EP1903100B1 - Waschmitteltablette - Google Patents

Waschmitteltablette Download PDF

Info

Publication number
EP1903100B1
EP1903100B1 EP06120889A EP06120889A EP1903100B1 EP 1903100 B1 EP1903100 B1 EP 1903100B1 EP 06120889 A EP06120889 A EP 06120889A EP 06120889 A EP06120889 A EP 06120889A EP 1903100 B1 EP1903100 B1 EP 1903100B1
Authority
EP
European Patent Office
Prior art keywords
phase
smooth
detergent tablet
preferred
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP06120889A
Other languages
English (en)
French (fr)
Other versions
EP1903100A1 (de
Inventor
Pieter Everhardus Maria c/o Unilever R&D Vlaardingen B.V Overdevest
Johannes Cornelis c/o Unilever R&D Vlaardingen B.V van de Pas
Remy Antal c/o Unilever R&D Vlaardingen B.V Verburgh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to ES06120889T priority Critical patent/ES2327953T3/es
Priority to EP06120889A priority patent/EP1903100B1/de
Priority to AT06120889T priority patent/ATE432976T1/de
Priority to DE602006007142T priority patent/DE602006007142D1/de
Publication of EP1903100A1 publication Critical patent/EP1903100A1/de
Application granted granted Critical
Publication of EP1903100B1 publication Critical patent/EP1903100B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • detergent tablets include tablets suitable for fabric treatment, e.g. fabric softening.
  • Detergent compositions in tablet form have advantages over powdered products in that they do not require measuring and are thus easier to handle and dispense into the wash load.
  • Tablets of a cleaning composition are generally made by compressing or compacting a quantity of the composition in particulate form.
  • WO 01/42416 describes the production of multi-phase moulded bodies comprising a combination of core moulded bodies and a particulate premix.
  • WO 00/04129 describes a multi-phase detergent tablet comprising a first phase in the form of a shaped body having at least one mould therein and a second phase in the form of a particulate solid compressed within said mould.
  • WO 00/61717 describes a detergent tablet which is characterised in that at least part of its outer surface is semi-solid. Said tablets are constituted from a compressed particulate tablet on top of which a (non-compressed) smooth layer is attached by pouring a mixture of nonionic and PEG followed by hardening.
  • WO 99/24549 describes a detergent tablet comprising a compressed solid body and a non-compressed gelatinous portion mounted in a mould of said body.
  • EP 1,491,622 B1 and EP 1,511,834 B1 disclose detergent tablets comprising a smooth or semi-solid phase and a solid compressed particulate phase. The majority of surfactants is present in the smooth or semi-solid phase.
  • EP 1,371,719 A1 , EP 1,405,901 A1 , and EP 1,405,902 A1 exemplify that the concentration of (sodium) soap in smooth phases of detergent tablets comparable to the tablet of the present invention, is generally about 5-10% of the weight of the smooth phase, combined with (amongst others) 55-80% non-soap surfactants like nonionics and synthetic anionics.
  • GB 1,578,289 discloses detergent gels, that can be used as detergent spotting sticks for use in wash or dry-cleaning pre-treatment.
  • the detergent gels comprise mixed sodium and potassium soaps (2-25% by weight of the composition, preferably 6-12% by weight), nonionic surfactants, anionic surfactants, organic solvents, and water.
  • detergent compositions that show this dual effect.
  • US 2002/0151454 discloses laundry detergent compositions comprising cationic polymers, e.g. cationic cellulose derivatives, delivering a softening benefit to the fabric.
  • WO 2006/012984 discloses fabric softening laundry compositions comprising cationic polymers (e.g. cationically modified polysaccharides), nonionic oils, and surfactants.
  • WO 2004/069979 discloses liquid laundry compositions comprising cationic polymers and one or more anionic surfactants at a ratio of smaller than 1:4.
  • a preferred form of the cationic polymer is a cationic substituted siloxane or polyquaternium-10.
  • one of the anionic surfactants is a soap, wherein the solubilising cation is preferably sodium or potassium. Most preferably the soap is combined with another anionic surfactant.
  • the examples show compositions comprising sodium soap, synthetic anionic surfactants like linear alkylbenzene suphonic acid, and cationic polymer.
  • a further object of the invention is to provide a detergent tablet with a high soap concentration.
  • a tablet can be manufactured with high soap content, good cleaning properties and rapid dissolution.
  • combining a mixed sodium-potassium soap especially with a cationic polymer in a detergent tablet results in a tablet with good cleaning properties, that also softens the fabric after the laundering process, and has good dissolution properties as well.
  • the smooth phase of the detergent tablet is substantially free from non-soap anionic surfactants, the softness results are improved.
  • a multi-phase detergent tablet comprising a smooth phase, wherein the smooth phase comprises a mixed sodium-potassium soap, having a weight ratio of sodium soap and potassium soap in the smooth phase of from 5:1 to 1:5, more preferred from 4:1 to 1:4, more preferred from 2:1 to 1:4, even more preferred from 1:1 to 1:4, and most preferred from 1:1 to 1:3.
  • the detergent tablet also comprises a compressed solid particulate phase.
  • a multi-phase detergent tablet comprising a smooth phase, wherein the smooth phase comprises a mixed sodium-potassium soap, having a weight ratio of sodium soap and potassium soap in the smooth phase of from 5:1 to 1:5, more preferred from 4:1 to 1:4, more preferred from 2:1 to 1:4, even more preferred from 1:1 to 1:4, and most preferred from 1:1 to 1:3, and wherein the smooth phase is substantially free from non-soap anionic surfactants.
  • the detergent tablet also comprises a solid compressed particulate phase.
  • the detergent tablet of the invention further comprises a cationic polymer, wherein the cationic polymer preferably is a cellulose derivative, more preferred a quaternary ammonium salt of modified cellulose, or mostly preferred a quaternary ammonium salt of hydroxyethylcellulose.
  • the cationic polymer is present in the solid compressed particulate phase.
  • Weight percentages are calculated based upon total weight of the tablet, unless indicated otherwise.
  • 'substantially free from' means a maximum concentration of a compound of 0.5 wt% based on the weight of the detergent tablet.
  • the detergent tablet of the invention is a multi-phase tablet comprising a smooth phase and preferably additionally one or more other phases.
  • these additional phases can be smooth, semi-solid or solid.
  • these additional phases are solid phases composed of compacted particulate solids.
  • smooth means that it can be smooth, semi-solid or both smooth and semi-solid.
  • smooth refers to compositions which are on the one hand solid enough to retain their shape at ambient temperature and on the other hand smooth in appearance. Smooth textures are generally of low or no porosity and have -at normal viewing distance- the appearance of a continuous phase for example as opposed to the porous and particulate appearance of a compacted particulate material.
  • a suitable test to check if a composition can be considered as semi-solid is for example described in EP 1,375,636 A1 .
  • the phases of the multi-phase detergent tablet are possibly separate layers within the tablet. However, a discrete region of a tablet could also have other forms for example one or more cores or inserts.
  • the first phase is a smooth layer and the second phase is a layer of compacted particulate material.
  • the first phase is a core or insert of smooth material embedded in the second region which is a layer of compacted particulate material.
  • both the smooth phase and the solid compressed particulate phase may be composed of a limited number of discrete regions.
  • the first smooth phase may be a single discrete part of the tablet but may also be a limited number (for example 1-5) discrete smooth parts.
  • each of these smooth parts are at least 1 gramme, also preferably each of these smooth parts is substantially of the same composition. If reference is made to the composition or weight of the smooth phase, then this concerns the total weight and composition of the smooth phases combined.
  • the solid compressed particulate phase may comprise 1 to 5 regions with different compositions.
  • the solid second phase may be composed of a limited number (for example 1-5) of solid parts, for example as separate layers in the tablet. If reference is made to the composition or weight of the solid compressed particulate phase, then this concerns the total weight and composition of these solid phases.
  • Each solid part is prepared by compression of a particulate composition.
  • one of the regions of the solid compressed particulate phase may serve as a intermediate phase between the solid compressed particulate phase and the smooth phase, in order to prevent interaction of incompatible compounds of the two phases, and to decrease leakage of compounds from the smooth phase to the solid compressed particulate phase.
  • the cleaning tablets of the invention may optionally comprise further regions, for example the tablet may be partly or completely coated.
  • the smooth phase of the multi-phase tablet of the invention is present as a distinctive region preferably having a weight of from 2 to 20 gram, more preferred from 3 to 10 gram.
  • the other phases together have a weight of 10 to 70 gram, more preferred 15 to 40 gram.
  • the weight of the tablets depends on the conditions of intended use, and whether it represents a dose for an average load in a washing 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 1050 g/litre up to 1600 g/litre.
  • the smooth phase of the detergent tablet of the present invention comprises a mixed sodium-potassium soap.
  • This mixed sodium-potassium soap may be produced by neutralising a mixture of fatty acids with a mixture of NaOH- and KOH-solutions in water.
  • the fatty acids are derived from naturally occurring materials, like for example coconut oil, beef tallow, sunflower oil or hardened rapeseed oil.
  • the fatty acid chain length and degree of saturation of the fatty acid chains both influence the structure of the smooth phases. A shorter chain length, and a higher degree of unsaturation lead to softer smooth phases, due to a lower melting point of these fatty acids as compared to saturated long chain fatty acids.
  • the preferred average fatty acid chain length is from 8 to 22 carbon atoms, more preferred from 12 to 18 carbon atoms. Also the ratio between fatty acids with different chain lengths is important.
  • the smooth phase of the present invention is rich in C 12 -C 14 soaps.
  • the weight ratio between C 12 -C 14 fatty acids and C 16 -C 18 fatty acids in the smooth phase is from 25:1 to 1:6, more preferred from 15:1 to 1:4, and most preferred from 10:1 to 1:3.
  • the weight ratio of sodium- and potassium soap in the smooth phase is from 5:1 to 1:5, more preferred from 4:1 to 1:4, more preferred from 2:1 to 1:4, and most preferred from 1:1 to 1:4.
  • An even more preferred weight ratio of sodium- and potassium soap in the smooth phase is from 1:1 to 1:3.
  • the concentration of mixed sodium-potassium soap in the smooth phase of the detergent tablet of the invention is from 2 to 50 wt%, more preferred from 4 to 45 wt%, most preferred from 5 to 40 wt% based on the weight of the smooth phase.
  • smooth phases comprising a mixed sodium-potassium soap is that higher amounts of soap can be incorporated in the gel and still having the same gel strength, as compared to sodium soaps.
  • a further advantage of smooth phases comprising a mixed sodium-potassium soap is that the dissolution rate of the smooth phase, and also of the detergent tablet, is increased compared to smooth phases without comprising potassium soaps.
  • the smooth phase comprises from 10-80 wt% of non-soap surfactants (based on the total weight of the smooth phase). It has been found that the combination of a separate smooth phase and these high surfactant levels provide very good dispersing and cleaning properties to the detergent tablet.
  • the non-soap surfactants may comprise any combination of anionic, non-ionic, zwitterionic or cationic surfactants, in any weight ratio.
  • the mixed sodium-potassium soap and non-soap surfactants may be present in the smooth phase in a weight ratio of from 25:1 to 1:25, more preferred 10:1 to 1:10, most preferred 5:1 to 1:5.
  • Further surfactants for example cationic surfactants, may equally be present for example at a level of 0.1 to 10 wt% based on the weight of the smooth phase.
  • the smooth phase is substantially free from non-soap anionic surfactants.
  • the non-soap surfactants are predominantly nonionic surfactants, optionally supplemented by low levels (e.g. up to 15 wt% based on the total weight of the non-soap surfactants) of zwitterionic or cationic surfactants.
  • the smooth phase additionally comprises a material selected from polyalkoxylated carbohydrates, as defined in EP 1,405,901 A1 .
  • alkoxylated carbohydrate materials are polyoxyethylene sorbitan mono fatty acid esters (for example Tween 20, Tween 40 and Tween 60, supplied by Uniqema, Gouda, The Netherlands), polyoxyethylene-sorbitol fatty esters, polyoxyethylene glycerol esters, polyoxyethylene glycerol sorbitan isostearate (for example Arlacel 582), polyoxyethylene sorbitan (for example obtainable by hydrolysing Tween 20, Tween 40 and Tween 60), polyoxyethylene sorbitol, polyoxyethylene glycerol, polyoxyethylene glycerol sorbitan, polypropoxylated sorbitan (for example Atlas G-2330 and Atlas G-2401, supplied by Uniqema, Gouda, The Netherlands)).
  • polyoxyethylene sorbitan mono fatty acid esters
  • the concentration of of the material selected from polyalkoxylated carbohydrates is from 5 to 50 wt%, more preferred 10 to 45 wt%.
  • the smooth phase of the tablet may also contain diluent materials, that are characterised by having a dielectric constant of about 10 to about 40 (as defined in EP 1,676,904 A1 ).
  • these diluents are polyethyleneglycol 400, dipropyleneglycol, monopropyleneglycol, and isopropanol.
  • the level of these diluents is from 0 to 40 wt%, more preferred 4 to 30 wt%, based on the weight of the smooth phase.
  • the smooth phase comprises no or only low levels of water.
  • the level of water is less than 20 wt% based on the weight of the smooth phase.
  • the smooth phases are free from added water, which means in this context that apart from low levels of moisture (e.g. for neutralisation or as crystal water) no additional added water is present.
  • the smooth phase may comprise active ingredients like enzymes, perfume, fluorescer, polymers, or dyes, and various other compounds, that will be exemplified later.
  • the multi-phase detergent tablet of the invention comprises a solid compressed particulate phase.
  • This solid compressed particulate phase is either substantially free from or comprises only low levels of surfactants. If present, preferably the concentration of surfactants in the solid compressed particulate phase is less than 15 wt% (based on the combined total weight of solid compressed particulate phases), more preferred from 0 to 12 wt%. If the solid compressed particulate phase of the multi-phase detergent tablet of the invention comprises surfactants, then preferably the ratio between amounts of surfactants (in grams per phase) in the smooth phase and in the solid compressed particulate phase is from about 20:1 to about 1:8, more preferred from about 10:1 to 1:5.
  • the multi-phase detergent tablet of the invention comprises a cationic polymer.
  • the cationic polymer is contained in the solid compressed particulate phase of the multi-phase detergent tablet.
  • a cationic polymer is here defined to mean polymers which, because of their molecular weight or monomer composition, are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C.
  • Water soluble cationic polymers include polymers in which one or more of the constituent monomers are selected from the list of copolymerizable cationic or amphoteric monomers. These monomer units contain a positive charge over at least a portion of the pH range 6-11.
  • the cationic polymers of a preferred embodiment of the present invention may be cationic derivatives of natural polymers such as polysaccharides, starch, guar, cellulose and their copolymers with certain cationic synthetic polymers.
  • the cationic polymer is a cationic cellulose derivative, more preferred a quaternary ammonium salt of modified cellulose.
  • the cationic polymer is a quaternary ammonium salt of hydroxyethylcellulose.
  • An example of this polymer is polyquaternium-10, marketed under the brand name UCARETM Polymer, for example types JR-400 and LR-400 (supplied by Amerchol Corporation).
  • the cationic polymers of a preferred embodiment of this invention are effective at surprisingly low concentrations.
  • concentration of cationic polymer in the detergent tablet will generally be from 0.05 to 2 wt%, based on detergent tablet weight. More preferred, the concentration of cationic polymer will be from 0.1 to 1 wt%, based on detergent tablet weight.
  • the species responsible for the softening effect is a cationic polymer - soap complex. It is believed that the cationic polymer forms a thin layer on the substrate (textile) through attractive forces, and the negative soap molecules are attracted by the positive charge of the cationic polymer. The long chains of the soap molecules will be sticking upwards from the textile, and this gives a soft feeling to the textile.
  • the weight ratio of cationic polymer to total surfactants in the composition should be well balanced, in order to obtain a softening effect on the fabric.
  • the weight ratio of cationic polymer to surfactants should preferably be from 1:200 to 1:5, more preferred from 1:100 to 1:10. More specifically, the weight ratio of cationic polymer to the mixed sodium-potassium soap in the smooth phase should preferably be from 1:100 to 1:1, and more preferably from 1:50 to 1:3.
  • the water-soluble cationic or amphoteric polymer used in this invention be of an appropriate molecular weight.
  • polymers that are too high in mass can entrap soils and prevent them from being removed.
  • the use of cationic polymers with an average molecular weight of less than about 850,000 daltons is preferred, and even more preferred those with an average molecular weight of less than 500,000 daltons.
  • the preferred minimum average molecular weight is about 10,000 daltons, because smaller molecules are believed to be too small to give an effective softening benefit.
  • the charge density of the cationic polymer can affect softening removal.
  • the charge density relates to the degree of cationic substitution, and can be expressed with nitrogen content of the cationic polymer.
  • the cationic polymer is contained in a co-granule, before being mixed with other compounds of the detergent tablet.
  • the co-granule comprises a binder, in addition to the cationic polymer. More preferably the co-granule also comprises either an organic or an inorganic salt.
  • Preferred binder materials are polyethylene glycol, soaps, and fatty acids.
  • a preferred organic salt is sodium citrate, and a preferred inorganic salt is sodium sulphate.
  • the compressed particulate phase comprises ingredients of the tablet other than surfactants.
  • these ingredients are for example builders, bleach systems, enzymes, perfumes, and various other compounds, that will be exemplified later.
  • Detergent tablets according to the invention are preferably manufactured by firstly preparing a smooth phase.
  • the preparation of the smooth phase may include the heating of the ingredients followed by cooling.
  • the preparation of the smooth phase may involve extrusion or casting.
  • the smooth phase is manufactured by a casting process.
  • a suitable casting process involves first liquidizing the composition of the smooth phase, for example by heating, followed by inserting the composition into a mould, followed by solidification, for example by ageing or cooling.
  • Extrusion processes for washing articles are known, for example WO 01/02532 describes the extrusion of washing articles with a pressure of less than 10 bar.
  • a preferred extrusion processes for preparing the smooth phases for use in tablets of the invention is exemplified in EP 1,371,719 . The process involves the forming of an extrudable mass which is then subsequently extruded from an extrusion device and optionally then partitioned into parts of the desired size and weight. Optionally the smooth parts may then be hardened.
  • the extrudable mass preferably has an initial elevated temperature for example from 60 to 120°C, more preferred from 70 to 90°C.
  • the extrudable mass is cooled during the production of the smooth phase, e.g. to a final temperature of 20°C. If extrusion is used this low temperature may for example be the temperature at the extrusion die, for example from 10 to 40°C, preferably from 15 to 25°C, most preferred at ambient temperature (20°C).
  • a preferred embodiment of the detergent tablet of the present invention may be manufactured by a process that comprises the steps of:
  • steps (a) and (b) take place before step (c).
  • step (a) is preceded by the following two steps:
  • the smooth phase can be made by spraying or otherwise applying a molten composition of a smooth phase onto a tablet comprising one or more compressed particulate compositions.
  • the particulate composition is pre-compressed at a force of 0.1 to 20 kN/cm 2 between steps (a) and (b). In another preferred embodiment the particulate composition is flattened between steps (a) and (b).
  • the (co-)compression of the combination of the smooth and the solid phases takes place at a force of from 0.05 to 20 kN/cm 2 .
  • the co-compression in step (c) can advantageously be at a force of 0.1 to 10 kN/cm 2 , more preferred 0.5 to 5 kN/cm 2 .
  • the co-compression preferably takes place at a force of 1 to 100 kN/cm 2 , more preferred 2 to 50 kN/cm 2 , most preferred 2 to 10 kN/cm 2 .
  • step (c) may lead to good adherence of the smooth phase to the solid compressed particulate phase and may avoid the need of applying an adhesive material between the smooth phase and solid compressed particulate phase (step (d)).
  • step (d) Another advantage of this method is that it can be carried out in a normal tablet press without the need of adaptation of the shape of the pressing surfaces.
  • the particulate composition that will be compressed into the solid compressed phase has an average particle size in the range from 200 to 2000 ⁇ m, more preferably from 250 to 1400 ⁇ m. Fine particles, smaller than 180 ⁇ m or 200 ⁇ m, may be eliminated by sieving before tableting, if desired.
  • the starting particulate composition may in principle have any bulk density
  • the present invention is especially relevant to tablets made by compacting powders of relatively high bulk density.
  • Such tablets have the advantage that, as compared with a tablet derived from a low bulk density powder, a given dose of composition can be presented as a smaller tablet.
  • the starting particulate composition may suitably have a bulk density of at least 400 kg/m 3 , preferably at least 500 kg/m 3 .
  • Tableting machinery able to carry out the manufacture of tablets of the invention is known, for example suitable tablet presses are available from Fette and from Korch.
  • 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.
  • compositions which are used in tablets of the invention will contain one or more detergent surfactants.
  • These surfactants preferably provide from 5 to 50% by weight of the overall tablet composition, more preferably from 8 or 9% up to 40% or 50% by weight of the overall composition.
  • Surfactants may be anionic (soap or non-soap), cationic, zwitterionic, amphoteric, nonionic or a combination of these.
  • Anionic surfactants may be present in an amount from 0 to 50 wt%, preferably from 1 wt% up to 30 wt% or 40 wt% by weight of the tablet composition.
  • the smooth phase is substantially free from non-soap anionic surfactants.
  • Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Other examples of commercially important anionic surfactants, are primary alkyl or alkenyl sulphates, having a chain length of 8 to 18 carbon atoms.
  • Linear alkyl benzene sulphonate or primary alkyl sulphate, or a mixture thereof will be the preferred (combination of) anionic surfactants and may provide 75 to 100 wt% of any anionic non-soap surfactant in the composition.
  • Suitable nonionic 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.
  • Nonionic surfactant compounds are alkyl (C 8-22 ) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C 8-20 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.
  • EO ethylene oxide
  • the use of ethoxylated nonionic surfactants based on branched alcohols is sometimes preferred.
  • the concentration of nonionic surfactants preferably lies in a range from 3 to 40%, more preferred 4 or 5 to 30% by weight of the whole tablet.
  • a composition which is used in detergent tablets of the invention will usually contain from 5 to 80%, more usually 15 to 60% by weight of detergency builder. This may be provided completely by water soluble materials, or may be provided in large part or even entirely by water-insoluble material with water-softening properties. Water-insoluble detergency builder may be present as 5 to 80 wt%, better 5 to 60 wt% of the composition.
  • Alkali metal aluminosilicates are 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. These materials contain some bound water (indicated as 'xH 2 O') and are required to have a calcium ion exchange capacity of at least 50 mg CaO per gram.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the general 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 1,429,143 .
  • the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, the zeolite P described and claimed in EP 384,070 and mixtures thereof.
  • a water-insoluble detergency builder could be a layered sodium silicate as described in US 4,664,839 .
  • other layered silicates can be used, such as those having 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.
  • Water-soluble phosphorous-containing inorganic detergency builders include the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
  • Non-phosphorous water-soluble builders may also be applied, and may be organic or inorganic.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate.
  • Organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and tri-succinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
  • Detergent tablets according to the invention preferably comprise 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 of from 10 to 25% by weight of the tablet.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator.
  • Bleach activators also referred to as bleach precursors, have been widely disclosed in the art.
  • Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), and perbenzoic acid precursors.
  • a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylene diamine tetra (methylene phosphonic acid), diethylenetriamine pentamethylene phosphonate, and tetrasodium 1-hydroxyethylidene biphosphonate.
  • the detergent tablets of the invention may also contain one or more of the detergency enzymes well known in the art for their ability to degrade and aid in the removal of various soils and stains.
  • Both the smooth phase, as well as the solid compressed particulate phase (if present) may contain enzymes.
  • 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. Examples of suitable proteases are Alcalase (trademark), and Savinase (trademark), as supplied by Novozymes A/S (Bagsvaerd, 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.
  • the detergent tablets of the invention may also contain a fluorescer (optical brightener), for example, Tinopal (trademark) DMS or Tinopal CBS available from Ciba Speciality Chemicals 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.
  • Both the smooth phase, as well as the solid compressed particulate phase (if present) may contain fluorescer.
  • An antifoam material is preferably included in the detergent tablet (either in the smooth phase, or the solid compressed particulate phase (if present), or both), especially if a detergent tablet is primarily intended for use in front-loading drum-type automatic washing machines.
  • Suitable antifoam materials are usually in granular form, such as those described in EP 266,863 .
  • Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, absorbed 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 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.
  • a detergent tablet for fabric washing will generally not contain more than 15 wt% silicate.
  • the silicate is present in the solid compressed particulate phase of the tablet.
  • ingredients which can optionally be employed in a 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, heavy metal sequestrants such as EDTA, perfumes, colourants, dyes, or coloured speckles. Said ingredients could be contained in the smooth phase, as well as the solid compressed particulate phase (if present).
  • dispersing aids preferably in the solid compressed particulate phase (when present).
  • suitable dispersing aids are water-swellable polymers (e.g. sodium carboxymethylcellulose), highly soluble materials (e.g. sodium citrate, potassium carbonate, sodium acetate, sodium sulphate) or sodium tripolyphospate.
  • the detergent tablet of the invention comprises granules comprising a well soluble organic salt (e.g. sodium acetate) and a zeolite.
  • DFS diametrical fracture stress in Pascal
  • F max is the applied load in Newton to cause fracture
  • D is the tablet diameter in metre
  • t is the tablet thickness in metre.
  • the test is carried out using an Instron type universal testing instrument to apply compressive force on a tablet diameter (i.e. perpendicular to the axis of a cylindrical tablet). It is preferred that tablets have a DFS of at least 20 kPa, more preferably at least 25 kPa, such as 30 kPa or above.
  • the dissolution rate of the smooth phases is determined by measuring the time necessary to dissolve 80% by weight of the smooth phase under standard conditions.
  • a biopt of about 5 gram smooth phase is taken from bulk smooth phase using a syringe having an internal diameter of 19 mm.
  • the consequent smooth phase cylinder is about 17 mm long.
  • the biopt is dissolved in 500 gram water of 20°C whilst stirring at 200 rpm with a two-blade (twisted) stirrer having a diameter of 6 cm and a height of 6 cm. The blades of the stirrer are positioned just below the water surface. Every 5 minutes the smooth phase weight is noted until less than 1 gram of smooth phase is remained.
  • the time necessary to dissolve exactly 80% of the smooth phase is obtained by interpolation.
  • the strength of the smooth phase is measured by a compressing technique using the MTS Synergy 1000 electromechanical testing machine.
  • a smooth phase cylinder is cut out of a smooth phase mass using a cork drill, diameter and length of the cylinder is 13 mm and 13 mm, respectively. This cylinder is compressed with a 500 N load-cell. The so-called 'force at failure' (in N) is measured, being the maximum in the force-compression curve.
  • the preparation method of the smooth phases involved the following steps. LAS-acid was added to dipropylene glycol while stirring, and after a homogeneous mixture had been obtained, followed by part of the caustic solution. Fatty acid flakes were added and the temperature was raised to 75°C. The rest of the caustic solution was added to fully neutralise the fatty acid to soap. The nonionic was added and the temperature was raised to 85°C, followed by pH adjustment to about 11 using caustic solution. The mix was stirred for 30 min, and finally cooled to give a finished smooth phase.
  • Tablet C is a comparative example of a detergent tablet without a mixed sodium and potassium soap, and without cationic polymer.
  • Tablet D is a comparative example of a detergent tablet comprising cationic polymer, but not a mixed sodium and potassium soap.
  • Tablet E is an example of a detergent tablet according to the invention comprising cationic polymer and a mixed sodium and potassium soap.
  • Table 3 Information on compounds used in the examples.
  • PEG 4000 polyethylene glycol, average M w 4000 g/mol TAED (83%) tetraacetyldiethylenediamine 83% Tween 40 polyoxyethylene (20) sorbitan monopalmitate
  • Preparation of the multi-phase detergent tablets was done using the following steps.
  • Each of the smooth phases was prepared by heating the composition as exemplified in table 2 under 'Smooth phase' to 80°C, followed by casting into moulds and cooling to 20°C.
  • the sodium and potassium soaps were formed in situ, resulting into the formation of firm circular smooth phases, weight 5.5 gram, 45 mm diameter, and about 2-3 mm thickness.
  • a powder was made of the composition as in table 2 under 'base powder'. This base-powder was mixed and pre-granulated.
  • the cationic polymer UCARETM LR-400
  • UCARETM LR-400 was co-granulated with sodium sulphate and PEG 4000. This co-granule was added to the other compounds of the post-dose premix (as in table 2).
  • Next step was dosing the post-dose premix to the pre-granulated base powder.
  • the particulate composition of pre-granulated base powder and post-dose premix was inserted into a 45 mm die of a tabletting machine, followed by a flattening step. The whole material was compressed at 30 kN into a single tablet.
  • a smooth phase was then applied to the tablet by glueing, on top of the intermediate phase. This resulted into a multi-phase detergent tablet with a total weight as indicated in table 2.
  • Washing of textile with detergent tablet D shows improved softness of the textile compared to washing with conventional detergent tablet C.
  • the softness even improves further when washing textile with detergent tablet E (according to the invention) compared to the softness of textile washed with detergent tablet D.
  • the effect is more pronounced after having washed the textile 4 times, as compared to washing only once.
  • Best textile softness results are obtained after washing with a detergent tablet that contains a mixed sodium-potassium soap in the smooth phase, a cationic polymer in the solid compressed particulate phase, and that is substantially free from LAS in the smooth phase.

Claims (21)

  1. Mehrphasen-Waschmitteltablette, die eine glatte Phase umfasst, wobei die glatte Phase eine gemischte Natrium-Kalium-Seife umfasst, die ein Gewichtsverhältnis von Natriumseife und Kaliumseife in der glatten Phase von 5:1 bis 1:5 hat.
  2. Waschmitteltablette gemäß Anspruch 1, die ein Gewichtsverhältnis von Natriumseife und Kaliumseife in der glatten Phase von 4:1 bis 1:4 hat.
  3. Waschmitteltablette gemäß Anspruch 1, die ein Gewichtsverhältnis von Natriumseife und Kaliumseife in der glatten Phase von 2:1 bis 1:4 hat.
  4. Waschmitteltablette gemäß Anspruch 1, die ein Gewichtsverhältnis von Natriumseife und Kaliumseife in der glatten Phase von 1:1 bis 1:4, bevorzugter von 1:1 bis 1:3, hat.
  5. Waschmitteltablette gemäß einem der vorangehenden Ansprüche, wobei die Konzentration an gemischter Natrium-Kalium-Seife von 2 bis 50 Gewichts-%, bevorzugter von 4 bis 45 Gewichts-%, am bevorzugtesten von 5 bis 40 Gewichts-%, bezogen auf das Gewicht der glatten Phase, ist.
  6. Waschmitteltablette gemäß einem der vorangehenden Ansprüche, wobei das Gewichtsverhältnis zwischen C12-C14- und C16-C18-Fettsäuren in der glatten Phase von 25:1 bis 1:6, bevorzugter von 15:1 bis 1:4, am bevorzugtesten von 10:1 bis 1:3 ist.
  7. Waschmitteltablette gemäß einem der vorangehenden Ansprüche, wobei die glatte Phase im Wesentlichen frei von anionischen Nicht-Seifen-Tensiden ist.
  8. Waschmitteltablette gemäß einem der vorangehenden Ansprüche, die außerdem eine fest komprimierte partikuläre Phase umfasst.
  9. Waschmitteltablette gemäß einem der Ansprüche 1 bis 7, die ein kationisches Polymer umfasst.
  10. Waschmitteltablette gemäß Anspruch 9, wobei das kationische Polymer ein kationisches Cellulosederivat ist.
  11. Waschmitteltablette gemäß Anspruch 9, wobei das kationische Polymer ein quaternäres Ammoniumsalz von modifizierter Cellulose ist.
  12. Waschmitteltablette gemäß Anspruch 9, wobei das kationische Polymer ein quaternäres Ammoniumsalz von Hydroxyethylcellulose ist.
  13. Waschmitteltablette gemäß einem der Ansprüche 8 bis 12, wobei das kationische Polymer in der festen komprimierten partikulären Phase vorliegt.
  14. Waschmitteltablette gemäß einem der Ansprüche 9 bis 13, wobei die Konzentration an kationischem Polymer von 0,05 bis 2 Gewichts-%, bevorzugter von 0,1 bis 1 Gewichts-%, bezogen auf das Waschmitteltablettengewicht, ist.
  15. Waschmitteltablette gemäß einem der Ansprüche 9 bis 13, wobei das durchschnittliche Molekulargewicht des kationischen Polymers 10 000 bis 850 000 Dalton, bevorzugter 10 000 bis 500 000 Dalton ist.
  16. Waschmitteltablette gemäß einem der Ansprüche 9 bis 13, wobei das kationische Polymer einen Stickstoffgehalt von 0,01 bis 2,2 %, bevorzugter von 0,3 bis 1,4 %, hat.
  17. Waschmitteltablette gemäß einem der Ansprüche 9 bis 13, wobei das Gewichtsverhältnis von kationischem Polymer zu der gemischten Natrium-Kalium-Seife in der glatten Phase von 1:100 bis 1:1, bevorzugter von 1:50 bis 1:3, ist.
  18. Waschmitteltablette gemäß einem der Ansprüche 9 bis 17, wobei das kationische Polymer in einem Co-Korn enthalten ist, wobei das Co-Korn außerdem ein Bindemittel umfasst.
  19. Waschmitteltablette gemäß Anspruch 18, wobei das Co-Korn außerdem ein organisches oder ein anorganisches Salz umfasst.
  20. Verfahren zur Herstellung einer Waschmitteltablette gemäß einem der Ansprüche 9 bis 17, umfassend die Schritte:
    a) Einsetzen einer partikulären Zusammensetzung in eine Tablettenform, um eine feste komprimierte partikuläre Phase zu bilden;
    b) gegebenenfalls Einsetzen einer zweiten partikulären Zusammensetzung in die Tablettenform oben auf die erste partikuläre Zusammensetzung, um eine zweite Region in der festen Phase zu bilden;
    c) gegebenenfalls Komprimieren der ersten und der zweiten partikulären Zusammensetzung zu einer Tablette, die zwei getrennte Regionen mit unterschiedlichen Zusammensetzungen umfasst;
    d) gegebenenfalls Auftragen von Leim auf die partikuläre(n) Zusammensetzung(en);
    e) Einsetzen einer oder mehrerer glatten Phasen in die Tablettenform;
    f) Co-Kompression der komprimierten partikulären Zusammensetzung(en) und der glatten Phase(n), um eine komprimierte Waschmitteltablette zu bilden, die getrennte glatte und feste komprimierte partikuläre Phasen umfasst.
  21. Verfahren zur Herstellung einer Waschmitteltablette gemäß Anspruch 18 oder 19, umfassend die Schritte:
    a) Granulieren eines Gemisches, das ein kationisches Polymer und Bindemittel umfasst, um ein Co-Korn zu bilden;
    b) Mischen des Co-Korns mit einer partikulären Zusammensetzung;
    c) Einsetzen der partikulären Zusammensetzung in eine Tablettenform, um eine feste komprimierte partikuläre Phase zu bilden;
    d) gegebenenfalls Einsetzen einer zweiten partikulären Zusammensetzung in die Tablettenform auf die erste partikuläre Zusammensetzung, um eine zweite Region in der festen Phase zu bilden;
    e) gegebenenfalls Komprimieren der ersten und zweiten partikulären Zusammensetzung zu einer Tablette, die zwei unterschiedliche Regionen mit unterschiedlichen Zusammensetzungen umfasst;
    f) gegebenenfalls Auftragen von Leim auf die partikuläre(n) Zusammensetzung(en);
    g) Einsetzen von einer oder mehreren glatten Phase(n) in die Tablettenform;
    h) Co-Kompression der komprimierten partikulären Zusammensetzung(en) und der glatten Phase(n), um eine komprimierte Waschmitteltablette zu bilden, die getrennte glatte und feste komprimierte partikuläre Phasen umfasst.
EP06120889A 2006-09-19 2006-09-19 Waschmitteltablette Not-in-force EP1903100B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES06120889T ES2327953T3 (es) 2006-09-19 2006-09-19 Composiciones detergentes de pastilla.
EP06120889A EP1903100B1 (de) 2006-09-19 2006-09-19 Waschmitteltablette
AT06120889T ATE432976T1 (de) 2006-09-19 2006-09-19 Waschmitteltablette
DE602006007142T DE602006007142D1 (de) 2006-09-19 2006-09-19 Waschmitteltablette

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06120889A EP1903100B1 (de) 2006-09-19 2006-09-19 Waschmitteltablette

Publications (2)

Publication Number Publication Date
EP1903100A1 EP1903100A1 (de) 2008-03-26
EP1903100B1 true EP1903100B1 (de) 2009-06-03

Family

ID=37651025

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06120889A Not-in-force EP1903100B1 (de) 2006-09-19 2006-09-19 Waschmitteltablette

Country Status (4)

Country Link
EP (1) EP1903100B1 (de)
AT (1) ATE432976T1 (de)
DE (1) DE602006007142D1 (de)
ES (1) ES2327953T3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021115724A1 (en) 2019-12-11 2021-06-17 Unilever Ip Holdings B.V. Detergent composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023025766A1 (en) 2021-08-25 2023-03-02 Unilever Ip Holdings B.V. Detergent composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2147674C (en) * 1994-05-16 1999-03-30 David Robert Zint Shaped semi-solid or solid dishwashing detergent
EP1354938A1 (de) * 2002-04-18 2003-10-22 Unilever N.V. Waschmitteltabletten mit verbessertem Auflöseverhalten
ES2287408T3 (es) * 2002-10-01 2007-12-16 Unilever N.V. Composiciones detergentes.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021115724A1 (en) 2019-12-11 2021-06-17 Unilever Ip Holdings B.V. Detergent composition
EP4073216B1 (de) * 2019-12-11 2023-08-09 Unilever IP Holdings B.V. Reinigungsmittelzusammensetzung

Also Published As

Publication number Publication date
ATE432976T1 (de) 2009-06-15
DE602006007142D1 (de) 2009-07-16
ES2327953T3 (es) 2009-11-05
EP1903100A1 (de) 2008-03-26

Similar Documents

Publication Publication Date Title
EP1705241B1 (de) Körperförmige Wasch- oder Reinigungsmittelzusammensetzungen
EP2179023A1 (de) Reinigungsmitteltablette
US20020028759A1 (en) Detergent compositions
EP1669438B1 (de) Wasch- und Reinigungsmitteltablette
EP1511834B1 (de) Waschmitteltabletten
EP1239029B1 (de) Wasch- oder Reinigungsmittel
EP1418224B1 (de) Verfahren zur Herstellung einer Reinigungsmitteltablette
EP1375636B1 (de) Waschmitteltabletten
EP1405901B1 (de) Waschmittel
EP1405902A1 (de) Wasch- und Reinigungsmittel
EP1903100B1 (de) Waschmitteltablette
EP1574563B1 (de) Verwendung von Waschmitteltabletten
EP1405900B1 (de) Waschmittelzusammensetzungen
US6310028B1 (en) Water-softening and detergent compositions containing partially hydrated Na acetate
EP1371720B1 (de) Waschmitteltabletten
US6153574A (en) Water-softening and detergent compositions
EP1746151A1 (de) Wasch- und Reinigungsmitteltabletten
EP1676904B1 (de) Wasch- und Reinigungsmittelformkörper
EP1496105B1 (de) Waschmittelzusammensetzungen
EP1522575B1 (de) Waschmittelzusammensetzungen
EP1469061B1 (de) Verfahren zur Herstellung Mehrphasiger Reinigungstabletten mit einer glatten Phase
EP1516916A1 (de) Waschmittelzusammensetzung
EP1746152A1 (de) Wasch- oder Reinigungsmittel
EP1496106A1 (de) Reinigungsmittelzusammensetzung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070907

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602006007142

Country of ref document: DE

Date of ref document: 20090716

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2327953

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090903

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091003

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091003

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090903

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

26N No opposition filed

Effective date: 20100304

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090904

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20100927

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20100930

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20100927

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20100927

Year of fee payment: 5

Ref country code: DE

Payment date: 20100929

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090919

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090603

BERE Be: lapsed

Owner name: UNILEVER N.V.

Effective date: 20110930

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20110919

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110930

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602006007142

Country of ref document: DE

Effective date: 20120403

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120403

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110930

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110919

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20131029

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110920