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WO1999031215A1 - Detergent tablet - Google Patents

Detergent tablet Download PDF

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Publication number
WO1999031215A1
WO1999031215A1 PCT/IB1998/002050 IB9802050W WO9931215A1 WO 1999031215 A1 WO1999031215 A1 WO 1999031215A1 IB 9802050 W IB9802050 W IB 9802050W WO 9931215 A1 WO9931215 A1 WO 9931215A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
detergent
detergent tablet
alkyl
sodium
Prior art date
Application number
PCT/IB1998/002050
Other languages
French (fr)
Inventor
Barry Rowland
Graeme Duncan Cruickshank
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
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to BR9813815-4A priority Critical patent/BR9813815A/en
Priority to EP98958365A priority patent/EP1047764A1/en
Priority to JP2000539116A priority patent/JP2002508440A/en
Priority to CA002314484A priority patent/CA2314484A1/en
Publication of WO1999031215A1 publication Critical patent/WO1999031215A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites

Definitions

  • the present invention relates to a detergent tablet comprising a granular component wherein the granular component dissolves at a faster rate than the other components of the detergent tablet.
  • Detergent tablets in tablet form are known in the art. Detergent compositions in tablet form hold several advantages over particulate detergent compositions, such as ease of handling, transportation and storage. It is the aim of detergent tablet manufacturers to make tablets that are sufficiently hard such that they do not crumble or disintegrate on handling, transportation or storage.
  • Detergent tablets are traditionally prepared by the compression of a particulate detergent composition in a tablet press.
  • the most common method used by detergent manufacturers to increase tablet hardness is to increase the compression pressure at which the tablets are formed. It has however, been found that the rate of dissolution of a tablet generally decreases with increasing compression pressure. Slow dissolution of a tablet means that the components of the detergent tablet are delivered to the wash water slowly and over a longer period of time and thus have less time to provide a detersive benefit in the wash.
  • EP-A- 504 091 describes a detergent tablet comprising citric acid which reacts with an alkali to form a gas that aids dissolution of the tablet.
  • a detergent tablet comprising a granular component having an average particle size of greater than 250 ⁇ m and less than 1200 ⁇ m in diameter and wherein 10 grams of the granule component dissolves in 1 litre of deionised water at 25°C in 80 seconds or less.
  • the granular component of the present invention can be any component suitable for incorporation into a detergent tablet that has the average particle size and meets the dissolution criteria as described in more detail below.
  • the average particle size of the granular component is greater than 250 ⁇ m and less than 1200 ⁇ m in diameter. More preferably the average particle size of the granular component is in the range of from 300 ⁇ m to 800 ⁇ m, most preferably from 350 ⁇ m to 700 ⁇ m in diameter.
  • Particle size is calculated using a series of Tyler sieves.
  • the series consists of a number of sieves each having a different aperture size.
  • Samples of a granular component are sieved through the series of sieves (typically 5 sieves).
  • the weight of a sample retained in the sieve is plotted against the aperture size of the sieve.
  • the average particle size of the granular component is defined as the aperture size through which 50% by weight of the sample would pass.
  • the detergent tablet of the present invention comprises a granular component, 10 grams of which dissolves in deionised water at 25°C in 80 seconds or less.
  • a granular component dissolves in deionised water at 25°C in 75 seconds or less, more preferably 60 seconds or less, most preferably 50 seconds or less.
  • the dissolution of the granular component is measured using the dissolution test method described below.
  • the rate of dissolution of the granular component is measured by taking measurement of the conductivity of the water on which the granular component is dissolved.
  • conductivity was measured using a Jenway 4020 conductivity meter calibrated against a standard sample of known conductivity; for example a 0.01M solution of potassium chloride provides conductivity of 1.413 milli Siemens/cm.
  • Figure 1 is a graphical representation of dissolution of granular NaHEDP, available from Solutia, in deionised water measured as conductivity of the deionised water over time. It can be seen from figure 1 that granular NaHEDP dissolves according to the dissolution test method described herein in 60 seconds.
  • the conductivity of the solution will increase. Once all the granular component has dissolved the conductivity of the solution will reach a plateau and remain at approximately the same conductivity (allowing for minor fluctuations in the equipment). The granular component is said to have dissolved when the conductivity plateau has been reached.
  • Preferred granular components are organo phosphonates.
  • a particularly preferred organo phosphonate is granular sodium 1-hydroxy ethane- 1,1-diphosphonate (NaHEDP; available from Solutia) or granular HEDP acid.
  • NaHEDP or HEDP acid has an average particle size of between 300 ⁇ m to 800 ⁇ m, more preferably from 350 ⁇ m to 700 ⁇ m in diameter, most preferably between 400 ⁇ m and 600 ⁇ m in diameter.
  • NaHEDP having the average particle size defined above dissolves according to the test method described above in 60 seconds or less, more preferably in 50 seconds or less.
  • the granular component is an agglomerate.
  • the agglomerate dissolves in 1 litre of deionised water in 80 seconds or less, preferably 75 seconds or less or even 60 seconds or less. Most preferably the agglomerate dissolves in 50 seconds or less.
  • the agglomerate comprises powdered NaHEDP having an average particle size of less than 250 ⁇ m and a liquid binder.
  • the liquid binder can comprise for example water, liquid silicate or a polymeric binder for example polyethylene glycol or polypropylene glycol or mixtures thereof.
  • Preferred binders comprise liquid NaHEDP, polyethylene glycol, polypropylene glycol or mixtures thereof.
  • the granular component as defined above is preferably uniformly distributed throughout the tablet.
  • uniform distribution it is meant that the granular component is randomly dispersed throughout the tablet such that substantially all of the granular component does not for example, segregate and settle in only one area of the tablet.
  • Uniform distribution is achieved by pre-mixing a granular component according to the present invention with other detergent components selected from those described below to form a detergent composition.
  • the premixed detergent composition is compressed using any suitable equipment, to form a detergent tablet.
  • the detergent tablet is a multiple layer tablet comprising at least 2 layers of compressed detergent components.
  • a granular component is present as a component of at least one of the layers of the tablet.
  • the detergent tablet comprises less than 10% free or unbound water, more preferably less than 8%, even more preferably less than 5%, 4% or even 2% free or unbound water.
  • the granular component is preferably present at a level of from 0.1% to 10% , more preferably from 0.5% to 5%, most preferably from 0.5% to 3% by weight of the detergent tablet.
  • the detergent tablet preferably dissolves in 10 minutes or less, more preferably in 8 minutes or less, most preferably in 6 minutes or less determined according to the DIN 44990 test method using a dishwashing machine available from Bosch on the normal 65°C washing programme with water hardness at 18°d.
  • the detergent composition of the present invention comprises a granular component as an essential component thereof but may also additionally comprise a variety of detergent components including builder compounds, 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.
  • detergent components including builder compounds, 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 tablet 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.
  • 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-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.
  • 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- tetrahydrofuran - 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 particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • 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.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • 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 tablets prepared for use in laundry cleaning methods.
  • 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.
  • 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.
  • 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), 110-116), 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 O.l ⁇ m .and 0.6 ⁇ m.
  • Zeolite A has the formula Na 12 [AlO 2 ) 12 (SiO 2 )i2]- *H 2 O
  • Zeolite X has the formula Nag6 [(Al ⁇ 2)86( sio 2)l06-- 276 H 2°- Zeolite MAP, as disclosed in EP-B-384,070 is a preferred zeolite builder herein.
  • 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.
  • Surfactants are preferred components of the detergent compositions described herein. 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 and thus the foaming of the surfactant system for use in dishwashing methods must be suppressed or more preferably be low foaming, typically nonionic in character. Sudsing caused by surfactant systems used in laundry cleaning methods need not be suppressed to the same extent as is necessary for dishwashing.
  • the 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 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • a suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula:
  • R 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.
  • the ethoxylated Cg-Cis fatty alcohols and Cg-C mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the Cl0"Cl8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the Ci 2-C ⁇ g 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 PluronicTM 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 surfactant Essentially any 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, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C-, . diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary CIQ-CIS alkyl sulfates, more preferably the C1 1-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ⁇ ⁇ -C ⁇ , most preferably C ⁇ ⁇ -C ⁇ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124. Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, Cg-C24 olefm 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 C6 to C18 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 j -CHR2- O)-R3 wherein R is a C to C ⁇ 8 alkyl group, x is from 1 to 25, Ri .and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 .and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l- decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid .and 2-pentyl-l- hept-anoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R- CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R 1 is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R 1 is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR4) ⁇ N ⁇ (R5)2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C10-C18 alkyl dimethylamine oxide, and C10-I8 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2COO ⁇ wherein R is a C6-C18 hydrocarbyl group, each R 1 is typically C1 -C3 alkyl, and R2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C y .18 dimethyl- ammonio hex.anoate and the C1 Q-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein. Cationic surfactants
  • 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 C5-C15, preferably Cg-Ci Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the detergent tablet compositions 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, ligninases, 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 disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
  • suitable cellulases are the 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- Phenothi-azinepropionicacid (PPT), lO-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".
  • Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli.
  • Especially suitable Upases are Upases such as Ml Lipase ⁇ - an ⁇ Lipomax ⁇ (Gist-Brocades) and Lipolase ⁇ and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • 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.
  • Protease C is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. 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 are described in WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • 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.
  • 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 Europe-an 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 Uquid 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. Bleaching agent
  • 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 S1O2 : 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, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to 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
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • R 3 ⁇ is an alkenyl chain containing from 1 to 8 carbon atoms
  • Y is H or a solubilizing group.
  • Any ofR 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
  • the preferred solubilizing groups are -SOPM , -CO 2 " M , -SO M , -N + (R 3 ) 4 X " and O ⁇ -N(R 3 ) 3 and most preferably -SO 3 " M + and -CO 2 " M + wherein R is an alkyl chain containing from 1 to 4 carbon atoms, 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 di.amine 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.
  • perbenzoic acid precursors include the benzoyl diacyl 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 prefe ⁇ ed class of substituted perbenzoic acid precursor compounds are the .amide substituted compounds of the following general formulae: R 1 — C — N — R 2 — C — L R 1 — N — C — R 2 — C — L
  • 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
  • R! preferably contains from 6 to 12 carbon atoms.
  • R2 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 example, tallow fat. Analogous structural variations are permissible for R ⁇ .
  • 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 are 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 monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a prefe ⁇ ed cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a prefe ⁇ ed cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Prefe ⁇ ed cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl .ammonium methylene benzoyl caprolactams, particularly trimethyl .ammonium methylene benzoyl caprolactam:
  • prefe ⁇ ed cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12, particularly from 1 to 5.
  • Another prefe ⁇ ed 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.
  • Prefe ⁇ ed precursors of this type provide peracetic acid on perhydrolysis.
  • Prefe ⁇ ed alkyl percarboxylic precursor compounds of the imide type include the N-.N.NlNl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly prefe ⁇ ed.
  • TAED Tetraacetyl ethylene diamine
  • prefe ⁇ ed alkyl percarboxylic acid precursors 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 ⁇ .
  • the substitution can include alkyl, 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 bleach activator compounds of this type are described in EP-A-0170386.
  • 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 prefe ⁇ ed 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 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 prefe ⁇ ed 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
  • R ⁇ 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 R2.
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or org.anic compounds.
  • R ⁇ is preferably H or methyl.
  • R and R5 should not contain more than 18 carbon atoms in total. Amide substituted org.anic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a prefe ⁇ ed organic peroxyacid herein.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • the bleach compositions described herein may additionally contain as a prefe ⁇ ed component, a metal containing bleach catalyst.
  • 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 sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic 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 sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • Prefe ⁇ ed types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594.
  • Prefe ⁇ ed examples of these catalysts include Mn ⁇ 2(u-O)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2- ( PF 6)2 > Mn ⁇ Cu-O) 1 (u-OAc) 2 ( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2- (ClO4)2, Mn IV 4 (u-O)6(l ,4,7-triazacyclononane)4-(Cl ⁇ 4)2, Mn III Mn IV 4(u- O) i (u-O Ac)2-( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Cl ⁇ 4)3 , .and mixtures thereof.
  • lig.ands suitable for use herein include l,5,9-trimethyl-l,5,9- triazacyclododecane, 2-methyl-l,4,7-triazacyclononane, 2 -methyl- 1,4,7- triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7- triazacyclononane, and mixtures thereof.
  • the bleach catalysts useful 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-l,4,7-triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, 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.
  • Prefe ⁇ ed ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
  • Said ligands are of the formula:
  • Prefe ⁇ ed 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.
  • Particularly prefe ⁇ ed is the ligand 2,2'- bispyridylamine.
  • Prefe ⁇ ed bleach catalysts include Co, Cu, Mn, Fe,- bispyridylmethane and -bispyridylamine complexes.
  • Highly prefe ⁇ ed catalysts include Co(2,2'-bispyridylamine)Ci2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridyl ⁇ tmine-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.
  • Prefe ⁇ ed examples include bmuclear Mn complexes with tetra-N-dentate and bi-N- dentate ligands, including N4MnH ⁇ -O)2MnIVN4) + and [Bipy2MnM(u- O) 2 MnI bipy2]-(Cl ⁇ 4)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 carboxyl 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 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.
  • Prefe ⁇ ed cobalt catalysts of this type have the formula:
  • the prefe ⁇ ed cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Y y , and especially [Co(NH 3 ) 5 Cl]Cl2.
  • Prefe ⁇ ed T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", 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., HPO42-, 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", SO4-2, 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., ⁇ PO ⁇ ' , HCO3", H2PO4", HOC(O)CH2C(O)O-, etc.)
  • M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
  • R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C1-C 8) unsubstituted and substituted alkyl, C ⁇ - C30 (preferably Cg-C s) unsubstituted .and substituted aryl, and C3-C30 (preferably C5-C13) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR'3, -NR'4 "1" , - C(O)OR', -OR', -C(O)NR'2, wherein R is selected from the group consisting of hydrogen and C -Cg moieties.
  • Such substituted R therefore include the moieties -(CH2) n OH .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.
  • prefe ⁇ ed 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 2 alkyl, and benzyl. Most prefe ⁇ ed R is methyl.
  • Prefe ⁇ ed 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 catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T y , wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 ) 5 OAc]Cl2; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](SO 4 ); [Co (NH 3 ) 5 OAc](BF 4 )2; and [Co(NH 3 ) 5 OAc](NO3)2 (herein "PAC").
  • PAC cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T y , wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 ) 5 OA
  • 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".
  • the detergent tablet composition optionally contains a water-soluble sulfate salt.
  • the water-soluble sulfate salt is at the 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 sulfate salt may be essentially any salt of sulfate with any counter cation.
  • Prefe ⁇ ed salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.
  • a prefe ⁇ ed component of the detergent composition is an alkali metal silicate.
  • a prefe ⁇ ed alkali metal silicate is sodium silicate having an SiO2:Na2O 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 than 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.
  • Another prefe ⁇ ed 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; prefe ⁇ ed hydrocarbons are saturated and/or branched; prefe ⁇ ed 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 prefer ⁇ ed 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 prepared by the process of the present invention suitable for use in dishwashing methods 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.
  • Prefe ⁇ ed 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.
  • compositions of the present invention and suitable for use in dishwashing methods may contain co ⁇ osion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing co ⁇ osion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • co ⁇ osion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing co ⁇ osion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • 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 polycarboxylic 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.
  • Prefe ⁇ ed 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.
  • the glycerol esters are also highly prefe ⁇ ed. 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, pahnityl 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 prefe ⁇ ed 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, pe.anut 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.
  • Prefe ⁇ ed 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.
  • Prefe ⁇ ed 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 methylammonium halides are also suitable.
  • suitable organic silver coating agents include certain polymeric materials.
  • Polyvinylpy ⁇ olidones with an average molecular weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpy ⁇ olidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such 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 C - 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., C1 -Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C1 -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 ethyl ene 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 sul foarolyl, end-capped terephthalate esters.
  • Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly prefe ⁇ ed soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,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)-ethanesulfonate.
  • a prefe ⁇ ed 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; prefe ⁇ ed 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.
  • Suitable nitrogen-containing co ⁇ osion 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 co ⁇ osion 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 R1 , R3, R4 .and R5 where R1 is any of H, CH 2 OH, CONH3, or COCH3, R 3 and R5 are any of Ci- C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2.
  • nitrogen-containing co ⁇ osion inhibitor compounds include benzotri.azole, 2-mercaptobenzothiazole, l-phenyl-5-mercapto-l,2,3,4-tetrazole, thionalide, morpholine, mel.amine, 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) co ⁇ osion 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 co ⁇ osion 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 C10-C20 f atr Y acids, or their salts, especially aluminium tristearate. The C 2-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are 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 co ⁇ osion 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 sti ⁇ er Hotplate, and the sti ⁇ er 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
  • Controlled rate of release - means
  • 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.
  • suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.
  • a prefe ⁇ ed 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 Si ⁇ 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating.
  • Suitable binders include the C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C 5-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • prefe ⁇ ed binders include certain polymeric materials.
  • Polyvinylpy ⁇ olidones 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 6 preferably 1000 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 ⁇ (3-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C ⁇ (3-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include the C10-C20 mono- .and diglycerol ethers .and also the C ⁇ 0-C20 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.
  • Prefe ⁇ ed 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.
  • compositions preferably contain an alkalinity system containing 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, present preferably at a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight of S1O2.
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • the alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% Si ⁇ 2 by weight.
  • 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.
  • 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. Prefe ⁇ ed 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.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates. Prefe ⁇ ed among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene
  • Suitable heavy metal ion sequestr.ant 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.
  • ethylenediamine-N,N'-disuccinic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Prefe ⁇ ed 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, incorporated 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 Ci -C4 diphosphonic acid, more preferably a C2 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 Ci -C4 diphosphonic acid more preferably a C2 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.
  • Prefe ⁇ ed 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 prefe ⁇ ed 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 incorporated 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.
  • Examples of such salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fi - imaric, maleic, itaconic, aconitic, mesaconic, broadlyconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Prefe ⁇ ed are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.
  • 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.
  • Prefe ⁇ ed 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 ⁇ (CO-O-R3)]- wherein at least one of the substituents Ri , R2 or R3, preferably R ⁇ or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R j or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • Most prefe ⁇ ed is a substituted acrylic monomer wherein R1 is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer).
  • the most prefe ⁇ ed 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.
  • the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • 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.
  • Prefe ⁇ ed lime soap disperant compounds are disclosed in PCT Application No. WO93/08877. Suds suppressing system
  • compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds. Prefe ⁇ ed suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 and EP- A-705 324.
  • 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-vinylpy ⁇ olidone and N- vinylimid.azole, polyvinylpy ⁇ olidonepolymers or combinations thereof.
  • the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R1 is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the prefe ⁇ ed hydrophilic optical brightener useful in the detergent compositions herein.
  • R1 is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • Rj is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
  • compositions of the invention include perfumes, colours .and filler salts, with sodium sulfate being a prefe ⁇ ed 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 11.8, most preferably from 9.5 to 11.5.
  • a prefe ⁇ ed machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware .and cutlery and mixtures thereof, with an aqueous Uquid having dissolved or dispensed therein an effective amount of a detergent tablet composition in accord with the invention.
  • an effective amount of the detergent tablet 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.
  • the detergent tablets are from 15g to 40g in weight, more preferably from 20g to 35g in weight.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent tablet composition in accord with the invention.
  • an effective amount of the detergent tablet composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • a dispensing device is employed in the washing method.
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle.
  • Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
  • the dispensing device containing the detergent product is placed inside the drum.
  • water is introduced into the drum and the drum periodically rotates.
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
  • the device may possess a number of openings through which the product may pass.
  • the device may be made of a material which is permeable to Uquid but impermeable to the solid product, which will allow release of dissolved product.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
  • Prefe ⁇ ed dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No . 0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene. Examples
  • Carbonat Anhydrous sodium carbonate having average particle size of 425 ⁇ m to e 700 ⁇ m and dissolving in approximately 180 seconds according to the dissolution test method described herein
  • P particle size of between 400 ⁇ m and 500 ⁇ m and dissolving in approximately 60 seconds according to the dissolution test method described herein.
  • MnTAC Mang.anese 1 ,4,7-trimethyl- 1 ,4,7-tri.azacyclononane.
  • Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.
  • Amylase Amylolytic enzyme Amylase Amylolytic enzyme.
  • PA30 Polyacrylic acid of average molecular weight approximately 4,500
  • Sulphate Anhydrous sodium sulphate having average particle size of from 425 ⁇ m to 700 ⁇ m and dissolving in 90 seconds according to the dissolution test method described herein pH Measured as a 1% solution in distilled water at 20°C
  • tablet detergent composition examples A to F in accord with the present invention were prepared by compression of a gr.anul.ar dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:

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Abstract

The present invention relates to a detergent tablet comprising a granular component having an average particle size greater than 250νm and less than 1200νm in diameter and wherein 10 grams of the granular component dissolves in 1 litre of deionised water at 25 °C in 80 seconds or less.

Description

Detergent Tablet
Technical Field
The present invention relates to a detergent tablet comprising a granular component wherein the granular component dissolves at a faster rate than the other components of the detergent tablet.
Background
Detergent tablets in tablet form are known in the art. Detergent compositions in tablet form hold several advantages over particulate detergent compositions, such as ease of handling, transportation and storage. It is the aim of detergent tablet manufacturers to make tablets that are sufficiently hard such that they do not crumble or disintegrate on handling, transportation or storage.
Detergent tablets are traditionally prepared by the compression of a particulate detergent composition in a tablet press. The most common method used by detergent manufacturers to increase tablet hardness is to increase the compression pressure at which the tablets are formed. It has however, been found that the rate of dissolution of a tablet generally decreases with increasing compression pressure. Slow dissolution of a tablet means that the components of the detergent tablet are delivered to the wash water slowly and over a longer period of time and thus have less time to provide a detersive benefit in the wash. EP-A- 504 091 describes a detergent tablet comprising citric acid which reacts with an alkali to form a gas that aids dissolution of the tablet.
It is the object of the present invention to provide a detergent tablet that is hard enough to withstand handling, transportation and storage but also dissolves more quickly than detergent tablets currently available on the market. It has been found that tablets incorporating a granular component having the average particle size and dissolution properties described herein, dissolve more quickly than tablets currently available on the market. It is believed that this is due to the fact that the granular component dissolves quickly in the wash water, leaving holes or channels in the tablet. The holes or channels increase the surface area of the tablet that is exposed to the wash water, thereby increasing the dissolution rate of the tablet.
Summary of the Invention
According to the present invention there is provided a detergent tablet comprising a granular component having an average particle size of greater than 250μm and less than 1200μm in diameter and wherein 10 grams of the granule component dissolves in 1 litre of deionised water at 25°C in 80 seconds or less.
Detailed Description of the Invention
Granular Component
The granular component of the present invention can be any component suitable for incorporation into a detergent tablet that has the average particle size and meets the dissolution criteria as described in more detail below.
The average particle size of the granular component is greater than 250μm and less than 1200μm in diameter. More preferably the average particle size of the granular component is in the range of from 300μm to 800μm, most preferably from 350μm to 700μm in diameter.
Particle size is calculated using a series of Tyler sieves. The series consists of a number of sieves each having a different aperture size. Samples of a granular component are sieved through the series of sieves (typically 5 sieves). The weight of a sample retained in the sieve is plotted against the aperture size of the sieve. The average particle size of the granular component is defined as the aperture size through which 50% by weight of the sample would pass.
It is an essential feature of the present invention that the granular component dissolves rapidly on contact with water in comparison to other components of the detergent tablet. The detergent tablet of the present invention comprises a granular component, 10 grams of which dissolves in deionised water at 25°C in 80 seconds or less. Preferably 10 grams of a granular component dissolves in deionised water at 25°C in 75 seconds or less, more preferably 60 seconds or less, most preferably 50 seconds or less. The dissolution of the granular component is measured using the dissolution test method described below.
Dissolution test method
The rate of dissolution of the granular component is measured by taking measurement of the conductivity of the water on which the granular component is dissolved.
For the purposes of the present invention, conductivity was measured using a Jenway 4020 conductivity meter calibrated against a standard sample of known conductivity; for example a 0.01M solution of potassium chloride provides conductivity of 1.413 milli Siemens/cm.
lOg of a granular component is poured into a beaker containing 1 litre of deionised water. The resulting solution is continuously stirred at a rate of 700 rpm using a 5 cm magnetic stirring rod. Conductivity readings are taken at regular intervals using the Jenway 4020 conductivity meter. Figure 1 is a graphical representation of dissolution of granular NaHEDP, available from Solutia, in deionised water measured as conductivity of the deionised water over time. It can be seen from figure 1 that granular NaHEDP dissolves according to the dissolution test method described herein in 60 seconds.
As the granular component starts to dissolve the conductivity of the solution will increase. Once all the granular component has dissolved the conductivity of the solution will reach a plateau and remain at approximately the same conductivity (allowing for minor fluctuations in the equipment). The granular component is said to have dissolved when the conductivity plateau has been reached.
Preferred granular components are organo phosphonates. A particularly preferred organo phosphonate is granular sodium 1-hydroxy ethane- 1,1-diphosphonate (NaHEDP; available from Solutia) or granular HEDP acid. Preferably the NaHEDP or HEDP acid has an average particle size of between 300μm to 800μm, more preferably from 350μm to 700μm in diameter, most preferably between 400μm and 600μm in diameter. NaHEDP having the average particle size defined above, dissolves according to the test method described above in 60 seconds or less, more preferably in 50 seconds or less. In another preferred aspect the granular component is an agglomerate. In this embodiment lOg of the agglomerate dissolves in 1 litre of deionised water in 80 seconds or less, preferably 75 seconds or less or even 60 seconds or less. Most preferably the agglomerate dissolves in 50 seconds or less. In a particularly preferred embodiment the agglomerate comprises powdered NaHEDP having an average particle size of less than 250 μm and a liquid binder. The liquid binder can comprise for example water, liquid silicate or a polymeric binder for example polyethylene glycol or polypropylene glycol or mixtures thereof. Preferred binders comprise liquid NaHEDP, polyethylene glycol, polypropylene glycol or mixtures thereof.
The granular component as defined above is preferably uniformly distributed throughout the tablet. By uniform distribution it is meant that the granular component is randomly dispersed throughout the tablet such that substantially all of the granular component does not for example, segregate and settle in only one area of the tablet. Uniform distribution is achieved by pre-mixing a granular component according to the present invention with other detergent components selected from those described below to form a detergent composition. The premixed detergent composition is compressed using any suitable equipment, to form a detergent tablet.
In an alternative embodiment of the present invention the detergent tablet is a multiple layer tablet comprising at least 2 layers of compressed detergent components. In this embodiment a granular component is present as a component of at least one of the layers of the tablet.
In another preferred aspect of the present invention the detergent tablet comprises less than 10% free or unbound water, more preferably less than 8%, even more preferably less than 5%, 4% or even 2% free or unbound water.
The granular component is preferably present at a level of from 0.1% to 10% , more preferably from 0.5% to 5%, most preferably from 0.5% to 3% by weight of the detergent tablet.
The detergent tablet preferably dissolves in 10 minutes or less, more preferably in 8 minutes or less, most preferably in 6 minutes or less determined according to the DIN 44990 test method using a dishwashing machine available from Bosch on the normal 65°C washing programme with water hardness at 18°d.
Detergent Components
The detergent composition of the present invention comprises a granular component as an essential component thereof but may also additionally comprise a variety of detergent components including builder compounds, 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.
Builder compound
The tablet 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.
Water-soluble builder compound
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. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1,1, 3 -propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.
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- tetrahydrofuran - 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.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
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.
Examples of 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. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from about 6 to 21, and salts of phytic acid.
Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound
The 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 tablets 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
NaMSixO2+l .yH2O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so called δ-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. For the purpose of the present invention, 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 δ- Na2Si2θ5 , 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.
Examples of largely water insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Naz[(AlO2)z(SiO2)y]- XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.
A preferred method of synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14(2), 110-116), 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 lμm in diameter and not more than 5% of particles are of size less then 0.05 μm in diameter. Preferably the aluminosilicate zeolite particles have an average particle size diameter of between 0.01 μm and lμm, more preferably between 0.05 μm and 0.9 μm, most preferably between O.lμm .and 0.6 μm.
Zeolite A has the formula Na 12 [AlO2) 12 (SiO2)i2]- *H2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(Alθ2)86(sio2)l06-- 276 H2°- Zeolite MAP, as disclosed in EP-B-384,070 is a preferred zeolite builder herein.
Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When employed as a component of a detergent composition 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.
A surprising finding is that 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.
Surfactant
Surfactants are preferred components of the detergent compositions described herein. 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 and thus the foaming of the surfactant system for use in dishwashing methods must be suppressed or more preferably be low foaming, typically nonionic in character. Sudsing caused by surfactant systems used in laundry cleaning methods need not be suppressed to the same extent as is necessary for dishwashing. The 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.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December, 30, 1975. A list of suitable cationic surfactants is given in U.S .P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants typically included in automatic dishwashing detergent compositions is given for example, in EP-A-0414 549 and PCT Applications No.s WO 93/08876 and WO 93/08874.
Nonionic surfactant
Essentially any nonionic surfactants useful for detersive purposes can be included in the compositions. Preferred, non-limiting classes of useful nonionic surfactants are listed below.
Nonionic ethoxylated alcohol surfactant
The 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 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
End-capped alkyl alkoxylate surfactant
A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula:
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I)
wherein R 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; and y is an integer having a value of at least about 15, more preferably at least about 20.
Preferably, the surfactant of formula I, at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present invention, 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.
Nonionic ethoxylated/propoxylated fatty alcohol surfactant
The ethoxylated Cg-Cis fatty alcohols and Cg-C mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the Cl0"Cl8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the Ci 2-Cιg ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably 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.
Nonionic EO/PO condensates with propylene glycol
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 PluronicTM surfactants, marketed by BASF.
Nonionic EO condensation products with propylene oxide/ethylene diamine adducts
The 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. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds, marketed by BASF.
Anionic surfactant Essentially any 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.
Other anionic surfactants include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, -C, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-C-, . diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary CIQ-CIS alkyl sulfates, more preferably the C1 1-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C \ \ -C \ , most preferably C \ \ -C \ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124. Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, Cg-C24 olefm sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant
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(CH2CH2θ)x CH2C00"M+ wherein R is a C6 to C18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2- O)-R3 wherein R is a C to C\ 8 alkyl group, x is from 1 to 25, Ri .and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 .and 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l- decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid .and 2-pentyl-l- hept-anoic acid. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R- CON (R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R1 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.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(OR4)χNθ(R5)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C10-C18 alkyl dimethylamine oxide, and C10-I8 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2COO~ wherein R is a C6-C18 hydrocarbyl group, each R1 is typically C1 -C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C y .18 dimethyl- ammonio hex.anoate and the C1 Q-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein. Cationic surfactants
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 C5-C15, preferably Cg-Ci Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Enzymes
The detergent tablet compositions 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, ligninases, pullulanases, tannases, pentosanases, malanases, β-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). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also 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- Phenothi-azinepropionicacid (PPT), lO-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.
Other preferred enzymes that can be included in the detergent compositions of the present invention include Upases. 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 Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli. Especially suitable Upases are Upases such as Ml Lipase^- an^ Lipomax^ (Gist-Brocades) and Lipolase^ and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
Also suitable are 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 replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, filed October 13, 1994.
Also suitable for the present invention are 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.
See also a high pH 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 are described in WO 92/03529 A to Novo. When desired, 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 (α and/or β) 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 α- and β-amylases. α-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). Other suitable amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A S Denmark. WO95/26397 describes other suitable amylases : α- 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® α-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.
The 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.
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 ).
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending Europe-an Patent application 92870018.6 filed on January 31, 1992. Examples of such 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 Uquid 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. Bleaching agent
A highly preferred component of the detergent composition is a bleaching agent. Suitable bleaching agents include chlorine and oxygen-releasing bleaching agents.
In one preferred aspect 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. In an alternative preferred aspect a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Inorganic perhydrate bleaches
The 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.
Examples of 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. For certain perhydrate salts however, 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 NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ2-3H2θ. 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 2Na2Cθ3-3H2θ2, 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. Such coatings together with coating processes have previously been described in GB- 1,466,799, granted to Interox on 9th March 1977. 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. Preferably, 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 S1O2 : Na2θ 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 Siθ2 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.
Other coatings which contain waxes, oils, fatty soaps can also be used advantageously within the present invention.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
O X- C-L
where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
O X- C -OOH
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, 1147871, 2143231 and EP-A-0170386.
Leaving groups
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:
Figure imgf000026_0001
O
II
N-C-R1 - Λ O N N — N-C II -CH— R4 k> 1 — 1 R U3 Y i
Y
-O-CH=
Figure imgf000026_0002
Figure imgf000026_0003
R3 O Y
II I
-O-C=CHR4 , , and — N— S- -CH- -R4 I , II R3 O
.and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing
3 from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , R3 ς is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group. Any ofR 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
The preferred solubilizing groups are -SOPM , -CO2 "M , -SO M , -N+(R3)4X" and O<-N(R3)3 and most preferably -SO3 "M+ and -CO2 "M+ wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, 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
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:
Figure imgf000027_0001
Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:
Figure imgf000027_0002
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene di.amine 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.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
Figure imgf000028_0001
Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
Figure imgf000028_0002
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
Figure imgf000028_0003
wherein n is from 0 to 8, preferably from 0 to 2, and R is a benzoyl group.
Perbenzoic acid derivative precursors
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 prefeπed class of substituted perbenzoic acid precursor compounds are the .amide substituted compounds of the following general formulae: R1 — C — N — R2 — C — L R1 — N — C — R2 — C — L
O R5 O or R5 O O
wherein R! is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group, R! preferably contains from 6 to 12 carbon atoms. R2 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 example, tallow fat. Analogous structural variations are permissible for R^. The 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 are described in EP-A-0170386.
Cationic peroxyacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
Typically, 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. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
A prefeπed cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
Figure imgf000030_0001
A prefeπed cationically substituted alkyl oxybenzene sulfonate has the formula:
Figure imgf000030_0002
Prefeπed cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl .ammonium methylene benzoyl caprolactams, particularly trimethyl .ammonium methylene benzoyl caprolactam:
Figure imgf000030_0003
Other prefeπed cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:
Figure imgf000031_0001
where n is from 0 to 12, particularly from 1 to 5.
Another prefeπed cationic peroxyacid precursor is 2-(N,N,N-trimethyl .ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Prefeπed precursors of this type provide peracetic acid on perhydrolysis.
Prefeπed alkyl percarboxylic precursor compounds of the imide type include the N-.N.NlNl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly prefeπed.
Other prefeπed alkyl percarboxylic acid precursors 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 precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:
R1 — C — N — R2 — C — L R1 — N — C — R2 C — L
O R5 O or R5 O O
wherein R is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and 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. R2 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^. The substitution can include alkyl, 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 bleach activator compounds of this type are described in EP-A-0170386.
Benzoxazin organic peroxyacid precursors
Also suitable are 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:
Figure imgf000032_0001
including the substituted benzoxazins of the type
Figure imgf000032_0002
wherein R, is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R~, R.,, R4, and R^ may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR^ (wherein Rfi is H or an alkyl group) -and carbonyl functions.
An especially prefeπed precursor of the benzoxazin-type is:
Figure imgf000033_0001
Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition.
A prefeπed class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
R1 C — N — R2 C — OOH
O R5 O or
R1 N — C — R2 C — OOH
R5 O O
wherein R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms, R! preferably contains from 6 to 12 carbon atoms. R2 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 R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or org.anic compounds. R^ is preferably H or methyl. R and R5 should not contain more than 18 carbon atoms in total. Amide substituted org.anic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a prefeπed organic peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Metal-containing bleach catalyst
The bleach compositions described herein may additionally contain as a prefeπed component, a metal containing bleach catalyst. Preferably the 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 sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Prefeπed types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Prefeπed examples of these catalysts include Mn^2(u-O)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2- (PF6)2> Mn^Cu-O) 1 (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2- (ClO4)2, MnIV 4(u-O)6(l ,4,7-triazacyclononane)4-(Clθ4)2, MnIIIMnIV4(u- O) i (u-O Ac)2-( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)3 , .and mixtures thereof. Others .are described in Europe.an patent application publication no. 549,272. Other lig.ands suitable for use herein include l,5,9-trimethyl-l,5,9- triazacyclododecane, 2-methyl-l,4,7-triazacyclononane, 2 -methyl- 1,4,7- triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7- triazacyclononane, and mixtures thereof.
The bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, 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. Prefeπed ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:
R2 R3
R1-N=C-B-C=N-R4
wherein R1, R2, R3, and R^ can each be selected from H, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six- membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Prefeπed ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly prefeπed is the ligand 2,2'- bispyridylamine. Prefeπed bleach catalysts include Co, Cu, Mn, Fe,- bispyridylmethane and -bispyridylamine complexes. Highly prefeπed catalysts include Co(2,2'-bispyridylamine)Ci2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridyl∑tmine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2Clθ4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
Prefeπed examples include bmuclear Mn complexes with tetra-N-dentate and bi-N- dentate ligands, including N4MnH ι-O)2MnIVN4)+and [Bipy2MnM(u- O)2MnI bipy2]-(Clθ4)3.
While the structures of 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 carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, 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 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.
Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal- containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
Other prefeπed examples include cobalt (III) catalysts having the formula:
Co[(NH3)nM'mB'bT'tQqPp] Yy
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably 4 or 5; most preferably 5); M' represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; most preferably 1); B' represents a bidentate ligand; b is an integer from 0 to 2; T' represents a tridentate ligand; t is 0 or 1 ; Q is a tetradentate ligand; q is 0 or 1 ; P is a pentadentate ligand; p is 0 or 1 ; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counteranions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt, prefeπed Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and wherein further at least one of the coordination sites attached to the cobalt is labile under automatic dishwashing use conditions and the remaining co-ordination sites stabilise the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than about 0.2 volts) versus a normal hydrogen electrode.
Prefeπed cobalt catalysts of this type have the formula:
[Co(NH3)n(M*)m] Yy
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M' is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is an appropriately selected counteranion present in a number y, which is .an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt.
The prefeπed cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Yy, and especially [Co(NH3)5Cl]Cl2.
More prefeπed are the present invention compositions which utilize cobalt (III) bleach catalysts having the formula:
[Co(NH3)n(M)m(B)b] Ty
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a ligand co-ordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m+n = 6, and when b=l, then m=0 .and n=4; and T is one or more appropriately selected counteranions present in a number y, where y is an integer to obtain a charge-balanced salt (preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion); and wherein further said catalyst has a base hydrolysis rate constant of less than 0.23 M~l s~l (25°C).
Prefeπed T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF4", B(Ph)4", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T can be protonated if more than one anionic group exists in T, e.g., HPO42-, HCO3", H2PO4", etc. Further, 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.).
The M moieties include, but .are not limited to, for example, F", SO4-2, NCS", SCN", S2O3-2, NH3, PO43-, .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). Optionally, M can be protonated if more than one anionic group exists in M (e.g., ΗPO^', HCO3", H2PO4", HOC(O)CH2C(O)O-, etc.) Prefeπed M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C1-C 8) unsubstituted and substituted alkyl, Cβ- C30 (preferably Cg-C s) unsubstituted .and substituted aryl, and C3-C30 (preferably C5-C13) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR'3, -NR'4"1", - C(O)OR', -OR', -C(O)NR'2, wherein R is selected from the group consisting of hydrogen and C -Cg moieties. Such substituted R therefore include the moieties -(CH2)nOH .and -(CH2)nNR'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.
Most prefeπed 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 2 alkyl, and benzyl. Most prefeπed R is methyl. Prefeπed 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).
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. For example, Table 1 at page 17, provides the base hydrolysis rates (designated therein as kQjj) f°r cobalt pentaamine catalysts complexed with oxalate (kQH= 2.5 x 10~4 M~l s~l (25°C)), NCS- (k0H= 5-° * !0~4 M"1 s"1 (25°C)), formate (k0H= 5.8 x lO"4 M"1 s"1 (25°C)), and acetate (k0H= 9.6 x 10"4 M"1 s'1 (25°C)). The most prefeπed cobalt catalyst useful herein .are 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(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](SO4); [Co (NH3)5OAc](BF4)2; and [Co(NH3)5OAc](NO3)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article hereinbefore and the references cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (T989 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952); as well as the synthesis examples provided hereinafter.
These 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".
Water-soluble sulfate salt
The detergent tablet composition optionally contains a water-soluble sulfate salt. Where present the water-soluble sulfate salt is at the 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 sulfate salt may be essentially any salt of sulfate with any counter cation. Prefeπed salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.
Alkali Metal Silicate
A prefeπed component of the detergent composition is an alkali metal silicate. A prefeπed alkali metal silicate is sodium silicate having an SiO2:Na2O 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 than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight of Siθ2- The alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
Hydrocarbon oils
Another prefeπed 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; prefeπed hydrocarbons are saturated and/or branched; prefeπed 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 preferπed 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.
Water-soluble bismuth compound
The compositions prepared by the process of the present invention suitable for use in dishwashing methods 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. Prefeπed 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.
Coπosion inhibitor compound
The compositions of the present invention and suitable for use in dishwashing methods may contain coπosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing coπosion 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 coπosion inhibitor compounds are disclosed in copending European Application no. EP-A-634,478. Mn(II) compounds for use in coπosion 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 polycarboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain. Suitable examples of 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 β,β'- dihydroxyisobutyric acid. Examples of 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. Examples of 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.
Preferably, 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.
Prefeπed 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.
The glycerol esters are also highly prefeπed. These are the mono-, di- or tri- esters of glycerol and the fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include: stearyl acetate, pahnityl 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 prefeπed 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, pe.anut 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. Prefeπed 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. Prefeπed 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 methylammonium halides are also suitable.
Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyπolidones with an average molecular weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyπolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such polymeric materials.
Certain 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 oxyethylene terephthalate :C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C5 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a combination of (a) and (b).
Typically, 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 Mθ3S(CH2)nOCH2CH2θ-, 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 C - 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., C1 -Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
Another suitable soil release agent is a copolymer having random blocks of ethyl ene 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, and the 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 sul foarolyl, end-capped terephthalate esters.
Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly prefeπed soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,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)-ethanesulfonate.
A prefeπed 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; prefeπed 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. A paraffin oil meeting these characteristics, having a ratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
Nitrogen-containing coπosion inhibitor compounds
Suitable nitrogen-containing coπosion 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.
Also suitable as nitrogen-containing coπosion 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 R1 , R3, R4 .and R5 where R1 is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of Ci- C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2.
Other suitable nitrogen-containing coπosion inhibitor compounds include benzotri.azole, 2-mercaptobenzothiazole, l-phenyl-5-mercapto-l,2,3,4-tetrazole, thionalide, morpholine, mel.amine, 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.
Mnfll coπosion inhibitor compounds
The compositions may contain an Mn(II) coπosion 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. Preferably, 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. In one prefeπed aspect the organic ligand is a heavy metal ion sequestrant. In another prefeπed aspect the organic ligand is a crystal growth inhibitor.
Other coπosion inhibitor compounds
Other suitable additional coπosion 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 C10-C20 fatrY acids, or their salts, especially aluminium tristearate. The C 2-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
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 coπosion inhibitor compounds. Total Available Oxygen (AvO) Level
It has been found that, for optimal anti-silver tarnishing performance, the level of available oxygen in the present compositions, measured in units of % available oxygen by weight of the composition, 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.
Rate of Release of AvO
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.
Method for Measuring Level of Total Available Oxygen (AvO and Rate of Release of AvO in a Detergent Composition
Method
1. A beaker of water (typically 2L) is placed on a stiπer Hotplate, and the stiπer speed is selected to ensure that the product is evenly dispersed through the solution.
2. The detergent composition (typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler), is added and simultaneously a stop clock is started.
3. The temperature control should be adjusted so as to maintain a constant temperature of 20°C throughout the experiment.
4. 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.
Titration Procedure
1. An aliquot from the detergent solution (above) and 2ml sulphuric acid are added into a stiπed beaker
2. Approximately 0.2g ammonium molybdate catalyst (tetra hydrate form) are added
3. 3mls of 10% sodium iodide solutionare added
4. Titration with sodium thiosulphate is conducted until the end point. The end point can be seen using either of two procedures. First procedure consists simply in seeing the yellow iodine colour fading to clear. The second and prefeπed procedure consists of adding soluble starch when the yellow colour is becoming faint, turning the solution blue. More thiosulphate is added until the end point is reached (blue starch complex is decolourised).
The level of AvO, measured in units of % available oxygen by weight, for the sample at each time interval coπesponds to the amount of titre according to the following equation
Vol S2O3(ml) x Molarity (S2O3) x 8 Sample mass (g)
AvO level is plotted versus time to determine the maximum level of AvO, and the rate of release of AvO
Controlled rate of release - means
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 prefeπed coating material, particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of Siθ2 : Na2θ 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 Siθ2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder materials to provide composite inorganic salt/organic binder coatings. Suitable binders include the C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C 5-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
Other prefeπed binders include certain polymeric materials. Polyvinylpyπolidones 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 106 preferably 1000 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. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C\ (3-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the C10-C20 mono- .and diglycerol ethers .and also the C\ 0-C20 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. Prefeπed 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.
Other 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.
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.
Alkalinity system
The compositions preferably contain an alkalinity system containing sodium silicate having an Siθ2 : Na2θ ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0, present preferably at a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight of S1O2. The alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
The alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% Siθ2 by weight. Sodium metasilicate has a nominal Siθ2 : Na2θ ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as Siθ2, is preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.
Heavy metal ion sequestrant
The detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By 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. Preferably 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. Prefeπed 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.
Other suitable heavy metal ion sequestr.ant 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.
Especially prefeπed is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Prefeπed EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
Crystal growth inhibitor component
The detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.
By 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 Ci -C4 diphosphonic acid, more preferably a C2 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.
Enzyme Stabilizing System
Prefeπed 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 compound
Organic polymeric compounds may be added as prefeπed components of the compositions in accord with the invention. By 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 incorporated 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.
Examples of 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. Examples of such salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fi - imaric, maleic, itaconic, aconitic, mesaconic, cifraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof. Prefeπed are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.
Prefeπed 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.
Prefeπed 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-CRι(CO-O-R3)]- wherein at least one of the substituents Ri , R2 or R3, preferably R\ or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, Rj or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt. Most prefeπed is a substituted acrylic monomer wherein R1 is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer). The most prefeπed 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.
The 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.
Clay softening system
The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
Lime soap dispersant compound
The 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. Prefeπed lime soap disperant compounds are disclosed in PCT Application No. WO93/08877. Suds suppressing system
The compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds. Prefeπed suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 and EP- A-705 324.
Polymeric dye transfer inhibiting agents
The 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-vinylpyπolidone and N- vinylimid.azole, polyvinylpyπolidonepolymers or combinations thereof.
Optical brightener
The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the structural formula:
Figure imgf000056_0001
wherein R\ is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the prefeπed hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, Rj is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours .and filler salts, with sodium sulfate being a prefeπed filler salt.
pH of the compositions
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 11.8, most preferably from 9.5 to 11.5.
Machine dishwashing method
Any suitable methods for machine washing or cleaning soiled tableware, particularly soiled silverware are envisaged.
A prefeπed machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware .and cutlery and mixtures thereof, with an aqueous Uquid having dissolved or dispensed therein an effective amount of a detergent tablet composition in accord with the invention. By an effective amount of the detergent tablet 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. Preferably the detergent tablets are from 15g to 40g in weight, more preferably from 20g to 35g in weight.
Laundry washing method
Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent tablet composition in accord with the invention. By an effective amount of the detergent tablet composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
In a prefeπed use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to Uquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
Prefeπed dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No . 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene. Examples
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:
STPP Sodium tripolyphosphate
Citrate Tri-sodium citrate dihydrate
Bicarbon Sodium hydrogen carbonate ate
Carbonat Anhydrous sodium carbonate having average particle size of 425μm to e 700μm and dissolving in approximately 180 seconds according to the dissolution test method described herein
Silicate Amorphous Sodium Silicate (SiO2:Na2O ratio = 1.6-3.2) having average particle size of 500μm to 700μm and dissolving in approximately 210 seconds according to the dissolution test method described herein
Metasili Sodium metasilicate (SiO2:Na2O ratio = 1.0) cate PB1 Anhydrous sodium perborate monohydrate PB4 Sodium perborate tetr.ahydrate of nominal formula
NaBO2.3H O.H2θ2
Percarbo Anhydrous sodium percarbonate of nominal formula nate 2.Na2CO3.3H2θ2
Plurafac C13-C 5 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the tradename Plurafac
TAED Tetraacetyl ethylene diamine
NaHED Granular sodium Ethane 1 -hydroxy- 1,1-diphosphonate having average
P particle size of between 400μm and 500μm and dissolving in approximately 60 seconds according to the dissolution test method described herein.
DETPM Diethyltriamine penta (methylene) phosphonate, marketed by
P monsanto under the tradename Dequest 2060
MnTAC Mang.anese 1 ,4,7-trimethyl- 1 ,4,7-tri.azacyclononane.
N PAAC Pentaamine acetate cobalt (III) salt
Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.
Protease Proteolytic enzyme
Amylase Amylolytic enzyme.
BTA Benzo triazole
PA30 Polyacrylic acid of average molecular weight approximately 4,500
MA/AA Randon copolymer of 4:1 acrylate/maleate, average molecular weight about 70,000
480N Random copolymer of 7:3 acrylate/methacrylate, average molecular weight about 3,500
Sulphate Anhydrous sodium sulphate having average particle size of from 425μ m to 700μm and dissolving in 90 seconds according to the dissolution test method described herein pH Measured as a 1% solution in distilled water at 20°C
In the following examples all levels are quoted as % by weight of the composition:
The following tablet detergent composition examples A to F in accord with the present invention were prepared by compression of a gr.anul.ar dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:
Figure imgf000061_0001
Figure imgf000062_0001

Claims

WHAT IS CLAIMED IS:
1. A detergent tablet comprising a granular component having an average particle size greater than 250╬╝m and less than 1200╬╝m in diameter and wherein 10 grams of the granular component dissolves in 1 litre of deionised water at 25┬░C in 80 seconds or less.
2. A detergent tablet according to claim 1 wherein the average particle size of the granular component is between 300╬╝m to 800╬╝m in diameter.
3. A detergent tablet according to any of the preceding claims wherein the granular component dissolves in 60 seconds or less.
4. A detergent tablet according to any of the preceding claims wherein the granular component is present at a level of from 0.1% to 10% by weight of the detergent tablet.
5. A detergent tablet according to any of the preceding claims wherein the detergent tablet comprises less than 10% free or unbound water
6. A detergent tablet according to any of the preceding claim wherein the tablet dissolves in 10 minutes or less determined according to the DIN 44990 test method using a dishwashing machine available from Bosch on the normal 65┬░C washing programme with water hardness at 18┬░d.
7. A detergent tablet according to any of the preceding claims wherein the granular component is an organo phosphonate.
8. A detergent tablet according to claim 7 wherein the organo phosphonate is 1- hydroxy ethane- 1,1 -diphosphonic acid, sodium 1 -hydroxy ethane- 1,1-diphosphonate or mixtures thereof.
9. A detergent tablet according to any of the preceding claims wherein the granular component is an agglomerate.
10. A detergent component according to claim 9 wherein the agglomerate comprises powdered sodium 1 -hydroxy ethane- 1,1-diphosphonate having an average particle size of less than 250╬╝m and a liquid binder.
11. A detergent tablet according to claim 10 wherein the Uquid binder comprises liquid sodium 1 -hydroxy ethane- 1,1-diphosphonate.
12. A detergent tablet according to claim 10 wherein the Uquid binder comprises a polymeric binder.
13. A detergent tablet according to any of the preceding claims also comprising a phosphate builder compound.
PCT/IB1998/002050 1997-12-17 1998-12-17 Detergent tablet WO1999031215A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9813815-4A BR9813815A (en) 1997-12-17 1998-12-17 "detergent tablet"
EP98958365A EP1047764A1 (en) 1997-12-17 1998-12-17 Detergent tablet
JP2000539116A JP2002508440A (en) 1997-12-17 1998-12-17 Cleaning tablets
CA002314484A CA2314484A1 (en) 1997-12-17 1998-12-17 Detergent tablet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9726604.3 1997-12-17
GB9726604A GB2332442A (en) 1997-12-17 1997-12-17 Detergent tablet

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EP1035199A3 (en) * 1999-03-12 2000-12-20 The Procter & Gamble Company Perfumed detergent tablet
EP1035198A3 (en) * 1999-03-12 2001-01-03 The Procter & Gamble Company Perfumed detergent tablet
US6630438B1 (en) 1999-03-12 2003-10-07 The Procter & Gamble Company Perfumed detergent tablet
US7084102B1 (en) 1999-03-12 2006-08-01 The Procter & Gamble Company Perfumed detergent tablet
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9518013B2 (en) 2014-12-18 2016-12-13 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents

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US8097047B2 (en) 2008-04-02 2012-01-17 The Procter & Gamble Company Fabric color rejuvenation composition
JP5631797B2 (en) * 2011-03-31 2014-11-26 花王株式会社 Detergent composition for automatic dishwasher
US10041026B2 (en) * 2014-02-27 2018-08-07 Conopco, Inc. Water soluble laundry capsule comprising reduced levels of fines in HEDP
WO2020047122A1 (en) 2018-08-29 2020-03-05 The Research Foundation For The State University Of New York Method for nitrogen removal and nitrogen salts recovery using carboxylated cellulose extracted by nitro-oxidation

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EP1035199A3 (en) * 1999-03-12 2000-12-20 The Procter & Gamble Company Perfumed detergent tablet
EP1035198A3 (en) * 1999-03-12 2001-01-03 The Procter & Gamble Company Perfumed detergent tablet
WO2000055294A3 (en) * 1999-03-12 2001-01-18 Procter & Gamble Perfumed detergent tablet
WO2000055287A3 (en) * 1999-03-12 2001-01-25 Procter & Gamble Perfumed detergent tablet
US6630438B1 (en) 1999-03-12 2003-10-07 The Procter & Gamble Company Perfumed detergent tablet
US7084102B1 (en) 1999-03-12 2006-08-01 The Procter & Gamble Company Perfumed detergent tablet
US10323218B2 (en) 2008-03-28 2019-06-18 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10017720B2 (en) 2008-03-28 2018-07-10 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10077415B2 (en) 2008-03-28 2018-09-18 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US10669512B2 (en) 2008-03-28 2020-06-02 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11015151B2 (en) 2008-03-28 2021-05-25 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9359295B2 (en) 2008-03-28 2016-06-07 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11827867B2 (en) 2008-03-28 2023-11-28 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US8858895B2 (en) 2010-12-29 2014-10-14 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US9365509B2 (en) 2010-12-29 2016-06-14 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9505715B2 (en) 2010-12-29 2016-11-29 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US11678664B2 (en) 2010-12-29 2023-06-20 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US9192909B2 (en) 2010-12-29 2015-11-24 Ecolab USA, Inc. Sugar ester peracid on site generator and formulator
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US8933263B2 (en) 2010-12-29 2015-01-13 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US11311011B2 (en) 2010-12-29 2022-04-26 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US12114656B2 (en) 2010-12-29 2024-10-15 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US9861101B2 (en) 2010-12-29 2018-01-09 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
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US10244751B2 (en) 2010-12-29 2019-04-02 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US10201156B2 (en) 2010-12-29 2019-02-12 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
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US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
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US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
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EP1047764A1 (en) 2000-11-02
JP2002508440A (en) 2002-03-19
GB2332442A (en) 1999-06-23
CA2314484A1 (en) 1999-06-24
BR9813815A (en) 2000-10-03
GB9726604D0 (en) 1998-02-18

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