WO2001060965A1 - Pastille de detergent - Google Patents

Pastille de detergent Download PDF

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Publication number
WO2001060965A1
WO2001060965A1 PCT/US2001/003933 US0103933W WO0160965A1 WO 2001060965 A1 WO2001060965 A1 WO 2001060965A1 US 0103933 W US0103933 W US 0103933W WO 0160965 A1 WO0160965 A1 WO 0160965A1
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WIPO (PCT)
Prior art keywords
acid
phase
preferred
alkyl
surfactants
Prior art date
Application number
PCT/US2001/003933
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English (en)
Inventor
Christopher James Binder
Original Assignee
The Procter & Gamble Company
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Filing date
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU2001234901A priority Critical patent/AU2001234901A1/en
Publication of WO2001060965A1 publication Critical patent/WO2001060965A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D17/0078—Multilayered 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to detergent tablets.
  • it relates to multi-phase tablets and a process for manufacturing such tablets, including a heating step by radiant heat.
  • the process improves the robustness, stability, integrity and dissolution characteristics of the tablet.
  • the process is very energy efficient and allows for an increase in production speed.
  • detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form hold several advantages over detergent compositions in particulate form, such as ease of dosing, handling, transportation and storage. In addition multi-phase tablets allow the incorporation of incompatible substances in the same tablet and a differential dissolution of different components.
  • multiphase tablets are made by compressing or compacting powdered solids or paste-like slurries of such solids, or by moulding the melt detergent components.
  • Usually the production of tablets by moulding melts requires heating and mixing of the raw materials and/or aqueous solutions in order to insure a homogeneous mixture.
  • thickening, pouring the melt mixture into moulds and cooling may also be required.
  • US-A-5, 133,892 discloses a multi-layer tablet containing an outer layer, a barrier layer and an inner layer. The tablet is prepared by successive compression steps.
  • US-A-4, 828,745 describes a process for making two layer tablets. The two layers are formed as separated melts, one melt is put into a mould to cool and partially solidify, the other melt is added to the mould whereby the layers fix to each other.
  • US-A-5, 658, 874 describes a process for making tablets of a detergent composition
  • a detergent composition comprising detergent active compound, detergency builder, additional ingredients and a binder.
  • the components are admixed and the binder preferably sprayed into the powder, the mixture is heated at least 5°C below the binder melting point and thereafter the mixture is compressed.
  • US-A-5, 858,299 describes a method to form a tablet by irradiation with subinfrared electromagnetic radiation of detergency particulate solids comprising some hydrated materials.
  • multi-phase detergent tablets are prepared by shaping a first phase, preferably by compaction.
  • One or more further phases are added in the form of a non- compacted particulate mixture to the first phase, this mixture comprising an adhesive which is meltable but solid at ambient temperature.
  • the additional phase is thereafter heated above the adhesive' s melting temperature.
  • the adhesive solidifies thermally-adhering the components of the particulate mixture and the separate phases together. Tablets produced according to this method are very convenient for differential component release.
  • the dissolution of the additional phases is fast because they are not compressed. Therefore, smaller amounts of dissolution aids, such as effervescent agents, are required and consequently the pH of the washing liquor can be increased, bringing cleaning benefits.
  • Another advantage of the present process is an increase in en__yme stability, since prolonged high temperatures are not required to affix the two phases together.
  • the tablet production process is faster and more energy efficient than by moulding molten constituents.
  • the process enables the second phase to be delivered directly to the first phase on the press, without adding a separate mould filling step. Therefore, the process is less capital intensive and higher speed than conventional method of making non-compresed phases.
  • a process of making a multiphase detergent tablet comprising: a) a first phase in the form of a shaped body; and b) a second phase comprising a non-compacted mixture of a particulate detergency-active solid and a meltable adhesive; the process comprising the steps of contacting the first and second phases at a temperature below the melting onset temperature of the meltable adhesive and thereafter thermally- adhering the phases to one another, for example, by subjecting the mixture to a temperature above the melting temperature of the meltable adhesive and thereafter lowering the temperature of the mixture to ambient.
  • the first phase is prepared by pre-mixing components of a detergent composition and forming the pre-mixed detergent components into a tablet using any suitable shaping equipment, preferably a tablet press.
  • the first phase is preferably subjected to an applied compression pressure of at least about 250 kg/cm 2 , preferably at least about 350 kg/cm 2 (3.43 kN/cm 2 or 34.3 MPa), more preferably from about 400 to about 2000 kg/cm 2 , and especially from about 600 to about 1400 kg/cm 2 (compression pressure herein is the applied force divided by the cross-sectional area of the tablet in a plane transverse to the applied force - in effect, the transverse cross-sectional area of the die of the rotary press).
  • the first phase is prepared by compression in a tablet press capable of preparing a tablet comprising a mould.
  • the first phase is prepared using a specially designed tablet press.
  • the punch(es) of this tablet press are modified so that the surface of the punch that contacts the detergent composition has a convex surface.
  • the second phase is prepared as a non-compacted mixture of a particulate detergency- active solid and a meltable adhesive which is also preferably in particulate form.
  • the adhesive for use herein is solid at ambient temperature and become liquid at not very high temperature.
  • the melting onset temperature is preferably in the range from about 35°C to about 65°C, preferable from about 40°C to about 60°C and more preferably from about 45°C to about 55°C.
  • the melting temperature of the adhesive is preferably between about 35°C and about 80°C, more preferably between about 40°C and about 70°C. Melting onset temperatures and melting temperatures are determined herein by differential scanning calorimetry (DSC) as described hereinbelow.
  • the adhesive can be selected from petroleum waxes such as paraffin wax and micro crystalline wax, synthetic waxes and resins such as polyethylene, polypropylene, ethylen-vinyl acetate copolymers, phenoxy resins, styrene-butadiene copolymers, ethylene- ethyl acrylate copolymers, polyesters, polyamides and polymethanes and mixture thereof. More preferred adhesives are those soluble in water, specially polyethylene glycols. Most preferred for use herein is polyethylene gly col (PEG), preferably of at least about 1500 molecular weight and more preferably of at least about 4000 molecular weight.
  • PEG polyethylene gly col
  • the adhesive is generally utilised in a level between about 0.1% and about 20% by weight, more preferably between about 0.3% and about 15% by weight and more preferably between about 0.5% and about 10% by weight of the second phase.
  • the non-compacted mixture of particulate detergency-active solid and meltable adhesive additionally comprises a tackifying agent, the function of which is to lightly adhere the second phase to the first phase prior to the thermal-adhering step.
  • the tackifying agent should thus be effective at ambient temperature and will usually take the form of a liquid adhesive which is sprayed onto the non-compacted mixture of the second phase.
  • the liquid adhesive should be liquid or fluid at 25°C and is preferably selected from water-soluble poly(C 2 -C 4 )-alkylene oxide polymers and copolymers, poly(C 2 -C )-alkoxylated nonionic surfactants, aqueous polymeric solutions and emulsions, and mixtures thereof.
  • a multi-phase detergent tablet for use in a washing machine, the tablet comprising a first phase in the form of a shaped body having a pre-formed depression or mould and a second phase adhesively contained within said depression or mould and wherein the second phase comprises a thermally-adhered, non-compacted mixture of a particulate detergency-active solid, a particulate meltable adhesive and optionally a tackifying agent.
  • the mixture of the particulate detergency-active solid, the meltable adhesive and the tackifying agent are introduced into the mould in the first phase and the mixture is heated above the melting temperature of the adhesive.
  • the tablet can be heated using any kind of heat, in a preferred embodiment radiant heating is used (having a wavelength in the range from about 750 nm to about 10 6 nm).
  • radiant heating is used (having a wavelength in the range from about 750 nm to about 10 6 nm).
  • the tablets are irradiated, from above, using infrared lamps.
  • the present invention also encompasses cleaning methods, more in particular, a method of washing tableware in a domestic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with the detergent tablet of the present invention.
  • the present invention provides a process for making tablets that provides a good physical and chemical stability and improved dissolution (especially differential dissolution) characteristics.
  • the process is fast and energy efficient.
  • the detergent tablets of the invention can include a variety of different detergent components including builder compounds, surfactants, enzymes, bleaching agents, rinse aids, alkalinity sources, colourants, perfume, lime soap dispersants, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers and dissolution agents.
  • builder compounds surfactants, enzymes, bleaching agents, rinse aids, alkalinity sources, colourants, perfume, lime soap dispersants, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers and dissolution agents.
  • highly preferred detergent components of the first phase include a builder compound, a surfactant, an enzyme, a bleaching agent and dissolution agents.
  • Highly preferred detergent components of the second phase include builder, enzymes, rinse aids and dissolution agents.
  • multi-phase tablets comprising a first phase in the form of a shaped body having at least one mould therein; and a second phase in the form of a non-compacted mixture of a particulate detergency-active solid (which term encompasses powders, granules, agglomerates, and other particulate solids) and a meltable adhesive at least partially contained and adhered within said mould.
  • a particulate detergency-active solid which term encompasses powders, granules, agglomerates, and other particulate solids
  • meltable adhesive at least partially contained and adhered within said mould.
  • the tablets of the invention will preferably have a CBS of at least about 6kg, preferably greater than about 8kg, more preferably greater than about 10kg, especially greater than about 12kg, and more especially greater than about 14kg, CBS being measured per the US Consumer Product Safety Commission Test Specification.
  • the first and second phases herein are in a relatively high weight ratio to one another, for example at least about 6: 1, preferably at least about 10:1; also that the tablet composition contain one or more detergent actives (for example enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents etc) which is predominantly concentrated in the second phase, for example, at least about 50%, preferably at least about 60%, especially about 80% by weight of the active (based on the total weight of the active in tablet) is in the second phase of the tablet.
  • one or more detergent actives for example enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents etc
  • compositions are optimum for tablet strength, dissolution, cleaning, and pH regulation characteristics providing, for example, tablet compositions capable of dissolving in the wash liquor so as to deliver at least 50%, preferably at least 60%, and more preferably at least 80% by weight of the detergent active to the wash liquor within 10, 5, 4 or even 3 minutes of the start of the wash process.
  • Multi-phase detergent tablets suitable herein will normally comprise a first phase in adhesive contact with one or more second phases (sometimes referred to herein as Optional subsequent phases').
  • the first phase is a compressed shaped body prepared at an applied compression pressure of at least about 250 kg/cm 2 , preferably at least about 350 kg/cm 2 (3.43 kN/cm 2 or 34.3 MPa), more preferably from about 400 to about 2000 kg/cm 2 , and especially from about 600 to about 1400 kg/cm 2 (compression pressure herein is the applied force divided by the cross-sectional area of the tablet in a plane transverse to the applied force - in effect, the transverse cross-sectional area of the die of the rotary press).
  • the second phase is formed by mixing a particulate solid comprising one or more active detergent components with a meltable adhesive.
  • This mixture is preferably then sprayed with a liquid adhesive as tackifying agent, delivered into the mould and heated by means of radiant heat to a temperature above the melting temperature of the meltable adhesive.
  • the adhesive is thereby melted and the phases adhered one to another on cooling to ambient.
  • the tablets herein comprise a meltable (or so-called hot-melt) adhesive.
  • Meltable adhesives are typically solvent-free adhesives, that are characteristically solid at ambient temperatures but which liquify above a pre-determined melting temperature.
  • the meltable adhesives herein are thermally characterised by having a melting transition range bounded at the bottom end by the melting onset temperature.
  • Melting onset temperature is the peritectic decomposition temperature. It physically represents the temperature at which a given composition in a solid state first evidences transition to a different composition in a liquid and a solid state.
  • the melting temperature of the adhesive is taken to be the temperature at which the adhesive is able to adsorb the maximum amount of heat with the minimum increase of temperature.
  • the thermal profile of the adhesives is determined using differential scanning calorimeter (DSC).
  • the DSC curves are determined using a model DCS-7 differential scanning calorimeter made by Perkin-Elmer. A sample of about 1 or 2 mg is weighed out and put into an aluminium pan and crimped with a crimper, after which it is placed in the DSC unit and the temperature raised.
  • the temperature is raised at a rate of 5° per minute.
  • the melting onset and melting temperatures are determined from the melting curves.
  • the melting temperature corresponds to the temperature of the highest peak in the DSC graph.
  • the melting onset temperature corresponds to the temperature determined by the intersection of the tangential line at the steepest part of the endotherm curve before the highest peak with the base line of the DSC graph.
  • the base line is determined by joining the plateaus on the low and high temperature sides of the endotherm.
  • Hot melt adhesives differ from conventional liquid-based adhesives which act by adsorption or evaporation of the liquid vehicle.
  • Hot melt adhesives form a strong bond quickly simply by cooling. In general, hot melts are unaffected by water, moisture, or humidity.
  • Suitable hot melt adhesives herein include petroleum waxes such as paraffin wax and micro crystalline wax, synthetic waxes and resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymers, phenoxy resins, styrene- butadiene copolymers, ethylene-ethyl acrylate copolymers, polyesters, polyamides and polyurethanes and mixture thereof.
  • compositions of the invention preferably comprise an alkoxylated nonionic surfactant, optionally together with one or more anionic, cationic, amphoteric and/or zwitterionic surfactants.
  • the non-ionic surfactant is selected from the group consisting of: poly(oxyalkylated) alcohols (eg: ethoxylated alcohols, ethoxylated/propoxylated alcohols), end-capped poly(oxyalkylated) alcohols, alkylene oxide condensates with propylene glycol or alkylene diamine adducts and mixtures thereof.
  • nonionic surfactants and mixtures thereof including nonionic alkoxylated surfactants (especially ethoxylates derived from C6-C ⁇ g primary alcohols), ethoxylated- propoxylated alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B - see WO- A-94/22800), ether-capped poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan.
  • nonionic alkoxylated surfactants especially ethoxylates derived from C6-C ⁇ g primary alcohols
  • ethoxylated- propoxylated alcohols e.g., Olin Corporation'
  • Additional surfactants suitable herein include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates and alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is C5-C20 . preferably C ⁇ Q-CIS linear or branched; cationic surfactants such as choline esters (US-A-4228042, US-A-4239660 and US-A-4260529) and mono C6-C 16
  • Surfactants suitable herein are disclosed, for example, in US-A-3, 929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874.
  • Surfactants are typically present at a total level of from about 0.5% to about 30% by weight, more preferably from about 1% to about 15% by weight and most preferably from about 1.5% to about 8% by weight of composition.
  • Dissolution promoters suitable for use herein can be selected from polymeric disintegrating agents, water-soluble (especially hydrated) salts, effervescent agents and mixtures thereof. They can be used to enhance the rate of tablet dissolution in the wash liquor.
  • Suitable polymeric disintegrants for use herein include polymers that swell on contact with water as well as those that facilitate water influx and/or efflux by forming channels in the detergent tablet.
  • polymeric disintegrating agents suitable for use herein can also act as tablet binders - in other words, they act to increase tablet strength as well as enhancing dissolution rate.
  • Polymeric disintegrants preferred for use herein include starch and cellulose and derivatives thereof, alginates, sugars, polyvinylpyrrolidones, swellable clays, and mixtures thereof.
  • Suitable disintegrating agent examples include starch and cellulose-based materials such as Arbocel (tradename), Vivapur (tradename) both available from Rettenmaier, Nymcel (tradename) available from Metsa-serla , burkeite, methyl cellulose, hydroxypropylcellulose, carboxymethylcellulose, cross-linked celluloses such as cross-linked carboxymethylcellulose (CMC), dextrans, cross-linked polyvinylpyrrolidones.
  • Vivapur and in particular Vivapur G200 a micro crystalline cellulose having an average particle size of about 0.18mm is particularly preferred from the viewpoint of providing both enhanced dissolution rate and tablet strength as well as excellent storage stability.
  • the water-soluble salt is preferably soluble to the extent of at least about 40g/100g, more preferably at least about 60g/100g of distilled water at 25°C.
  • the water-soluble salt preferably has a melting point in the range from about 30°C to about 95°C, more preferably from about 30°C to about 75°C.
  • Preferred water-soluble salts are selected from sodium acetate, sodium metaborate, sodium orthophosphate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium potassium tartrate, potassium aluminium sulphate, calcium bromide, calcium nitrate, sodium citrate, potassium citrate and hydrates and mixtures thereof.
  • Particularly suitable materials include sodium acetate trihydrate, sodium metaborate tetrahydrate or octahydrate, sodium orthophosphate dodecahydrate, sodium dihydrogen phosphate dihydrate, the di-, hepta- or dodeca-hydrate of disodium hydrogen phosphate, sodium potassium tartrate tetrahydrate, potassium aluminium sulphate dodecahydrate, calcium bromide hexahydrate, calcium nitrate tetrahydrate and sodium citrate dihydrate and tripotassium citrate monohydrate.
  • the water-soluble salt is selected from water-soluble mono-, di- tri- and tetrahydrate salts and mixtures thereof. Highly preferred herein is sodium acetate trihydrate and tripotassium citrate monohydrate.
  • Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervescing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervesing include perborate, percarbonate, carbonate, bicarbonate and inorganic acids or carboxylic acids such as citric or maleic acid. Preferred herein is a (bicarbonate aid effervescing system.
  • Enzymes suitable herein include bacterial and fungal cellulases such as Carezyme and Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano Pharmaceutical Co.), Ml Lipase R and Lipomax 5" (Gist-Brocades) and Lipolase R and Lipolase Ultra R (Novo); cutinases; proteases such as Esperase R , Alcalase R Durazym R and Savinase R (Novo) and Maxatase R Maxacal R Properase R and Maxapem R (Gist-Brocades); and ⁇ and ⁇ amylases such as Purafect Ox Am R (Genencor) and Termamyl R Ban R Fungamyl R Duramyl R and Natalase R (Novo); and mixtures thereof. Enzymes are preferably added herein as prills, granulates, or cogranulates at levels typically in the range from about 0.0001% to about
  • Builders suitable for use herein include water-soluble builders such as citrates, carbonates and polyphosphates e.g. sodium tripolyphosphate and sodium tripolyphosphate hexahydrate; and partially water-soluble or insoluble builders such as crystalline layered silicates (EP-A-0164514 and EP-A-0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HS and MAP.
  • the builder is typically present at a level of from about 1% to about 80% by weight, preferably from about 10% to about 70% by weight, most preferably from about 20% to about 60% by weight of composition.
  • Amorphous sodium silicates having an Si ⁇ 2:Na2 ⁇ ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0 can also be used herein although highly preferred from the viewpoint of long term storage stability are compositions containing less than about 22%), preferably less than about 15% total (amorphous and crystalline) silicate.
  • Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release (see, for example, GB- A-1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and/or transition metal-containing bleach catalysts (especially manganese or cobalt).
  • Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 40% by weight, preferably from about 2% to about 30%) by weight and more preferably from abut 5% to about 25% by weight of composition.
  • Peroxyacid bleach precursors preferred for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5- trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807).
  • Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of composition.
  • Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and related complexes(US-A-4810410).
  • suitable components herein include organic polymers having dispersant, anti- redeposition, soil release or other detergency properties invention in levels of from about 0.1% to about 30%, preferably from about 0.5% to about 15%, most preferably from about 1% to about 10% by weight of composition.
  • Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.
  • Heavy metal sequestrants and crystal growth inhibitors are suitable for use herein in levels generally from about 0.005%) to about 20%, preferably from about 0.1%> to about 10%, more preferably from about 0.25% to about 7.5% and most preferably from about 0.5% to about 5% by weight of composition, for example diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-1,1- diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'- disuccinate in their salt and free acid forms.
  • diethylenetriamine penta methylene phosphonate
  • ethylene diphosphonate hydroxy-ethylene-1,1
  • compositions herein can contain a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%, preferably from about 0.1%> to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see GB-A- 1137741) and Mn(II) compounds, particularly Mn(II) salts of organic ligands in levels of from about 0.005% to about 5%, preferably from about 0.01%) to about 1%, more preferably from about 0,02% to about 0.4%> by weight of the composition.
  • a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%, preferably from about 0.1%> to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see
  • Suitable components herein include colourants, water-soluble bismuth compounds such as bismuth acetate and bismuth citrate at levels of from about 0.01% to about 5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%, lime soap dispersants (see WO-A- 93/08877), suds suppressors (see WO-93/08876 and EP-A-0705324) and perfumes.
  • water-soluble bismuth compounds such as bismuth acetate and bismuth citrate at levels of from about 0.01% to about 5%
  • enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%
  • lime soap dispersants see WO-A- 93/08877
  • suds suppressors see WO-93/08876 and EP-A-0705324
  • the detergent tablets herein are preferably formulated to have a not unduly high pH, preferably a pH in 1% solution in distilled water of from about 8.0 to about 12.5, more preferably from about 9.0 to about 11.8, most preferably from about 9.5 to about 11.5.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, silverware, metallic items, cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of the herein described compositions.
  • an effective amount is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • the detergent tablets are from 15g to 40g in weight, more preferably from 20g to 35g in weight.
  • Amylase Amylolytic enzyme Amylase Amylolytic enzyme.
  • the following illustrates detergent tablets of the present invention suitable for use in a dishwashing machine.
  • the tablet compositions are prepared as follows.
  • the detergent active composition of phase 1 is prepared by admixing the granular and liquid components and is then passed into the die of a conventional rotary press.
  • the press includes a punch suitably shaped for forming a mould.
  • the cross-section of the die is approximately 30x38 mm.
  • the composition is then subjected to a compression force of 940 kg/cm 2 and the punch is then elevated exposing the first phase of the tablet containing the mould in its upper surface.
  • the detergent active composition of phase 2 is mixed with the meltable adhesive (PEG 4000), the PEG 400 (where present) sprayed onto the admix, the mixture thereafter being delivered into the mould and heated from the top with an infrared lamp until the adhesive is melted.
  • the tablet is thereafter allowed to cool.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa- 1,1, 3 -propane tricarboxylates described in GB-A-1,387,447.
  • Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB- A-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 GB-A-1,398,421, GB-A-1,398,422 and US-A- 3,936,448, and the sulfonated pyrolysed citrates described in GB-A-1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5, 5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5, 6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A- 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • B orate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that 50°C, especially less than 40°C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in DE-A-2,321,001.
  • Highly preferred builder compounds for use in the present compositions are water-soluble phosphate builders.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21, and salts of phytic acid.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • compositions herein can contain a partially water-soluble or water-insoluble builder compound.
  • Partially soluble and insoluble builder compounds are particularly suitable for use in tablets prepared for use in laundry cleaning methods.
  • partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A- 0164514 and EP-A-0293640. Preferred are the crystalline layered sodium silicates of general formula
  • Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so called ⁇ -layered structure, as described in EP-A-0164514 and EP-A-0293640. Methods for preparation of crystalline layered silicates of this type are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2,3 or 4 and is preferably 2.
  • the most preferred crystalline layered sodium silicate compound has the formula ⁇ - Na2S_2 ⁇ 5 , known as NaSKS-6 (trade name), available from Hoechst AG.
  • the crystalline layered sodium silicate material can be added, especially in granular detergent compositions, as a particulate in intimate admixture with a solid, water-soluble ionisable material as described in WO-A-92/18594.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.
  • Examples of largely water insoluble builders include the sodium alumino silicates.
  • Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na z [(Al ⁇ 2) z (Si ⁇ 2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.
  • a preferred method of synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14(2), 110-116), in which the author describes a method of preparing colloidal aluminosilicate zeolites.
  • the colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles are of size greater than l ⁇ m in diameter and not more than 5%> of particles are of size less then 0.05 ⁇ m in diameter.
  • the aluminosilicate zeolite particles have an average particle size diameter of between 0.01 ⁇ m and l ⁇ m, more preferably between 0.05 ⁇ m and 0.9 ⁇ m, most preferably between 0. l ⁇ m and 0.6 ⁇ m.
  • Zeolite A has the formula
  • Zeolite X has the formula Nag ⁇ [(AlO 2 )86(Si ⁇ 2)l06-- 276 H 2°- Zeolite MAP, as disclosed in EP-B-384,070 is a suitable zeolite builder herein.
  • Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
  • colloidal aluminosilicate zeolites especially colloidal zeolite A, provide enhanced builder performance, especially in terms of improved stain removal, reduced fabric encrustation and improved fabric whiteness maintenance.
  • Mixtures of colloidal zeolite A and colloidal zeolite Y are also suitable herein providing excellent calcium ion and magnesium ion sequestration performance.
  • Suitable surfactants are selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • Automatic dishwashing machine products should be low foaming in character and thus the foaming of the surfactant system for use in dishwashing should be suppressed or more preferably be low foaming, typically nonionic in character. Sudsing caused by surfactant systems used in laundry cleaning methods need not be suppressed to the same extent as is necessary for dishwashing.
  • a listing of surfactants typically included in automatic dishwashing detergent compositions is given in EP-A-0414549 and WO-A-93/08876 and WO-A-93/08874.
  • Nonionic ethoxylated alcohol surfactants The alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • a suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula:
  • Rj is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms;
  • R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to
  • x is an integer having an average value of from 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20.
  • the surfactant of formula I at least 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2].
  • Suitable surfactants of formula I are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO-A-94/22800.
  • Suitable surfactants for use herein include ether-capped poly(oxyalkylated) alcohols having the formula: R 1 0[CH 2 CH(R 3 )O] x [CH 2 ] CH(OH)[CH2]jOR 2
  • R and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms;
  • R 3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms;
  • x is an integer having an average value from 1 to 30, wherein when x is 2 or greater R 3 may be the same or different and k and j are integers having an average value of from 1 to 12, and more preferably 1 to 5.
  • R! and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms is most preferred for R 3 .
  • x is an integer having an average value of from 1 to 20, more preferably from 6 to 15.
  • R? may be the same or different. That is, ? may vary between any of the alkyleneoxy units as described above. For instance, if x is 3, R ⁇ may be be selected to form ethyleneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO).
  • the integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, mulitple (EO) units and a much small number of (PO) units.
  • Particularly preferred surfactants as described above include those that have a low cloud point of less than 20°C. These low cloud point surfactants may then be employed in conjunction with a high cloud point surfactant as described in detail below for superior grease cleaning benefits.
  • Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those wherein k is 1 and j is 1 so that the surfactants have the formula:
  • R , R 2 and R 3 are defined as above and x is an integer with an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18.
  • Most preferred are surfactants wherein R and R 2 range from 9 to 14, R 3 is H forming ethyleneoxy and x ranges from 6 to 15.
  • the ether-capped poly(oxyalkylated) alcohol surfactants comprise three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap.
  • the alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.
  • surfactants exhibit significant improvements in spotting and filming characteristics and removal of greasy soils, when used in conjunction with high cloud point surfactants, relative to conventional surfactants.
  • the ether-capped poly(oxy alkylene) alcohol surfactants may be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention.
  • Nonionic ethoxylated/propoxylated fatty alcohol surfactants are nonionic ethoxylated/propoxylated fatty alcohol surfactants.
  • the ethoxylated Cg-C ⁇ g fatty alcohols and Cg-C ⁇ g mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the C ⁇ Q-CI 8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C12-C18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility.
  • Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000.
  • this type of nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by BASF.
  • compositions herein can also include a mixed nonionic surfactant system comprising at least one low cloud point nonionic surfactant and at least one high cloud point nonionic surfactant.
  • Cloud point is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the
  • a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30°C, preferably less than 20°C, and most preferably less than 10°C.
  • Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy- capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in WO-A-94/22800) and the ether-capped poly(oxyalkylated) alcohol surfactants.
  • ethoxylated-propoxylated alcohol e.g., Olin Corporation's Poly-Tergent® SLF18
  • epoxy- capped poly(oxyalkylated) alcohols e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in WO-A-94/22800
  • Nonionic surfactants can optionally contain propylene oxide in an amount up to 15% by weight.
  • Other suitable nonionic surfactants can be prepared by the processes described in US-A-4,223,163.
  • Low cloud point nonionic surfactants additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound.
  • Block polyoxyethylene-polyoxypropylene polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound.
  • Certain of the block polymer surfactant compounds designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are also suitable herein.
  • Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants are typically useful herein as low cloud point nonionic surfactants.
  • a "high cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of greater than 40°C, preferably greater than 50°C, and more preferably greater than 60°C.
  • the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • the high cloud point nonionic surfactant further have a hydrophile- lipophile balance ("HLB"; see Kirk Othmer hereinbefore) value within the range of from 9 to 15, preferably 11 to 15.
  • HLB hydrophile- lipophile balance
  • Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • high cloud point nonionic surfactant is derived from a straight or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon atoms (C6-C20 alcohol), including secondary alcohols and branched chain primary alcohols.
  • high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/11 or Cl l/15 branched alcohol ethoxylates, condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.
  • Anionic surfactants Essentially any anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, 2 -Ci o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C 14 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C ⁇ o- C j g alkyl sulfates, more preferably the Cn ⁇ Ci ⁇ branched chain alkyl sulfates and the C.12" l4 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cl0 ⁇ l8 a lkyl 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 Cu-Cjg, most preferably C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule. Mixtures of alkyl sulfate and alkyl ethoxysulfate surfactants are also suitable herein (WO-A-93/18124).
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C5-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-0)-R3 wherein R is a Cg to C ⁇ g alkyl group, x is from 1 to 25, R j and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl-l-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 Ci - 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 Ci - C4 alkyl group
  • M is an alkali metal ion.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula 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 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl amphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R 2 COO ⁇ wherein R is a Cg-Ci g hydrocarbyl group, each R is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are Ci 2_i8 dimethyl-ammonio hexanoate and the C 10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Other suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US-A-4228042, US-A-4239660 and US-A-4260529.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono Cg-Ci ⁇ , preferably Cg-C ⁇ o N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Enzymes
  • Enzymes suitable for use herein included cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, upases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and mixtures thereof.
  • Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit).
  • CEVU Cellulose Viscosity Unit
  • Suitable cellulases are disclosed in US-A-4,435,307, J61078384 and WO-A-96/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP-A-0739982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275, DE-A-2.247.832 and WO-A-95/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in WO-A- 91/17243.
  • suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO-A-94/21801.
  • Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO-A- 91/17244 and WO-A-91/21801.
  • Other suitable cellulases for fabric care and/or cleaning properties are described in WO-A-96/34092, WO-A-96/17994 and WO-A-95/24471.
  • Said cellulases are normally incorporated in detergent compositions at levels from 0.0001% to 2% of active enzyme by weight of composition.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in WO-A-89/099813, WO-A-89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
  • Preferred enhancers are substitued phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10- phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO-A- 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said cellulases and/or peroxidases are normally incorporated in detergent composition at levels from 0,0001% to 2%> of active enzyme by weight of composition.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB-A-1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • lipases include Amano- CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
  • lipases such as Ml Lipase ⁇ an(3
  • Lipoma ⁇ (Gist-Brocades) and Lipolase ⁇ and Lipolase Ultra- ⁇ -fNovo) which have found to be very effective when used in combination with the compositions of the present invention.
  • lipolytic enzymes described in EP-A-0258068, WO-A- 92/05249, WO-A-95/22615, WO-A-94/03578, WO-A-95/35381 and WO-A-96/00292.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367, WO-A-90/09446, WO-A-94/14963 and WO-A-94/14964.
  • the lipases and/or cutinases are normally incorporated in detergent composition at levels from 0.0001% to 2% of active enzyme by weight of composition.
  • Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN').
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
  • Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein “Protease B”, and in EP-A-0199404 which refers to a modified bacterial serine protealytic enzyme which is called “Protease A” herein.
  • Suitable is what is called herein “Protease C”, which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in WO-A-91/06637. Genetically modified variants, particularly of Protease C, are also included herein.
  • a suitable protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO-A-95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease
  • proteases described in EP-A-0251 446 and WO-A-91/06637 are also suitable.
  • protease BLAP® described in WO-A-91/02792 and their variants described in WO-A-95/23221.
  • protease from Bacillus sp. NCIMB 40338 described in WO-A- 93/18140.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO-A-92/03529.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO-A- 95/07791.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO-A- 94/25583.
  • Other suitable proteases are described in EP-A-0516 200.
  • protease enzymes which are a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived by replacement of a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme correspond to position +210 in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions correspond to naturally-occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin).
  • Preferred enzymes of this type include those having position changes +210,
  • the proteolytic enzymes are incorporated in detergent compositions at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of composition.
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • WO-A- 94/02597 describes cleaning compositions which incorporate mutant amylases. See also WO-A-95/10603.
  • Other amylases known for use in cleaning compositions include both Gland ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US-A- 5,003,257; EP-A-0252, 666; WO-A-91/00353; FR-A-2, 676,456; EP-A-0285,123; EP-A- 525,610; EP-A-0368,341; and GB-A-1,296,839.
  • amylases are stability- enhanced amylases described in WO-A-94/18314 and WO-A-96/05295 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are amylases described in EP-A- 0277216, WO-A-95/26397 and WO-A-96/23873. Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and
  • WO-A-95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25%) higher than the specific activity of
  • Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to
  • Preferred amylase enzymes include those described in WO-A-95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • amylolytic enzymes are incorporated in detergent compositions at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048%) pure enzyme by weight of composition
  • compositions herein comprise amylase enzymes, particularly those described in WO-A-95/26397 and co-pending application by Novo Nordisk PCT/DK96/00056 in combination with a complementary amylase.
  • complementary it is meant the addition of one or more amylase suitable for detergency purposes.
  • Examples of complementary amylases ( ⁇ and/or ⁇ ) are described below.
  • WO-A-94/02597 and WO-A-95/10603 describe cleaning compositions which incorporate mutant amylases.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US-A-5,003,257; EP-A-0252, 666; WO-A-91/00353; FR-A-2, 676,456; EP-A- 0 285123; EP-A-0525610; EP-A-0368341; and GB-A-1,296,839.
  • Other suitable amylases are stability-enhanced amylases described in WO-A-94/18314 and WO-A-96/05295 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are amylases described in
  • EP-A-0277 216 examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and Termamyl®,- Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of
  • Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to
  • Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermo stability and a higher activity level are described in WO-A-95/35382.
  • Preferred complementary amylases for the present invention are the amylases sold under the tradename Purafect Ox Am ⁇ described in WO- A- 94/18314, WO-A-96/05295 sold by Genencor; Termamyl®, Fungamyl®, Ban® Natalase ® and Duramyl®, all available from Novo Nordisk A/S and Maxamyl® by Gist-Brocades.
  • the complementary amylase is generally incorporated in detergent compositions at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048%) pure enzyme by weight of composition.
  • a weight of pure enzyme ratio of specific amylase to the complementary amylase is comprised between 9:1 to 1:9, more preferably between 4: 1 to 1:4, and most preferably between 2: 1 and 1:2.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesopbilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.
  • Enzymes are normally incorporated in detergent composition at levels from 0.0001% to 2% of active enzyme by weight of composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • enzyme oxidation scavengers which are described in copending European Patent application 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO-A-9307263, WO-A-9307260, WO-A-8908694 and US-A-3,553,139. Enzymes are further disclosed in US-A-4, 101,457 and US-A- 4,507,219. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in US-A- 4,261,868. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in US-A-3, 600,319, EP-A-0199405 and EP-A-0200586.
  • Enzyme stabilisation systems are also described, for example, in US-A- 3,519,570.
  • a useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO-A- 9401532.
  • Suitable bleaching agents herein include chlorine and oxygen-releasing bleaching agents.
  • the oxygen-releasing bleaching agent contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt can be included as the crystalline solid without additional protection. For certain perhydrate salts however, a coated form of the material is used in order to provide better storage stability.
  • Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise.
  • the percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-A-1,466,799.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4-.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material providing in product stability comprises sodium silicate of Si ⁇ 2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1, preferably
  • sodium metasilicate preferably applied at a level of from 2% to 10%, (normally from 3% to 5%>) of Si ⁇ 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable. Other coatings which contain waxes, oils, fatty soaps can also be used herein.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
  • 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, GB-A-864798, GB-A-1147871, GB-A-2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilise for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • R ⁇ is an alkenyl chain containing from 1 to 8 carbon atoms
  • Y is H or a solubilizing group.
  • 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 , -C0 2 " M , -SO M , -N (R ) C and
  • R 3 is an alkyl chain containing from 1 to 4 carbon atoms
  • M is a cation which provides solubility to the bleach activator
  • 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
  • X is a halide, hydroxide, methylsulfate or acetate anion.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all sacharides with benzoylating agents including for example:
  • Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
  • Suitable N-acylated lactam perbenzoic acid precursors have the formula:
  • n is from 0 to 8, preferably from 0 to 2
  • R is a benzoyl group.
  • Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
  • Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (i.e.; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
  • a preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • R! is an aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R! preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R* may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R-> is preferably H or methyl, R! and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
  • Cationic peroxyacid precursors are described in US-A-4,904,406; US-A-4,751,015; US- A-4,988,451; US-A-4,397,757; US-A-5,269,962; US-A-5, 127,852; US-A-5,093,022; US- A-5,106,528; GB-A-1,382,594; EP-A-0475512, EP-A-0458396 and EP-A-0284292; and in JP87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • N-acylated caprolactam class examples include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12, particularly from 1 to 5.
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
  • TAED Tetraacetyl ethylene diamine
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:
  • R is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R ⁇ preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R* may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat.
  • R 2 Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R5 is preferably H or methyl.
  • R and R ⁇ should not contain more than 18 carbon atoms in total.
  • Amide substituted bleach activator compounds of this type are described in EP- A-0170386.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-0332294 and EP-A-0482807, particularly those having the formula:
  • R is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R «, R , R 4 , and R_- may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR fi (wherein R fi is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • a suitable class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R! is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • R* preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R! may be straight chain or branched alkyl, substituted "aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R! and R ⁇ should not contain more than 18 carbon atoms in total.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a preferred organic peroxyacid herein.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • Controlled rate of release - means
  • a means may be provided for controlling the rate of release of bleaching agent, particularly oxygen bleach to the wash solution.
  • Means for controlling the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution.
  • Such means could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.
  • Suitable controlled release means can include confining the bleach to one portion of the composition.
  • Another mechanism for controlling the rate of release of bleach may be by coating the bleach with a coating designed to provide the controlled release.
  • the coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.
  • the coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2, preferably from 1 :49 to 1 :9.
  • Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
  • Other suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.
  • a preferred coating material particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of S1O2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%>) of Si ⁇ 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating.
  • Suitable binders include the Cio-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10 ⁇ preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned CJQ-
  • binders include the C10-C20 ono- and diglycerol ethers and also the
  • Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.
  • One method for applying the coating material involves agglomeration.
  • Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
  • Suitable means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compression, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.
  • particle size Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.
  • Additional protocols for providing the means of controlled release include the suitable choice of any other components of the composition such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved.
  • Bleach-cintaining compositions herein can additionally contain a metal containing bleach catalyst.
  • the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt-containing bleach catalyst.
  • a suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a heavy metal cation of defined bleach catalytic activity such as copper, iron cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminium cations
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include the manganese-based complexes disclosed in US-A- 5,246,621 and US-A-5,244,594. Preferred examples of these catalysts include
  • ligands suitable for use herein include l,5,9-trimethyl-l,5,9- triazacyclododecane, 2-methyl-l,4,7-triazacyclononane, 2-methyl-l,4,7-triazacyclononane, l,2,4,7-tetramethyl-l,4,7-triazacyclononane, and mixtures thereof.
  • suitable bleach catalysts see US-A-4,246,612 and US-A-5,227,084.
  • Still another type of bleach catalyst is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • US-A-5, 114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
  • Said ligands are of the formula:
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • 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)C_2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2Cl ⁇ 4, Bis-(2,2'- bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
  • Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including [Bipy2Mn III (u-0)2Mn I Vbipy 2 ]- (ClO 4 ) 3 .
  • the bleach-catalyzing manganese complexes have not generally been elucidated, it may be speculated that they comprise chejates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
  • the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+III), .(+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn-ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stains such as tea, ketchup, coffee, wine, juice, and the like.
  • bleach catalysts are described, for example, in EP-A-0408131 (cobalt complex catalysts), EP-A-0384503, and EP A-0306089 (metallo-porphyrin catalysts), US-A- 4,728,455 (manganese/multidentate ligand catalyst), US-A-4,711,748 and EP-A-0224952, (absorbed manganese on aluminosilicate catalyst), US-A-4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), US-A-4, 626,373 (manganese/ligand catalyst), US-A- 4,119,557 (ferric complex catalyst), DE-A-2, 054,019 (cobalt chelant catalyst), CA-A-866,191 (transition metal-containing salts), US-A-4,430,243 (chelants with manganese cations and non-catalytic metal cations), and US-A-4,728,455 (manganeses
  • Preferred cobalt catalysts of this type have the formula:
  • the preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH 3 ) 5 Cl] Y y , and especially [Co(NH3) 5 Cl]Cl 2 .
  • T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFg", BF4", B(Ph)4", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof.
  • T can be protonated if more than one anionic group exists in T, e.g., HPO4 2 ",
  • T may be selected from the group consisting of non- traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).
  • anionic surfactants e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.
  • anionic polymers e.g., polyacrylates, polymethacrylates, etc.
  • the M moieties include, but are not limited to, for example, F-, SO4- 2 NCS", SCN",
  • M can be protonated if more than one anionic group exists in M (e.g., HPO 4 2 ", HCO3-, H 2 PO 4 -, HOC(0)CH 2 C(O)O-
  • Preferred M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
  • R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably Ci-Cjg) unsubstituted and substituted alkyl, C6-C30 (preferably Cg-Ci g) unsubstituted and substituted aryl, and C3-C30 (preferably C5-C18) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of - NR'3, -NR'4 + , -C(O)OR', -OR 1 , -C(0)NR' 2 , wherein R' is selected from the group consisting of hydrogen and C ⁇ -C6 moieties.
  • Such substituted R therefore include the moieties -(CH2) n C ⁇ and -(CH2) n NR'4 + , wherein n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.
  • M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 alkyl, and benzyl. Most preferred R is methyl.
  • Preferred carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triftate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.
  • the B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine).
  • carboxylates e.g., oxalate, malonate, malic, succinate, maleate
  • picolinic acid e.g., glycine, alanine, beta-alanine, phenylalanine.
  • Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. (1983), 2, pages 1-94.
  • cobalt pentaamine acetate salts having the formula [Co( H3)5OAc] T y , wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 )5OAc]Cl 2 ; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 )2; [Co(NH 3 )5 ⁇ Ac](S ⁇ 4); [Co(NH 3 ) 5 OAc](BF 4 )2; and [Co(NH 3 )5 ⁇ Ac](NO 3 )2 (herein "PAC").
  • PAC cobalt pentaamine acetate salts having the formula [Co( H3)5OAc] T y , wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 )5OAc]Cl 2 ; as
  • cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article hereinbefore and the references cited therein, in US-A- 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (19891 66 (12), 1043- 45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice- Hall; 1970), pp. 461-3; Inorg. Chem.. 18, 1497-1502 (1979); Inorg. Chem.. 21, 2881- 2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (I960); and Journal of Physical Chemistry. 56, 22-25 (1952); as well as the synthesis examples provided hereinafter.
  • Cobalt catalysts suitable for incorporation into the detergent tablets of the present invention may be produced according to the synthetic routes disclosed in US-A-5, 559,261, US-A-5,581,005, and US-A-5,597,936.
  • catalysts may be co-processed with adjunct materials so as to reduce the colour impact if desired for the aesthetics of the product, or to be included in enzyme-containing particles as exemplified hereinafter, or the compositions may be manufactured to contain catalyst "speckles".
  • Organic polymeric compounds may be added as preferred components of the detergent tablets in accord with the invention.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly found in detergent compositions having dispersant, anti-redeposition, soil release agents or other detergency properties.
  • organic polymeric compounds include the water soluble organic homo- or copolymeric polycarboxylic acids, modified polycarboxylates or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.
  • Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N, 480N, 460N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90%) to 10%>, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10%> to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CR ⁇ (CO-O-R3)]- wherein at least one of the substituents R , R2 or R3, preferably R or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R. ⁇ or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • R is a substituted acrylic monomer wherein Ri is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer).
  • the most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40%) to 20%) by weight of methacrylic acid.
  • polyamine and modified polyamine compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-0305282, EP-A-0305283 and EP-A-0351629.
  • Other optional polymers may polyvinyl alcohols and acetates both modified and non- modified, cellulosics and modified cellulosics, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, both modified and non-modified, terephthalate esters of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units. Suitable examples are disclosed in US-A-5,591,703, US-A-5,597,789 and US-A-4,490,271.
  • Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50%> oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene
  • poly (vinyl ester) segments preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C ⁇ -
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in US-A-4,721,580.
  • Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or ' propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see US-A-4, 000,093.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci -Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See EP-A-0219048.
  • Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See US-A- 3,959,230 and US-A-3, 893,929.
  • Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80%) by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in US-A-4, 968,451.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of US-A-4,711,730, the anionic end-capped oligomeric esters of US-A-4,721,580 and the block polyester oligomeric compounds of US-A-4,702,857.
  • Other polymeric soil release agents also include the soil release agents of US-A-4,877,896 which discloses anionic, especially sulfoarolyl, end- capped terephthalate esters.
  • Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)- ethanesulfonate.
  • the tablets of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo tri ethylene phosphonates.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo tri ethylene phosphonates.
  • Preferred among the above species are diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra (methylene phosphonate) and hydroxy-ethylene- 1 , 1 -diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccmic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • the detergent tablets preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.
  • a crystal growth inhibitor component preferably an organodiphosphonic acid component
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a
  • C2 diphosphonic acid such as ethylene diphosphonic acid, or most preferably ethane 1- hydroxy- 1,1 -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1- hydroxy- 1,1 -diphosphonic acid
  • compositions herein optionally contains a water-soluble sulfate salt.
  • the water-soluble sulfate salt is at the level of from 0.1% to 40%), more preferably from 1%) to 30%, most preferably from 5%> to 25% by weight of composition.
  • the water-soluble sulfate salt may be essentially any salt of sulfate with any counter cation.
  • Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.
  • a suitable alkali metal silicate is sodium silicate having an Si ⁇ 2:Na2 ⁇ ratio of from 1.8 to
  • Sodium silicate is preferably present at a level of less than 20%>, preferably from 1% to 15%, most preferably from 3% to 12% by weight of S1O2.
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • compositions herein can also contain sodium metasilicate, present at a level of at least 0.4% Si ⁇ 2 by weight.
  • Sodium metasilicate has a nominal S1O2 : Na2 ⁇ ratio of 1.0.
  • the weight ratio of said sodium silicate to said sodium metasilicate, measured as Si ⁇ 2, is preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.
  • colourant means any substance that absorbs specific wavelengths of light from the visible light spectrum. Such colourants when added to a detergent composition have the effect of changing the visible colour and thus the appearance of the detergent composition.
  • Colourants may be for example either dyes or pigments.
  • the colourants are stable in composition in which they are to be incorporated. Thus in a composition of high pH the colourant is preferably alkali stable and in a composition of low pH the colourant is preferably acid stable.
  • suitable dyes include reactive dyes, direct dyes, azo dyes.
  • Preferred dyes include phthalocyanme dyes, anthraquinone dye, quinoline dyes, monoazo, disazo and polyazo. More preferred dyes include anthraquinone, quinoline and monoazo dyes.
  • Preferred dyes include SANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING BLUE (tradename), TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename) all available from Clariant UK, HEXACOL QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename) both available from Pointings, UK, ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFIX TURQUISE BLUE EBA (tradename) available from Bayer, USA.
  • the colourant may be incorporated by any suitable method. Suitable methods include mixing all or selected detergent components with a colourant in a drum or spraying all or selected detergent components with the colourant in a rotating drum.
  • Colourant is typically added at a level of from 0.001% to 1.5%, preferably from 0.01% to 1.0%, most preferably from 0.1% to 0.3%) by weight of composition.
  • compositions herein can contain a corrosion inhibitor preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • organic silver coating agents are described in WO-A-94/16047 and EP-A-690122.
  • Nitrogen-containing corrosion inhibitor compounds are disclosed in EP-A-0634478.
  • Mn(II) compounds for use in corrosion inhibition are described in EP-A-0672 749.
  • the functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied.
  • the silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.
  • Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and ⁇ , ⁇ '- dihydroxyisobutyric acid.
  • suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
  • the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • glycerol esters are also highly preferred. These are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above.
  • fatty alcohol esters for use herein include: stearyl acetate, palmityl di- lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl proprionate.
  • Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono- oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.
  • Glycerol monostearate glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
  • Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.
  • Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
  • Waxes including microcrystalline waxes are suitable organic silver coating agents herein.
  • Preferred waxes have a melting point in the range from 35°C to 110°C and comprise generally from 12 to 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
  • Alginates and gelatin are suitable organic silver coating agents herein.
  • Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C12-C20 niethylammonium halides are also suitable.
  • suitable organic silver coating agents include certain polymeric materials.
  • perfume materials particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.
  • Polymeric soil release agents can also be used as an organic silver coating agent.
  • a preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predominantly branched C25-45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1.
  • Nitrogen-containing corrosion inhibitor compounds Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139, 279 and GB-A- 1,137,741, which also discloses a method for making imidazole compounds.
  • nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Ri , R3, R4 and R5 where R is any of H,
  • R 3 and R 5 are any of alkyl or hydroxyl, and R4 is any of H, NH2 or NO2.
  • nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2- mercaptobenzothiazole, l-phenyl-5-mercapto-l,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.
  • Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulphate or diammonium hydrogen citrate are also suitable.
  • the Mn(II) compound is preferably incorporated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in bleaching solution.
  • the Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride.
  • the Mn(II) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.
  • the Mn(II) compound may be a salt or complex of an organic ligand.
  • the organic ligand is a heavy metal ion sequestrant.
  • the organic ligand is a crystal growth inhibitor.
  • additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated C ⁇ Q-
  • C20 fatty acids, or their salts especially aluminium tristearate.
  • the C12-C20 hydroxy fatty acids, or their salts are also suitable.
  • Phosphonated octa-decane and other anti- oxidants such as betahydroxytoluene (BHT) are also suitable.
  • Copolymers of butadiene and maleic acid particularly those supplied under the trade reference no. 07787 by Polysciences Inc have been found to be of particular utility as corrosion inhibitor compounds.
  • compositions herein can contain a water-soluble bismuth compound, preferably present at a level of from 0.005%) to 20%>, more preferably from 0.01%) to 5%, most preferably from 0.1%> to 1% by weight of composition.
  • the water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion.
  • Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate.
  • Bismuth acetate and citrate are preferred salts with an organic counter anion.
  • Preferred enzyme-containing compositions herein can comprise from 0.001% to 10%, preferably from 0.005%) to 8%>, most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • compositions herein can contain a lime soap dispersant compound, preferably present at a level of from 0.1 %> to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of composition.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
  • Preferred lime soap disperant compounds are disclosed in WO-A-93/08877.
  • compositions herein preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds.
  • Preferred suds suppressing systems and antifoam compounds are disclosed in WO-A-93/08876 and EP-A-0705324.
  • compositions herein can also comprise from 0.01% ' to 10 %>, preferably from 0.05% to 0.5%) by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • compositions can also contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • R is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ 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-triaz_ne-2- yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • 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'-stilbenedisulfoi_ic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM- GX by Ciba-Geigy Corporation.
  • 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 is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • compositions herein can contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US-A-3,862,058, US-A-3,948,790, US-A-3,954,632 and US-A- 4,062,647.
  • EP-A-0299575 and EP-A-0313146 describe suitable organic polymeric clay flocculating agents.
  • Cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1514276 and EP-A-0011340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1%> to 5% by weight.

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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)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une pastille de détergent à état multiple. Ledit procédé comprend a) un premier état caractérisé par un corps formé et b) un second état comprenant un mélange non comprimé d'un solide particulaire et d'un adhésif fusible, et consiste à mettre en contact les premier et seconds états à une température inférieure à celle du début de la fusion de l'adhésif fusible et faire adhérer les états l'un avec l'autre par exposition du mélange à une température supérieure à celle de la réalisation de la fusion dudit adhésif, et faire ensuite baisser la température du mélange à la température ambiante. Ce procédé permet d'améliorer la robustesse, l'intégrité et la dissolution de la pastille. Par ailleurs, ce procédé est très économique sur le plan énergétique et accroît la vitesse de production.
PCT/US2001/003933 2000-02-17 2001-02-07 Pastille de detergent WO2001060965A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001234901A AU2001234901A1 (en) 2000-02-17 2001-02-07 Detergent tablet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0003592A GB0003592D0 (en) 2000-02-17 2000-02-17 Detergent tablet
GB0003592.3 2000-02-17

Publications (1)

Publication Number Publication Date
WO2001060965A1 true WO2001060965A1 (fr) 2001-08-23

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PCT/US2001/003933 WO2001060965A1 (fr) 2000-02-17 2001-02-07 Pastille de detergent

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Country Link
AU (1) AU2001234901A1 (fr)
GB (1) GB0003592D0 (fr)
WO (1) WO2001060965A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1340807A1 (fr) * 2002-03-01 2003-09-03 Henkel Kommanditgesellschaft auf Aktien Corps moulés contenant des tensio-actifs ajoutés postérieurement
WO2004029191A1 (fr) * 2002-09-18 2004-04-08 Henkel Kommanditgesellschaft Auf Aktien Comprimes a cavite remplis et procede de fabrication desdits comprimes
WO2004046296A1 (fr) * 2002-11-16 2004-06-03 Henkel Kommanditgesellschaft Auf Aktien Pastilles a cavite remplie et leur procede de production ii
WO2005017088A1 (fr) * 2003-08-08 2005-02-24 Henkel Kommanditgesellschaft Auf Aktien Detergent

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5658874A (en) * 1994-11-14 1997-08-19 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent tablet compositions
EP0851025A2 (fr) * 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un système d'agent blanchissant oxygéné
GB2330362A (en) * 1997-10-09 1999-04-21 Mcbride Robert Ltd Dishwasher tablets
WO2000004116A2 (fr) * 1998-07-17 2000-01-27 The Procter & Gamble Company Pastilles detergentes
WO2000070008A1 (fr) * 1999-05-17 2000-11-23 Reckitt Benckiser N.V. Procede de production d'une pastille de detergent a plusieurs couches
DE19939992A1 (de) * 1999-08-24 2001-03-01 Henkel Kgaa Wasch- oder Reinigungsmittelformkörper mit befülltem Hohlvolumen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5658874A (en) * 1994-11-14 1997-08-19 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent tablet compositions
EP0851025A2 (fr) * 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un système d'agent blanchissant oxygéné
GB2330362A (en) * 1997-10-09 1999-04-21 Mcbride Robert Ltd Dishwasher tablets
WO2000004116A2 (fr) * 1998-07-17 2000-01-27 The Procter & Gamble Company Pastilles detergentes
WO2000070008A1 (fr) * 1999-05-17 2000-11-23 Reckitt Benckiser N.V. Procede de production d'une pastille de detergent a plusieurs couches
DE19939992A1 (de) * 1999-08-24 2001-03-01 Henkel Kgaa Wasch- oder Reinigungsmittelformkörper mit befülltem Hohlvolumen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1340807A1 (fr) * 2002-03-01 2003-09-03 Henkel Kommanditgesellschaft auf Aktien Corps moulés contenant des tensio-actifs ajoutés postérieurement
WO2004029191A1 (fr) * 2002-09-18 2004-04-08 Henkel Kommanditgesellschaft Auf Aktien Comprimes a cavite remplis et procede de fabrication desdits comprimes
WO2004046296A1 (fr) * 2002-11-16 2004-06-03 Henkel Kommanditgesellschaft Auf Aktien Pastilles a cavite remplie et leur procede de production ii
WO2005017088A1 (fr) * 2003-08-08 2005-02-24 Henkel Kommanditgesellschaft Auf Aktien Detergent

Also Published As

Publication number Publication date
GB0003592D0 (en) 2000-04-05
AU2001234901A1 (en) 2001-08-27

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