EP1133548B2 - Reinigungsmittelzusammensetzungen in tablettenform - Google Patents

Reinigungsmittelzusammensetzungen in tablettenform Download PDF

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Publication number
EP1133548B2
EP1133548B2 EP99961011A EP99961011A EP1133548B2 EP 1133548 B2 EP1133548 B2 EP 1133548B2 EP 99961011 A EP99961011 A EP 99961011A EP 99961011 A EP99961011 A EP 99961011A EP 1133548 B2 EP1133548 B2 EP 1133548B2
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Prior art keywords
weight
tablet
particles
detergent
composition
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EP99961011A
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English (en)
French (fr)
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EP1133548B1 (de
EP1133548A1 (de
Inventor
R. Unilever Thai Holdings Ltd. LAMMERS
Seeng Djiang Unilever Research Vlaardingen LIEM
H. Unilever Research Vlaardingen TAMMES
G. M. Unilever Res. Port Sunlight VERSCHELLING
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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

Definitions

  • This invention relates to detergent compositions in the form of tablets, especially tablets for use in fabric washing.
  • Such tablets have the advantage that they do not require the user to measure out a volume of powder or liquid. Instead one or several tablets provide an appropriate quantity of composition for washing a single load in a washing machine or possibly by hand. They are thus easier for the consumer to handle and dispense.
  • Such tablets are generally made by compressing or compacting a quantity of detergent composition in particulate form. It is desirable that tablets should have adequate mechanical strength when dry before use, yet disintegrate and disperse/dissolve quicklywhen added to wash water. There is difficulty in achieving both properties simultaneously. As more pressure is used when a tablet is compacted, so the tablet density and strength rise, but there is also a reduction in the speed of disintegration/dissolution when the tablet comes into contact with wash water at the time of use. Organic detergent serves as a binder, but a typical quantity of such detergent can also retard disintegration and dissolution of a tablet. Our EP-A-466485 explains that as a tablet is wetted, anionic detergent can form viscous phases which retard penetration of water into the tablet interior.
  • This EP-A-466485 describes detergent tablets in which anionic detergent is contained within a first particulate component of the composition. This first particulate component provides from 2 to 40% of the overall composition. In most examples in this document the nonionic detergent was mixed with or carried in particles which provided a majority of the overall composition. Detergent compositions and tablets comprising nonionic surfactant as a minor proportion of the particles in which the surfactant is present in are also disclosed in EP 716 144, EP 711 827, EP 839 906, EP 838 519 and WO 98/42817.
  • the anionic and nonionic detergent are jointly incorporated into a base powder which is mixed with other ingredients to form the composition stamped into tablets.
  • the spray-dried base powder constitutes about 40% of the composition. It contains anionic detergent as approximately 25% of the base powder and nonionic detergent as approximately 12% of the same powder.
  • detergent tablets are made using particles which incorporate a higher proportion of nonionic detergent. According to the present invention, there is provided a detergent tablet according to claim 1.
  • these tablets 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 heterogenous tablet, each discrete region of the tablet will preferably constitute at least 10% of the overall weight of the tablet.
  • the particles may contain enough nonionic detergent to constitute at least 50% of their own weight.
  • the composition of the tablet or region contains from 1 to 40 % by weight of nonionic detergent, at least half of which is present as said particles.
  • Anionic detergent will frequently also be present and may be provided as particles which contain at least 20% of their own weight of non-soap anionic detergent.
  • a tablet of this invention intended for fabric washing will generally contain, overall,
  • the invention could also be embodied as tablets for machine dishwashing, with a small percentage of nonionic detergent present such as 1 to 8% by weight, provided the tablet comprises said particles containing at least 45% nonionic detergent, from 20 to 99% detergency builder,and possibly no anionic detergent at all.
  • the nonionic detergent particles used in this invention contain at least 45%, better at least 50% of their own weight of nonionic detergent (that is one or more organic compounds which are nonionic and have detersive surfactant properties). Preferably they contain less than 10% by weight of synthetic (i.e. non-soap) anionic detergent, and preferably substantially no non-soap anionic detergent.
  • the nonionic detergent is primary or secondary alcohol ethoxylates, especially the C 9-11 and C 12-15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
  • the nonionic detergent particles contain an inorganic carrier material which is water-insoluble.
  • the insoluble carrier material may comprise silica or aluminosilicate, such as zeolite. However, it is preferred that, if aluminosilicate is present, the quantity is less than 10% by weight of the particles.
  • the quantity of nonionic detergent may exceed 50% by weight of the pulpe, e.g. 52% or above.
  • Particles containing nonionic detergent absorbed on a solid carrier material can be made by spraying the nonionic detergent onto the carrier material in a granulator or some other type of mixing apparatus.
  • structuring agents are polyethylenelpolypropylene glycol of average molecular weight in the region 4,000-12,000, sodium soap, polyvinyl alcohol of average molecular weight in the range 30,000-200,000, alkaline metal succinate etc may be present.
  • the preferred quantity of structuring agent is in the region from 0.5 to 20% by weight.
  • a structuring agent may be added with other ingredients or during a second step of granulation.
  • a preferred carrier is silica having an oil absorption capacity of at least 1.0 ml/g.
  • Oil absorption capacity is a parameter which is will known and can be measured by the technique described in DIN ISO 787/5.
  • the oil absorption capacity is at least 1.5 ml/g, more preferably at least 2.0 ml/g.
  • the quantity of silica in the particles is greater than the quantity if any, of aluminosilicate.
  • the particles may contain less than 10% of their own weight of aluminosilicate.
  • Nonionic detergent particles can be manufactured in a one step or two step process by mixing together components in a granulator (for example an Eirich RV02 granulator, or in equipment such as the Fukae mixer from Fukae Powtech Co of Japan, the Diosna V-series supplied by Dierks & Sohne Germany, the Pharma Matrix ex TH Fielder Ltd England, the Lodige CB series and the Dais T160 series from Dais Werke GmbH, Mannheim, Germany).
  • a granulator for example an Eirich RV02 granulator, or in equipment such as the Fukae mixer from Fukae Powtech Co of Japan, the Diosna V-series supplied by Dierks & Sohne Germany, the Pharma Matrix ex TH Fielder Ltd England, the Lodige CB series and the Dais T160 series from Dais Werke GmbH, Mannheim, Germany.
  • Nonionic detergent particles preferably have mean particle size in a range from 200 to 2,000 ⁇ m such that at least 80% of these particles have a particle size in the range from 180 to 2,000 ⁇ m.
  • Nonionic detergent particles may provide from 1, better 2 or 3% up to 30% or possibly more of a tablet or a region of a tablet. More especially, such particles may constitute from 8 to 20% of a tablet or region of a tablet.
  • a tablet or region of a tablet in accordance with this invention will contain from 1 % preferably from 3 to 40% by weight of nonionic detergent, at least half of which is present as said particles containing at least 40% of their own weight of nonionic detergent.
  • a tablet will frquently contain anionic detergent which is one or more non-soap organic compounds with detersive surfactant properties.
  • the anionic detergent may comprise, wholly or predominantly, linear alkyl benzene sulphonate of the formula where R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium.
  • Primary alkyl sulphate having the formula ROSO 3 - M + in which 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 detergent and may be used in this invention.
  • linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired non-soap anionic detergent and may provide 75 to 100wt% of the anionic non-soap detergent.
  • non-soap anionic detergents examples include olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • the anionic detergent particles may contain some nonionic detergent.
  • the anionic detergent particles may also contain minor ingredients such as water, sodium carboxymethylcellulose, fluorescers, dyes, etc.
  • Anionic detergent is preferably incorporated as particles which contain at least 20% of their own weight of anionic detergent, possitily a higher proportion such as at least 50% of their own weight. Particles which contain between 20 and 40% of anionic detergent can be prepared by spray-drying or ganulation processes.
  • WO 96/06916A and WO 96/06917A Processes for producing particles containing high concentrations of anionic detergent are set out in WO 96/06916A and WO 96/06917A (Unilever).
  • an aqueous paste containing an anionic detergent, or alternatively an acid detergent precursor and also an alkaline neutralising agent are fed into a drying zone where the paste material is heated to reduce the water content thereof, the dried material being subsequently cooled in a cooling zone to form detergent particles.
  • the drying zone is under a slight vacuum to facilitate the removal of water and volatiles.
  • the vacuum may be from 100 Torr up to atmospheric pressure as this provides significant process flexibility.
  • a vacuum in excess of 500 Torr up to atmospheric has the advantage of reducing capital investment whilst providing vacuum operation.
  • the process may be carried out in any suitable apparatus, but it is preferred that a flash reactor is employed. Suitable flash reactors include e.g. the Flash Drier system available from VRV Spa Impianti Industriali.
  • the drying zone may have a heat transfer area of at least 10m 2
  • the cooling zone desirably has a heat transfer area of at least 5m 2 .
  • the material in the cooling zone may be treated with a stream of cooling gas.
  • finely divided non-detergent solid material such as zeolite or silica particles, may be introduced into this zone to adhere to the surface of the particles.
  • Such material may provide from 3 to 25% of the weight of the particles.
  • the above process routes can provide flash-dried detergent particles comprising at least 60% by weight of the particle of an anionic detergent and not more than 5% by weight of the particle of water.
  • anionic detergent particles may comprise anionic detergent in an amount of at least 66% by weight of the particles, even better at least 70% but possibly not over 96%.
  • the particles may have a porosity of from 0 to 25% by volume of the particle and a particle size distribution such that at least 80% of the particles have a particle size of 180-1500 microns.
  • the anionic detergent may be formed in situ by neutralisation of a free acid.
  • the neutralising agent may be sodium hydroxide solution or sodium carbonate.
  • in situ neutralisation is unlikely to be appropriate when the anionic detergent is primary alkyl sulphonate (PAS) because its acid form is unstable.
  • PAS primary alkyl sulphonate
  • Anionic detergent particles may provide from 5% to at least 30% of the weight of the tablet or region of a tablet. The amount of them may be at least 8% or 10%. Their amount may be not over 20% of the weight of the tablet or region, especially when the particles contain at least 70 or 75% of their own weight of non-soap anionic detergent.
  • organic detergent such as amphoteric detergent
  • amphoteric detergent may be included but are not preferred. It is preferred that at least 50%, better at least 90% by weight of all non-soap organic detergent in the tablet or region of a tablet is contained either in the said particles which contain at least 40% nonionic detergent or in other particles which contain at least 20% of their own weight of non-soap organic detergent.
  • a constituent of the tablet or region is particles containing material which serves to accelerate tablet disintegration in water and is either a material of high water-solubility or is a specified form of sodium tripolyphosphate, or a combination of the two.
  • material may be present as at least 15 or 20% of the composition of a tablet or region thereof, possibly at least 25% up to 50, 55 or 60%, possibly more.
  • Highly water soluble materials which are one of the two possibilities are compounds, especially salts, with a solubility at 20°C of at least 50 gms per 100 gms of water.
  • 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.
  • solubilities of some other common materials at 20°C are:- Material Water Solubility (g/100g) Sodium chloride 36 Sodium sulphate decahydrate 21.5 Sodium carbonate anhydrous 8.0 Sodium percarbonate anhydrous 12 Sodium perborate anhydrous 3.7 Sodium tripolyphosphate anhydrous 15
  • this highly water soluble material is incorporated as particles of the material in a substantially pure form (i.e. each such particle contains over 95% by weight of the material).
  • the said particles may contain material of such solubility in a mixture with other material, provided that material of the specified solubility provides at least 50% by weight of these particles, better at least 80%.
  • the said particles which promote disintegration are particles containing sodium tripolyphosphate with more than 50% of it (by weight of the particles) in the anhydrous phase I form.
  • Such particles may contain at least 80% by weight tripolyphosphate and possibly at least 95%.
  • 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.
  • phase I form will often contain the phase I form of sodium tripolyphosphate as at least 55% by weight of the tripolyphosphate in the particles.
  • Other forms of sodium tripolyphosphate will usually be present to a lesser extent.
  • Other salts may be included in the particles, although that is not preferred.
  • this sodium tripolyphosphate is partially hydrated.
  • the extent of hydration should be at least 1% by weight of the sodium tripolyphosphate in the particles. It may lie in a range from 2.5 to 4%, or it may be higher, eg up to 8%.
  • Suitable material is commercially available. Suppliers include Rhone-Poulenc, France and Albright & Wilson, UK.
  • Rhodiaphos HPA 3.5 from Rhone-Poulenc has been found particularly suitable. It is a characteristic of this grade of sodium tripolyphosphate that it hydrates very rapidly in a standard Olten test. We have found that it hydrates as quickly as anhydrous sodium tripolyphosphate, yet the prehydration appears to be beneficial in avoiding unwanted crystallisation of the hexahydrate when the material comes into contact with water at the time of use.
  • a tablet or tablet region will generally contain detergency builder This may be sodium tripolyphosphate of the type just described. It may include sodium tripolyphosphate which has more of the phase form or is hydrated. It may be some other type of detergency builder. It may containing overall from 30 to 60% by weight sodium tripolyphosphate, reckoned as anhydrous.
  • detergency builder This may be sodium tripolyphosphate of the type just described. It may include sodium tripolyphosphate which has more of the phase form or is hydrated. It may be some other type of detergency builder. It may containing overall from 30 to 60% by weight sodium tripolyphosphate, reckoned as anhydrous.
  • Water-soluble phosphorous-containing inorganic detergency builders include the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates, as well as sodium and potassium tripolyphosphates
  • Alkali metal aluminosilicates are strongly favoured as environmentally acceptable water-insoluble builders for fabric washing.
  • Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8 - 1.5 Na 2 O.Al 2 O 3 - 0.8 - 6 SiO 2 . xH 2 O
  • xH2O xH2O
  • xH2O calcium ion exchange capacity
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 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.
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, and the novel maximum aluminium zeolite P described and claimed in EP 384070 (Unilever).
  • This form of zeolite P is also referred to as zeolite MAP.
  • zeolite A24 One commercial form of it is denoted zeolite A24.
  • Water insoluble detergency builder could be a layered sodium silicate as described in US 4664839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6").
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as described in DE-A-3,417,649 and DE-A-3,742,043.
  • Other such layered silicates, which can be used have the general formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0.
  • Non-phosphorous water-soluble builders may be organic or inorganic.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers, such as polyacrylates and acrylic/maleic copolymers, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
  • alkali metal generally sodium
  • organic builders include polycarboxylate polymers, such as polyacrylates and acrylic/maleic copolymers, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetate
  • Tablet compositions preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which can function as builders and also inhibit unwanted deposition onto fabric from the wash liquor.
  • Builder materials may be incorporated as particles which contain from 40 to 80% by weight of builder, the balance being other material, probably not detergent. Such particles may provide 10 to 60% of the composition of the tablet or region of the tablet.
  • a tablet made in accordance with this invention will contain overall from 2 or 5wt% up to 40 or 50wt% non-soap detergent, and from 5 or 10wt% up to 60 or 80wt% detergency builder.
  • a discrete region of a heterogenous tablet may or may not contain these proportions of detergent and builder.
  • Detergent tablets according to the invention may contain a bleach system.
  • 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. If any peroxygen compound is present, the amount is likely to lie in a range from 10 to 25% by weight of the tablet.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • Bleach activators have been widely disclosed in the art. Preferred examples include peracetic acid precursors, for example tetraacetylethylene diamine (TAED), and perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 (Lever Brothers Company) are also of interest.
  • Another type of bleach activator which may be used, but which is not a bleach precursor is a transition metal catalyst as disclosed in EP-A-458397, EP-A-458398 and EP-A-549272.
  • a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
  • Bleach activator is usually present in an amount from 1 to 10% by weight of the tablet, possibly less in the case of a transition metal catalyst which may be used as 0.1 % or more by weight of the tablet.
  • the detergent tablets of the invention may also contain one of the detergency enzymes well known in the art for their ability to degrade various soils and stains and so aid in their removal. 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. Detergency enzymes are commonly employed in the form of particles or marumes, optionally with a protective coating, in amount of from about 0.1 % to about 3.0% by weight of the tablet.
  • the detergent tablets of the invention may also contain a fluorescer (optical brightener), for example, Tinopal (Trade Mark) 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.
  • Antifoam material is advantageously included, especially if a detergent tablet is primarily intended for use in front-loading drum-type automatic washing machines.
  • Antifoam materials in granular form are described in EP 266863A (Unilever).
  • Such antifoam particles 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.
  • a detergent tablet of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, meta- or disilicate.
  • an alkali metal silicate particularly sodium ortho-, meta- or disilicate.
  • the presence of such alkali metal silicates may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some detergency building.
  • the detergent-rich particles contain from 5 to 15% silicate by weight of the particles. This improves the strength and free flow of these particles prior to tabletting.
  • compositions which can optionally be employed in fabric washing detergent tablet 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.
  • Tableting entails compaction of a particulate composition which includes the detergent containing particles, the disintegration promoting particles and any other ingredients.
  • 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 mould.
  • Tableting may be carried out without application of heat, so as to take place at ambient temperature or at a temperature above ambient.
  • 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.
  • 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 60 g, 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 preferably lies in a range from 1040 or 1050gm/litre, possibly 1100 gm/litre, up to 1450gm/litre or more. The tablet density may well lie in a range up to 1350 or 1400gm/litre.
  • the tablets may be made by a process comprising mixing said particles which themselves contain at least 45% of their own weight of nonionic detergent with other detergent ingredients, and compacting the resulting composition into tablets.
  • Anionic detergent adjunct particles containing 70% (of their own weight) of linear alkyl benzene sulphonate were prepared using a 1.2m 2 VRV Flash Drier, in the manner described in WO 97/32002. It had three equal jacket sections. Dosing ports for both liquids and powders were situated just prior to the first hot section, with mid-jacket dosing ports available in the final two sections. Zeolite was added via this port in the final section. An electrically-powered oil heater provided the heating to the first two jacket sections, with oil temperatures between 120°C and 190°C being used. Ambient process water at 15°C was used for cooling the jacket in the final section. Make-up air flow through the reactor was controlled between 10 and 50 m 3 /hr by opening a bypass on the exhaust vapour extraction fan. The motor was run at full speed, giving a top speed of about 30m/sec.
  • a mono pump was calibrated to dose ambient temperature LAS acid, and a peristaltic pump was calibrated to dose 47% sodium hydroxide.
  • Screw feeders were calibrated to dose both sodium carbonate and zeolite A24. The sodium carbonate and the liquids were added just prior to the first hot section, but the zeolite was added into the third section which was cold.
  • the product was in the form of free-flowing particles containing LAS-A: Ingredients % by weight Linear alkyl benzene sulphonate (LAS) 70% Sodium carbonate 2% Zeolite 25% Non-detergent impurities and moisture 3%
  • LAS-A Ingredients % by weight Linear alkyl benzene sulphonate (LAS) 70% Sodium carbonate 2% Zeolite 25% Non-detergent impurities and moisture 3%
  • Nonionic detergent particles (ND1) containing 56% of nonionic detergent were prepared by granulating nonionic detergent with silica and soap in an Eirich RV02 granulator. (For larger scale a Loedige recycler would be appropriate).
  • the silica was Sorbosil TC15 supplied by Crosfield, Warrington, UK.
  • the nonionic detergent was warmed and mixed with fatty acid, then sprayed on to the silica in the granulator, while simultaneously spraying on sufficient alkali to neutralise the fatty acid.
  • the product was cooled in a fluidised bed which also removed fines. Oversize particles (> 1400 ⁇ m) were sieved out.
  • ND1 contained: Ingredient % by weight Nonionic detergent 56% Silica 30% Soap and moisture 14%
  • Comparative nonionic detergent particles were produced by granulating zeolite A24 which is maximum aluminium zeolite P from Crosfields with trisodium citrate in a Lödige recycler. Nonionic detergent was mixed with fatty acid and sprayed in while also spraying in sufficient 50% aqueous sodium hydroxide to neutralise the fatty acid.
  • the resulting product contained ND2 : Ingredient % by weight Zeolite A24 53.8 Sodium Citrate 7.9 Nonionic detergent 24.2 Soap 4.1 Water 10.0
  • Zeolite builder particles ZB1 were produced by continuously dosing zeolite A24, granular trisodium citrate and a 40% solution of acrylate/maleate copolymer (Sokolan CP5 solution) into a Lödige CB30 recycler. The CB30 was operated at 1500 rpm. The exiting powder was led through a Lödige KM300 ploughshare (120 rpm), in which densification took place. The resulting powder was dried in a fluid bed with an air temperature of 110°C. The composition of the resulting builder particle was: ZB1 :Ingredient % by weight Zeolite A24 53.6 Trisodium Citrate 17.2 Sokolan CP5 19.0 Moisture 10.2
  • the detergent particles LAS-A and ND1 and the builder particles ZB1 and other ingredients were used to make tablets of formulation shown in the table below.
  • Comparative tablets used the ND2 particles in place of the ND1 particles. parts by weight comparative Example 1 Anionic detergent particles LAS-A 5.43 5.43 Nonionic on zeolite particles ND2 6.91 - Nonionic on silica particles ND1 - 2.99 Zeolite particles ZB1 6.39 13.33 Sodium carbonate 1.26 1.26 Acrylate/maleate copolymer 0.53 0.53 Sodium disilicate 1.44 1.44 Sodium carboxymethylcellulose particles 0.17 0.17 Sodium percarbonate 5.92 5.92 TAED particles 2.09 2.09 Sodium acetate trihydrate mixed with 1% of its own weight of zeolite 10.38 10.38 Anti-foam particles 0.74 0.74 Sequestrant, fluorescer, soil-release polymer and coloured sodium carbonate particles 1.68 1.68 TOTAL 42.94 45.96
  • Tablets were made containing 43 grams of the comparative composition, or 46 grams of the composition of Example 1. These tablets all contained 3.8 parts of alkylbenzene sulphonate, 1.67 parts of nonionic detergent, 8.5 parts of zeolite and 10.4 parts of sodium acetate trihydrate. The tablets were compacted with an applied force of 9.7 kN.
  • the speed of dissolution of the soluble constituents of the tablets was tested by means of a test procedure in which a tablet was placed on a plastic sieve with 2mm mesh size, immersed in 9 litres of tap water at ambient temperature of 20°C. The sieve was fastened to a stirrer, which rotated at 200 rpm. The water conductivity was monitored until it reached a constant value. The time for dissolution of the tablets was taken as the time (T 90 ) for change in the water conductivity to reach 90% of its final magnitude.
  • Tablet strength was tested by a procedure in which a cylindrical tablet is compressed radially between the platens of a materials testing machine until the tablet fractures. At failure, the tablet cracks and the applied force needed to maintain the displacement of the platens drops. Measurement is discontinued when the applied force needed to maintain the displacement has dropped by 25% from its maximum value.
  • the force to cause fracture and the diametral fracture stress calculated from it are a direct assessment of strength and indicate the tablets' resistance to breakage when handled by a consumer at the time of use.
  • LAS-B Anionic detergent adjunct particles (LAS-B) were made as described in Example 1, but with a higher content of detergent. They contained LAS-B: Ingredient % by weight Linear alkyl benzene sulphonate 82% Sodium carbonate 4% Zeolite 10% Non-detergent impurites and moisture 4%
  • the above particles LAS-B and the nonionic particles ND1 described in the previous example were mixed with other materials to make two detergent compositions set out in the table below. These included particles of sodium tripolyphosphate specified to contain 70% phase I form and contain 3.5% water of hydration (Rhodia-Phos HPA 3.5 available from Rhone-Poulenc).
  • Example 3 Anionic detergent particles (LAS-B) 13.5 13.5 Nonionic detergent particles (ND1) 8.9 8.9 Rhodiaphos HPA3.5 tripolyphosphate 46.65 30.2 Acrylate/maleate copolymer 1.5 1.5 Sodium silicate 4.0 4.0 Sodium carboxymethylcellulose particles (SCMC) 0.3 0.3 Fluorescer on inert carrier 0.15 0.15 Sodium percarbonate 15.1 15.1 TAED particles 3.4 3.4 Anti-foam particles 3.2 3.2 Sequestrant, soil-release polymer and coloured sodium carbonate particles 2.7 2.7 TOTAL 99.4 82.95
  • a comparative detergent composition was made, starting with a spray-dried base powder (BP1) of the following composition: BP1 : Ingredient Parts by Weight Sodium linear alkylbenzene sulphonate 11.0 C 13-15 fatty alcohol 7EO 2.6 C 13-15 fatty alcohol 3EO 2.4 Soap 0.2 Sodium tripolyphosphate* 16.9 Acrylate/maleate copolymer 1.5 Sodium silicate 4.0 Sodium carboxymethylcellulose particles 0.3 Fluorescer on inert carrier 0.15 moisture and impurities 5.95 TOTAL 45 Added to the slurry as anhydrous sodium tripolyphosphate containing at least 70% phase II form.
  • BP1 Ingredient Parts by Weight Sodium linear alkylbenzene sulphonate 11.0 C 13-15 fatty alcohol 7EO 2.6 C 13-15 fatty alcohol 3EO 2.4 Soap 0.2 Sodium tripolyphosphate* 16.9 Acrylate/maleate copolymer 1.5 Sodium silicate 4.0 Sodium carboxymethylcellulose particles 0.3 Fluorescer on inert carrier
  • This powder was mixed with other ingredients as follows: Ingredient Parts by Weight Base powder (BP1) 45 Rhodiaphos HPA3.5 tripolyphosphate 30.2 Sodium percarbonate 15.1 TAED particles 3.4 Anti-foam particles 3.2 Sequestrant, soil-release polymer and coloured sodium carbonate particles 2.7 TOTAL 99.6
  • Example 2 Comparative Sodium linear alkylbenzene sulphonate 11.0 11.0 11.0 Nonionic detergent 5.0 5.0 5.0 aluminosilicate 1.35 1.35 0 silica 2.65 2.65 0 Rhodiaphos HPA3.5 tripolyphosphate 46.65 30.2 30.2 other tripolyphosphate 0 0 16.9 Acrylate/maleate copolymer 1.5 1.5 1.5 Sodium silicate 4.0 4.0 4.0 Sodium percarbonate 15.1 15.1 15.1 TAED particles 3.4 3.4 3.4 Anti-foam particles 3.2 3.2 3.2 SCMC and fluorescer on carrier 0.45 0.45 0.45 Sequestrant, soil-release polymer and coloured sodium carbonate particles 2.7 2.7 2.7 Soap, sodium carbonate, moisture and other impurities 2.35 2.35 6.15 Total 99.35 82.9 99.6
  • Example 2 40 gram portions of each composition were stamped into cylindrical tablets of 44 mm diameter. Various amounts of compaction force were used. The composition of Example 2 was also stamped into 32 gram tablets, so as to provide tablets of this composition containing the same amount of detergent as the 40 gram comparative tablets.
  • Example 2 as 40 gram tablets Comparative as 40 gram tablets DFS (kPa) T 90 (sec) E b (mJ) DFS (kPa) T 90 (sec) E b (mJ) 30 55.8 180 20.5 9.7 54.2 400 15 15 27.4 140 13.9 9.7 18.6 105 6.7 5.0 20.9 220 6.4 5.0 7.4 115 2.8 2.5 6.5 190 2.25
  • Compaction force (kN) Example 3 as 40 gram tablets
  • Example 3 as 32 gram tablets Comparative as 40 gram tablets DFS (kPa) T 90 (sec) E b (mJ) DFS (kPa) T 90 (sec) E b (mJ) T 90 (sec) E b (mJ) T 90 (sec) E b (mJ) 9.7 54.2 400 15 15 39.1 250 20.3 36.1 275 22.9 7.5 36.
  • the invention makes it possible to increase break energy, reduce dissolution time and/or reduce the tablet weight which is needed to deliver the same quantity of detergent.
  • Adjunct particles LAS-B and ND1 as described in the preceding examples were used to make tablets of the following formulation: Parts by Weight Anionic detergent particles (LAS-B) 16.0 Nonionic detergent particles (ND1) 10.0 Rhodiaphos HPA3.5 tripolyphosphate 48.0 Acrylate/maleate copolymer 2.0 Sodium silicate 4.0 Sodium carboxymethylcellulose particles 0.5 Polyvinylpyrrolidone 1.0 Sodium carbonate 7.0 Sodium sulphate 5.0 Anti-foam particles 3.5 Sequestrant, soil-release polymer and coloured sodium carbonate particles 3.0 TOTAL 100
  • Adjunct particles (LAS-B and ND1) as described in previous Examples were used together with further ingredients to make 40 gram tablets with two layers of unequal weight (10 grams and 30 grams).
  • the overall formulation was similar to Example 2 but contained slightly more alkylbenzene sulphonate and slightly less tripolyphosphate.
  • a base powder (BP1A) with the same composition as used in Examples 2 and 3 but taken from a different batch, was used to make comparative tablets with two layers of unequal weight. The overall formulation was the same as for the previous comparative tablets.
  • composition for one layer was placed in a mould and lightly compacted, the composition for the other layer was then added to the mould, and compaction force was applied to the mould contents.
  • Example 5 Comparative two layer tablets DFS (kPa) T 90 (sec) E b (mJ) DFS (kPa) T 90 (sec) E b (mJ) 30 55.8 120 41.7 20 43.1 115 28.0 9.7 21.4 105 10.6 52.1 275 15.7 5.0 8.2 105 2.7 21.8 210 7.1 2.5 7.0 135 2.6

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Claims (17)

  1. Waschmitteltablette aus verdichteter, teilchenförmiger Zusammensetzung, wobei die Tablette oder ein Bereich davon organisches Waschmittel und in Wasser löslichen Waschmittelbuilder umfasst, dadurch gekennzeichnet, dass die Tablette oder der Bereich davon aus einer Zusammensetzung verdichtet ist, die enthält:
    (i) Teilchen, die selbst mindestens 45% ihres Eigengewichts nichtionisches Waschmittel enthalten, wobei die Teilchen ein anorganisches, in Wasser unlösliches Trägermaterial enthalten, und das Nichtionische primäres oder sekundäres Alkoholethoxylat ist, und
    (ii) weitere Bestandteile.
  2. Tablette nach Anspruch 1, wobei die Zusammensetzung Teilchen enthält, die mindestens 50 Gew.-% nichtionisches Waschmittel enthalten.
  3. Tablette nach Anspruch 1 oder 2, wobei die Zusammensetzung der Tablette oder des Bereichs 3 bis 40 Gew.-% nichtionisches Waschmittel enthält, wobei mindestens die Hälfte davon als die Teilchen vorliegt.
  4. Tablette nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung der Tablette oder des Bereichs auch Teilchen einschließt, die mindestens 20% ihres Eigengewichts anionisches Nicht-Seifen-Waschmittel enthalten.
  5. Tablette nach Anspruch 4, wobei die Zusammensetzung der Tablette oder des Bereichs 5 bis 50 Gew.-% Nicht-Seifen-Waschmittel enthält, wobei mindestens die Hälfte davon als die Teilchen vorliegt, die mindestens 45 Gew.-% des nichtionischen Waschmittels enthalten oder als Teilchen, die mindestens 20% ihres Eigengewichts anderes Nicht-Seifen-Waschmittel enthalten.
  6. Tablette nach einem der vorangehenden Ansprüche, wobei mindestens 90% des organischen Nicht-Seifen-Waschmittels in der Tablette oder dem Bereich davon in den Teilchen, die mindestens 45% ihres Eigengewichts nichtionisches Waschmittel enthalten oder in Teilchen, die mindestens 20% ihres Eigengewichts anderes Nicht-Seifen-Waschmittel enthalten, enthalten sind.
  7. Tablette nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung der Tablette oder des Bereichs Teilchen einschließt, die mindestens 80% ihres Eigengewichts von einem oder mehreren in wasserlöslichen Materialien, ausgewählt aus Verbindungen mit einer Wasserlöslichkeit, die 50 g pro 100 g Wasser bei 20°C übersteigt, Natriumtripolyphosphat, das mindestens 50% seines Eigengewichts der wasserfreien Phase I-Form enthält und Gemischen davon, enthalten.
  8. Tablette nach Anspruch 7, wobei die Zusammensetzung der Tablette oder des Bereichs 15 bis 60 Gew.-% der Teilchen enthält, die mindestens 80% ihres Eigengewichts von einem oder mehreren in Wasser löslichen Materialien enthalten.
  9. Tablette nach Anspruch 7, wobei die Zusammensetzung der Tablette oder des Bereichs 25 bis 50 Gew.-% der Teilchen enthält, die mindestens 80% ihres Eigengewichts von einem oder mehreren in Wasser löslichen Materialien enthalten.
  10. Tablette nach einem der Ansprüche 7 bis 9, wobei die Zusammensetzung der Tablette oder des Bereichs 20 bis 60 Gew.-% des Tripolyphosphats enthält, welches teilweise hydratisiert ist, sodass Hydratationswasser in einer Menge enthalten ist, die mindestens 1 Gew.-% des Natriumtripolyphosphats beträgt.
  11. Tablette nach einem der Ansprüche 7 bis 9, wobei die Zusammensetzung der Tablette oder des Bereichs bis 55 Gew.-% der Teilchen enthält, die mindestens 95% ihres Eigengewichts von dem Tripolyphosphat enthalten, welches teilweise hydratisiert ist, sodass Hydratationswasser in einer Menge enthalten ist, die mindestens 1 Gew.-% des Natriumtripolyphosphats beträgt.
  12. Tablette nach einem der Ansprüche 7 bis 9, wobei die Zusammensetzung der Tablette oder des Bereichs mindestens 20 Gew.-% der Teilchen enthält, die selbst mindestens 80% ihres Eigengewichts von einem oder mehreren Salzen mit einer Wasserlöslichkeit, die 50 g/100 g Wasser bei 20°C übersteigt, enthalten.
  13. Tablette nach Anspruch 12, wobei die Verbindung eine oder mehrere von teilweise oder vollständig hydratisiertem Natriumcitrat, teilweise oder vollständig hydratisiertem Natriumacetat und Kaliumacetat ist.
  14. Tablette nach einem der vorangehenden Ansprüche, wobei die Tablette insgesamt 5 bis 40% organisches Nicht-Seifen-Waschmittel und 15 bis 80% Waschmittelbuilder enthält.
  15. Tablette nach Anspruch 14, die insgesamt 30 bis 60 Gew.-% Natriumtripolyphosphat, als wasserfrei berechnet, enthält.
  16. Tablette nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung der Tablette oder des Bereichs davon 10 bis 60% Teilchen enthält, die 40 bis 80% ihres Eigengewichts Waschmittelbuilder und 20 bis 60% ihres Eigengewichts von anderem Nicht-Waschmittelmaterial enthält.
  17. Verfahren zur Herstellung einer Tablette, wie in einem der vorangehenden Ansprüche definiert, wobei das Verfahren Vermischen der Teilchen, die selbst mindestens 45% ihres Eigengewichts nichtionisches Waschmittel enthalten, mit anderen Waschmittelbestandteilen, und anschließend Verdichten der erhaltenen Zusammensetzung zu Tabletten umfasst.
EP99961011A 1998-11-27 1999-11-24 Reinigungsmittelzusammensetzungen in tablettenform Expired - Lifetime EP1133548B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9826105 1998-11-27
GBGB9826105.0A GB9826105D0 (en) 1998-11-27 1998-11-27 Detergent compositions
PCT/EP1999/009175 WO2000032740A1 (en) 1998-11-27 1999-11-24 Detergent compositions in tablet form

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EP1133548A1 EP1133548A1 (de) 2001-09-19
EP1133548B1 EP1133548B1 (de) 2002-10-02
EP1133548B2 true EP1133548B2 (de) 2006-07-12

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CN (1) CN1328599A (de)
AR (1) AR021413A1 (de)
AT (1) ATE225395T1 (de)
AU (1) AU1777500A (de)
BR (1) BR9915649B1 (de)
CA (1) CA2350620A1 (de)
DE (1) DE69903343T3 (de)
ES (1) ES2184514T5 (de)
GB (1) GB9826105D0 (de)
ID (1) ID29192A (de)
TR (1) TR200101437T2 (de)
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US3329615A (en) † 1964-07-23 1967-07-04 Stauffer Chemical Co Tableted detergent and detergentbleach compositions comprising alkyl orthophosphate salts
US3562165A (en) † 1966-03-24 1971-02-09 Renato Altieri Process for preparing a dry compacted detergent composition
US3769222A (en) † 1971-02-09 1973-10-30 Colgate Palmolive Co Free flowing nonionic surfactants
US3920586A (en) † 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
US4219436A (en) † 1977-06-01 1980-08-26 The Procter & Gamble Company High density, high alkalinity dishwashing detergent tablet
EP0355626A1 (de) † 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung phosphatreduzierter Waschmitteltabletten
EP0508934A1 (de) † 1991-04-12 1992-10-14 Cleantabs A/S Waschmittelzusammensetzung
WO1992018596A1 (en) † 1991-04-19 1992-10-29 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
EP0513824A2 (de) † 1991-05-17 1992-11-19 Kao Corporation Verfahren zur Herstellung von nichtionischen Detergenskörnchen
WO1993014182A1 (en) † 1992-01-14 1993-07-22 The Procter & Gamble Company Granular laundry compositions having improved solubility
GB2272450A (en) † 1992-11-13 1994-05-18 Albright & Wilson Aqueous surfactant VI phase compositions
EP0710717A1 (de) † 1994-11-04 1996-05-08 Amway Corporation Aus einem Spender verteilbares Pulvermittel
WO1997033959A1 (en) † 1996-03-15 1997-09-18 Amway Corporation Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
US5714451A (en) † 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
EP0903404A1 (de) † 1995-11-02 1999-03-24 Kao Corporation Waschmittelkorner und -zusammensetzung
EP0936267A2 (de) † 1998-02-09 1999-08-18 Henkel Kommanditgesellschaft auf Aktien Alkalimetallsilicat/Niotensid-Compound
US5990068A (en) † 1996-03-15 1999-11-23 Amway Corporation Powder detergent composition having improved solubility
EP1074608A1 (de) † 1999-08-02 2001-02-07 Robert McBride Ltd Waschmitteltabletten

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GB9015504D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergents composition
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
GB9114184D0 (en) * 1991-07-01 1991-08-21 Unilever Plc Detergent composition
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB9422895D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
GB2318575A (en) * 1996-10-22 1998-04-29 Unilever Plc Detergent tablet
GB2318800A (en) * 1996-11-01 1998-05-06 Unilever Plc Detergent composition
PL335883A1 (en) * 1997-03-24 2000-05-22 Unilever Nv Detergent composition
CZ20001498A3 (cs) 1997-10-22 2001-09-12 Unilever N. V. Tableta čistícího prostředku

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329615A (en) † 1964-07-23 1967-07-04 Stauffer Chemical Co Tableted detergent and detergentbleach compositions comprising alkyl orthophosphate salts
US3562165A (en) † 1966-03-24 1971-02-09 Renato Altieri Process for preparing a dry compacted detergent composition
US3769222A (en) † 1971-02-09 1973-10-30 Colgate Palmolive Co Free flowing nonionic surfactants
US3920586A (en) † 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
US4219436A (en) † 1977-06-01 1980-08-26 The Procter & Gamble Company High density, high alkalinity dishwashing detergent tablet
EP0355626A1 (de) † 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung phosphatreduzierter Waschmitteltabletten
EP0508934A1 (de) † 1991-04-12 1992-10-14 Cleantabs A/S Waschmittelzusammensetzung
WO1992018596A1 (en) † 1991-04-19 1992-10-29 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
EP0513824A2 (de) † 1991-05-17 1992-11-19 Kao Corporation Verfahren zur Herstellung von nichtionischen Detergenskörnchen
WO1993014182A1 (en) † 1992-01-14 1993-07-22 The Procter & Gamble Company Granular laundry compositions having improved solubility
GB2272450A (en) † 1992-11-13 1994-05-18 Albright & Wilson Aqueous surfactant VI phase compositions
EP0710717A1 (de) † 1994-11-04 1996-05-08 Amway Corporation Aus einem Spender verteilbares Pulvermittel
EP0903404A1 (de) † 1995-11-02 1999-03-24 Kao Corporation Waschmittelkorner und -zusammensetzung
WO1997033959A1 (en) † 1996-03-15 1997-09-18 Amway Corporation Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
US5714451A (en) † 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
US5990068A (en) † 1996-03-15 1999-11-23 Amway Corporation Powder detergent composition having improved solubility
EP0936267A2 (de) † 1998-02-09 1999-08-18 Henkel Kommanditgesellschaft auf Aktien Alkalimetallsilicat/Niotensid-Compound
EP1074608A1 (de) † 1999-08-02 2001-02-07 Robert McBride Ltd Waschmitteltabletten

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EP1133548B1 (de) 2002-10-02
WO2000032740A1 (en) 2000-06-08
CA2350620A1 (en) 2000-06-08
AU1777500A (en) 2000-06-19
ATE225395T1 (de) 2002-10-15
ES2184514T5 (es) 2007-03-16
GB9826105D0 (en) 1999-01-20
BR9915649A (pt) 2001-08-07
EP1133548A1 (de) 2001-09-19
AR021413A1 (es) 2002-07-17
TR200101437T2 (tr) 2001-11-21
ID29192A (id) 2001-08-09
DE69903343T3 (de) 2006-11-23
ES2184514T3 (es) 2003-04-01
DE69903343T2 (de) 2003-06-18
CN1328599A (zh) 2001-12-26
BR9915649B1 (pt) 2009-12-01
DE69903343D1 (de) 2002-11-07

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