+

WO1998026038A1 - Procede de fabrication de compositions detergentes se presentant sous forme de pastilles - Google Patents

Procede de fabrication de compositions detergentes se presentant sous forme de pastilles Download PDF

Info

Publication number
WO1998026038A1
WO1998026038A1 PCT/US1997/022918 US9722918W WO9826038A1 WO 1998026038 A1 WO1998026038 A1 WO 1998026038A1 US 9722918 W US9722918 W US 9722918W WO 9826038 A1 WO9826038 A1 WO 9826038A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
detergent
preferred
alkyl
process according
Prior art date
Application number
PCT/US1997/022918
Other languages
English (en)
Inventor
Alasdair Duncan Mcgregor
Jane Margaret Warwick
Steven Baldwin Mcgowan
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 US09/319,808 priority Critical patent/US6177393B1/en
Priority to EP97952416A priority patent/EP0944710A1/fr
Publication of WO1998026038A1 publication Critical patent/WO1998026038A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons

Definitions

  • the present invention relates to a process for making detergent tablets suitable for use in either laundry or automatic dishwashing methods.
  • Detergent compositions in tablet form are known in the art. It is understood that tabletted detergent compositions hold several advantages over granular detergent compositions. Examples of such advantages include ease of handling, transportation and storage. Tablets are therefore required to be of sufficient hardness such that they do not crumble or disintegrate on handling, transportation or storage.
  • Detergent tablets are traditionally prepared by the compression or compaction of granular detergent compositions. It has however, been found that solubility of the tablet generally decreases with increasing compression/compaction force. Detergent manufacturers have directed tablet development efforts toward striking a balance between strength and solubility.
  • Henkel EP- 0170791 describes a process for making a tablet detergent composition comprising per compounds and tabletting aids. The detergent composition is compacted at a pressure of 5 x 10 ⁇ to 10 ⁇ Pa resulting in tablets having a breaking strength of between 50 and 120 N. Other methods of controlling tablet hardness and dissolution have been discussed in the prior art. Detergent manufacturers have for example, introduced alterations in the detergent formulation, thereby changing the characteristics of the tablet.
  • Henkel WO93/00419 describes increasing tablet hardness by providing a detergent composition comprising polymer.
  • Unilever EP-0466484 and EP-0522766 describe increasing tablet hardness by providing a tabletted detergent composition comprising liquid binder and particles of specific size ranges.
  • Japanese patent application Kao J06207199 A describes a process for making a detergent composition in tablet form wherein the process consists of the mixing nonionic surfactant and an oil absorbing material, granulating the mixture to provide particles of specific size and density, then compacting the resulting particles to form a tablet.
  • Henkel EP-0579659 describes a process for preparing a detergent tablet wherein the alkaline detergent additives are agglomerated with builder, water and nonionic surfactant resulting in a tablet having a high break strength.
  • the present invention provides a process for making a detergent composition in tablet form, wherein the tablet produced has increased hardness.
  • Detergent tablets comprise a particulate base detergent matrix and liquid components.
  • a process for making a detergent tablet by tabletting a detergent composition comprising solid components which form a total particulate base detergent matrix and non-aqueous liquid components having viscosity of 1000 cp or less measured at ambient temperature, the process comprising the steps of
  • step (b) admixing the product of step (b) with remaining components of the detergent composition
  • the particulate base detergent matrix may comprise essentially any particulate component traditionally used in detergent compositions. This includes for example builder compounds, bleaching agents, alkalinity sources, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, enzymes and enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • the particulate base detergent matrix essentially comprises a high porosity fraction.
  • the high porosity fraction of the particulate base detergent matrix comprises particulate matrix components, either raw materials or processed particles (eg produced by spray drying, agglomeration or any other conventional particle-producing method) that are selected from the total particulate base detergent matrix for their high porosity characteristics.
  • the high porosity fraction is characterised in that the average porosity of this fraction is at least 5 % greater, preferably 10 % greater, most preferably 20 % greater than the average porosity of the particulate base detergent matrix.
  • Particularly preferred components of the high porosity fraction include builder compounds and alkalinity sources.
  • the high porosity fraction generally comprises at least 5% by weight, preferably at least 10%, or even at least 15% or 20% by weight of the total particulate base detergent matrix.
  • the amount of high porosity fraction should be sufficient to substantially absorb the non-aqueous low viscosity liquids.
  • the weight ratio of high porosity fraction to non-aqueous low viscosity liquids is at least 1 :1 preferably at least 1.5:1 and most preferably 2: 1 or even at least 5: 1 or 10: 1.
  • the porosity of the components of the particulate base detergent matrix and particularly the high porosity fraction can be measured by any known method. Suitable methods may include, for example, image analysis, mercury porosimetry, determination and comparison of volume and mass, determination and comparison of surface area and diameter, gas chromatography, x-ray small angle scattering and displacement methods. A preferred method of measuring porosity is the mercury porosimetry method. However, for particles of less than 1 mm in diameter, an alternative method may be preferred.
  • any liquid component that is substantially non-aqueous traditionally used as a component of a tablet detergent composition can be used.
  • substantially non-aqueous liquids comprising less than 10% , preferably less than 5 %, most preferably less than 2% by weight water.
  • Non-aqueous liquid components of viscosity 1000 cp or less measured at ambient temperature are applied to the high porosity fraction.
  • Preferred examples of non-aqueous liquid components employed in the process of the present invention are surfactants, especially non-ionic surfactant, and hydrocarbon oils as described below. Viscosity is measured as described below.
  • the non-aqueous low viscosity liquid can be applied to the high porosity fraction by any known application method.
  • the preferred method of application is by spraying the liquid on to the high porosity fraction.
  • the viscosity of the liquid components can be measured by any known method for determining viscosity. Viscosity for the purposes of the present invention is measured by a Brookf eld Laboratory Viscometer, available from Brookfield Viscometer Ltd. at ambient temperature, generally at 25°C.
  • the total particulate base detergent matrix preferably at least the high porosity fraction, comprises particulates which are prepared by agglomeration.
  • Agglomerates can be prepared using any conventional agglomeration equipment which facilitates mixing and intimate contacting of a liquid binder with the components of the base detergent matrix such that it results in agglomerated particles.
  • the average porosity of the agglomerated particles suitable for use in the high porosity fraction in the present invention is preferably at least 5 % greater, preferably 10 % greater, most preferably 20% greater than the average porosity of the components of the particulate base detergent matrix.
  • the agglomerated particles may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • Suitable agglomerators include vertical agglomerators (e.g. Schugi Flexomix or Bepex Tirboflex), rotating drums, inclined pan agglomerators and any other device with suitable means.
  • Most preferred are the vertical blender type agglomerators as manufactured by Schugi (Holland) BV, 29 Chroomstraat 821 1 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • the tablet compositions prepared by the process of the present invention contain as a highly preferred component 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.
  • 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.
  • at least a proportion of the builder compounds selected for use in the present invention have porosity at least 5 % greater, preferably 10 % greater, most preferably 20 % greater than the average porosity of the particulate base detergent matrix so that they form at least part of the high porosity fraction.
  • the porosity of the builder compound is 0.04 ml/g or greater, preferably 0.1 ml/g or greater as measured by the mercury porosimetry method.
  • 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.
  • 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 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. W092/ 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 Na z [(Al ⁇ 2) z (Si ⁇ 2)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 1 ⁇ 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
  • Zeolite X has the formula Na 86 [(Al ⁇ 2)86(Si ⁇ 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.
  • the detergent tablet of the present invention may comprise a water- soluble sulfate salt, preferably present at a level of from 0.1% to 40%, more preferably from 1% to 30%, most preferably from 5% to 25% by weight of the detergent composition.
  • a proportion of the water-soluble sulfate salts selected for use in the present invention have porosity at least 5% greater, preferably 10 % greater, most preferably 20 % greater than the average porosity of the particulate base detergent matrix so that they form at least part of the high porosity fraction.
  • the porosity of the water-soluble sulfate salt is 0.04 ml/g or greater, preferably 0.1 ml/g or greater as measured by mercury porosimetry.
  • the water-soluble sulfate salt may be essentially any salt of sulfate with any counter cation.
  • Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.
  • the preferred alkali metal silicate is sodium silicate having an Si ⁇ 2:Na2 ⁇ ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0.
  • Sodium silicate is preferably present at a level of less 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.
  • Sodium silicate selected for use in the present invention has porosity at least 5 % greater, preferably 10 % greater, most preferably 20 % greater than the average porosity of the particulate base detergent matrix.
  • the porosity of the alkali metal silicate is 0.05 ml/g or greater, preferably 0.1 ml/g or greater.
  • a preferred liquid component for use in the process of this invention is a surfactant 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 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 Nos. WO 93/08876 and WO 93/08874.
  • the surfactants used in the process of this invention are of viscosity from 0.1 to lOOOcp.
  • 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.
  • the ethoxylated C -C 18 fatty alcohols and C -C 18 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the Cjo-Cl S ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C ⁇ 2-Ci8 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 C1 -C 1 o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C 1 ⁇ 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-(C -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-C18 a lkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ branched chain alkyl sulfates and the C 12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CI O-C J S alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ⁇ 1-C1 , most preferably Ci 1-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2COO-M+ wherein R is a C ⁇ to Ci s alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-0)-R3 wherein R is a C to Cj alkyl group, x is from 1 to 25, R ⁇ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2- methyl-1-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l- nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl 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
  • Rl 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) X NO(R5) 2 wherein R3 is selected from an alkyl, hydroxy alkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxy alky lene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxy alkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Cjo-Cl ⁇ a ⁇ dimethylamine oxide, and C ⁇ o-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ. Zwitterionic 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 C ⁇ -Ci s hydrocarbyl group, each R! is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-C16, preferably C -C ⁇ Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxy ethyl or hydroxypropyl groups.
  • Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents Nos. 4228042, 4239660 and 4260529.
  • hydrocarbon oil typically predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from 20 to 50.
  • Preferred hydrocarbons are saturated and/or branched.
  • Preferred hydrocarbon oils are selected from predominantly branched C 25-45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 :10 to 2:1, preferably from 1 :5 to 1 :1.
  • a preferred 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 WI OG 70.
  • the tablet detergent composition may optionally contain various components including bleaching agents, alkalinity sources, additional builder compounds, lime soap dispersants, alkalinity organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, enzymes and enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • various components including bleaching agents, alkalinity sources, additional builder compounds, lime soap dispersants, alkalinity organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, enzymes and enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • An optional component of the detergent composition is an oxygen- releasing bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • 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 Na2S ⁇ 4.n.Na2C ⁇ 3 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 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. Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB- A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1 147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilise for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • R 5 is an alkenyl chain containing from 1 to 8 carbon atoms
  • Y is H or a solubilizing group.
  • Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
  • the preferred solubilizing groups are -SO-5 _ M , -CO2 M , -SO ⁇ ' M , -N + (R 3 ) 4 X " and 0 ⁇ N(R 3 ) 3 and most preferably -SQ 3 " M + and -CO2 M + wherein R 3 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 diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N- benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • 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 preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • Rl 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
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R2 preferably contains from 4 to 8 carbon atoms.
  • Rl may be aryl, substituted aryl oralkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total.
  • Amide substituted 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 preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • N-acylated caprolactam class examples include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12, particularly from 1 to 5.
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • 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 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 include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
  • Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:
  • Rl 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 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R2 preferably contains from 4 to 8 carbon atoms.
  • Rl 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 R2.
  • the substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R5 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 j is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R , R3, R 4 , and Rr may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR ⁇ (wherein Rg is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R2 preferably contains from 4 to 8 carbon atoms.
  • Rl 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 organic compounds.
  • R5 is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a preferred 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 preferred 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 aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a 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 aluminum cations
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnlV2(u-0)3 (1 ,4,7- trimethyl- 1 ,4,7-triazacyclononane)2-(PF6)2, MnH ⁇ u-O) i (u- OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Cl ⁇ 4)2, MnI V 4(u- 0)6( 1 ,4,7-triazacyclononane)4-(C104)2, MnIIlMnIV 4 ( u _ ⁇ ) j (u-OA - (l,4,7-trimethyl-l ,4,7-triazacyclononane)2-(Cl ⁇ 4)3, and mixtures thereof.
  • ligands suitable for use herein include 1 ,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7- triazacyclononane, 2-methyl- 1, 4, 7-triazacyclononane, 1,2,4,7- tetramethyl- 1 ,4,7-triazacyclononane, and mixtures thereof.
  • 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( 1 ,4,7-trimethyl- 1,4,7- triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso- inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)- cyclic ligand.
  • Said ligands are of the formula:
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine- cobalt(II) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2Cl ⁇ 4, Bis-(2,2'- bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
  • Preferred examples include binuclear Mn complexes with tetra-N- dentate and bi-N-dentate ligands, including N4MnHl(u- 0)2MnI N4)+and [Bipy2Mnn i (u-0)2MnI bi py2 ]-(C104)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. 4,1 19,557 (ferric complex catalyst), German Pat.
  • the preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Y y , and especially [Co(NH 3 ) 5 Cl]Cl2.
  • T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ⁇ ", 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, NH 3 , 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).
  • carboxylates which preferably are mono-carboxylates, but more than one carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety may be protonated or in its salt form).
  • M can be protonated if more than one anionic group exists in M (e.g., HPO4 -, HCO3", H2PO4-, HOC(0)CH2C(0)0-, etc.)
  • Preferred M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
  • R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C j-Cis) unsubstituted and substituted alkyl, C6-C30 (preferably C ⁇ -Cjs) unsubstituted and substituted aryl, and C3-C30 (preferably C5-C18) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR'3, -NR'4 + , - C(0)OR*, -OR * , -C(0)NR'2, wherein R* is selected from the group consisting of hydrogen and Cj-C6 moieties.
  • Such substituted R therefore include the moieties -(CH2)nOH and - (CH2) n R'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 preferred 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-C12 alkyl, and benzyl. Most preferred R is methyl.
  • Preferred carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.
  • the B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine).
  • carboxylates e.g., oxalate, malonate, malic, succinate, maleate
  • picolinic acid e.g., glycine, alanine, beta-alanine, phenylalanine.
  • Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. (1983), 2, pages 1- 94.
  • cobalt pentaamine acetate salts having the formula [Co(NH3)5 ⁇ Ac] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH3)5 ⁇ Ac]Cl2; as well as [Co(NH 3 )5 ⁇ Ac](OAc)2; [Co(NH3)5 ⁇ Ac](PF 6 ) 2 ; [Co(NH ) 5 OAc](S ⁇ 4); [Co(NH 3 )5 ⁇ Ac](BF 4 )2; and [Co(NH3) 5 OAc](N ⁇ 3)2 (herein "PAC").
  • PAC cobalt pentaamine acetate salts having the formula [Co(NH3)5 ⁇ Ac] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH3)5 ⁇ Ac]Cl2; as well as [Co(NH 3 )5 ⁇ Ac]
  • 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".
  • 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.
  • Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate.
  • Bismuth acetate and citrate are preferred salts with an organic counter anion.
  • compositions prepared by the process of the present invention and suitable for use in dishwashing methods may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • organic silver coating agents are described in PCT Publication No. W094/ 16047 and copending UK Application No. UK 9413729.6.
  • Nitrogen-containing corrosion inhibitor compounds are disclosed in copending European Application no. EP 93202095.1.
  • Mn(II) compounds for use in corrosion inhibition are described in copending UK Application No. 9418567.5.
  • Organic silver coating agent may be incorporated at a level of from 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition.
  • the functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied.
  • the silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.
  • Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain.
  • monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and ⁇ , ⁇ '- dihydroxyisobutyric acid.
  • suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
  • the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • glycerol esters are also highly preferred. These are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above.
  • fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl proprionate.
  • Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.
  • Glycerol monostearate glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
  • Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.
  • Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
  • Waxes including microcrystalline waxes are suitable organic silver coating agents herein.
  • Preferred waxes have a melting point in the range from about 35°C to about 110°C and comprise generally from 12 to 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
  • Alginates and gelatin are suitable organic silver coating agents herein.
  • Dialkyl amine oxides such as 2-C2O methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the 2-C20 methylammonium halides are also suitable.
  • suitable organic silver coating agents include certain polymeric materials.
  • perfume materials particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.
  • Polymeric soil release agents can also be used as an organic silver coating agent.
  • Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C 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 ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end- capped oligomeric esters of U.S.
  • Patent 4,721,580 issued January 26, 1988 to Gosselink
  • block polyester oligomeric compounds of U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink.
  • Other polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-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 preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predominantly branched C25-.45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 : 10 to 2:1, preferably from 1 :5 to 1 :1.
  • Nitrogen-containing corrosion inhibitor compounds Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139, 279 and British Patent GB-A- 1,137,741, which also discloses a method for making imidazole compounds.
  • nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Rl, R3, R4 and R5 where Ri is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of C1-C20 alkyl or hydroxy 1, and R4 is any ofH, NH2 or N ⁇ 2-
  • nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, l-phenyl-5-mercapto- 1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.
  • Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulphate ordiammonium hydrogen citrate are also suitable.
  • the compositions may contain an Mn(II) corrosion inhibitor compound.
  • the Mn(II) compound is preferably incorporated at a level of from 0.005% to 5% by weight, more preferably from 0.01% to 1%, most preferably from 0.02% to 0.4% by weight of the compositions.
  • the Mn(II) compound is incorporated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.
  • the Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride.
  • the Mn(II) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.
  • the Mn(II) compound may be a salt or complex of an organic ligand.
  • the organic ligand is a heavy metal ion sequestrant.
  • the organic ligand is a crystal growth inhibitor.
  • additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated C10-C20 fatty acids, or their salts, especially aluminium tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa- decane and other anti-oxidants such as betahydroxytoluene (BHT) 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 corrosion inhibitor compounds.
  • the level of available oxygen in the present compositions is preferably controlled; the level of available oxygen should hence preferably be in the range from 0.3%) to 2.5%, preferably from 0.5% to 1.7%, more preferably from 0.6% to 1.5%, most preferably from 0.7% to 1.2%, measured according to the method described hereunder.
  • the rate of release of available oxygen is preferably also controlled; the rate of release of available oxygen from the compositions herein preferably should be such that, when using the method described hereinafter, the available oxygen is not completely released from the composition until after 3.5 minutes, preferably the available oxygen is released in a time interval of from 3.5 minutes to 10.0 minutes, more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0 minutes to 8.5 minutes.
  • a beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrer speed is selected to ensure that the product is evenly dispersed through the solution.
  • the detergent composition typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler
  • the detergent composition is added and simultaneously a stop clock is started.
  • the temperature control should be adjusted so as to maintain a constant temperature of 20°C throughout the experiment.
  • Samples are taken from the detergent solution at 2 minute time intervals for 20 minutes, starting after 1 minute, and are titrated by the "titration procedure" described below to determine the level of available oxygen at each point.
  • AvO level is plotted versus time to determine the maximum level of AvO, and the rate of release of AvO
  • 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 preferred coating material particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of Si ⁇ 2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1, preferably 1.8: 1 to 2.4: 1, and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of 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 5-C20 primary alcohol ethoxy lates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10 6 preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methyl vinyl 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 C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include the C 10-C2O 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.
  • Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
  • Suitable means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compaction, 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 Si ⁇ 2-
  • 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.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1 , 1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • the detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, 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 C1-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.
  • HEDP ethane 1 -hydroxy- 1 ,1 -diphosphonic acid
  • Another optional ingredient useful in the compositions is one or more enzymes.
  • Preferred enzymatic materials include the commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%) to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is described in Granted European Patent, EP-B-0218272.
  • An especially preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza.
  • Preferred enzyme-containing compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • Organic polymeric compounds may be added as preferred components of the compositions in accord with the invention.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.
  • Organic polymeric compound is typically 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.
  • salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.
  • Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA 15, PA 10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90%) to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CRj(CO-0- R3)]- wherein at least one of the substituents R1 , R2 or R3, preferably Rl or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • R1 , R2 or R3, preferably Rl or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group R or R2 can be a hydrogen
  • R3 can be a hydrogen or alkali metal salt.
  • Most preferred is a substituted acrylic monomer wherein Ri is methyl, R2 is hydrogen (i.e. a methacrylic
  • 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 Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents Nos. 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.
  • Preferred lime soap dispersant compounds are disclosed in PCT Application No. WO93/08877.
  • 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.
  • Preferred suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 and copending European Application No. 93870132.3
  • compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05%) to 0.5% by weight of polymeric dye transfer ⁇ in- ⁇ hl-»tiVbktit iinngrr a ogrroennttcs
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • the detergent compositions for use in laundry cleaning methods may 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:
  • Ri is selected from anilino, N-2-bis-hydroxy ethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • 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 preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • 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.
  • R ⁇ 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 Co ⁇ oration.
  • Cationic fabric softening agents can also be inco ⁇ orated into compositions for use in laundry cleaning methods 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 inco ⁇ orated 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 preferred filler salt.
  • the detergent compositions used in the present invention are preferably not formulated to have an unduly high pH, in preference having a pH measured as a 1% solution in distilled water of from 8.0 to 12.5, more preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.
  • compositions prepared by way of the process described in the present invention are in tablet form.
  • Tablets may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting.
  • tablets are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm2, more preferably from 5 to 1 lKN/cm2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 hardness test as supplied by I. Holland instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape.
  • tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention.
  • an effective amount of the machine dishwashing 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.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from 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 liquid 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.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • 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. 001 1500, 001 1501 , 001 1502, and 001 1968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • the abbreviated component identifications have the following meanings, porosity is measured by way of the mercury porosimetry method and viscosity as measured by a Brookfield viscometer;
  • Citrate Tri-sodium citrate dihydrate Non-porous Carbonate Anhydrous sodium carbonate; porosity 0.95 ml/g
  • Carbonate/sulphate/PA Component characteristics as per this list 30 agglomerate porosity 0.042ml/g PB1 Anhydrous sodium perborate monohydrate; porosity 0.43 ml/g
  • PAAC Pentaamine acetate cobalt (III) salt BzP Benzoyl Peroxide Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall; viscosity 181 cp Protease Proteolytic enzyme of activity 4KNPU/g sold under the tradename Savinase by Novo
  • Te ⁇ olymer Te ⁇ olymer of average molecular weight approx. 7,000 comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20
  • Tablet composition D is a comparative composition prepared by existing methods.
  • the high porosity fraction is selected from the components of the particulate base detergent matrix.
  • the high porosity fraction for the pu ⁇ ose of the examples above include carbonate, sulfate, silicate and the carbonate/sulphate/PA30 agglomerate.
  • the high porosity fraction is then sprayed with low viscosity liquid components having viscosity below
  • the liquid components are nonionic surfactant and paraffin oil.
  • the remaining particulate base detergent matrix and liquid components are admixed with the high porosity fraction plus nonionic/paraffin oil particles.
  • the detergent composition is then compacted into tablet form using a standard 12 head rotary press at a pressure of 18KN/cm2
  • compositions A and B and the average porosity of the high porosity fraction of the detergent composition are described in the table below.
  • composition D is prepared by conventional methods, that is to say all detergent ingredients are premixed. Nonionic surfactant is then sprayed onto the entire detergent composition. The detergent composition is then compacted to form a tablet in the same manner as described above.
  • the following table represents the results obtained when measuring the hardness of the tablets as a function of the child bite strength (CBS).
  • CBS is measured as per the U.S. Consumer Product Safety Commission Test Specification (1500.51, 1500.52, 1500.53).
  • the tablet is placed horizontally between two strips/plates of metal.
  • the upper and lower plates are hinged, such that the plates resemble a human jaw.
  • a increasing downward force is applied to the upper plate, mimicking the closing action of a jaw, until the tablet breaks.
  • the CBS of the tablet is thus the force in kilograms, needed to break the tablet.
  • the acceptable child bite strength as set by the US Consumer Product Safety Commission is 50Kg. It is therefore the aim of the present invention to provide tablets of hardness greater than the 50Kg CBS Standard.

Landscapes

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

Abstract

L'invention porte sur un procédé de fabrication d'une pastille détergente appropriée pour être utilisée en blanchisserie ou dans des processus de lavage de la vaisselle. Ce procédé consiste à fabriquer sous forme de pastilles une composition détergente comprenant des composants solides qui forment une matrice détergente à base particulaire et des composants liquides non aqueux ayant une viscosité égale ou inférieure à 1000 cp, mesurée à température ambiante. Ce processus consiste à appliquer une proportion de composants liquides non aqueux ayant une viscosité égale ou inférieure à 1000 cp sur une fraction de grande porosité sélectionnée dans la totalité de la matrice détergente à base particulaire.
PCT/US1997/022918 1996-12-12 1997-12-12 Procede de fabrication de compositions detergentes se presentant sous forme de pastilles WO1998026038A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/319,808 US6177393B1 (en) 1996-12-12 1997-12-12 Process for making tabletted detergent compositions
EP97952416A EP0944710A1 (fr) 1996-12-12 1997-12-12 Procede de fabrication de compositions detergentes se presentant sous forme de pastilles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9625973.4 1996-12-12
GB9625973A GB2320255A (en) 1996-12-12 1996-12-12 Process for making tabletted detergent compositions

Publications (1)

Publication Number Publication Date
WO1998026038A1 true WO1998026038A1 (fr) 1998-06-18

Family

ID=10804439

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/022918 WO1998026038A1 (fr) 1996-12-12 1997-12-12 Procede de fabrication de compositions detergentes se presentant sous forme de pastilles

Country Status (3)

Country Link
EP (1) EP0944710A1 (fr)
GB (1) GB2320255A (fr)
WO (1) WO1998026038A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000039261A1 (fr) * 1998-12-23 2000-07-06 Henkel Kommanditgesellschaft Auf Aktien Adjuvant de lavage soluble et de faible dosage
DE19919444B4 (de) * 1999-04-29 2016-06-30 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittelformkörper mit Bindemittelcompound, Verfahren zu seiner Herstellung sowie Verwendung von Bindemittelcompounds
EP1048720A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes
EP1048721A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes
EP1048712A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé pour le traitement de textiles en utilisant un additif pour la lessive en forme de comprimés
EP1048719A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes
EP1048716A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Composition détergente
EP1048715A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Procédé de distribution d'une composition détergente
EP1048718A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes
EP1048717A1 (fr) * 1999-04-30 2000-11-02 The Procter & Gamble Company Compositions détergentes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674700A (en) * 1967-07-18 1972-07-04 Conrad J Gaiser Detergent tablet of amorphous sodium silicate having inherent binding properties,containing a surfactant,and method of making such tablet
WO1992018604A1 (fr) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Procede de production de pastilles de detergent pour machines a laver la vaisselle
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung
WO1996029387A1 (fr) * 1995-03-22 1996-09-26 Unilever N.V. Procede de formation de detergents en comprimes fortement caustiques
DE19606765A1 (de) * 1996-02-23 1997-08-28 Henkel Kgaa Verfahren zur Herstellung von Geschirrspülmitteltabletten

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674700A (en) * 1967-07-18 1972-07-04 Conrad J Gaiser Detergent tablet of amorphous sodium silicate having inherent binding properties,containing a surfactant,and method of making such tablet
WO1992018604A1 (fr) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Procede de production de pastilles de detergent pour machines a laver la vaisselle
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung
WO1996029387A1 (fr) * 1995-03-22 1996-09-26 Unilever N.V. Procede de formation de detergents en comprimes fortement caustiques
DE19606765A1 (de) * 1996-02-23 1997-08-28 Henkel Kgaa Verfahren zur Herstellung von Geschirrspülmitteltabletten

Also Published As

Publication number Publication date
EP0944710A1 (fr) 1999-09-29
GB2320255A (en) 1998-06-17
GB9625973D0 (en) 1997-01-29

Similar Documents

Publication Publication Date Title
US6159922A (en) Bleaching composition
US6599871B2 (en) Detergent tablet
US6177393B1 (en) Process for making tabletted detergent compositions
US6162259A (en) Machine dishwashing and laundry compositions
WO1999006521A1 (fr) Pastille detergente
EP1047764A1 (fr) Comprime detergent
WO2000004129A2 (fr) Pastilles detergentes
WO1998011185A1 (fr) Composition de detergent
SK642001A3 (en) Detergent tablet
SK592001A3 (en) Detergent tablet
GB2324495A (en) Multi-layer detergent tablet
EP0944710A1 (fr) Procede de fabrication de compositions detergentes se presentant sous forme de pastilles
US6177398B1 (en) Process for making tabletted detergent compositions
CA2296354C (fr) Composition de detergent
GB2311541A (en) Oxygen-releasing bleach composition
EP0904340A2 (fr) Composition pour machine a laver la vaisselle
CA2250293A1 (fr) Composition detergente pour lave-vaisselle
WO1997036989A1 (fr) Composition de blanchiment
EP0944711A1 (fr) Procede de fabrication de compositions detergentes se presentant sous forme de pastilles
EP0972005A1 (fr) Procede de production de compositions pour detergent en pastilles
GB2327948A (en) Dish-washer detergent composition containing a high cloud point surfactant
MXPA99006899A (en) Process for making tabletted detergent compositions

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CZ HU JP MX TR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

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

Ref document number: 09319808

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1997952416

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1997952416

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: 1997952416

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1997952416

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载