WO2001012767A1 - Composant de desintegration et composition detergente contenant ce composant - Google Patents

Composant de desintegration et composition detergente contenant ce composant Download PDF

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Publication number
WO2001012767A1
WO2001012767A1 PCT/US1999/018379 US9918379W WO0112767A1 WO 2001012767 A1 WO2001012767 A1 WO 2001012767A1 US 9918379 W US9918379 W US 9918379W WO 0112767 A1 WO0112767 A1 WO 0112767A1
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WIPO (PCT)
Prior art keywords
water
cross
agent
swellable
detergent
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PCT/US1999/018379
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English (en)
Inventor
Barry Thomas Ingram
Stephen Wayne Heinzman
Arnaud Pierre Struillou
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The Procter & Gamble Company
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Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU55591/99A priority Critical patent/AU5559199A/en
Priority to PCT/US1999/018379 priority patent/WO2001012767A1/fr
Publication of WO2001012767A1 publication Critical patent/WO2001012767A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0082—Coated tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • This invention relates to disintegrating components suitable for use in detergent or other compositions which will provide dissolution and/or dispensing benefits.
  • the invention also relates to detergent or other compositions or components thereof containing such disintegrating components.
  • US4642197 discloses the use of more than one disintegrant such as a mixture of cross-linked polyvinylpyrrolidone and/or celluolse ethers and/or swellable magnesium aluminium silicate.
  • detergent tablets preferably disintegrate very quickly or tablet fragments will be entrapped in either the dispenser, or in "dead areas" in the machine such as the area between the drum and the porthole in front loading automatic machines, or in the folds, creases and pockets of garments where the detergent is a laundry detergent.
  • the inventors of the present invention have now found that particular cellulose compounds, and that a particular combination of components used together, are highly effective disintegrants.
  • a detergent composition or component thereof comprising a cross-linked cellulose, preferably in an amount of from 0.1-25 wt%,
  • a detergent composition comprising a combination of the cross-linked cellulose disintegrant with an additional water-swellable disintegrant.
  • a disintegrating component for use in a detergent composition
  • a detergent composition comprising such a disintegrating component and a method for making a preferred disintegrating component.
  • the Wicking Agent comprises a compound or mixture of compounds which enables fast water penetration into the detergent composition containing the disintegrating component, when the detergent composition is contacted with water in the wash.
  • the wicking agent is generally substantially water-insoluble in cold water at 15°C.
  • the wicking agent has a lower density than the density of the composition as a whole in which it is incorporated.
  • the density of the wicking agent may be at least 10%, more preferably at least 20% (based on the density of the detergent composition as a whole) lower than the density of the composition as a whole in which it is incorporated.
  • the wicking agent has low compressibility and maintains porosity under processing conditions, particularly compaction.
  • Suitable wicking agents are generally cellulose-based.
  • the cellulose-based compounds may optionally be microcrystalline or mechanically ground and processed cellulose such as ArbocelTM.
  • the wicking agent may be in the form of a powder, which may be obtained by mechanical grinding, a microcrystalline powder or it may be in the form of a granule e.g. an agglomerate of fine particle size wicking agent, or as a fibre, or mixtures thereof.
  • Particularly preferred wicking agents are fibrous, for example, those having a length to diameter ratio of at least 3:1, preferably at least 5:1 or even at least 10:1.
  • Suitable fibres include those having a length of at least 0.1mm, or at least 0.2mm, or even at least 0.4mm.
  • Particularly preferred wicking agents are cross-linked.
  • the cross-linked celluloses for use in the detergent compositions of the present invention have been found to provide surprisingly effective disintegration of detergent compositions in which they are incorporated. It is believed that this is because they resist detergent processing conditions and enable retention of a relatively high degree of porosity in the detergent matrix. They also provide hydrophilic structures which rapidly transport water molecules into the detergent composition.
  • the cellulose is generally substantially water-insoluble in cold water at
  • the cellulose may have a lower density than the density of the composition as a whole in which it is incorporated.
  • the density of the cross-linked cellulose may be at least 10%, more preferably at least 20% (based on the density of the detergent composition as a whole) lower than the density of the composition or component as a whole in which it is incorporated.
  • the cross-linked cellulose has low compressibility and maintains porosity under processing conditions, particularly compaction.
  • the cross-linked cellulose may be in the form of a powder which may be microcrystalline, a fibre, or a granule.
  • a powder may be obtained by mechanical grinding.
  • a granule may be for example an extrudate or an agglomerate comprising fine particle size and/or fibrous cellulose or mixtures thereof.
  • Particularly preferred cross-linked cellulose is fibrous, for example, fibres having a length to diameter ratio of at least 3:1, preferably at least 5 : 1 or even at least 10:1. Suitable fibres include those having an average length of 0.1mm, or 0.2mm, or even 0.4mm.
  • Particularly preferred wicking agents are cross-linked.
  • Particularly preferred wicking agents are cross-linked cellulose fibres as described in US 5 137 537, US 5 183 707, US 5 190 563, US 5 562 740, US 5 549 791, US 5 549 863, US 5 709 774 or US 5 716 703.
  • These particularly preferred cross-linked celluloses are in a substantially individualized form i.e. the cellulosic fibres have primarily intrafibre chemical cross-link bonds. That is, the cross-link bonds are primarily between cellulose molecules of a single fibre rather than between cellulose molecules of separate fibres.
  • Processes for making such cross-linked fibres may be either dry cross-linking processes such as is described in US 3 224 926, or aqueous solution, as described in US 3 241 553 or non-aqueous solution cross-linking, as described in US 4 035 147.
  • Preferred cellulose is cross-linked with dialdehydes (as described in US 4 689 118 or
  • the most preferred cellulose is cross-linked with citric acid.
  • the cross-linked cellulose is preferably fluff-dried and is generally incorporated into a detergent composition or component thereof in amounts greater than 0.2 wt% or even greater than 0.5 wt%.
  • cross-linked cellulose will be incorporated in amounts below 10 wt% of a detergent composition, preferably below 7 wt%.
  • the cross-linked cellulose is used in combination with a water-swellable agent. It is particularly preferred that it should be pre-mixed with the water-swellable agent prior to addition to other detergent components.
  • the water-swellable agent may be any compound or mixture of compounds which swells in contact with water, for example to form a gel.
  • the water-swellable agent may be inorganic such as clays or water-swellable salts, or organic such as polymeric materials.
  • the water-swellable agent comprises a water-swellable polymer. It may comprise a polyelectrolyte polymer such as poly(meth)acrylates or carboxymethylcellulose, copolymers or derivatives thereof such as polyacrylate esters, polymethacrylae esters, acrylate maleate copolymers or mixtures thereof. Polyvinyl pyrrolidones and their copolymers and derivatives are also suitable.
  • the water-swellable polymer may comprise polysaccharide polymers, such as guars, alginates, starches, carboxymethyl starches, optionally colloidal microcrystalline cellulose, their copolymers or derivatives or mixtures thereof. Mixtures of polyelectrolyte and polysacchride polymers are also suitable.
  • the polymers may be in the acid or salt form with varying degrees of charge/neutralisation and of varying molecular weight and have varying degrees of and distribution of substituents, as long as they are swellable.
  • the polymers are optionally cross-linked.
  • Carboxymethylcellulose and its derivatives are particularly preferred, especially those having a degree of substitution of from 0.2 to 0.7, preferably from 0.4 to 0.6 and a molecular weight of from 250,000 to 1,000,000, preferably from 250,000 to 700,000 measured for example by GPC using styrene as a standard.
  • the wicking agent and water-swellable agent are preferably present in weight ratios of less than 2:1, preferably less than 1:1.
  • the weight ratio is generally no less than 1 :20, preferably no less than 1 :10.
  • the water- swellable agent may be used in combination with the cross-linked cellulose preferably in weight ratios of less than 2:1, preferably less than 1:1.
  • the weight ratio is generally no less than 1 :20, preferably no less than 1 :10.
  • the disintegrating component is formed as an intimate mixture of the wicking agent, preferably the cross-linked cellulose, and water-swellable agent in a pre-mix for incorporation into a composition such as a detergent composition
  • the pre-mix may be in the form of a detergent component, for example in the form of a particle.
  • the pre-mix preferably comprises more than 50 wt%, preferably more than 75 wt% or even up to 90 wt% of wicking agent and water-swellable polymer and less than 50 wt %, preferably less than 25 wt% or even less than 10 wt% other ingredients optionally comprising a binder.
  • Other ingredients suitable for incorporation into the pre-mix are dependent on the final application of the disintegrating component.
  • the disintegrating component When the disintegrating component is for incorporation into a detergent composition, conventional detergent ingredients are suitable as the other ingredients.
  • the binder may be present in relatively high levels, for example up to 50 wt% of the pre-mix or detergent component, however the binder is generally present in amounts no greater than 25 wt% of the pre-mix, or even amounts below 20 wt% or below 10 wt%.
  • the disintegrating component may be added to a composition for disintegrating such as a detergent composition, preferably a detergent tablet, preferably as a pre-formed component or may be added as the individual components of the disintegrating component directly and individually into detergent processing steps.
  • a composition for disintegrating such as a detergent composition, preferably a detergent tablet, preferably as a pre-formed component or may be added as the individual components of the disintegrating component directly and individually into detergent processing steps.
  • the respective components or a pre-formed particle or other detergent component may be added as a dry-add, or into a crutcher mix for forming a spray dried detergent product or may be incorporated into an agglomeration step.
  • the cross-linked cellulose and optional water-swellable agent may be incorporated into a detergent composition (preferably a detergent tablet), individually, or where used in combination, preferably as a pre-mix comprising the water-swellable agent and cross-linked cellulose, into detergent processing steps.
  • the cross-linked cellulose and optional water-swellable agent or pre-mix may be added as a dry-add, or into a crutcher mix for forming a spray dried detergent product or may be incorporated into a granulation process such as an agglomeration or extrusion step.
  • a granulation process such as an agglomeration or extrusion step.
  • the disintegrating component is generally present in amounts no greater than 20 wt%, preferably no greater than 10 wt% based on the finished detergent composition as a whole.
  • the amount of water-swellable agent is generally from at least 1.5 wt% based on the composition for disintegrating, as a whole, generally being no greater than 10 wt % of a finished composition, preferably from 1.5-7 wt%.
  • the disintegrating agents of the invention are particularly useful in detergent compositions, especially detergent particles or tablets, or in pesticidal, herbicidal, sanitizing or pharmaceutical compositions.
  • the cross-linked cellulose may be in the form of a detergent component, for example in the form of a particle.
  • the detergent component will generally comprise no more than 95 wt% of water-swellable agent and/or other detergent ingredients and/or binders.
  • a detergent component comprises no more than 50 wt%, of water- swellable agent and/or other detergent ingredients and/or binders, most preferably no more than 45 wt%.
  • the binder may be present in relatively high levels, for example up to 50 wt% of the detergent component, however the binder is generally present in amounts no greater than 25 wt% , or even amounts below 20 wt% or below 10 wt%.
  • the disintegrating component may be added to a composition for disintegrating such as a detergent composition, preferably a detergent tablet, preferably as a pre-formed component or may be added as the individual components of the disintegrating component directly and individually into detergent processing steps.
  • a composition for disintegrating such as a detergent composition, preferably a detergent tablet, preferably as a pre-formed component or may be added as the individual components of the disintegrating component directly and individually into detergent processing steps.
  • the respective components or a pre-formed particle or other detergent component may be added as a dry-add, or into a crutcher mix for forming a spray dried detergent product or may be incorporated into an agglomeration step.
  • the amount of water-swellable agent in the detergent composition is generally from 1.5 wt% based on the composition for disintegrating, as a whole, generally being no greater than 10 wt % of a finished composition, preferably from 1.5-7 wt%.
  • the wicking agent and water-swellable agent of the disintegrating component are added to a composition for improving disintegration/dissolution in the form of an intimate mixture of the two components optionally with additional components and/or binder as described above.
  • intimate mixture is meant that the at least two components are mixed together to form a pre-mix which is a substantially homogeneous mixture.
  • the detergent composition comprises cross-linked cellulose in combination with a water-swellable agent in an intimate mixture of the two components optionally with additional components and/or binder as described above.
  • This may be achieved by dry mixing solid wicking agent, preferably cross-linked cellulose, and solid water-swellable agent with an optional binder.
  • the pre-mix may be in the form of a particle and this can be achieved for example by granulation , such as by agglomeration, extrusion or dry compaction.
  • the water-swellable agent is present as a coating on the wicking agent, preferably cross-linked cellulose. This is particularly beneficial where the wicking agent, preferably cross-linked cellulose, is fibrous.
  • the wicking agent preferably cross-linked cellulose, and water-swellable agent may be mixed together, optionally with a binder and then ground to enhance mixing and reduce particle size. This is particularly useful if the wicking agent is provided as relatively large particles or fibres. Grinding as a mixture enables more effective reduction of the length of the fibres or particle size in combination with effective mixing.
  • Providing a coating of the water-swellable agent on the wicking agent, preferably cross-linked cellulose may be achieved in any convenient way, for example by mixing the cross-linked cellulose and water-swellable agent with a solvent for the water-swellable agent, in any order of addition, such that a gel or solution is formed or a slurry comprising partially swollen water-swellable agent. Preferably mixing is continued until a substantially homogeneous mixture is obtained.
  • the mixture of wicking agent, preferably cross-linked cellulose, and water-swellable agent is then recovered by separating out from the solvent by any conventional technique, such as by evaporating off the solvent or by addition of a non-solvent for the water-swellable agent to form a precipitate of the mixture, such mixture is then separated from the solvent by any conventional technique such as by subsequent filtration or decanting off the solvent.
  • the separated solid is preferably recovered directly in an appropriate particle size for direct addition into a detergent composition processing stage.
  • the solid mixture may be recovered having a particle size greater than that required for final use and if so, may be treated to reduce the particle size, for example by grinding. Should the product mixture be obtained as fine particulates these may be mixed with optional binder or additional detergent components and formed into a granule as described above, for example, by agglomeration to produce very fine particulates adhered to one another in the form of a disintegrating component which is a granule.
  • the water-swellable agent preferably polymer, and solvent, preferably water
  • solvent preferably water
  • the wicking agent preferably cross-linked cellulose
  • the wicking agent may be added directly to the mixture in solvent prior to recovery. This may be particularly useful, for example, where the water-swellable agent comprises a polymer.
  • this method can be applied where the polymer comprises CMC as in the manufacture of CMC, a very viscous slurry of CMC is obtained in water and then the wicking agent, preferably fibrous wicking agent (such as cross- linked cellulose), may be added directly to the slurry prior to the recovery of the CMC.
  • the mixture of wicking agent, preferably cross-linked cellulose, and water- swellable polymer may then be recovered as described above.
  • the particle size of the disintegrating component may be selected to give particularly beneficial disintegrating properties in use in a detergent composition.
  • Disintegrating components or the respective materials in a disintegrating component preferably have a particle size of at least lOO ⁇ m, preferably at least 150 ⁇ m.
  • Preferred disintegrating components have a particle size of no greater than 2000 ⁇ m, most preferably below 1700 ⁇ m. In practice, the particles obtained may have a size distribution.
  • the particle size is preferably such that at least 80 wt%, preferably at least 90 wt% and most preferably at least 95 wt% of the components of the disintegrating component or a particulate disintegrating component is at least lOO ⁇ m, more preferably at least 150 ⁇ m.
  • at least 80 wt%, preferably at least 90 wt% and most preferably at least 95 wt% disintegrating agent is below 2000 ⁇ m, most preferably below 1700 ⁇ m, or even below 1500 ⁇ m, to obtain the maximum disintegrating benefits.
  • the optional binder which may be incorporated as part of the disintegrating component may be any conventional binder.
  • Water, organic acids, hydratable salts or alcohols are all suitable. Water or alcohols such as glycerol are particularly preferred.
  • the optional binder which may be incorporated into the pre-mix or granule comprising cross-linked cellulose optionally in combination with water-swellable agent may be for example water, organic acids, hydratable salts, alcohols or mixtures thereof. Water or alcohols such as glycerol are particularly preferred.
  • the disintegrating component of the invention may contain additional ingredients which depend on the final use of the component.
  • the additional ingredients may comprise optional additional detergent components.
  • detergent ingredients mentioned below as suitable ingredients for the detergent composition are all suitable as the optional additional detergent components which may be present in the disintegrating component. It may be particularly preferred to incorporate a surfactant, such as an anionic, nonionic, zwitterionic or cationic surfactant as this may increase the wicking/swelling action of the respective components.
  • a surfactant such as an anionic, nonionic, zwitterionic or cationic surfactant as this may increase the wicking/swelling action of the respective components.
  • the cross-linked cellulose may be pre-mix with a surfactant, such as an anionic, nonionic, zwitterionic or cationic surfactant, prior to incorporation into a detergent composition, as this may increase the effectiveness of the cross-linked cellulose.
  • a surfactant such as an anionic, nonionic, zwitterionic or cationic surfactant
  • a detergent composition comprising a disintegrating component as described above.
  • the disintegrating component is particularly useful in detergent compositions comprising high levels of surfactant, for example at least 20 % by weight, preferably at least 25% by weight or even at least 40 or 45% by weight based on the detergent composition.
  • high surfactant formulations dispensing and gelling of the detergent composition are a particular problem and the benefits of the invention may be most significant.
  • the detergent compositions of the invention may take a variety of physical forms but are preferably solid forms such as tablet, flake, pastille and bar, and preferably granular or tablet forms.
  • the particulate processing composition may be made by a variety of methods, including dry-mixing, agglomerating, compaction, or spray- drying of the various compounds comprised in the detergent composition, or mixtures of these techniques.
  • compositions in accordance with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine or oxygen bleach.
  • Detergent compositions herein in particular laundry detergents, preferably have a bulk density of from 450 g/litre to 1500 g/litre, or preferably from 500 g/litre or even 600g/litre or 650g/litre to 2000g/litre or more preferably to 1500g/litre.
  • the tablets are generally prepared by compaction of a particulate starting material. Any conventional tabletting process and apparatus may be used.
  • the optimum compaction pressure will depend to some extent on the starting composition; for example a formulation containing a high proportion of organic ingredients (for example, surfactants) and a relatively low proportion of inorganic salts generally requires a compaction pressure lower than that required for a formulation containing a lower proportion of organic ingredients and a higher proportion of inorganic salts.
  • a dry-mixed formulation generally requires a higher pressure than a spray-dried powder.
  • the detergent composition of the invention is preferably a complete heavy-duty laundry composition.
  • one tablet may contain sufficient detergent components to provide cleaning for an average wash load, the tablets formed may be smaller such that the consumer may choose the number of detergent tablets required according to the size and nature of the wash load.
  • tablet sizes may be chosen such that two tablets are sufficient for an average wash load, with one additional tablet to be used for particularly heavily soiled laundry.
  • a smaller tablet may be preferred.
  • the tablet will generally be from 10-160 g and may be any suitable shape.
  • the tablet may be homogenous or may consist of more than one discrete region.
  • the tablet may comprise two or more layers of different detergent composition or a core region may be surrounded by outer regions of different detergent compositions.
  • the tablet may be coated or uncoated. Suitable coating materials are described for example in EP-A-2293, GB-A-0989683 and EP-A-716144.
  • composition or component thereof according to the present invention is preferably a detergent composition or component thereof which will comprise additional detergent ingredients.
  • additional detergent ingredients The precise nature of these 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.
  • the detergent compositions of the invention preferably contain one or more additional detergent components selected from bleaches, bleach catalysts, alkalinity systems, additional builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brighteners, photobleaching agents and additional corrosion inhibitors.
  • compositions of the invention contain one or more surfactants.
  • the surfactant may comprise any surfactant known in the art, selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants such as those discussed below and mixtures thereof.
  • Anionic Surfactant may comprise any surfactant known in the art, selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants such as those discussed below and mixtures thereof.
  • compositions in accordance with the present invention preferably comprise an anionic surfactant.
  • anionic surfactant useful for detersive purposes can be present in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate and sulfonate surfactants are preferred.
  • surfactants systems comprising a sulfonate, preferably a linear or branched alkyl benzene sulfonate, as described herein, preferably combined with a cationic surfactant as described herein.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, ⁇ -C, « 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 detergent composition comprises at least one anionic surfactant, preferably an anionic sulphonate surfactant, preferably an alkyl sulphonate surfactant, as described herein. More preferably, the anionic surfactant comprises from 50% to 100% or even from 60% to 100% or even from 75% to 100% by weight of the surfactant content of the detergent composition.
  • Highly preferred surfactants are anionic sulphonate surfactants.
  • Particularly suitable for use herein include the salts of C5-C20 linear or branched alkylbenzene sulphonates, but also may be used alkyl ester sulphonates, C6-C22 primary or secondary alkane sulphonates, Cg-C24 olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, and any mixtures thereof.
  • Most preferred are C 9 -C !4 linear alkyl benzene sulphonates.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary Cl0"Cl8 alkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl e hoxysulfate surfactants are preferably selected from the group consisting of the Cjo-Ci8 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cl I-C18, most preferably Cj ⁇ -C ⁇ alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2-O)-R3 wherein R is a
  • Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof
  • R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl- 1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Soaps may also be included as suds suppressors and if so, is generally present in low levels up to 5 wt % as finely divided particulates or flakes.
  • Suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
  • RI is a C1-C4 alkyl group and M is an alkali metal ion.
  • Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
  • alkoxylated nonionic surfactant is suitable for use herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Particularly preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • Nonionic surfactant may be present in the detergent compositions of the invention. It may be preferred that the level of ethoxylated nonionic surfactants in the intimate mixture are below 10% by weight of the mixture, preferably even 5% by weight.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain 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 10 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-
  • C31 hydrocarbyl preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C ⁇ ⁇ -C ⁇ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R ⁇ CON(R ⁇ )2 wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R' is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • 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.
  • Suitable amphoteric surfactants for use in the detergent compositions of the invention herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula
  • R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each
  • R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are CJ O-CI S alkyl dimethylamine oxide, and CJ Q-18 acylamido alkyl dimethylamine oxide.
  • An example of a suitable alkyl aphodicarboxylic acid is MiranolTM C2M Cone. manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants may also be incorporated into the detergent compositions 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 + R2C00 " wherein R is a C ⁇ -Cig hydrocarbyl group, each R is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ . dimethyl-ammonio hexanoate and the Cj ⁇ -18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants for incorporation into the detergent composition of the invention include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono C ⁇ -Ci ⁇ , preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • Cationic mono-alkoxylated amine surfactants Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:
  • 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
  • R 2 and R-> are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R ⁇ are methyl groups;
  • R 4 is selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
  • Particularly preferred ApR 4 groups are — CH CH 2 OH, — CH2CH 2 CH 2 OH, —
  • R ⁇ groups are linear alkyl groups. Linear Rl groups having from 8 to 14 carbon atoms are preferred.
  • R is CjO'Cl ⁇ hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably CJQ and C12 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(CH3)CH2O] and
  • the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
  • Suitable cationic bis-alkoxylated amine surfactants preferably have the general formula II:
  • R is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R ⁇ and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy,
  • 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 C ⁇ Q-CI S hydrocarbyl and mixtures thereof, preferably CJO > Cj2 > 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 Cjo-Ci8 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • a preferred additional component of the detergent compositions of the invention is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • the detergent composition of the invention preferably comprise 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 O
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight 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-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R 3 is an alkyl chai •n containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • Y is H or a solubilizing group.
  • Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
  • the preferred solubilizing groups are -SO, " M , -CO- M , -SO M , -N (R ).X " and
  • M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • 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* is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those 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 are useful N-acyl group- containing perbenzoic acid precursors.
  • Other useful N-acyl group- containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
  • organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R I is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A- 0170386.
  • Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • the composition can contain a transition metal containing bleach catalyst.
  • a transition metal containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • Such catalysts are disclosed in U.S. Pat. 4,430,243.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnlY2( u ⁇ O)30A7-trimethyl-l,4,7-friazacyclononane)2-(PF6)2, Mn"l2( u "
  • ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl-l,4,7-triazacyclononane, 1,2,4,7-tetramethyl- 1,4,7- triazacyclononane, and mixtures thereof.
  • the bleach catalysts useful herein may also be selected as appropriate for the present invention.
  • suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a non-(macro)-cyclic ligand.
  • Said ligands are of the formula:
  • B is a bridging group selected from O, S.
  • R ⁇ , R ⁇ and R ⁇ can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups.
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2,
  • binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands include [Bipy2MnIH(u-
  • the bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein.
  • catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor.
  • 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3- 5 fold may be required under U.S. conditions to achieve the same results.
  • the detergent compositions according to the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight of the composition.
  • the detergent compositions of the invention may comprise phosphate-containing builder material, preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous or partially hydrated sodium tripolyphosphate, present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40. It may be preferred that the compositons are free of phosphate-containing builder material.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • the most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from
  • 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.
  • 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.
  • Water-soluble builders may also prove to be useful binding agents.
  • compositions according to the present invention may contain an insoluble builder compound, but preferably in relatively low amounts at a level of from 0% to 25% by weight, most preferably from 0% to 15% weight of the composition, or even 0% to 10% by weight of the composition.
  • insoluble builder compounds include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]-
  • XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
  • Zeolite X has the formula Na86 [(AlO 2 ) 8 6(Si ⁇ 2)l06]- 276 H 2 O.
  • Zeolite MAP is described in EP 384070 A (Unilever). It is defined as an alkali metal alumino-silicate 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.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from
  • the d5o 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.
  • Crystalline layered silicate builder may also be incorporated in the detergent compositions of the invention. These have the general formula
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A- 0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE- A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
  • M is preferably H, K or Na or mixtures thereof, preferably Na.
  • the most preferred material is ⁇ -Na2Si2 ⁇ 5 R. Na2Si2 ⁇ 5 or ⁇
  • -Na2Si2 ⁇ 5, or mixtures thereof preferably being at least 75% -Na2Si2 ⁇ 5 for example available from Clariant as NaSKS-6.
  • crystalline layered silicate is present as a coarse material having a weight average particle size above 150 microns, as measurable by sieving on Tyler sieves, or fine material of weight average particle size below 20 microns, Malvern Instruments SB.OC light scattering equipment.
  • Heavy metal ion sequestrants are also useful additional ingredients in the detergent compositions of the invention.
  • heavy metal ion sequestrant is meant components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferably 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 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
  • 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Another preferred ingredient useful herein is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1, 269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S.
  • Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are optional additional components of the compositions of the present invention.
  • organic polymeric compound any polymeric organic compound commonly used as anti-redeposition or 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 in accord with the invention. Additional 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 co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • salts are polyacrylates of 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 nonionic group selected from the group consisting of H, Ci -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 as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cl8"C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di- alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises: (a) 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 (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound; wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight; (b) 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 copoly
  • DCO544 commercially available from DOW Corning under the tradename DCO544; and (c) an inert carrier fluid compound, most preferably comprising a C j g-Cis 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, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers are optionally cross-linked polymers.
  • compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brightener s.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl;
  • R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)- s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
  • Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
  • SRAs Polymeric soil release agents, hereinafter "SRA" can optionally be employed in the present compositions. If utilized, SRAs 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 SRAs 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 SRAs 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 cross-linked overall structure.
  • Suitable SRAs 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) ethoxy lating 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 nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to
  • Gosselink such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT,
  • SRAs also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRAs include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRAs with carboxylate terminal groups made by adding trimellitic anhydride to known SRAs 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 nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S.
  • compositions of the invention include perfumes, speckles, colours or dyes, filler salts, with sodium sulfate 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.
  • Machine laundry methods for using laundry detergent compositions according to the present invention typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention.
  • an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • composition may also be formulated such that it is suitable for disinfecting, sanitisation, hard-surface cleaning or hand washing or for pre-treatment or soaking of soiled and stained fabrics.
  • Citric acid intra-cross-linked fibrous cellulose made by Wayerhauser
  • Na ⁇ 2 (AlO 2 SiO ) ⁇ .27H 2 O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • NaSKS-6 (I Crystalline layered silicate of formula ⁇ - Na2Si2 ⁇ 5 of Clariant
  • Citric acid Anhydrous citric acid
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • MA/AA Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000
  • Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
  • 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
  • Lipolytic enzyme having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
  • DOBA Decanoyl oxybenzoic acid
  • TAED Tetraacetylethylenediamine DTPA
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Opacifier Water based monostyrene latex mixture, sold by
  • Disintegrating components according to the present invention were prepared as follows.
  • Finely ground curly cellulose CMF (3 g) is placed in the 11 pot of a Braun Combimax 700 food processor with Nymcel (9 g).
  • Glycerol (2.2 g) is added dropwise as a binder and the mixture is stirred gently for 2 minutes before being sieved such that all retained agglomerate material has a diameter d ⁇ 2 mm. This yields 14 g of agglomerate [85% (25% CMF with 75% Nymcel) + 15% Glycerol].
  • Example 2 Preparation of 66 wt % Agglomerate (25% CMF with 75% Nvmcel) + 33 wt % stearic acid
  • a disintegrating component agglomerate was prepared as for example 1 , but using 6 g of melted stearic acid instead of 2.2 g of glycerol.
  • a disintegrating component agglomerate was prepared as in example 1 but using 3 g of Arbocel instead of 3 g of curly cellulose CMF
  • Example 4 Preparation of 25 wt % CMF coated with 75 wt % Nymcel
  • Curly cellulose CMF (15 g) was placed in the 21 pot of a Braun Combimax 700 food processor with 1200 ml of water. To this was slowly added Nymcel (45 g), with gentle stirring. Once the addition had been completed, the mixture was stirred for 10 minutes, allowed to stand for 15 minutes and finally stirred for 2 minutes. The mixture was then transferred into a 5 litre beaker and acetone (2.51) added. The mixture was stirred for 15 minutes before the acetone was decanted off. More acetone (360 ml) was then added to the wet solid mass and stirred for 15 minutes before the acetone was decanted off.
  • Example 5 Preparation of 85 wt % active Disintegrating Component(25% CMF coated with 75% Nvmcel) + 15% Glycerol
  • Curly cellulose CMF (15 g) was placed in the 21 pot of the Braun Combimax 700 food processor with 1200 ml of water. To this was slowly added Nymcel (45 g), with gentle stirring. Once the addition was completed, the mixture was stirred for 10 minutes, allowed to stand for 15 minutes and finally stirred for 2 minutes. The mixture was then transferred into a 5 litre beaker and acetone (2.51) added. The mixture was stirred for 15 minutes before the acetone was decanted off. More acetone (360 ml) was then added to the wet solid mass and stirred for 15 minutes before the acetone was decanted off.
  • Example 6 Preparation of 85 wt % active Disintegrating Component (50% CMF coated with 50% Nvmcef) + 15% Glycerol
  • the preparation was in example 5 but using 30 g of Curly cellulose CMF instead of 15 g and 30 g of Nymcel instead of 45 g.
  • Example 7 Preparation of 85 wt % active Disintegrant Component (10% CMF coated with 90% Nvmcel) + 15% Glycerol
  • the preparation was in example 5 but using 6 g of Curly cellulose CMF instead of 15 g and 54 g of Nymcel instead of 45 g.
  • Example 8 Preparation of 66 wt % active Disintegrating Component (25% CMF coated with 75% Nvmcel) + 33% stearic acid
  • the preparation was in example 5 but using 23.6 g of melted stearic acid instead of 8.33 g of glycerol in the final agglomeration step.
  • Example 9 Preparation of 85 wt % active Disintegrating Component(25% CMF coated with 75% CMC MW 250 000,d.s. 0.7) + 15% Glycerol
  • the preparation was in example 5 but using 45 g of Carboxymethyl Cellulose (CMC) of average molar weight 250000 and average degree of substitution d.s. 0.7 instead of
  • Example 10 Preparation of 85 wt % active Disintegrating Component (25% CMF coated with 75% CMC MW 700 OOO.d.s. 0.9) + 15% Glvcerol
  • the preparation was in example 5, but using 45 g of Carboxymethyl Cellulose (CMC) of average molar weight 700000 and average degree of substitution d.s. 0.9 instead of 45 g of Nymcel.
  • CMC Carboxymethyl Cellulose
  • Example 11 Preparation of 85 wt % active Disintegrating Component (25% Arbocel coated with 75% Nymcel) + 15% Glycerol
  • the preparation was as in example 5 but using 15 g of Arbocel instead of 15 g of Curly cellulose CMF.
  • examples 1 to 11 were mixed, by dry mixing into a pre-formed detergent composition comprising on a parts by weight basis 2.5 pbw LAS, 2.0 pbw AS, 8 pbw AES, 1 pbw QAS, 6 pbw sodium citrate, 13 pbw zeolite, 9 pbw Na SKS- 6 , 12 pbw sodium percarbonate, 5 pbw TAED, 0.25 pbw chelant, 0.5 pbw HEDP, 0.45 pbw CMC, 0.31 pbw SRP, 2.87 pbw MA/AA, 0.12 pbw Brightener 15, 0.02 pbw Brightener 49, 0.96 pbw, 17.36 pbw Carbonate, 0.52 pbw Sodium Sulphate, 0.37 pbw Silicate 2,0R, 1.43 pbw PEG, 0.20 pbw suds supressor (silicone) 1.30 pbw Soap.
  • the tablets of the present invention were prepared by compaction of a particulate detergent composition, according to the procedures described in European Patent
  • the tablets were prepared using either an InstronTM 4469 Compaction and Tension
  • Preferred tablets of the invention have a diametral fracture stress of at least
  • a tablet is gently deposited into a 2 litre beaker containing 1 litre of cold water and 7 ice cubes (20 g each). The tablet is left there unstirred for 2 minutes after which any residual solid lumps are manually picked out and weighed.
  • They may be particulate or may be compressed in a tablet press into tablets.

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Abstract

L'invention concerne des composants de désintégration pouvant être utilisés dans des compositions détergentes qui offrent des avantages en ce que concerne leur dissolution et/ou leur répartition, de préférence des compositions détergentes contenant de la cellulose réticulée. Ces compositions détergentes présentent de bonnes propriétés de désintégration et donc de bonnes propriétés en ce que concerne leur répartition et/ou la formation de résidus. L'invention concerne également des compositions détergentes ou des composants de celles-ci qui contiennent de tels composants de désintégration. Les compositions détergentes selon l'invention peuvent se présenter sous la forme de comprimés. De préférence, la cellulose réticulée est combinée avec des agents de désintégration additionnels, et mieux encore, les composants de désintégration comprennent un agent à effet de mèche et un agent gonflant dans l'eau, de préférence sous forme d'un mélange intime.
PCT/US1999/018379 1999-08-12 1999-08-12 Composant de desintegration et composition detergente contenant ce composant WO2001012767A1 (fr)

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PCT/US1999/018379 WO2001012767A1 (fr) 1999-08-12 1999-08-12 Composant de desintegration et composition detergente contenant ce composant

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003069996A1 (fr) * 2002-02-21 2003-08-28 Bayer Cropscience Aktiengesellschaft Molluscicides
US10293566B2 (en) 2014-05-28 2019-05-21 Eurotab Multi-layer tablet with recess, device and method for compacting such a tablet
WO2022263172A1 (fr) * 2021-06-15 2022-12-22 Unilever Ip Holdings B.V. Composition en comprimé monodose

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462723A1 (fr) * 1990-06-19 1991-12-27 BP Chemicals Limited Granules à solubilité rapide contenant un liant
WO1992001777A1 (fr) * 1990-07-17 1992-02-06 Micro Vesicular Systems, Inc. Shampooing sec
WO1998003064A1 (fr) * 1996-07-23 1998-01-29 Fmc Corporation Composition desintegrante pour solides dispersibles
WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
CA2217238A1 (fr) * 1997-10-24 1999-04-24 Louis Cartilier Cellulose reticulee employee comme excipient de comprimes
DE29909404U1 (de) * 1999-05-31 1999-09-30 Thurn-Produkte Inhaber Adolf Thurn jun., 53804 Much Scheibenförmiger Preßling
GB2339575A (en) * 1998-07-15 2000-02-02 Procter & Gamble Cellulose disintegrant for detergent compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462723A1 (fr) * 1990-06-19 1991-12-27 BP Chemicals Limited Granules à solubilité rapide contenant un liant
WO1992001777A1 (fr) * 1990-07-17 1992-02-06 Micro Vesicular Systems, Inc. Shampooing sec
WO1998003064A1 (fr) * 1996-07-23 1998-01-29 Fmc Corporation Composition desintegrante pour solides dispersibles
WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
CA2217238A1 (fr) * 1997-10-24 1999-04-24 Louis Cartilier Cellulose reticulee employee comme excipient de comprimes
GB2339575A (en) * 1998-07-15 2000-02-02 Procter & Gamble Cellulose disintegrant for detergent compositions
DE29909404U1 (de) * 1999-05-31 1999-09-30 Thurn-Produkte Inhaber Adolf Thurn jun., 53804 Much Scheibenförmiger Preßling

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003069996A1 (fr) * 2002-02-21 2003-08-28 Bayer Cropscience Aktiengesellschaft Molluscicides
US10293566B2 (en) 2014-05-28 2019-05-21 Eurotab Multi-layer tablet with recess, device and method for compacting such a tablet
US10828856B2 (en) 2014-05-28 2020-11-10 Eurotab Multi-layer tablet with recess, device and method for compacting such a tablet
WO2022263172A1 (fr) * 2021-06-15 2022-12-22 Unilever Ip Holdings B.V. Composition en comprimé monodose

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