WO2002042398A2 - Compositions detergentes - Google Patents

Compositions detergentes Download PDF

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Publication number
WO2002042398A2
WO2002042398A2 PCT/EP2001/013479 EP0113479W WO0242398A2 WO 2002042398 A2 WO2002042398 A2 WO 2002042398A2 EP 0113479 W EP0113479 W EP 0113479W WO 0242398 A2 WO0242398 A2 WO 0242398A2
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WO
WIPO (PCT)
Prior art keywords
weight
composition
tablet
materials
base particles
Prior art date
Application number
PCT/EP2001/013479
Other languages
English (en)
Other versions
WO2002042398A3 (fr
Inventor
Olaf Cornelis Beers
Erik Christiaan Berden
René LAMMERS
Alastair Richard Sanderson
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Lever Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/EP2000/011815 external-priority patent/WO2001038478A1/fr
Priority claimed from GB0031504A external-priority patent/GB0031504D0/en
Application filed by Unilever N.V., Unilever Plc, Hindustan Lever Ltd. filed Critical Unilever N.V.
Priority to CA002406776A priority Critical patent/CA2406776A1/fr
Priority to AU2002227936A priority patent/AU2002227936A1/en
Priority to EP01989494A priority patent/EP1337615A2/fr
Publication of WO2002042398A2 publication Critical patent/WO2002042398A2/fr
Publication of WO2002042398A3 publication Critical patent/WO2002042398A3/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • This invention relates to detergent tablets for use in the washing of fabrics. These tablets are intended to disintegrate completely when placed in water and thus to be consumed in a single use.
  • Tablets of a detergent composition have frequently been made by compressing or compacting a composition in particulate form; tablets of the present invention are also made this way.
  • Tablets formed using a low compaction pressure tend to crumble and disintegrate on handling and packing; while more forcefully compacted tablets may be sufficiently cohesive but then fail to disintegrate or disperse to an adequate extent in the wash. Tableting will often be carried out with enough pressure to achieve a compromise between these desirable but antagonistic properties. However, it remains desirable to improve one or other of these properties without detriment to the other so as to improve the overall compromise between them.
  • Organic surfactants function as a binder in tablets and help to plasticise the tablets. However, they can also retard disintegration of the tablet by forming a viscous gel when the tablet comes into contact with water. Thus, the presence of surfactant can make it more difficult to achieve both good strength and speed of disintegration: the problem has proved especially acute with tablets formed by compressing powders comprising organic surfactant and built with insoluble detergency builder such as sodium aluminosilicate (zeolite) .
  • insoluble detergency builder such as sodium aluminosilicate (zeolite)
  • compositions which consist of (i) base-powder particles which comprise organic surfactant and other materials and (ii) various other ingredients, including water-soluble salts.
  • detergent tablets like detergent compositions generally, can be made using water-soluble or water-insoluble detergency builder.
  • the water-soluble builder which is commonly used is sodium tripolyphosphate .
  • WO-A-00/32741, O-A-98/55590 and O-A-00/32740 disclose highly soluble materials such as sodium tripolyphosphate having at least 50% by weight thereof in the phase I form with surfactant granules comprising high levels of organic surfactant which surfactant granules may comprise zeolite.
  • US 4,543,204 discloses extruded detergent bars which may comprise sodium tripolyphosphate having a high content of the phase 1 material .
  • O-A-00/53716 discloses washing tablets comprising non-ionic surfactants, phosphate builders and low levels of zeolite of the Faujasite type, wherein the ratio of non-ionic surfactants: zeolite is between 1:20 and 1:1.
  • WO-A-01/04256 published 18 January 2001 (Henkel Lichtandit GmbH Auf Atkien) discloses an auxiliary disintegration agent comprising 20 to 95% wt phosphate and 0.1 to 9%wt zeolite for shaped bodies.
  • detergent tablets incorporating base particles which comprise a mixture of aluminosilicate detergency builder and organic surfactant can be made to disintegrate more readily by incorporating in the composition sodium tripolyphosphate having at least 50% of said sodium tripolyphosphate in the phase I form.
  • a detergent tablet of compacted particulate material wherein the tablet or a region thereof is compacted from a particulate composition which comprises; a) 25% to 100% by weight of the composition of base particles, which particles comprise by weight of themselves: from 15% to 40%wt organic surfactant comprising no more than 5% by weight primary alkyl sulphate, from 20% to 60%wt aluminosilicate detergency builder, and from 0 to 60%wt other ingredients, and b) 0 to 75% by weight of the composition of other materials mixed with these particles, and wherein the composition comprises from 5% to 60% by weight of the composition of sodium tripolyphosphate having at least 50% by weight thereof in the phase I form.
  • a detergent tablet of compacted particulate material wherein the tablet or a region thereof is compacted from a particulate composition
  • a particulate composition comprising; a) 25% to 100% by weight of the composition of base particles, which particles comprise by weight of themselves: from 15% to 40%wt organic surfactant comprising .alkylbenzene sulphonate, from 20% to 60%wt aluminosilicate detergency builder, and from 0 to 60%wt other ingredients, and b) 0 to 75% by weight of the composition of other materials mixed with these particles, and wherein the composition comprises from 5% to 60% by weight of the composition of sodium tripolyphosphate having at least 50% by weight thereof in the phase I form.
  • the aluminosilicate preferably comprises maximum aluminium zeolite P or zeolite A, more preferably maximum aluminium zeolite P or zeolite 4A, and especially maximum aluminium zeolite P.
  • the tablet or a region thereof is compacted from a particulate composition which comprises 25% to 95% by weight of the base particles a) , maximum aluminium zeolite P as the aluminosilicate and 5 to 75% by weight of the said other materials b) .
  • a method of making a detergent tablet of compacted particulate material comprising the steps of; (1) forming detergent base particles comprising (by weight of themselves) 15 to 40%wt organic surfactant with either (i) no more than 5%wt by weight primary alkyl sulphate or (ii) comprising alkylbenzene sulphonate, 20 to 60%wt aluminosilicate detergency builder and 0 to 60%wt other materials, and (2) mixing the base particles with other materials as necessary to form a particulate composition comprising 25 to 100% by weight of the base particles a)- and 0 to 75% by weight of the other materials b) ; and wherein the particulate composition comprises from 5% to 60% by weight thereof sodium tripolyphosphate having at least 50% by weight thereof is in the Phase I form, and
  • the base particles a) are prepared by a granulation method and mixed with other materials b) to form a composition comprising 25 to 95% by weight of the base particles and 5 to 75% by weight of the other materials, with maximum aluminium zeolite P or zeolite A as the aluminosilicate.
  • the other materials b) comprise from 5% to 60% by weight of the overall composition of sodium tripolyphosphate having at least 50% by weight thereof is in the Phase I form.
  • These tablets exhibit a good combination of disintegration and strength properties. Furthermore they exhibit good storage stability especially at 37°C, 70% relative humidity for ingredients which are prone to degradation upon tablet storage, especially bleaching agents and their activators, and, enzymes.
  • This may be utilised to provide tablets comprising zeolite, but without restriction to zeolite MAP as the only form of zeolite which can be used.
  • a detergent tablet may be made from one or more compositions and so may be either homogeneous or heterogeneous.
  • the term “homogeneous” is used to mean a tablet produced by compaction of a single particulate composition, but does not imply that all the particles of that composition will necessarily be of identical composition.
  • the term “heterogeneous” is used to mean a tablet consisting of a plurality of discrete regions, for example layers, inserts or coatings, each derived by compaction from a particulate composition. In a heterogeneous tablet each discrete region of the tablet will preferably have a mass of at least 10% of the whole tablet, which may be a mass of at least 4 gram.
  • a tablet is a heterogeneous tablet having more than one discrete region, for example a tablet with two layers of different composition
  • one region will be provided by a composition in accordance with this invention while another region will be provided by some other composition. It is also possible that two regions would be provided by different compositions both of which however, embody the present invention.
  • the detergent tablets of the invention comprise compacted particulate material which comprises 25 to 100% by weight of base particles a) and 0 to 75% by weight of other material b) mixed therewith.
  • compositions comprise 30%, 33% or 40% to 60% or 70% by weight of base particles a) and 30% or 40% to 60%, 67%, or 70% by weight of other material b) .
  • the compositions may comprise for example from 35% to 98%wt of the base particles a) and from 2% to 65%wt of the other materials b) .
  • the base particles may be made by spray-drying as described in EP 839906 and WO 98/42819. Alternatively they may be made by a granulation process.
  • EP 838519 and WO 99/20730 describe tablets containing granulated particles in which detergent active (i.e. organic surfactant) is mixed with zeolite A24.
  • This form of zeolite also known as zeolite MAP, is a special form of zeolite which is the subject of EP-A- 384070.
  • the base particles a) do not comprise the sodium tripolyphosphate, they can be made by a spray-drying process.
  • granulation is the most appropriate method of preparation and is preferred whether the particles comprise sodium tripolyphosphate or not.
  • a suitable method of granulating is disclosed in WO 00/77147 (Unilever) .
  • One or more organic detergent surfactants are present in the base particles a) and preferably provide from 7 to 40% by weight of the total composition, more preferably from 8, 10 or 12% by weight of the overall composition up to 40% by weight.
  • Organic surfactant may be present solely in the base particles a) , or some may additionally be present as part of the other material b) . Preferably at least 80%, better 90%wt of the organic surfactant in the composition is present in the base particles .
  • the organic surfactant in the base particles preferably comprises anionic surfactant, either alone or mixed with nonionic surfactant.
  • Anionic surfactant may be present in an amount from 0.5 to 40% by weight, preferably from 2% or 4% up to 30% or 40% by weight of the total composition.
  • Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, olefin sulphonates, alkane sulphonates, dialkyl sulphosuccinates, and fatty acid ester sulphonates. Linear alkyl benzene sulphonate of the formula:
  • R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium, is also a commercially significant anionic surfactant.
  • the organic surfactant comprises alkylbenzene sulphonates,- particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of Cs-Ci 5 .
  • Such linear alkyl benzene sulphonates are usually the desired anionic surfactant and may provide 75 to 100 wt% of any anionic non-soap surfactant in the composition.
  • anionic surfactants which may be used are fatty acyl ester sulphonates of formula:
  • R is an alkyl or alkenyl chain of 8 to 18 carbon atoms and M + is a solubilising cation.
  • anionic surfactants are available and can be used. Examples include olefin sulphonates of formula:
  • R is alkyl of 6 to 18 carbon atoms
  • R 1 is methyl or ethyl and M + is a solubilising cation.
  • the amount of non-soap anionic surfactant preferably lies in a range from 5 or 10% to 20 or 25 %wt of the overall tablet composition.
  • the amount of non-soap anionic surfactant in the base particles a) preferably lies in a range from 10 to 40%wt of the weight of the particles themselves, preferably 15 to 35%wt, more preferably 18 to 30wt%.
  • R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M + is a solubilising cation, is also commercially significant as an anionic surfactant .
  • the base particles a) are substantially free of primary alkyl sulphate.
  • the base, particles a) comprise no more than 5%wt of primary alkyl sulphate based on the weight of these particles and especially that they are substantially thereof.
  • Primary alkyl sulphate may still be added to the composition as part of the other material b) . If added, it may be present in an amount as specified above for the non-soap anionic surfactant.
  • detergent tablets comprising protease enzyme and low levels, or no, primary alkyl sulphate in the base particles a) exhibit improved stability of protease upon storage compared to detergent tablets which comprise higher amounts of this type of surfactant in the base particles a) .
  • soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
  • Suitable non-ionic surfactant compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide.
  • Non-ionic surfactant compounds are alkyl (C 8 _ ) phenol- ethylene oxide condensates, the condensation products of linear or branched aliphatic Cs-o primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine .
  • the primary and secondary alcohol ethoxylates especially the C 9 _n and C12- 15 primary and secondary alcohols ethoxylated with an average of from 2 to 20 moles of ethylene oxide per mole of alcohol, preferably 5 to 9 moles.
  • the C 9 _n and C12-15 primary and secondary alcohols ethoxylated with an average of from 5, 6, 7 or 8 moles of ethylene oxide per mole of alcohol are especially preferred.
  • compositions comprise less than 2% by weight, based upon the total weight of the composition, more preferably less than 1 %wt, of C 9 _n and/or C 12 - 15 primary and secondary alcohols ethoxylated with an average of 4 or less moles of ethylene oxide per mole of alcohol .
  • compositions are substantially free of said primary and secondary ethoxylated alcohols .
  • the amount of non-ionic surfactant may lie in a range of from 2 to 40%, better 2.5 or 3% up to 20%wt of the composition.
  • Many non-ionic surfactants are liquids and may be absorbed onto particles of the composition prior to compaction into tablets.
  • the weight ratio of anionic surfactant: nonionic surfactant is preferably in the range from 4:1 to 1:2, more preferably 3:1 to 1.1.5, most preferably 2.5:1 to 1:1.2.
  • Amphoteric surfactants which may be used jointly with anionic or non-ionic surfactants or both include amphopropionates of the formula :
  • RCO is a acyl group of 8 to 18 carbon atoms, especially coconut acyl.
  • the category of amphoteric surfactants also includes amine oxides and also zwitterionic surfactants, notably betaines of the general formula:
  • R 4 is an aliphatic hydrocarbon chain which contains 7 to 17 carbon atoms
  • R 2 and R 3 are independently hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms such as CH 2 0H
  • Y is CH 2 or of the form CONHCH 2 CH 2 CH 2 (amidopropyl betaine)
  • Z is either a COO " (carboxybetaine) , or of the form CHOHCH 2 S0 3 - (sulfobetaine or hydroxy sultaine) .
  • amphoteric surfactant is amine oxide of the formula
  • Ri is Cio to C 2 o alkyl or alkenyl
  • R 2 , R 3 and R 4 are each hydrogen or Ci to C 4 alkyl, while n is from 1 to 5.
  • Cationic surfactants may possibly be used. These frequently have a quaternised nitrogen atom in a polar head group and an attached hydrocarbon group of sufficient length to be hydrophobic .
  • a general formula for one category of cationic surfactants is;
  • each R independently denotes an alkyl group or hydroxyalkyl group of 1 to 3 carbon atoms and denotes an 5 aromatic, aliphatic or mixed aromatic and aliphatic group of 6 to 24 carbon atoms, preferably an alkyl or alkenyl group of 8 to 22 carbon atoms and X " is a counterion.
  • the amount of amphoteric surfactant, if any, may be from 3% to 10 20 or 30% by weight of the tablet or region of a tablet, the amount of cationic surfactant, if any, may be from 0.5% to 10 or 20% by weight of the tablet or region of a tablet.
  • Granulated base particles a) may provide at least 50% or even 15 more such as at least 52 or at least 55% of the tablet or tablet region.
  • concentration of surfactant I in the tablet or region may be substantial such as from 15% to ' 40% by weight of the tablet or tablet region. It is preferred that the amount of total organic surfactant in the tablet or 20 region thereof is at least 10% or 12% by weight in any event.
  • the base particles comprise 20 to 60% by weight of aluminosilicate detergency builder.
  • Alkali metal aluminosilicates are strongly favoured as environmentally acceptable water-insoluble softening agents (detergency builders) for fabric washing.
  • Alkali metal (preferably sodium) aluminosilicates may be either crystalline
  • xH0 calcium ion exchange capacity
  • xH0 calcium ion exchange capacity
  • the preferred sodium aluminosilicates contain 1.5-3.5 Si0 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. They remove calcium ions from water by ion exchange.
  • the aluminosilicate detergency builder may zeolite P, A, X or Y and mixtures thereof, with zeolite P and zeolite A being preferred.
  • Zeolite A is one, well known, form of crystalline sodium aluminosilicate. Zeolite A may be used even though it does not assist disintegration and it is readily available. Zeolite 4A has been found to be especially suitable.
  • Zeolite P is especially preferred.
  • the base particles a) preferably comprise aluminosilicate detergency builder in an amount from 20, 30 or 35% to 40 or 55% by weight of these particles.
  • the detergent tablet compositions comprises from 5% to 60% by weight of the composition of sodium tripolyphosphate having at least 50% by weight thereof in the phase I form.
  • phase II which is the low temperature form
  • phase I which is stable at high temperature.
  • the conversion of phase II to phase I proceeds fairly rapidly on heating above the transition temperature, which is about 420°C, but the reverse reaction is slow. Consequently phase I sodium tripolyphosphate is metastable at ambient temperature.
  • the resulting product is generally a mixture of the Phase I and Phase II forms .
  • Phase I material is known to hydrate to the hexahydrate more rapidly than phase II material. It is also known to dissolve somewhat more rapidly when there is no obstacle to dispersion in the solution. However, during dissolution, this phase I material can form a viscous or solid mass which, in a confined space can hinder dissolution. For instance when making a slurry for spray drying, phase I tripolyphosphate can form so-called "grit", which is a mass of interlocked crystals.
  • At least 70%wt, more preferably at least 80%wt, most preferably substantially all of said sodium tripolyphosphate is in the phase I form.
  • the sodium tripolyphosphate which is at least partially in the Phase I form is also partially hydrated.
  • the extent of hydration is desirably at least 0.5%wt e.g., 1 to 4% by weight, preferably 2 to 4% by weight of the tripolyphosphate.
  • the extent of hydration may extend up to at least 5% or at least 10% by weight.
  • Suitable sodium tripolyphosphate is commercially available. Suppliers include Courbevoie, France and Rhodia, UK.
  • the sodium tripolyphosphate in the tablet or region thereof may consist partly of sodium tripolyphosphate which comprises the Phase I form and partly of some other form of sodium tripolyphosphate provided the overall amount of tripolyphosphate complies with the requirement that at least 50% of it is in the Phase I form.
  • the base particles might comprise sodium tripolyphosphate in which the content of Phase I form was well above 50% by weight of that tripolyphosphate while the composition of the tablet or region also comprises additional sodium tripolyphosphate which is in the anhydrous Phase II form.
  • the sodium tripolyphosphate is preferably hydrated by a process which leads to a homogenous distribution of the water of hydration within the tripolyphosphate. This can be accomplished by exposing anhydrous sodium tripolyphosphate to steam or moist air.
  • the sodium tripolyphosphate is preferably in a porous form so as to have high surface area. This can be achieved by spray drying the tripolyphosphate . Porosity can be enhanced by spray drying the tripolyphosphate as a mixture with a blowing agent, that is a compound such as ammonium carbonate which decomposes to yield a gas during the course of the spray drying. This gives the dried material a higher surface area than porous beads of tripolyphosphate obtained without blowing agent.
  • a blowing agent that is a compound such as ammonium carbonate which decomposes to yield a gas during the course of the spray drying.
  • Particles of sodium tripolyphosphate preferably have a small mean particle size, such as not over 300 ⁇ m, preferably 280 ⁇ m or less. Small particle size can, if necessary, be achieved by grinding.
  • Rhodiaphos HPA 3.5 is a grade of sodium tripolyphosphate from Rhodia-Chemie (previously from Rhone-Poulenc) which has been found to be particularly suitable. It consists of porous particles of small particle size (mean size below 250 ⁇ m) with 70% Phase I and prehydrated with 3.5% water of hydration.
  • the base particles a) include some of the sodium tripolyphosphate then it is typically in an amount of from 7- 40% of their own weight. However in some aspects of the invention it is preferred that the base particles a) comprise less than 10% of the sodium tripolyphosphate, more preferably less than 5%wt of their own weight, especially less than 2%wt and most especially are substantially free thereof. The remainder of the sodium tripolyphosphate is present in the other particles b) . In some aspects of the invention the other material b) preferably comprises at least 60% by weight, more preferably at least 80% by weight, and especially substantially all of the sodium tripolyphosphate present in the whole composition of the tablet or region thereof .
  • the total amount of the sodium tripolyphosphate in the total composition is at least 15% by weight, better in a range from 20 or 25 to 50% by weight.
  • the preferred weight ratio of the sodium tripolyphosphate: aluminosilicate builder is in the range of from 3:1 to 2:5, better 2.5:1 to 1:1.5, especially 2.2:1 to 1:1.
  • All detergent tablets according to the invention may comprise disintegrant materials to aid in the disintegration of the tablets. If present, the amount is preferably in the range of from 2% to 10% by weight of the composition. These materials are preferably added as part of the other materials (b) .
  • the tablet or region thereof comprises from 35% to 98% by weight of granulated base particles mixed with 2 to 10% by weight of further disintegrant materials (and optionally other ingredients up to 100%wt as appropriate) .
  • the tablets of this invention optionally comprise from 2% to 10% of a material, such as a salt, which has a solubility in deionised water at 20°C of at least 50 grams per 100 grams of water. Preferably amounts of from 2 to 5 or 7% by weight are used.
  • the highly soluble material may be included in the base particles a) or as part of the material b) .
  • a solubility of at least 50 grams per 100 grams of water at 20°C is an exceptionally high solubility: many materials which are classified as water soluble are less soluble than this.
  • this highly water soluble material is incorporated as particles thereof in a substantially pure form (i.e. each such particle contains over 95% by weight of the material) .
  • the said particles may comprise material of such solubility in a mixture with other material, provided that material of the specified solubility provides at least 40% by weight of these particles .
  • Preferred materials are sodium acetate in a partially or fully hydrated form, urea or sodium citrate dihydrate.
  • Optional water-swellable disintegrant Another material which may be present is a water-swellable but dispersible material.
  • a number of water-insoluble, water-swellable materials are known to be useful as tablet disintegrants, in particular for pharmaceutical tablets. Although insoluble, these materials are generally dispersible in water. A discussion of such materials is found in "Drug Development and Industrial Pharmacy", Volume 6, pages 511-536 (1980) . Such materials are mostly polymeric in nature and many of them are of natural origin.
  • Such disintegrants include starches, for example, maize, rice and potato starches, and starch derivatives, such as PrimojelTM, and ExplotabTM, which are both forms of sodium carboxymethyl starch also known as sodium starch glycolate; celluloses, for example Arbocel ® -B and Arbocel®-BC (beech cellulose) , Arbocel®-BE (beech-sulphite cellulose) , Arbocel ® -B- SCH (cotton cellulose) , Arbocel®-FIC (pine cellulose) as well as further Arbocel® types from Rettenmaier and cellulose derivatives, from example CourloseTM and NymcelTM, sodium carboxymethyl cellulose, Ac-di-SolTM cross-linked modified cellulose, and HanflocTM microcrystalline cellulosic fibers; and various synthetic organic polymers .
  • starch derivatives such as PrimojelTM, and ExplotabTM, which are both forms of sodium carboxymethyl starch also known
  • Cellulose-containing fibrous materials originating from timber may be compacted wood pulps.
  • So-called mechanical pulps generally incorporate lignin as well as cellulose whereas chemical pulps generally contain cellulose but little of the original lignin remains .
  • Pulp obtained by a mixture of chemical and mechanical methods may retain some by not all of the original lignin.
  • Suitable disintegrants include granules based upon water swellable inorganic materials such as aluminosilicates.
  • the impregnated swellable material which is incorporated into a tablet composition may well have a mean particle size in a range from 250 ⁇ m to l,500 m, more preferably from 700 m to 1, lOO ⁇ .
  • compositions according to the invention may be bleach-free or may contain a bleach system. If present, this preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures.
  • peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator. If any peroxygen compound is present, the amount is likely to lie in a range from 5 to 50% by weight of the composition, preferably 10 to 20%.
  • Bleach activators also referred to as bleach precursors
  • Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED) , now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • N-alkyl ammonium acetonotriles as described in WO 96/40061 and US 6 225 274 may be used as may sodium nonanoyloxy benzene sulphonate (SNOBS) and (6-nonanamidocaproyl) oxy benzene sulphonate (Na.COBS) as described in US 6 207 632 and EP 170 386.
  • SNOBS sodium nonanoyloxy benzene sulphonate
  • Na.COBS (6-nonanamidocaproyl) oxy benzene sulphonate
  • a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate, diethylenetriamine pentamethylene phosphonate or ethylene diamine di-succinate.
  • a bleach stabiliser such as ethylenediamine tetramethylene phosphonate, diethylenetriamine pentamethylene phosphonate or ethylene diamine di-succinate.
  • the bleach and/or activator are is preferably included as the other material b) mixed with the base particles a) .
  • compositions which may be present, typically as 0.5 to 5% of the composition are one or more polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which have some function as water-softening agents and also inhibit unwanted deposition onto fabric from the wash liquor.
  • Tablets may comprise one of the detergency enzymes well known in the art for their ability to degrade and aid in the removal of various soils and stains.
  • Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics.
  • suitable proteases are MaxataseTM, as supplied by Gist-Brocades N.V. , Delft, Holland and AlcalaseTM, and SavinaseTM, as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the composition; and these granules or marumes present no problems with respect to compaction to form a tablet.
  • compositions of the invention have been found to be particularly advantageous for the storage stability of protease enzymes.
  • protease enzymes are especially preferred.
  • Tablets may also comprise a fluorescer (optical brightener) , for example, TinopalTM DMS or Tinopal CBS available from Ciba- Geigy AG, Basel, Switzerland.
  • Tinopal DMS is disodium 4,4'bis- (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate
  • Tinopal CBS is disodium 2 , 2 ' -bis- (phenyl- styryl) disulphonate .
  • An antifoam material may be included. Suitable antifoam materials are usually in granular form, such as those described in EP 266863A (Unilever) . Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbed water-soluble carbonate-based inorganic carrier material. Antifoam granules may be present in an amount up to 5% by weight of the composition.
  • a tablet includes an amount of an alkali metal silicate, particularly sodium ortho- , meta- or disilicate.
  • an alkali metal silicate particularly sodium ortho- , meta- or disilicate.
  • a composition for fabric washing will generally not comprise more than 15 wt% silicate.
  • compositions which can optionally be employed in fabric washing detergent tablets of the invention include anti- redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents; heavy metal sequestrants such as EDTA; perfumes; and colorants or coloured speckles.
  • anti- redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents
  • heavy metal sequestrants such as EDTA
  • perfumes and colorants or coloured speckles.
  • a number of these further ingredients are typically used in small amounts such as not more than 5% by weight of the tablet or tablet region. They may be incorporated amongst the post- dosed constituents of the composition. Some of them, notably fluorescer, polycarboxylate polymers and anti-redeposition agents may be incorporated into the granulated particles . Any constituents which are liquids such as non-ionic detergents or perfumes may possibly be incorporated within the granulated particles or may be sprayed onto those particles or the overall mixture. Preferably perfumes are sprayed onto the overall mixture so that they are the last ingredient added to the overall composition before tableting.
  • detergent compositions in particulate form by granulation processes is well known.
  • a granulation process for making particles which comprise surfactant, zeolite and water-soluble salts is described in EP-A-340013 for example.
  • Processes as described in the above documents can be modified to include sodium tripolyphosphate among the solids supplied to the granulation process to produce the base particles a) .
  • a suitable method of granulating is disclosed in WO 00/77147 (Unilever) wherein a liquid binder is contacted with a solid starting material in a high-speed mixer and the resulting mixture treated in a medium- or low-speed mixer and finally in a gas fluidisation granulator, where more liquid binder is added.
  • the particles may have average particle size in the range from 200 to 2000 ⁇ m, more preferably from 250 to 1400 ⁇ m. Fine particles, such as those smaller than 180 ⁇ m or 200 ⁇ m and oversized particles may be eliminated by sieving before tableting, if desired, although we have observed that this is not always essential. Sieved out particles may be returned to the granulation stage if oversized.
  • the starting particulate composition may suitably have a bulk density of at least 500g/litre, preferably at least 600g/litre, and possibly at least 700g/litre.
  • Tableting entails compaction of a particulate composition.
  • a variety of tableting machinery is known, and can be used. Generally it will function by stamping a quantity of the particulate composition which is confined in a die.
  • the mould in which the tablet is formed may be provided by an aperture within a rigid structure and a pair of dies which can be urged into the aperture towards each other, thereby compacting the contents of the aperture.
  • a tableting machine may have a rotary table defining a number of apertures each with a pair or associated dies which can be driven into an apertures.
  • Each die may be provided with an elastomeric layer on its surface which contacts the tablet material, as taught in WO 98/46719 or WO 98/46720.
  • Tableting may be carried out at ambient temperature or at a temperature above ambient which may allow adequate strength to be achieved with less applied pressure during compaction.
  • the particulate composition is preferably supplied to the tableting machinery at an elevated temperature. This will of course supply heat to the tableting machinery, but the machinery may be heated in some other way also.
  • a method of forming the detergent composition comprises;
  • aluminosilicate detergency builder 60% by weight of aluminosilicate detergency builder, 7 to 40% by weight of sodium tripolyphosphate, at least 50% of which is in Phase I form, and optionally 0 to 58% of other ingredients;
  • composition comprising 33 to 100% by weight of base particles and 0 to 67% by weight of other ingredients, wherein the composition comprises from 5 to 50% by weight of sodium tripolyphosphate having at least 50% in the Phase I form, and
  • any heat is supplied, it is envisaged that this will be supplied conventionally, such as by passing the particulate composition through an oven, rather than by any application of microwave energy.
  • the size of a tablet will suitably range from 10 to 160 grams, preferably from 15 to 60g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
  • the tablets may be of any shape. However, for ease of packaging they are preferably blocks of substantially uniform cross-section, such as cylinders or cuboids .
  • the overall density of a tablet for fabric washing preferably lies in a range from 1000 or 1040g/litre up to 1400 or 1450 g/litre.
  • the overall density of a tablet of some other cleaning composition such as a tablet for machine dishwashing or as a bleaching additive, may range up to 1700gm/litre and will often lie in a range from 1300 to 1550gm/litre.
  • Tablets for use in fabric washing were made, starting with a granulated base powder of the following composition:
  • Particulate compositions were made by mixing this powder with further ingredients as tabulated below.
  • the sodium tripolyphosphate in the granulated base powder was anhydrous sodium tripolyphosphate consisting predominantly of the Phase II anhydrous form.
  • the sodium tripolyphosphate which was mixed with the granulated base powder particles comprised over 75% of its own weight in the Phase I form and was partially hydrated to contain 3.5% of its own weight of water of hydration.
  • This sodium tripolyphosphate was supplied by Rhodia Chemie under their designation Rhodiaphos HPA 3.5 and it had a porous structure resulting from the spray-drying procedure employed prior to partial hydration.
  • composition was sieved to remove all particles smaller than 250 ⁇ m or larger than 1400um. Then 40g portions of the composition were compacted into tablets of 44mm diameter using a hand press .
  • diametral fracture stress which we have used in the past, can be calculated using the equation:
  • ⁇ is the diametral fracture stress in Pascals
  • F f is the applied force in Newtons to cause fracture
  • D is the tablet diameter in meters
  • t is the tablet thickness in meters.
  • the value of DFS measured for these tablets was 40 kPa. (It is desirable that the value of DFS is at least 20 or 25kPa) .
  • a spray-dried base powder of the following composition was prepared:
  • Example 3 Tablets for use in fabric washing were made, starting with a granulated base powder of the following compositions.
  • Example 3A is a comparative example where the base powder particles do not comprise aluminosilicate detergency builder.
  • Example 3 is an example according to the invention.
  • Particulate compositions were made by mixing this powder with further ingredients as tabulated below.
  • the sodium tripolyphosphate in the base powder of Example 3A was a mixture of about 55 parts of anhydrous sodium tripolyphosphate phase II and about 45 parts of anhydrous sodium tripolyphosphate phase I.
  • the 70/30 AA/MA co-polymer salt (100%) was Sokalan CP5 (ex BASF) .
  • a further comparative laundry detergent tablet was made from a granulated base powder with the other ingredients added thereto. The amounts are given for the base powder on the basis of the amount of each ingredient present in the final composition.
  • a quantity of the tablets were packaged in flow-wrap packaging and stored in normal carton packs at 37°C/70 % relative humidity for up to 8 weeks.
  • a tablet was selected and tested for the presence of TAED, protease and percarbonate.
  • the results are given in the table below.
  • the numbers in the (results) column show the initial level of the ingredient detected in the tablet and the level after the given storage time.
  • the numbers in the (%) column show the percentage of the ingredient remaining after the given storage time, expressed as a percentage of the original level detected in the tablet.
  • the percarbonate results are expressed as % available oxygen.
  • the protease result is expressed as enzyme activity GU/mg.
  • the tablets of the invention show better storage stability at 37°C, 70% relative humidity for TAED, percarbonate and especially for protease enzyme (savinese) than do the tablets comprising no aluminosilicate builder (Ex 3A) . They also show better stability for protease than do tablets comprising conventional amounts of primary alkyl sulphate and no linear alkyl benzene sulphonate (Ex 3B) .

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Abstract

L'invention concerne une pastille détergente ou une partie de cette dernière faite de particules compactées à partir d'une composition particulaire renfermant a) 25 % à 100 % en pds de la composition de particules de base comprenant elles-mêmes 15 % à 40 % en pds d'un tensio-actif organique qui contient (i) pas plus de 5 % en pds d'un sulphate d'alkyle primaire ou (ii) du sulphonate d'alkylbenzène, 20 % à 60 % en pds d'un adjuvant détergent d'aluminosilicate et 0 % à 60 % d'autres ingrédients, et b) 0 à 75 % en pds de la composition d'autres matières mélangées à ces particules. La composition comprend en outre 5 à 60 % de tripolyphosphate de sodium dont au moins 50 % en pds en phase I. Les pastilles présentent une bonne combinaison de propriétés de résistance et de désintégration.
PCT/EP2001/013479 2000-11-21 2001-11-19 Compositions detergentes WO2002042398A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002406776A CA2406776A1 (fr) 2000-11-21 2001-11-19 Compositions detergentes
AU2002227936A AU2002227936A1 (en) 2000-11-21 2001-11-19 Detergent compositions
EP01989494A EP1337615A2 (fr) 2000-11-21 2001-11-19 Compositions detergentes

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US71846900A 2000-11-21 2000-11-21
US07/718,469 2000-11-21
PCT/EP2000/011815 WO2001038478A1 (fr) 1999-11-26 2000-11-24 Compositions detergentes
EPPCT/EP00/11815 2000-11-24
GB0031504A GB0031504D0 (en) 2000-12-22 2000-12-22 Detergent compositions
GB0031504.4 2000-12-22
EP01306604.8 2001-08-01
EP01306604 2001-08-01

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WO2002042398A2 true WO2002042398A2 (fr) 2002-05-30
WO2002042398A3 WO2002042398A3 (fr) 2002-11-07

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003014286A1 (fr) * 2001-08-01 2003-02-20 Unilever N.V. Compositions detergentes
EP1418226A1 (fr) * 2002-11-07 2004-05-12 Unilever N.V. Composition détergente
EP1466965A1 (fr) * 2003-02-11 2004-10-13 Unilever N.V. Compositions nettoyantes
EP1466964A1 (fr) * 2003-02-11 2004-10-13 Unilever N.V. Compositions nettoyantes
US7304015B2 (en) 2002-10-18 2007-12-04 Promega Corporation Compositions for separating molecules

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999020730A1 (fr) * 1997-10-22 1999-04-29 Unilever Plc Compositions detergentes en pastilles
WO2001038478A1 (fr) * 1999-11-26 2001-05-31 Unilever N.V. Compositions detergentes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999020730A1 (fr) * 1997-10-22 1999-04-29 Unilever Plc Compositions detergentes en pastilles
WO2001038478A1 (fr) * 1999-11-26 2001-05-31 Unilever N.V. Compositions detergentes

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003014286A1 (fr) * 2001-08-01 2003-02-20 Unilever N.V. Compositions detergentes
US7304015B2 (en) 2002-10-18 2007-12-04 Promega Corporation Compositions for separating molecules
US7304016B2 (en) 2002-10-18 2007-12-04 Promega Corporation Compositions for separating molecules
US7354750B2 (en) 2002-10-18 2008-04-08 Promega Corporation Methods for separating molecules
EP1418226A1 (fr) * 2002-11-07 2004-05-12 Unilever N.V. Composition détergente
EP1466965A1 (fr) * 2003-02-11 2004-10-13 Unilever N.V. Compositions nettoyantes
EP1466964A1 (fr) * 2003-02-11 2004-10-13 Unilever N.V. Compositions nettoyantes

Also Published As

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AU2002227936A1 (en) 2002-06-03
WO2002042398A3 (fr) 2002-11-07
AR031487A1 (es) 2003-09-24
CA2406776A1 (fr) 2002-05-30
EP1337615A2 (fr) 2003-08-27

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