution
WO2001048132A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Pastilles de detergent
WO2002034869A1 (fr) * 2000-10-25 2002-05-02 Unilever Plc Compositions pour lave-vaisselle
WO2002044312A2 (fr) * 2000-11-29 2002-06-06 The Procter & Gamble Company Composition de lavage de vaisselle a la main, contenant un agent de suppression de mousse
WO2003010263A1 (fr) * 2001-07-24 2003-02-06 Henkel Kommanditgesellschaft Auf Aktien Detergents pour lave-vaisselle comportant des tensioactifs a coefficients de diffusion determines
WO2005108537A1 (fr) * 2004-04-27 2005-11-17 Henkel Kommanditgesellschaft Auf Aktien DETERGENT CONTENANT UN TENSIO-ACTIF DE RINÇAGE ET UNE α-AMYLASE SPECIALE
US8071520B2 (en) 2009-11-06 2011-12-06 Ecolab Usa Inc. Sulfonated alkyl polyglucoside use for enhanced food soil removal
US8172953B2 (en) 2009-11-06 2012-05-08 Ecolab Usa Inc. Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant
US8216994B2 (en) 2009-11-09 2012-07-10 Ecolab Usa Inc. Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal
US8389463B2 (en) 2009-11-09 2013-03-05 Ecolab Usa Inc. Enhanced dispensing of solid compositions
EP2520641B1 (fr) 2005-06-30 2019-03-13 The Procter & Gamble Company Composition détergente pour lave-vaisselle automatique contenant une teneur limitée en phosphates
US11834624B2 (en) 2014-03-07 2023-12-05 Ecolab Usa Inc. Alkyl amides for enhanced food soil removal and asphalt dissolution

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2443113C (fr) * 2001-05-14 2009-12-01 The Procter & Gamble Company Produit de nettoyage comprenant trois zones distinctes
DE102007019457A1 (de) * 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
JP5774757B1 (ja) * 2014-10-07 2015-09-09 株式会社ニイタカ 洗浄剤組成物及び洗浄方法
JP5797829B1 (ja) * 2014-12-22 2015-10-21 株式会社ニイタカ 洗浄剤組成物及び洗浄方法
US10717952B2 (en) * 2015-10-26 2020-07-21 Basf Se Granulates, method for the production and use thereof
PL3436558T3 (pl) * 2016-03-31 2022-02-07 Rohm And Haas Company Surfaktanty w kompozycjach do automatycznego zmywania naczyń do zapobiegania plamom
JP6067168B1 (ja) * 2016-05-30 2017-01-25 株式会社ニイタカ 自動洗浄機用洗浄剤組成物
JP7400144B1 (ja) 2023-08-24 2023-12-18 株式会社アルボース 自動食器洗浄機用液体洗浄剤組成物および自動食器洗浄機による食器の洗浄方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4162987A (en) * 1976-06-24 1979-07-31 The Procter & Gamble Company Enzyme-containing automatic dishwashing detergent composition
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US5458802A (en) * 1992-04-10 1995-10-17 Solvay Interox Limited Liquid bleach and detergent compositions
US5540866A (en) * 1995-02-28 1996-07-30 Colgate-Palmolive Co. Dishwashing power including alkyl benzene sulphonates and magnesium or calcium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4162987A (en) * 1976-06-24 1979-07-31 The Procter & Gamble Company Enzyme-containing automatic dishwashing detergent composition
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US5458802A (en) * 1992-04-10 1995-10-17 Solvay Interox Limited Liquid bleach and detergent compositions
US5540866A (en) * 1995-02-28 1996-07-30 Colgate-Palmolive Co. Dishwashing power including alkyl benzene sulphonates and magnesium or calcium

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
WO1999006468A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Procede utile pour preparer des tensioactifs a base d'alcool poly(alcoxyle) a coiffe d'ether
WO1999006467A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO1999006466A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO2000027516A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
US6495727B1 (en) 1998-11-05 2002-12-17 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
WO2001048134A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Corps moules d"agents de lavage et de nettoyage presentant des proprietes de decomposition ameliorees
WO2001048131A2 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Granulats de tensioactifs presentant une plus grande vitesse de dissolution
WO2001048132A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co. Kg Pastilles de detergent
WO2001048131A3 (fr) * 1999-12-24 2001-11-22 Cognis Deutschland Gmbh Granulats de tensioactifs presentant une plus grande vitesse de dissolution
WO2001048133A1 (fr) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh & Co.Kg Detergent solide
US7087570B2 (en) * 1999-12-24 2006-08-08 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2002034869A1 (fr) * 2000-10-25 2002-05-02 Unilever Plc Compositions pour lave-vaisselle
WO2002044311A2 (fr) * 2000-11-29 2002-06-06 The Procter & Gamble Company Composition pour lavage de vaisselle a la main contenant un suppresseur de mousse et procede d'utilisation afferent
WO2002044312A3 (fr) * 2000-11-29 2003-01-16 Procter & Gamble Composition de lavage de vaisselle a la main, contenant un agent de suppression de mousse
WO2002044311A3 (fr) * 2000-11-29 2003-02-20 Procter & Gamble Composition pour lavage de vaisselle a la main contenant un suppresseur de mousse et procede d'utilisation afferent
WO2002044312A2 (fr) * 2000-11-29 2002-06-06 The Procter & Gamble Company Composition de lavage de vaisselle a la main, contenant un agent de suppression de mousse
WO2003010263A1 (fr) * 2001-07-24 2003-02-06 Henkel Kommanditgesellschaft Auf Aktien Detergents pour lave-vaisselle comportant des tensioactifs a coefficients de diffusion determines
US7053032B2 (en) 2001-07-24 2006-05-30 Henkel Kommanditgesellschaft Auf Aktien Machine dishwashing detergents containing surfactants with specific diffusion coefficients
WO2005108537A1 (fr) * 2004-04-27 2005-11-17 Henkel Kommanditgesellschaft Auf Aktien DETERGENT CONTENANT UN TENSIO-ACTIF DE RINÇAGE ET UNE α-AMYLASE SPECIALE
EP2520641B1 (fr) 2005-06-30 2019-03-13 The Procter & Gamble Company Composition détergente pour lave-vaisselle automatique contenant une teneur limitée en phosphates
US8071520B2 (en) 2009-11-06 2011-12-06 Ecolab Usa Inc. Sulfonated alkyl polyglucoside use for enhanced food soil removal
US8172953B2 (en) 2009-11-06 2012-05-08 Ecolab Usa Inc. Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant
US8216994B2 (en) 2009-11-09 2012-07-10 Ecolab Usa Inc. Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal
US8389463B2 (en) 2009-11-09 2013-03-05 Ecolab Usa Inc. Enhanced dispensing of solid compositions
US11834624B2 (en) 2014-03-07 2023-12-05 Ecolab Usa Inc. Alkyl amides for enhanced food soil removal and asphalt dissolution

Also Published As

Publication number Publication date
EP0925341A1 (fr) 1999-06-30
TR199901131T2 (xx) 1999-07-21
BR9712817A (pt) 1999-11-23
JP2000502750A (ja) 2000-03-07
CA2264916A1 (fr) 1998-03-19
AU4263897A (en) 1998-04-02

Similar Documents

Publication Publication Date Title
US6599871B2 (en) Detergent tablet
EP0960187B1 (fr) Procede pour laver la vaisselle
EP0925341A1 (fr) Composition de detergent
EP0998552A1 (fr) Pastille detergente
EP0960188B1 (fr) Procede pour laver la vaisselle
EP0976819B1 (fr) Comprimé détergent
WO1999031215A1 (fr) Comprime detergent
AU762815B2 (en) Detergent tablet
US6551981B1 (en) Detergent tablet
EP0922756B2 (fr) Composition détergente
EP0979865B1 (fr) Comprimé détergent
EP1097192B1 (fr) Pastille detergente
GB2324495A (en) Multi-layer detergent tablet
EP1327677A2 (fr) Tablette détergente
US6544943B1 (en) Detergent tablet
US6544944B1 (en) Detergent tablet
WO2001060965A1 (fr) Pastille de detergent
GB2327948A (en) Dish-washer detergent composition containing a high cloud point surfactant
WO2000012671A1 (fr) Detergent en pain

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT LU MC

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2264916

Country of ref document: CA

Ref document number: 2264916

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 09254727

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1997940976

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1999/01131

Country of ref document: TR

WWP Wipo information: published in national office

Ref document number: 1997940976

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1997940976

Country of ref document: EP