EP1115832A1 - Compositions detergentes - Google Patents

Compositions detergentes

Info

Publication number
EP1115832A1
EP1115832A1 EP98950950A EP98950950A EP1115832A1 EP 1115832 A1 EP1115832 A1 EP 1115832A1 EP 98950950 A EP98950950 A EP 98950950A EP 98950950 A EP98950950 A EP 98950950A EP 1115832 A1 EP1115832 A1 EP 1115832A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
acid
preferred
surfactants
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98950950A
Other languages
German (de)
English (en)
Inventor
Kevin Todd Norwood
Eugene Joseph Pancheri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/US1998/020221 external-priority patent/WO2000018869A1/fr
Priority claimed from PCT/US1998/020222 external-priority patent/WO2000018859A1/fr
Priority claimed from PCT/US1998/020220 external-priority patent/WO2000018873A1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1115832A1 publication Critical patent/EP1115832A1/fr
Withdrawn legal-status Critical Current

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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the invention relates to detergent compositions in particular, to laundry detergent compositions.
  • detergents for laundry applications contain surfactants and builders.
  • most detergents comprise a base powder, made by spray-drying or by granulation of builder components and surfactant components for example, by agglomeration or extrusion.
  • the base powder is often further treated with post-treatment steps such as dry-adding additional particulate detergent components, spray-on of further liquid components such as surfactants, particularly non-ionic surfactants and/or post-dusting steps using finely particulate solid materials to reduce caking and stickiness of the solid detergents produced.
  • solid detergents tend to form lumps or gel upon contact with water. Lumps of gelled material may then fall into the sump of a washing machine where they are not disturbed mechanically, or because of their method of use in a machine, solid detergents do not dissolve, poor delivery of the product from a dispensing drawer of a washing machine or from a dispensing device and/or once in the machine itself, results. Poor use of all of the detergent components is therefore achieved, generally preferred that the compositions are free of phosphate-containing builder material.
  • inorganic compounds in a detergent formulation can affect the phase chemistry of surfactants via their contribution to the ionic strength of the solution, certain surfactant phases can trap inorganic species in a phase that is conducive to hydrate formation; certain inorganic hydrates, once formed, can interlock with each other and produce a tough framework that is persistent and provides micro-regions that are conducive to surfactant phase formation Further complicating this situation is the fact that many of the inorganic hydrates and surfactant phases are affected by the concentration of the detergent in water by the hardness of the water and by the temperature of the water Thus nothing is known in the art that quantitatively describes this complex situation and leads to a solution for providing detergent compositions which will avoid such problems The inventors have now surprisingly found that a thorough understanding of these complex inter-related factors has enabled them to provide detergent compositions avoiding the problems discussed above. Novel detergent compositions are therefore provided which have a thorough understanding of these complex inter-related factors has enabled them to provide detergent compositions avoiding the problems discussed above. Novel detergent compositions are therefore provided which have
  • novel detergent compositions result which provide good washing performance with minimum amounts of detergent and good detergent delivery into the wash are achieved and fabric damage due to high localised bleach concentrations is minimised
  • a solid detergent composition comprising from 8-60 wt % of a surfactant system and having a minimum Grand Compatability Index of 0.5, preferably 0.6, more preferably 0 7 or even 0 8 or 0 9
  • the Grand Compatability Index is a function of a Compatability Index and a Secondary Compatibility Index.
  • the Compatibility Index can be determined in the following way:
  • the paddle is positioned in the centre of the Sotax apparatus with a distance between the bottom of the paddle and the bottom of the tergitometer of 25mm.
  • the overall height of the paddle blades is 19mm.
  • a wire basket is provided having side walls and base formed from 20 mesh (850 ⁇ ) stainless steel wire, a diameter of 25mm and a height of 41mm.
  • the wire basket is filled with a detergent product, the surface of the detergent product is levelled off and a non-permeable lid is used to close off the top of the wire basket.
  • the quantity of sample is gravimetrically determined by weight difference.
  • the wire basket is then suspended in a stationary position midway between the central axis of the Sotax and the side wall, at a height such that the base of the wire basket is 7mm above the upper surface of the paddle.
  • the water remaining in the Sotex apparatus is also analyzed in its entirety. First it is filtered through a 0.45 micron filter and analyzed for the number of moles of carbonate, sulfate, borate, and phosphate ions. It will be appreciated that this filtration should be accomplished immediately to avoid formation of insoluble salts from the soluble salts in the solution.
  • the filtered solution should be analyzed for the number of moles of any carbonate, sulfate, borate, and phosphate ions that are in solution. All carbonate, sulfate, borate, and phosphate salts that may have precipitated from the solution after the filtration are also analyzed and are added to the numbers that were found to be in solution.
  • the Compatibility Index is calculated according to the following formula:
  • Residue Index (I, + I ⁇ 8 ,, + O 0 *(I 0 - I>8i,)/I 0 )/(I 0 + O flesh)
  • I s number of moles of the above mentioned inorganics (carbonate, sulfate, borate and phosphate) ions determined in the aqueous solution;
  • I ⁇ 8h number of moles of the above mentioned inorganic hydrate salts containing less than 8 moles of water of hydration per mole determined in the wire basket residue;
  • I >8h number of moles of the above mentioned inorganic hydrate salts containing more than 8 moles of water of hydration per mole determined in the wire basket residue;
  • the Secondary Compatibility Index is determined in the following way:
  • the Secondary Compatibility Index is calculated according to the following formula:
  • I s total number of moles of the above mentioned inorganics (carbonate, borate, sulphate and phosphate) ions determined in the aqueous solution
  • l ⁇ /2h number of moles of the above mentioned inorganic hydrate salts containing less than 1/2 moles of water of hydration per mole determined in the filter cake
  • I 0 number of moles of the above mentioned inorganic salts that were placed in the Sotax at the start of the experiment;
  • O 0 number of moles of anionic, nonionic, cationic and semipolar surfactants (as described in pages 13 through 25) that were placed in the Sotax at the start of the experiment.
  • novel detergent formulations according to the invention have a surfactant system and an inorganic system that are well matched and compatible, these yield Grand Compatibility Indices of at least 0.5, preferably at least 0.6, more preferably at least 0.7 or even at least 0.8 or at least 0.9.
  • the detergent compositions of the invention preferably comprise no more than 3 wt% inorganic phosphate salts, more preferably no more than 1 wt % phosphate salts and most preferably no more than 0 5 wt% phosphate salts
  • the compositions of the invention comprise no more than 5 wt% inorganic borate salts, more preferably no more than 2 wt% inorganic borate salts and most preferably no more than 0 5 wt% inorganic borate salts
  • the detergent compositions of the invention contain less than 10 wt% inorganic chloride salts, more preferably less than 5 wt%, or even less than 2 wt% or 0.5 wt% inorganic chloride salts
  • Preferred compositions comprise at least 5 wt% sodium or potassium carbonate, bicarbonate or sesquicarbonate or mixtures thereof
  • Sesquicarbonate and/or bicarbonate are preferably present in amounts of at least 5 wt%, most preferably at least 10 wt% in the composition
  • the detergent compositions comprise a builder system which may be provided by one or mixtures of more than one builder Water soluble and/or water insoluble builders may be used.
  • the builder system generally comprises from 1 to 90 wt % of the detergent composition, preferably from 20 to 80 wt % of the composition
  • the builder system in the compositions according to the invention preferably contains a water-soluble and/or partially water-soluble builder compound, typically present at a level of from 1% to 80% by weight, preferably in amounts up to 50 wt %, or up to 40% or even 35%.
  • water-soluble builders are present in amounts from at least 3% or 8%, but they are preferably present in amounts from 6 to 25 wt%
  • the detergent compositions of the invention may comprise phosphate-containing builder material, such as tetrasodium pyrophosphate or more preferably anhydrous sodium tripolyphosphate.
  • Phosphate builders may be present at a level of from 0 5% to 60%, or from 5% to 50%, or even from 8% to 40% by weight However, it is Crystalline layered silicates are also suitable partially water-soluble builders The preferred crystalline layered silicate herein has the general formula
  • x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
  • M is preferably H, K or Na or mixtures thereof, preferably Na
  • the most preferred material is ⁇ -Na2Si2U5 ) ⁇ _ Na2Si2U5 or 5-Na2Si2 ⁇ 5, or mixtures thereof, preferably being at least 75% -Na2Si2 ⁇ 5 for example available from Clariant as NaSKS-6
  • the crystalline layered silicate material, in particular of the formula Na2Si2U5 may optionally comprise other elements such as B, P, S, for example obtained by processes as described in EP 578986-B.
  • Partially water-soluble builder is preferably present at a level up to 40%, more preferably up to 35%). When present it may be preferred that the composition of the invention comprises from 10% to 40%>, more preferably from 12% to 35% or even from 15% to 25% by weight of the composition of the partially water-soluble builder
  • the water soluble builders include organic carboxylic acids and salts thereof
  • 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 and mixtures of any of the foregoing
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • polymeric polycarboxylates may be present, including homo and copolymers of maleic acid and acrylic acid and their salts.
  • 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, malic and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1, 1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • 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.
  • acetic acid citric acid, malic acid, and fumaric acid, or their salts or mixtures thereof. It may be preferred that mixtures of the salt and acid form are present.
  • the water soluble builder is preferably present at a level up to 40%, more preferably up to 35%. When present it may be preferred that the composition of the invention comprises from 10% to 40%, more preferably from 12% to 35% or even from 15% to 25% by weight of the composition of the water-soluble builder.
  • polymeric or oligomeric polycarboxylates are present at levels of less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the compositions.
  • Suitable water-soluble builder materials are polymeric polycarboxylic acids or polycarboxylates, including the water soluble homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • Examples of such salts are polyacrylates of MWt 1000- 50000, preferably 10000 or even 7000 and copolymers of (poly)acrylate and maleic acid or anhydride, such copolymers having preferably a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • the water-soluble or partially insoluble builder and in particular, crystalline layered silicate when present, is at least partially, for example at least 50 wt % present, in an intimate mixture with a surfactant, preferably an anionic surfactant.
  • a preferred particulate component in the detergent compositions of the invention herein may comprise an intimate mixture of preferably from 25% to 75% by weight, more preferably from 35% to 68%, even more preferably from 45% to 62% by weight of the component of a of a crystalline layered silicate or water-soluble builder and from 25% to 75%) by weight, more preferably from 32% to 62% by weight more preferably from 38% to 48% by weight of the component of an anionic surfactant.
  • Such a particulate component preferably comprises less than 10% by weight of free moisture, preferably less than 5%, or even less than 3% or even less than 2% by weight.
  • the free moisture content as used herein can be determined by placing 5 grams of the particulate component in a petri dish and placing this petri dish in a convection oven at 50°C for 2 hours, and subsequently measuring the weight loss, due to water evaporation
  • the anionic surfactant preferably comprises from 50% to 100% by weight, preferably from 60% or even 75% to 100% of the anionic surfactant of a sulphonate surfactant preferably an alkyl benzene sulphonate surfactant, as described below. As much as 50 % by weight or more based on the total amount of anionic surfactant in the detergent composition is preferably incorporated into such a particulate component.
  • such a particulate component is present in the detergent composition in amounts of from 0.5 to 60 wt %, preferably from 3% to 50%, more preferably from 5% to 45%o, even more preferably at a level of at least 7% by weight of the composition.
  • the weight ratio of the crystalline layered silicate and/or one or more water- soluble builders to the anionic surfactant in the intimate mixture is from 4:5 to 7:3, more preferably from 1:1 to 2:1, most preferably from 5:4 to 3:2.
  • Such a component may also comprise additional ingredients, for example in amounts of from 0%> to 25%o, generally no greater than 20% or even 15%> by weight of the particulate component.
  • additional ingredients for example in amounts of from 0%> to 25%o, generally no greater than 20% or even 15%> by weight of the particulate component.
  • additional ingredients for example in amounts of from 0%> to 25%o, generally no greater than 20% or even 15%> by weight of the particulate component.
  • additional ingredients, and levels of incorporation thereof will depend on the application of the component or compositions and the physical form of the components and the compositions. It may be preferred that the particulate composition comprises less than 15% or even less 10% or even 5% by weight of the granulate of non-ionic ethoxylated alcohol surfactant, preferably less than 15%, or even less than 10% or even less than 5%> of any non-ionic surfactant.
  • the particulate composition comprises less than 10% by weight, preferably less than 5%> by weight of an aluminosilicate material. If any aluminosilicate material is present, it may be preferred that the particulate composition is dusted with the aluminosilicate material.
  • the particulate component may comprise polymeric binder material, although it is preferred to use as little binder material as possible. It may be preferred that the intimate mixture comprises less than 25%, preferably less than 10%, more preferably less than 5% by weight, most preferably 0% by weight of ethylene oxide polymers.
  • the particulate component preferably has a weight average particle size of at least 50 microns, preferably from 150 microns to 1500 microns, or more preferably 80% by weight of the particles has an particle size of more than 300 microns (80% by weight on Tyler sieve mesh 48) and less than 10%) by weight of the particles has a particle size of more than 1180 microns or even 710 microns (on Tyler mesh sieve24).
  • the density of the particulate component is from 380g/litre to 1500gr/litre, or more preferably from 500 g/litre to 1200 g/litre, more preferably from 550 g/litre to 900g/litre.
  • the particulate component can be present in the detergent compositions of the invention as a separate particle, or it may be further mixed with other detergent ingredients, including by further agglomeration, compaction, tabletting or extrusion.
  • Such an intimate mixture or particulate component may be prepared by any well-known method for forming such detergent particulates e.g. agglomeration, spray-drying, roll compaction and/or extrusion or combinations of these process steps. Such processes may optionally be followed by a drying step or a dusting step and/or a spray-on step The granulate produced is then preferably mixed with the other detergent ingredients.
  • the crystalline layered silicate and/or highly water-soluble builder may also be in an intimate mixture with other materials, including one or more of the water-soluble builders or polymeric compounds such as acrylic and/ or maleic acid polymers, inorganic acids or salts, including carbonates and sulphates, or small levels of other silicate material, including amorphous silicate, meta silicates, and aluminosilicates, as described herein.
  • water-soluble builders or polymeric compounds such as acrylic and/ or maleic acid polymers, inorganic acids or salts, including carbonates and sulphates, or small levels of other silicate material, including amorphous silicate, meta silicates, and aluminosilicates, as described herein.
  • part or even all of the water-soluble builder in particular, monomeric or oligomeric (poly)carboxylic acid or salt thereof is in the form of a separate particle, whereby it may be preferred that the average particle size of this builder material is then preferably less than 150 microns, or even less than 100 microns. It may be preferred that part of the water-soluble or partially water-soluble builder is used as dusting agent, to reduce the caking of the product when necessary.
  • a polycarboxylate polymer such as polymer and copolymer of maleic anhydride or acid and (poly)acrylic acid and their salts may be incorporated at a level of from 0.5% to 15%, preferably from 1% to 12% or even from 2% to 8% by weight of the composition.
  • the water-insoluble builder and the polymer are not in an intimate mixture with one another.
  • the inventors have also found that when a polymeric polycarboxylate is present, it may be preferred that the polymer is comprised in an intimate mixture with other detergent components, preferably in a spray-dried particle, which is prepared by first mixing a carbonate salt and the polymer and then addition and intimately mixing of other ingredients.
  • Insoluble Builders preferably in a spray-dried particle, which is prepared by first mixing a carbonate salt and the polymer and then addition and intimately mixing of other ingredients.
  • compositions of the invention may contain an insoluble builder compound Generally these are present in amounts no more than 30 wt%> based on the detergent composition as a whole, preferably no greater than 25 wt %.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have 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. Zeolite A has the formula:
  • Zeolite X has the formula Nag6 [(Al ⁇ 2)86(Si ⁇ 2)i06J- 276 H 2 O.
  • Zeolite MAP is zeolite MAP builder.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • the zeolite MAP detergent builder has a particle size, expressed as a d5o value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5Q value indicates that 50%) by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A.
  • Water insoluble-builders in particular aluminosilicates, have been found to contribute to the problems of poor overall use of components of detergent compositions. Therefore, their incorporation into detergent compositions is generally at low levels, or requires specific processing to enable maximum efficiency of all the detergent ingredients in a detergent composition.
  • aluminosilicate builder is preferably present in amounts below 9 wt %, preferably below 6 wt % or 4 wt %. It may even be preferred that substantially no water-insoluble builder is present.
  • a detergent composition will contain low levels of amorphous silicates, for example less than 5 wt % of the composition of amorphous sodium silicate, most preferably less than 2 wt %.
  • the detergent composition preferably comprises a builder system which comprises less than 30% or even less than 20% or even less than 10% by weight of water insoluble builder, whereby in the preferred embodiments the balance of the builder system are the water-soluble builders and/ or partially water soluble builders.
  • the aluminosilicate may be contained in a component containing other detergent ingredients, such as surfactants for example, in a detergent agglomerate, extrudate or a blown powder It may even be preferred that substantially no aluminosilicate is present as a separate (dry-added) particulate ingredient
  • amorphous silicate is preferably contained in a component containing other detergent ingredients, such as surfactant for example, in a detergent agglomerate, extrudate or a blown powder It may be preferred that substantially no amorphous silicate is present as separate particulate ingredient
  • detergent compositions of the invention preferably comprise at least one particulate component containing an intimate mixture of one or more of the water soluble or partially water soluble builders and one or more surfactants Preferably, at least two of such particulate components are present in the detergent composition
  • M is from 0 to 0 6, or even from 0 to 0 5
  • the detergent composition herein comprises at least two multi-ingredient (1 e no more than 95 wt % of a single ingredient in each component) components which comprise an anionic surfactant or an aluminosilicate or mixtures thereof, whereby if mixtures of aluminosilicate and the surfactant are present in one or more of the components, the degree of mixture M is less than 0.7, as defined by the formula.
  • each component comprises part or all of the aluminosilicate, all or part of the anionic surfactant or mixtures thereof, provided that M is from 0 to 0.7.
  • the components together comprise the aluminosilicate builder at a level of least 5% by weight of the composition of and the anionic surfactant at a level of at least 5% by weight of the composition.
  • the components comprise the aluminosilicate at a level of at least 7%, or more preferably at least 10%> or even 15% by weight of the composition.
  • the compositions of the invention can even comprise higher levels of aluminosilicate, such as more than 20% or even more than 25%, whilst still providing an improved delivery of the detergent to the wash.
  • At least 7% or more preferably at least 10%) or even at least 12%> by weight of the composition of anionic surfactant is present in the components.
  • levels of anionic surfactants may be preferred to have 18% by weight of the composition or more.
  • Such components are prepared as described above: by any granulation method such as agglomeration, co-compaction, spray-drying or extrusion.
  • a preferred effervescence system for incorporation in the particle of the invention comprises an acid source, capable of reacting with an alkali source in the presence of water to produce a gas.
  • the effervescence system comprises two or more reactants, these will be provided in an intimate mixture as an effervescence component.
  • the effervescence component comprises an intimate mixture of substantially anhydrous stabilising agent with acid and alkaline reactants.
  • the acid source component may be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof.
  • the acid source component comprises an organic acid.
  • the acid source is preferably substantially anhydrous or non-hygroscopic and the acid is preferably water-soluble. It may be preferred that the acid source is overdried.
  • Suitable acid source components include citric, malic, maleic, fumaric, aspartic, glutaric, tartaric succinic or adipic acid, monosodium phosphate, boric acid, or derivative thereof Citric acid, maleic or malic acid are especially preferred.
  • the acid source provides acidic compounds which have an average particle size in the range of from about 75 microns to 1 180 microns, more preferably from 150 microns to about 710 microns, calculated by sieving a sample of the source of acidity on a series of Tyler sieves.
  • the effervescence system preferably comprises an alkali source, however, for the purpose of the invention, it should be understood that the alkali source may be part of the effervescence particle or can be part of the cleaning composition comprising the particle, or can be present in the washing liquor, whereto the particle or the cleaning composition is added.
  • any alkali source which has the capacity to react with the acid source to produce a gas may be present in the particle, which may be any gas known in the art, including nitrogen oxygen and carbondioxide gas.
  • Preferred can be perhydrate bleaches, including perborate, and silicate material.
  • the alkali source is preferably substantially anhydrous or non- hydroscopic. It may be preferred that the alkali source is overdried.
  • this gas is carbon dioxide
  • the alkali source is a preferably a source of carbonate, which can be any source of carbonate known in the art.
  • the carbonate source is a carbonate salt.
  • preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium or potassium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No 2,321 ,001 published on November 15, 1973
  • Alkali metal percarbonate salts are also suitable sources of carbonate species, which may be present combined with one or more other carbonate sources
  • the carbonate and bicarbonate preferably have an amorphous structure
  • the carbonate and/ or bicarbonates may be coated with coating materials It can be preferred that the particles of carbonate and bicarbonate can have a mean particle size of 75 microns or preferably 150 ⁇ m or greater, more preferably of 250 ⁇ m or greater, preferably 500 ⁇ m or greater.
  • the carbonate salt is such that fewer than 20% (by weight) of the particles have a particle size below 500 ⁇ m, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves
  • the fewer than 60% or even 25% of the particles have a particle size below 150 ⁇ m
  • fewer than 5% has a particle size of more than 1.18 mm
  • more preferably fewer than 20%o have a particle size of more than 212 ⁇ m, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves.
  • the molecular ratio of the acid source to the alkali source present in the particle core is preferably from 50: 1 to 1 :50, more preferably from 20 1 to 1 20 more preferably from 10: 1 to 1: 10, more preferably from 5: 1 to 1.3, more preferably from 3 1 to 1.2, more preferably from 2: 1 to 1.2.
  • the preferred stabilising agents are substantially anhydrous stabilising agent
  • the stabilising agent can comprise one or more components It can be preferred that the stabilising agent comprises compounds which are, at least partially, water-soluble
  • the stabilising agent is solid under normal storage conditions, e.g. the component preferably has a melting point above 30°C, more preferably above 45°C, or even more preferably above 50°C and it may be preferred that the stabilising agent is such that it readily forms a melt above 80°C.
  • the stabilising agent comprises one or more components, selected from the group comprising alkoxylated alcohols, including polyethylene and/or propylene glycols, and alkoxylated alcoholamides, including ethanolamides, alkoxylated ethanol amides, alkoxylated fatty acid amides or ethanolamides and specific non-ionic surfactants, including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants and specific alkylpolysaccharides surfactant, and mixtures of any of these compounds, as described herein.
  • alkoxylated alcohols including polyethylene and/or propylene glycols
  • alkoxylated alcoholamides including ethanolamides, alkoxylated ethanol amides, alkoxylated fatty acid amides or ethanolamides and specific non-ionic surfactants, including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants and specific alkylpolysaccharides surfactant, and mixture
  • one or more of the components comprised in the stabilising agent are a detergent active which can contribute to the cleaning performance of the particle or the cleaning composition comprising the particle.
  • Highly preferred substantially anhydrous components suitable in the stabilising agent of the particle of the invention are one or more non-ionic surfactant, selected from the group of non-ionic alkoxylated surfactants, including alkoxylated alcohol surfactants, polyhydroxyfattyacid amide surfactants, fatty acid amide surfactants, alkoxylated fatty acid amides, alkyl esters of fatty acids and alkylpolysaccharide surfactants, and mixtures thereof, as described herein after.
  • the stabilising agent comprises a mixture of polyhydroxy fatty acid amides and/ or polyethylene glycols, and/ or alkoxylated fatty acid amides and/ or condensation products of aliphatic alcohols with from 1 to 15, or more preferably 11, moles of alkylene oxide, as described in more detail below in the description of suitable surfactants.
  • the ratio of the polyhydroxy fatty acid amides to the condensation products of aliphatic alcohols is preferably from 20: 1 to 1 :20, more preferably from 10: 1 to 1 :10, more preferably from 8: 1 to 1 :8, more preferably from 6: 1 to 1:6, most preferably from 2:1 to 1 :3.
  • the ratio of the polyhydroxy fatty acid amides to the polyethylene glycol is preferably from 20: 1 to 1 :8, more preferably from 15:1 to 1 :3, more preferably from 12: 1 to 1 : 1, more preferably from 10: 1 to 1 : 1.
  • the ratio of the polyhydroxy fatty acid amides to the alkoxylated fatty acid amides is preferably from 20:1 to 1:20, more preferably from 15: 1 to 1 : 10, more preferably from 10:1 to 1 : 10.
  • the detergent compositions of the invention can contain one or more surfactants selected from anionic, cationic, ampholytic, amphoteric and zwitterionic surfactants or nonionic surfactants as described below, and mixtures thereof.
  • anionic surfactant can be incorporated in the compositions of the invention.
  • the anionic surfactant herein preferably comprises at least a sulphate surfactant and/ or a sulphonate surfactant or mixtures thereof. It may be preferred that the anionic surfactant comprises only alkyl sulphonate surfactant or optionally combined with fatty acids or soap salts thereof. Alternatively, it may be preferred that the composition comprises only akly sulphate surfactant, but hereby it is preferred that at least a mid-chain branched alkyl surfactant is present or at least two alkyl surfactants are present.
  • compositions herein comprise a particulate component, as descriebd above, preferably in the form of a flake of an alkyl sulfate or sulphonate surfactant, preferably an alkyl benzene sulphonate, present at a concentration of from 85% to 95% of the particle or flake, the balance being an sulfate salt and moisture, the particle or flake being admixed to the other detergent component(s) or ingredients.
  • a particulate component preferably in the form of a flake of an alkyl sulfate or sulphonate surfactant, preferably an alkyl benzene sulphonate, present at a concentration of from 85% to 95% of the particle or flake, the balance being an sulfate salt and moisture, the particle or flake being admixed to the other detergent component(s) or ingredients.
  • anionic surfactants include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C , -, monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C.--C, , diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • the compositions herein comprise a component which contains high levels of an alkyl sulphate or sulphonate surfactant or mixtures thereof, preferably an alkyl benzene sulphonate, intimately mixed with an sulphate salt and moisture.
  • a component comprising from 85% to 95% of one an anionic sulphate or sulphonate surfactant and from 15% to 5% sulphate salt and moisture.
  • Such a component may be in the form f a flake, which can be admixed or dry-added to the other components of the detergent composition herein.
  • anionic Sulphonate surfactants in accordance with the invention include the salts of C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates, C6-C22 primary or secondary alkane sulphonates, Cg-C24 olefin sulphonates, sulphonated polycarboxylic acids, and any mixtures thereof.
  • Preferred salts are sodium and potassium salts.
  • alkyl ester sulphonated surfactant are also suitable for the invention, preferably those of formula R 1 - CH(SO 3 M) - (A) x - C(O) - OR 2
  • R! is a Cg-C22 hydrocarbyl
  • R 2 is a Cj-Cg alkyl
  • A is a C6-C22 alkylene
  • alkenylene x is 0 or 1
  • M is a cation.
  • the counterion M is preferably sodium, potassium or ammonium.
  • the alkyl ester sulphonated surfactant is preferably a ⁇ -sulpho alkyl ester of the formula above, whereby thus x is 0.
  • R 1 is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0.
  • R 2 is preferably ethyl or more preferably methyl.
  • Rl of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R 1 of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.
  • the anionic sulphate surfactant herein include the linear and branched primary and secondary alkyl sulphates and disulphates, alkyl ethoxysulphates having an average ethoxylation number of 3 or below, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, the C5-C17 acyl-N-(C 1 -C4 alkyl) and -N-(C ]-C2 hydroxyalkyl) glucamine sulphates, and sulphates of alkylpolysaccharides.
  • Primary alkyl sulphate surfactants are preferably selected from the linear and branched primary C10-C1 g alkyl sulphates, more preferably the Ci 1-C15 linear or branched chain alkyl sulphates, or more preferably the Ci 2-C14 linear chain alkyl sulphates.
  • Preferred secondary alkyl sulphate surfactant are of the formula R 3 -CH(SO 4 M)-R 4
  • R 3 is a Cs-C 2 ohydrocycarbyl
  • R 4 is a hydrocycarbyl
  • M is a cation
  • Alkyl ethoxy sulphate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulphates which have been ethoxylated with from 0.5 to 3 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulphate surfactant is a C ⁇ 1 -Ci 8, most preferably C j-Ci 5 alkyl sulphate which has been ethoxylated with from 0 5 to 3, preferably from 1 to 3, moles of ethylene oxide per molecule
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulphate and alkyl ethoxysulphate surfactants.
  • Preferred salts are sodium and potassium salts.
  • Preferred mid-chain branched primary alkyl_sulfate surfactants for use herein are of the formula
  • surfactants have a linear primary alkyl sulfate chain backbone (i e , the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms
  • the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17 5
  • the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.
  • R, R1, and R 2 are each independently selected from hydrogen and C1 -C3 alkyl group (preferably hydrogen or C1 -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, Rl, and R 2 are not all hydrogen. Further, when z is 1, at least R or R* is not hydrogen.
  • M is hydrogen or a salt forming cation depending upon the method of synthesis.
  • w is an integer from 0 to 13;
  • x is an integer from 0 to 13;
  • y is an integer from 0 to 13;
  • z is an integer of at least 1; and
  • w + x + y + z is an integer from 8 to 14.
  • a preferred mid-chain branched primary alkyl sulfate surfactant is, a C 16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and having 1, 2, or 3 branching units (i.e., R, R* and/or R 2 ) of in total 3 carbon atoms, (whereby thus the total number of carbon atoms is at least 16).
  • Preferred branching units can be one propyl branching unit or three methyl branching units.
  • Another preferred surfactant are branched primary alkyl sulfates having the formula
  • the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5;
  • R and R 2 are each independently hydrogen or C1 -C3 alkyl;
  • M is a water soluble cation;
  • x is from 0 to 11;
  • y is from 0 to 11;
  • z is at least 2; and
  • x + y + z is from 9 to 13; provided Rl and R 2 are not both hydrogen.
  • dianionic surfactants are also useful anionic surfactants for the present invention, in particular those of formula
  • R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Ci to C28, preferably C3 to C24, most preferably Cg to C20, or hydrogen;
  • a nad B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain length C ⁇ to
  • C28 preferably Ci to C5, most preferably C ⁇ or C2, or a covalent bond, and preferably A and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms;
  • X and Y are anionic groups selected from the group comprising carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably 1 ; and
  • M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
  • the most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from C]o to Cjg, A and B are independently C ⁇ or C2, both X and
  • Y are sulfate groups
  • M is a potassium, ammonium, or a sodium ion.
  • Preferred dianionic surfactants herein include: (a) 3 disulphate compounds, preferably 1,3 C7-C23 (i.e., the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C 20;
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Ci g; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Ci 8- It can be preferred that the dianionic surfactants of the invention are alkoxylated dianionic surfactants.
  • the alkoxylated dianionic surfactants of the invention comprise a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart are attached. At least one of said anionic substituent groups is an alkoxy- linked sulphate or sulphonate group.
  • Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups.
  • Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof.
  • the structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms.
  • the structural skeleton comprises only carbon- containing groups and more preferably comprises only hydrocarbyl groups.
  • the structural skeleton comprises only straight or branched chain alkyl groups.
  • the structural skeleton is preferably branched. Preferably at least 10 % by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulphate or sulphonate group attached to the branching).
  • a preferred alkoxylated dianionic surfactant has the formula
  • R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇ to C28, preferably C3 to C24, most preferably C$ to C20 > or hydrogen;
  • a and B are independently selected from, optionally substituted, alkyl and alkenyl group of chain length Cj to C28 > preferably C ⁇ to C5, most preferably C ⁇ or C2, or a covalent bond;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1;
  • a and B in total contain at least 2 atoms;
  • A, B, and R in total contain from 4 to about 31 carbon atoms;
  • X and Y are anionic groups selected from the group consisting of sulphate and sulphonate,
  • the most preferred alkoxylated dianionic surfactant has the formula as above where R is an alkyl group of chain length from CJ Q to C ⁇ g, A and B are independently C ⁇ or C2, n and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
  • Preferred alkoxylated dianionic surfactants herein include: ethoxylated and/or propoxylated disulphate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates, more preferably having the formulae:
  • R is a straight or branched chain alkyl or alkenyl group of chain length from about
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and n and m are independently within the range of from about 0 to about 10 (preferably from about 0 to about 5), with at least m or n being 1.
  • 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
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a Cg to C j g alkyl group, x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from 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- 1 -decanoic acid, 2-propyl- 1 -nonanoic acid, 2-butyl- 1 - 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*) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R! is a C J - C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R! is a C J - C4 alkyl group
  • M is an alkali metal ion.
  • the components of the compositors herein are free of sprayed-on non-ionic alkoxylated alcohol surfactants. It has been found that hereby the delivery of the composition to the washing water can be improved and the caking of the product can be reduced. It may be preferred that the composition comprises a non-ionic surfactant which is solid at temperatures below 30°C or even 40°C, preferably present in an intimate mixture with other ingredients.
  • any alkoxylated non-ionic surfactants can also be comprised in the detergent compositions of the invention.
  • the ethoxylated and propoxylated non-ionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the non- ionic condensates of alkyl phenols, non-ionic ethoxylated alcohols, non-ionic ethoxylated/propoxylated fatty alcohols, non-ionic ethoxylate/propoxylate condensates with propylene glycol, and the non-ionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • non-ionic alkoxylated alcohol surfactants being the condensation products of aliphatic alcohols with from 1 to 75 moles of alkylene oxide, in particular about 50 or from 1 to 15 moles, preferably to 1 1 moles, particularly ethylene oxide and/or propylene oxide, are highly preferred non-ionic surfactant comprised in the anhydrous component of the particles of the invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides are highly preferred non-ionic surfactants for use in the invention , in particular those having the structural formula R ⁇ CONR ⁇ Z wherein : Rl is H, Ci _i 8, preferably C C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight- chain C5-C19 or C 7 -C 19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (
  • a highly preferred non-ionic polyhydroxy fatty acid amide surfactant for use herein is a C12-C14 , a C15-C17 and/or Cj6-Ci8 alkyl N-methyl glucamide.
  • the polyhydroxy fatty acid amide can be prepared by any suitable process.
  • One particularly preferred process is described in detail in WO 9206984.
  • Fatty acid amide surfactants or alkoxylated fatty acid amides include those having the formula: R ⁇ CON(R ⁇ ) (R ⁇ ) wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R 7 anc * R 8 are each individually selected from the group consisting of hydrogen, C1-C4 alkyl, C ] -C4 hydroxyalkyl, and -(C2H4O) x H, where x is in the range of from 1 to 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R 7 is different to R ⁇ > one having x being 1 or 2, one having x being from 3 to 1 1 or preferably 5.
  • Alkyl esters of fatty acids include those having the formula: R9COO(R10) wherein R9 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 1 1 to 13 carbon atoms and R ⁇ is a C1-C4 alkyl, C1-C4 hydroxyalkyl, or -(C2H ⁇ ) x H, where x is in the range of from 1 to 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R 10 is a m ⁇ or eth y! S rou P-
  • Alkylpolysaccharides can also be comprised in the anhydrous material of the particle of the invention, such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Cationic Surfactant Another preferred component of the compositions of the invention is a cationic surfactant, which is preferably be present at a level of from 0.1% to 60% by weight of the composition, more preferably from 0 4% to 20%, most preferably from 0 5% to 5% by weight of the composition.
  • the ratio of the anionic surfactant to the cationic surfactant is preferably from 25:1 to 1 :3, more preferably from 15:1 to 1 :1. most preferably from 10: 1 to 1 1
  • the ratio of cationic surfactant to the stabilising agent is preferably from 1 30 to 20 1, more preferably from 1:20 to 10.1.
  • the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixtures thereof.
  • the optional cationic mono-alkoxylated amine surfactant for use herein has the general formula:
  • R ⁇ is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 11 carbon atoms;
  • R 2 and R- are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl;
  • R ⁇ is selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulphate, or the like, to provide electrical neutrality;
  • A is selected from C ⁇ -C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and
  • p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.
  • R! is C6-C ⁇ g hydrocarbyl and mixtures thereof, preferably Cg-C ⁇ , especially C6-C1 1 alkyl, preferably Cg and Ci Q alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH 3 )CH 2 O] and [CH 2 CH(CH 3 O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
  • EO ethoxy
  • i-Pr isopropoxy units
  • Pr n-propoxy units
  • the cationic bis-alkoxylated amine surfactant for use herein has the general formula:
  • Rl is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 1 1, most preferably from about 8 to about 10 carbon atoms;
  • R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R ⁇ and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulphate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy,
  • p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • R is C6-C]8 hydrocarbyl and mixtures thereof, preferably Cg, C8, Cjo > C12, C14 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • R ⁇ is Cg-Ci 8 hydrocarbyl, preferably Cg-C ⁇ alkyl, independently p is 1 to about
  • R 2 is C1-C3 alkyl, preferably methyl
  • X is an anion, especially chloride or bromide.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R (OR4) X NO(R5)2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from
  • each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C JQ- I S alkyl dimethylamine oxide, and C J O-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the particle of the invention or the compositions containing the particle of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2cOO" wherein R is a C6-C ⁇ g hydrocarbyl group, each R is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C 12-.18 dimethyl-ammonio hexanoate and the i ⁇ -18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • the detergent composition of the invention can comprise any additional detersive actives or ingredients known in the art.
  • additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.
  • compositions thereof comprise a perfume, brightener or dye or mixtures thereof, which may be sprayed onto the particular component herein.
  • compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, builders, chelants, (additional) alkalinity sources, organic polymeric compounds, enzymes, brightners, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • additional detergent components selected from surfactants, bleaches, builders, chelants, (additional) alkalinity sources, organic polymeric compounds, enzymes, brightners, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Heavy metal ion sequestrant are also useful additional ingredients herein.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3%) to 2%> by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1, 1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3 -sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2- phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'- disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • diethylenetriamine pentacetic acid ethylenediamine-N,N'- disuccinic acid (EDDS) and 1, 1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N,N'- disuccinic acid
  • the detergent compositions of the invention comprise oxygen bleach, preferably comprising a hydrogen peroxide source and a bleach precursor or activator. Since the present invention improves product delivery to the wash, it increases bleach efficiency and reduces the risk of fabric damage by bleaches present in the detergent.
  • a preferred source of hydrogen peroxide is a perhydrate bleach, such as metal perborates, more preferably metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
  • percarbonate salts are preferably coated.
  • Suitable coating agent are known in the art, and include silicates, magnesium salts and carbonates salts.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • composition herein is an organic peroxyacid 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, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5%o to 20% by weight, more preferably from 1%> to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • Y is H or a solubilizing group.
  • Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -SO-. " M , -CO- M , -SO M , -N (R ) 4 X " and
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is a halide, hydroxide, methylsulfate or acetate anion
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
  • TAED Tetraacetyl ethylene diamine
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: R 1 C — N — R 2 C L R 1 N — C — R 2 C L
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic Acid Precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • the detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10%o by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R N C — OOH N R ⁇ OOH
  • R* is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
  • Another preferred ingredient useful herein is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available upases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533, 139.
  • Organic polymeric compounds are preferred additional components of the compositions herein.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as binder, dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5%) to 10%> by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or copolymeric 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 MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmefhylcellulose and hydroxyethylcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
  • Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
  • X is a non-ionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • the detergent compositions of the invention when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%), preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component Such silicone antifoam compounds also typically contain a silica component
  • silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci 8-
  • C40 ketones e.g. stearone
  • N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e g sodium, potassium, lithium) phosphates and phosphate esters
  • a preferred suds suppressing system comprises:
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95%> by weight of the silicone antifoam compound, and
  • silica at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound
  • silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight,
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 0 9 to 1 1 1, at a level of from 0 5% to 10%, preferably 1% to 10% by weight
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544,
  • an inert carrier fluid compound most preferably comprising a Cjg-Ci 8 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight,
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid
  • compositions herein may also comprise from 0 01% to 10 %, preferably from 0 05% to 0.5%) by weight of polymeric dye transfer inhibiting agents
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • compositions herein also optionally contain from about 0 005% to 5% by weight of certain types of hydrophilic optical brighteners, as known in the art
  • SRA Polymeric soil release agents, hereinafter "SRA"
  • SRA's will generally comprise from 0 01% to 10 0%, typically from 0.1%) to 5%, preferably from 0 2% to 3.0% by weight, of the compositions
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • SRA's include the non-ionic end- capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. 4,71 1,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the non-ionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRA's include: (I) non-ionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either non-ionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
  • compositions of the invention include perfumes, speckles, colours or dyes, filler salts, with sodium sulphate being a preferred filler salt.
  • minor amounts e.g., less than about 20% by weight
  • neutralizing agents e.g., buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.
  • Highly preferred are encapsulated perfumes, preferably comprising a starch encapsulte.
  • compositions of the invention it may be preferred that when dyes and/ or perfumes are sprayed onto the another component, the component does not comprise spray-on non- ionic alkoxylated alcohol surfactant.
  • composition of the invention thereof can be made via a variety of methods involving the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying.
  • compositions herein can take a variety of physical solid forms including forms such as tablet, flake, pastille and bar, and preferably the composition is in the form of granules or a tablet.
  • compositions in accordance with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
  • compositions preferably have a density of more than 350 gr/litre, more preferably more than 450 gr/litre or even more than 570 gr/litre.
  • density of more than 350 gr/litre, more preferably more than 450 gr/litre or even more than 570 gr/litre.
  • Nai 2(AlO2SiO2)i2-27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • NaSKS-6 Crystalline layered silicate of formula ⁇ - Na2Si2U5 0 f weight average particle size of 18 microns and at least 90%) by weight being of particle size of below 65.6 microns
  • NaSKS-6 (II) Crystalline layered silicate of formula ⁇ - Na2Si2 ⁇ 5 0 f weight average particle size of 18 microns and at least 90%) by weight being of particle size of below 42 1 microns
  • Citric acid Anhydrous citric acid
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Protease Proteolytic enzyme having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
  • Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A S Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by NOVO Industries A S under the tradename Termamyl 120T
  • Amylase II Amylolytic enzyme as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename
  • Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 Sodium perborate tetrahydrate of nominal formula
  • DPDA Diperoxydodecanedioc acid NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate LOBS Dodecanoyloxybenzene sulfonate in the form of the sodium salt
  • DOBS Decanoyloxybenzene sulfonate in the form of the sodium salt
  • Photoactivated bleach Sulfonated zinc phthlocyanine encapsulated in or carried by soluble polymer or sulfonated alumino phthlocyanine encapsulated in or carried by soluble polymer
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino- 1.3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate
  • HEDP 1,1 -hydroxyethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x (typically
  • PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000
  • PVP VI Copolymer of polyvinylpyrolidone and vinylimidazole with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • Opacifier Water based monostyrene latex mixture, sold by BASF
  • a detergent composition comprising blown powder, an agglomerate comprising crystalline layered silicate and anionic surfactant, an effervescent particle and dry-mixed bleach activator particle, sodium percarbonate, sodium citrate and suds supressor.
  • the individual particulates were prepared and dry-mixed together with gentle mixing e.g. in a Nautamixer for a period of at least 4 minutes.
  • composition of the final blown powder was as follows:-
  • the blown powder was prepared by a standard spray drying process.
  • the above ingredients were mixed into a slurry with water.
  • the aqueous slurry may be prepared by a batch or continuous process.
  • a batch mixer, or "crutcher” was used in which the various detergent components were dissolved in, or slurried with, water to provide a slurry containing 35%> water.
  • the water content my be varied from about 20% to about
  • aqueous slurry 60% by weight of water, preferably it is about from about 30% to about 40% by weight water.
  • order of addition of the ingredients to water to form the aqueous slurry was as listed above in the final composition of the blown powder.
  • the aqueous slurry was then pumped at high pressure through atomising nozzles into a spray- drying tower where excess water was driven off, producing a flowable powder product
  • Particles were prepared having the following composition:
  • the particle was made via a roller compaction process.
  • the raw materials in the proportions indicated above, were fed at a press force of 80kN into a Pharmapaktor L200/50 P roller, set up with concave smooth rolls with a 0.3mm axial corrugation installed.
  • the flakes produced were then compacted using a Flake Crusher FC 200 with a mesh size selected to produce the required particle size.
  • the product was screened to remove the fines.
  • detergent compositions of the invention are given as formulations A-

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

Abstract

Cette invention concerne des compositions à base de détergent solide qui comprennent de 8 à 60 % en poids d'un système tensioactif, et qui possèdent un indice de compatibilité de Grand d'au moins 0,5 et, de préférence, d'au moins 0,6. Elle concerne également l'utilisation qui est faite de ces compositions détergentes pour lessiver des tissus souillés.
EP98950950A 1998-09-25 1998-10-05 Compositions detergentes Withdrawn EP1115832A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
PCT/US1998/020221 WO2000018869A1 (fr) 1998-09-25 1998-09-25 Compositions detergentes solides
WOPCT/US98/20222 1998-09-25
PCT/US1998/020222 WO2000018859A1 (fr) 1998-09-25 1998-09-25 Compositions detergentes solides
WOPCT/US98/20221 1998-09-25
WOPCT/US98/20220 1998-09-25
PCT/US1998/020220 WO2000018873A1 (fr) 1998-09-25 1998-09-25 Compositions detergentes
PCT/US1998/021022 WO2000018870A1 (fr) 1998-09-25 1998-10-05 Compositions detergentes

Publications (1)

Publication Number Publication Date
EP1115832A1 true EP1115832A1 (fr) 2001-07-18

Family

ID=27378541

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98950950A Withdrawn EP1115832A1 (fr) 1998-09-25 1998-10-05 Compositions detergentes

Country Status (8)

Country Link
EP (1) EP1115832A1 (fr)
JP (1) JP2003522213A (fr)
CN (2) CN1322242A (fr)
AR (1) AR020515A1 (fr)
AU (1) AU9686298A (fr)
BR (1) BR9816029B1 (fr)
CA (1) CA2343895C (fr)
WO (1) WO2000018870A1 (fr)

Families Citing this family (13)

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Publication number Priority date Publication date Assignee Title
US6010729A (en) 1998-08-20 2000-01-04 Ecolab Inc. Treatment of animal carcasses
US7150884B1 (en) 2000-07-12 2006-12-19 Ecolab Inc. Composition for inhibition of microbial growth
JP5106717B2 (ja) * 2000-12-27 2012-12-26 ライオン株式会社 洗浄剤組成物
DE10153551A1 (de) * 2001-10-30 2003-05-22 Henkel Kgaa Im wesentlichen sedimentfrei dispergierbares Wasch- oder Reinigungsmittel
US7771737B2 (en) 2004-01-09 2010-08-10 Ecolab Inc. Medium chain peroxycarboxylic acid compositions
EP1703791B1 (fr) 2004-01-09 2014-07-23 Ecolab Inc. Compositions d'acide peroxycarboxylique a chaine moyenne
US8999175B2 (en) 2004-01-09 2015-04-07 Ecolab Usa Inc. Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions
CA2573996C (fr) * 2004-08-11 2010-09-21 The Procter & Gamble Company Composition detergente solide pour blanchisserie, hautement hydrosoluble, formant une liqueur de lavage limpide par dissolution dans l'eau
US7754670B2 (en) 2005-07-06 2010-07-13 Ecolab Inc. Surfactant peroxycarboxylic acid compositions
US8075857B2 (en) 2006-10-18 2011-12-13 Ecolab Usa Inc. Apparatus and method for making a peroxycarboxylic acid
JP5785747B2 (ja) * 2011-03-18 2015-09-30 ライオン株式会社 粒状洗剤組成物
JP7334174B2 (ja) 2018-02-14 2023-08-28 エコラボ ユーエスエー インコーポレイティド 膜からバイオフィルムおよび胞子を低減するための組成物および方法
GR1009928B (el) * 2019-09-16 2021-02-01 Ιωαννης Φωτιου Φωτακοπουλος Σκονη καθαρισμου πλυντηριου ρουχων για τον καθαρισμο λεκεδων απο αντιηλιακα και καλλυντικα προϊοντα προσωπου και σωματος με χρωστικες ουσιες

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ230842A (en) * 1988-10-21 1992-05-26 Colgate Palmolive Co Nonionic heavy duty particulate detergent containing protease, amylase and cellulase
ATE190091T1 (de) * 1993-01-11 2000-03-15 Quest Int Parfümierte waschmittelpulvern
DE4310671A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa alpha-Sulfofettsäurealkylester enthaltendes Granulat
GB2307695A (en) * 1995-11-30 1997-06-04 Unilever Plc Detergent compositions containing soil release polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0018870A1 *

Also Published As

Publication number Publication date
BR9816029B1 (pt) 2009-01-13
CN1322242A (zh) 2001-11-14
CN1168815C (zh) 2004-09-29
CA2343895A1 (fr) 2000-04-06
WO2000018870A1 (fr) 2000-04-06
BR9816029A (pt) 2001-05-29
CA2343895C (fr) 2005-12-06
JP2003522213A (ja) 2003-07-22
CN1322236A (zh) 2001-11-14
AR020515A1 (es) 2002-05-15
AU9686298A (en) 2000-04-17

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