WO2002062939A1 - Compositions de nettoyage - Google Patents

Compositions de nettoyage Download PDF

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Publication number
WO2002062939A1
WO2002062939A1 PCT/EP2002/000945 EP0200945W WO02062939A1 WO 2002062939 A1 WO2002062939 A1 WO 2002062939A1 EP 0200945 W EP0200945 W EP 0200945W WO 02062939 A1 WO02062939 A1 WO 02062939A1
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WO
WIPO (PCT)
Prior art keywords
water
tablet
weight
disintegrant
composition
Prior art date
Application number
PCT/EP2002/000945
Other languages
English (en)
Inventor
Jelles Vincent Boskamp
Ian Callaghan
Somdath Choennie
Paulus Jacobus Maria Loomans
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Lever Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc, Hindustan Lever Ltd filed Critical Unilever N.V.
Priority to AT02716699T priority Critical patent/ATE520768T1/de
Priority to EP02716699A priority patent/EP1358311B1/fr
Publication of WO2002062939A1 publication Critical patent/WO2002062939A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention relates to cleaning compositions in the form of tablets. These tablets are intended to disintegrate when placed in water and thus are intended to be consumed in a single use.
  • the tablets may be suitable for use in machine dishwashing, the washing of fabrics or other cleaning tasks.
  • Products in tablet form have several advantages over powdered products: for example, they do not require measuring and are thus easier to handle and dispense into the wash-load, and they are more compact, hence facilitating more economical storage.
  • Detergent compositions in tablet form and intended for fabric washing have been described in a number of patent documents including, for example GB 911204, EP-A-711827, WO-98/42817 and O-99/20730 (all Unilever), GB 1,029,263 (Procter & Gamble), US 3953350 (Kao) , DE 19 637 606 (Henkel) and are now sold commercially. Tablets of composition suitable for machine dishwashing have been disclosed in EP-A-318204, WO96/23530 and US-A-5691293 and are sold commercially.
  • Tablets of a cleaning composition are generally made by compressing or compacting a composition in particulate form. Although it is desirable that tablets have adequate strength when dry, yet disperse and dissolve quickly when brought into contact with water, it can be difficult to obtain both properties together. Tablets formed using a low compaction pressure tend to crumble and disintegrate on handling and packing; while more forcefully compacted tablets may be sufficiently cohesive but then fail to disintegrate or disperse to an adequate extent in the wash. Tabletting will often be carried out with enough pressure to achieve a compromise between these desirable but antagonistic properties. However, it remains desirable to improve one or other of these properties without detriment to the other so as to improve the overall compromise between them. US-A-3018267 (Procter & Gamble) taught that the force, and hence pressure, applied when compacting a composition into tablets should be limited, or else the tablets would take too long to dissolve.
  • a tablet contains organic surfactant, this can function as a binder, plasticising the tablet. However, it can also retard disintegration of the tablet by forming a viscous gel when the tablet comes into contact with water. Thus, the presence of surfactant can make it more difficult to achieve both good strength and speed of disintegration: the problem has proved especially acute with tablets formed by compressing powders containing surfactant and built with insoluble detergency builder such as sodium aluminosilicate (zeolite) .
  • insoluble detergency builder such as sodium aluminosilicate (zeolite)
  • EP-A-711 827 (Unilever) teaches the use of sodium citrate for this purpose and EP-A-838519 and WO 00/32741 (both Unilever) teach the use of sodium acetate trihydrate for this purpose .
  • Typical water-swellable agents which have been disclosed as possible tablet disintegrating agents are starches, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinyl pyrrolidones, gelatines and formaldehyde casein as well as a wide variety of clay minerals and certain ion-exchange resins.
  • W098/55575 and DE 199 01 063 both Henkel
  • cellulose disintegrating aids with a particle size of less than 100 um in order to minimise deposition.
  • the cellulose material is mixed with a material of a given oil absorbing capacity, which includes some zeolites.
  • a water swellable disintegrating aid is co-granulated with a water-insoluble inorganic material before being incorporated into a tablet, and, the disintegrant granule is used in a tablet comprising certain water-soluble disintegration-promoting particles, or, an aluminosilicate builder and an enzyme, then the disintegration granule is more effective. Less of the disintegrating aid then needs to be used for effective disintegration of the tablet in turn lowering the probability of deposition of the disintegrating aid on the substrate being cleaned.
  • the present invention provides a tablet of compacted particulate detergent composition comprising non-soap surfactant and detergency builder, wherein the tablet or a discrete region thereof comprises; a) disintegrant granules comprising a water insoluble inorganic material and a water swellable agent which, in its anhydrous state, comprises no more than 20% by weight of the combined weight of the inorganic material and the water swellable agent, and b) water-soluble disintegration-promoting particles containing at least 40%, by weight of the particles, of one or more materials selected from the group consisting of; i) compounds with water-solubility exceeding 50 grams per 100 grams water at 20°C,and ii) sodium tripolyphosphate containing at least 50% of its own weight of the phase I anhydrous form, and iii) sodium tripolyphosphate which is partially hydrated so as to contain water of hydration in an amount which is at least 0.5% by weight of the sodium tripolyphosphat
  • the present invention provides a tablet of compacted particulate detergent composition comprising non-soap surfactant and detergency builder, wherein the tablet or a discrete region thereof comprises; a) disintegrant granules comprising a water insoluble inorganic material and a water swellable agent which, in its anhydrous state, comprises no more than 20% by weight of the combined weight of the inorganic material and the water swellable agent, and b) 10 to 60% by weight of an aluminosilicate builder, and c) one or more detergency enzymes.
  • a process for making a tablet of compacted particulate composition comprises mixing disintegrant granules with either water-soluble disintegration-promoting particles or with aluminosilicate builder material and one or more detergency enzymes, and with other constituents of the composition to produce a particulate composition, placing a quantity of the resultant particulate composition within a mould and compacting the composition within the mould to produce the tablet.
  • a tablet of the present invention may be either homogeneous or heterogeneous.
  • 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 be of identical composition.
  • 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.
  • each discrete region of the tablet will preferably have a mass of at least 5 grams.
  • a tablet according to the invention comprises non-soap surfactant, detergency builder and a disintegrant in the form of granules, said disintegrant comprising a water- insoluble inorganic material and a water-swellable agent which in its anhydrous state comprises no more than 20% by weight of the combined weight of said inorganic material and said water-swellable agent of the granular disintegrant.
  • water-insoluble in relation to the inorganic material, is meant a compound with a solubility in water at 25°C of less than 5 grams per 100 grams of water, preferably less than 1 gram per 100 grams of water.
  • the inorganic material used in the formation of the disintegrant granules may comprise a silica.
  • the inorganic material may comprise an inorganic material which acts as a functional ingredient of the cleaning composition, for example an aluminosilicate.
  • Preferred aluminosilicates are zeolites, such as zeolites P,A,X or Y or mixtures thereof, with Zeolite P and A being preferred. Zeolite P is especially preferred.
  • a type of Zeolite P, maximum aluminimum zeolite P, known as zeolite MAP and so referred to herein e.g. DOUCIL A24 ex Ineos Silicas UK) has been found to be especially effective.
  • the granular disintegrants of the invention comprise zeolite as the inorganic material, said disintegrants are more effective if the zeolites contain relatively little water.
  • the preferred amount of water in the zeolite depends upon the type of zeolite used. For zeolites A and P, it is preferred that the amount of water is less than 21% by weight of the zeolite, more preferably less than 15% by weight, especially 8 to 13% by weight.
  • Zeolite MAP contains from about 9 to about 12% by weight of water and is especially useful according to the present invention.
  • zeolite P we have found that good results are obtained from the partially hydrated material, e.g. zeolite MAP. As the water content in zeolite P is increased above this range (12% by weight for zeolite MAP) , the effectiveness as a disintegrant decreases with increasing water content . Fully hydrated zeolite P (denoted "DOUCIL" A28 in the examples herein) has been found to be less effective as a disintegrant when compared to zeolite MAP.
  • Alkali metal aluminosilicates are used in detergent compositions as builders as further described hereinbelow.
  • a composition according to the invention comprises an alkali metal aluminosilicate as a detergency builder
  • at least a part of the aluminosilicate constituent of the cleaning composition is employed as the inorganic material used in the formation of the disintegrant granules.
  • the builder e.g. aluminosilicate constituent, typically comprises 10 to 60% by weight of the total composition.
  • zeolite when used in the disintegrant granules and as a detergency builder in the composition, then at least 1% by weight of the total weight of the composition comprises a zeolite constituent employed in the form of disintegrant granules .
  • the water-swellable agent preferably comprises, in its anhydrous state, no more than 15% by weight, preferably no more than 10% by weight, of the combined weight of said inorganic material and said water-swellable agent of the granular disintegrant.
  • the water-swellable agent comprises, in its anhydrous state, no more than 8% by weight, e.g. 7.5% or less of the combined weight of said inorganic material and said agent.
  • at least 1% of the combined weight of said inorganic material and said water-swellable agent in the granules comprises water- swellable agent. It is preferred that the water swellable agent comprises in its anhydrous state 1 to 15% by weight of the combined weight of said inorganic material and said water-swellable agent.
  • a relatively small amount of the water-swellable agent may, surprisingly, be used in the tabletted composition of the invention whilst still providing an acceptable effect.
  • the amount of water-swellable based on the total weight of the tabletted composition, is less than 2% by weight, preferably less than 1% of the composition.
  • at least 0.2% by weight of the water- swellable agent is present in the tabletted composition.
  • the water-swellable agent comprises polymer, often a wholly or partially cross-linked polymer, e.g. natural cellulose, cross-linked cellulose, (sodium) carboxymethyl cellulose, cross-linked sodium carboxymethyl cellulose, pre-gelatinised starch, cross-linked starch or cross-linked polyvinyl pyrrolidone.
  • polymer often a wholly or partially cross-linked polymer, e.g. natural cellulose, cross-linked cellulose, (sodium) carboxymethyl cellulose, cross-linked sodium carboxymethyl cellulose, pre-gelatinised starch, cross-linked starch or cross-linked polyvinyl pyrrolidone.
  • Aquasorb A500 ex Hercules
  • Ac-Di-Sol and Nilyn XL90 ex FMC Corporation, USA
  • the water swellable agent in the disintegrant granule is preferably a cross-linked carboxymethyl cellulose, such as Aquasorb A500, Ac-Di-Sol and Nilyn as mentioned above. It is believed that these cross-linked carboxymethyl celluloses have particularly suitable levels of cross- linking and/or degree of substitution for use in the present invention.
  • compositions of the invention will contain from 1% to 20% by weight of the disintegrant granules based on the total weight of the compositions, preferably 2 to 15%, more preferably 3 to 10%, e.g. 4 to 8% by weight. If the granules are included to aid dissolution only of the tablets rather than disintegration, then the amount of the granules in the tablets could be as low as 1% by weight.
  • the water-swellable agent preferably has an average primary particle size up to about 600um, but, conveniently, has an average primary particle size of no more than 200 urn, preferably no more than lOOum.
  • the disintegrant granules When the water insoluble inorganic material in the disintegrant granule is a zeolite it is preferred that the disintegrant granules have a mean particle size in the range 700 to 1200 micrometers. When the water insoluble inorganic material is silica it is preferred that the disintegrant granules have a mean particle size in the range 250 to 700 micrometers.
  • the water swellable agent preferably has a water-swelling capacity of at least 5 cm 3 /gram, preferably 10cm 3 /gram and more preferably 20cm 3 /gram as determined in the test described hereinbelow.
  • the disintegrant granules comprising the inorganic material and the water-swellable agent may be prepared by any of the methods that will be known to those skilled in the art, e.g. by blending the dry ingredients in a mixer (such as a Pek mixer available from George Tweedy & Co of Preston - 281b S.A. Machine) and compacting on a roller compactor (Alexanderwerk WP50 - manufactured by Alexanderwerk AG, D 5630 Rem Kunststoff 1, Germany) .
  • a mixer such as a Pek mixer available from George Tweedy & Co of Preston - 281b S.A. Machine
  • a roller compactor Alexanderwerk WP50 - manufactured by Alexanderwerk AG, D 5630 Rem Kunststoff 1, Germany
  • Silica and the water-swellable agent are blended together in appropriate portions, in a Pek mixer for 30 minutes.
  • a minimum of 2 kg of blended material so prepared is compacted by feeding into an Alexanderwerk roller compactor, fitted with a sintered block vacuum de-aeration system.
  • the roller pressure is selected according to the strength of granule desired, higher pressures leading to stronger granules. Generally, roller pressure is between 8 and 25 Mpa and a typical roller pressure is 10 Mpa.
  • the compacted material from the compactor is fed into a granulator, which forms part of the machine, and forced through a mesh and the resulting granules are then screened to the desired particle size range, e.g.
  • the granules comprise an intimate mixture of particles of water insoluble inorganic material and water-swellable agent.
  • compositions of this invention contain one or more non- soap surfactants.
  • these preferably provide from 5 to 50% by weight of the composition of the tablet or region thereof, more preferably from 8 or 9% by weight of the composition up to 35% or 40% by weight. If the tablet is composed of more than one discrete region, then these preferred amounts of surfactant may apply to the tablet as a whole.
  • the organic surfactant may be present as a component in granulated particles in an amount between 10 and 70% by weight of the particles, more preferably 15 to 50% by weight based on the total weight of the granulated particles. All the surfactant in the composition may be contained within these particles.
  • the surfactant may be anionic (soap or non-soap) , cationic, zwitterionic, amphoteric, nonionic or a combination of these.
  • anionic surfactant may be present in an amount from 0.5 to 50% by weight, preferably from 2% or 4% up to 30% or 35% or 40% by weight of the tablet or region thereof.
  • organic surfactant is likely to constitute from 0.5 to 8%, more likely from 0.5 to 5% of the composition of the tablet or region thereof and is likely to consist of nonionic surfactant, either alone or in a mixture with anionic surfactant.
  • Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art. Examples include alkyl benzene sulphonates, particularly sodium linear alkyl benzene sulphonates having an alkyl chain length of C 8 -C 15 ; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • 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 commercially significant as an anionic surfactant .
  • R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium, is also a commercially significant anionic surfactant.
  • such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired anionic surfactant and may provide 75 to 100 wt% of any anionic non-soap surfactant in the composition.
  • the amount of non-soap anionic surfactant lies in a range from 5 to 20 or 25 wt% of the tablet or region thereof.
  • soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rape seed oil .
  • 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 -2o primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine .
  • the primary and secondary alcohol ethoxylates especially the Cg- n and C 12 - 15 primary and secondary alcohols ethoxylated with an average of from 5 to 20 moles of ethylene oxide per mole of alcohol.
  • the amount of nonionic surfactant lies in a range from 4 to 40%, better 4 or 5 to 30% by weight of the composition of the tablet or region thereof.
  • Many nonionic surfactants are liquids. These may be absorbed onto particles of the composition prior to compaction into tablets.
  • Amphoteric surfactants which may be used jointly with anionic or nonionic surfactants or both include amphopropionates of the formula
  • RCO is an acyl group of 8 to 18 carbon atoms, especially coconut acyl .
  • amphoteric surfactants also includes amine oxides and also zwitterionic surfactants, notably betaines of the general formula;
  • R is an aliphatic hydrocarbon chain which contains 7 to 17 carbon atoms
  • R 2 and R 3 are independently hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms such as CH 2 OH
  • Y is CH 2 or of the form CONHCH 2 CH 2 CH 2 (amidopropyl betaine)
  • Z is either a COO " (carboxybetaine) , or of the form CHOHCH 2 S0 3 - (sulfobetaine or hydroxy sultaine) .
  • amphoteric surfactant is amine oxide of the formula
  • Ri is C ⁇ 0 to C 20 alkyl or alkenyl
  • R 2 , R 3 and R 4 are each hydrogen or Ci to C 4 alkyl, while n is from 1 to 5.
  • Cationic surfactants may possibly be used. These frequently have a quaternised nitrogen atom in a polar head group and an attached hydrocarbon group of sufficient length to be hydrophobic .
  • a general formula for one category of cationic surfactants is; where each R independently denotes an alkyl group or hydroxyalkyl group of 1 to 3 carbon atoms and R h denotes an aromatic, aliphatic or mixed aromatic and aliphatic group of 6 to 24 carbon atoms, preferably an alkyl or alkenyl group of 8 to 22 carbon atoms and X " is a counterion.
  • the amount of amphoteric surfactant, if any, may possibly be from 3% to 20 or 30% by weight of the tablet or region of a tablet; the amount of cationic surfactant, if any, may possibly be from 1% to 10 or 20% by weight of the tablet or region of a tablet.
  • Detergency Builder A composition which is compacted to form tablets or tablet regions typically contains a detergency builder which serves to remove or sequester calcium and/or magnesium ions in the water. Thus the builder acts as a water softener. In detergent tablets the amount of builder is likely to be from 5% to 80%, more usually 10% or 15% to 40%, 55% or 60% by weight of the tablet .
  • the detergency builder may be present in granulated particles in an amount of from 20 to 80% by weight, more preferably 20%, 25% or 30 to 60% by weight.
  • Detergency builders may be provided wholly by water soluble materials, or may be provided in large part or even entirely by water-insoluble material with water-softening properties.
  • Alkali metal aluminosilicates are strongly favoured as environmentally acceptable detergency builders for fabric washing, and are preferred in this invention.
  • Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula:
  • These materials contain some bound water (indicated as xH 2 0) and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 Si0 2 units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion-exchange materials are described, for example, in GB 1 429 143
  • zeolites A and X the newer zeolite P described and claimed in EP 384 070 (Unilever) and mixtures thereof.
  • This form of maximum aluminium zeolite P is also referred to as "zeolite MAP" as discussed hereinabove and one commercial form thereof is available under the trade name "DOUCIL A2 " from Ineos Silicas UK.
  • Conceivably a detergency builder could be a layered sodium silicate as described in US 4 664 839.
  • 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 Si0 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 such as those having the general formula NaMSi x 0 2 ⁇ + ⁇ .y H 2 ⁇ 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 can be used.
  • the less preferred category of water-soluble phosphorus- containing inorganic softeners includes the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates .
  • Specific examples of inorganic phosphate detergency builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates .
  • Non-phosphorus water-soluble detergency builders may be organic or inorganic .
  • Inorganics that may be present include alkali metal (generally sodium) carbonate; while organics include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates , dipicolinates and hydroxyethyliminodiacetates .
  • Tablet compositions preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which have some function as water-softening agents and also inhibit unwanted deposition onto fabric from the wash liquor.
  • the tablet contains water soluble builder it is preferably present in an amount of from 10 to 80% by weight based on the total weight of the tablet or region thereof. Where the tablet contains water in-soluble builder it is preferably present in an amount of from 5 to 80% by weight based on the total weight of the tablet or region thereof.
  • Tablets comprising from 4 to 50% by weight of surfactant and from 5 to 80% by weight of builder are especially preferred for fabric washing tablets. Tablets comprising from 1 to 5% by weight of surfactant and from 50 to 98% of detergency builder are especially preferred for machine dishwashing tablets.
  • the percentage ranges for the components referred to herein may apply to the overall composition of the tablet, as well as to at least one region of the tablet.
  • the compositions of the invention in either the whole tablet or in a region thereof, contain water-soluble isintegration promoting particles in addition to the disintegrant granules. These particles may also be present according to the second aspect of the invention. It is preferred that such disintegration-promoting particles make up from 2%, 3%, 5%, 8% or 10% up to 15%, 20%, 25% or 30% by weight of the composition of the tablet or region thereof. It is especially preferred that such disintegration-promoting particles make up from 5% to 25% by weight of the composition, based on the total weight of the composition.
  • Such soluble particles typically contain at least 40% (of their own weight) of one or more materials which is other than soap or organic surfactant and which has a solubility in deionised water of at least 30g/100g at 20°C.
  • at least a part of the water-soluble disintegration-promoting particles is added to a pre- granulated portion of the composition which may contain organic surfactant and/or detergency builder used to produce the tablet.
  • a proportion of such soluble material may also be included in granulated particles, in an amount of preferably 1 to 25% by weight, more preferably 3 or 5% to 10% or 15% by weight of these granulated particles.
  • this water-soluble material is selected from compounds containing at least 40% (by weight of the particles) of one or more materials selected from the group consisting of; compounds with a water-solubility exceeding 50 grams/100 grams in water at 20°C; or sodium tripolyphosphate containing at least 50% of its own weight of the phase I anhydrous form; or sodium tripolyphosphate which is partially hydrated so as to contain water of 5 hydration in an amount which is at least 0.5% by weight of the sodium tripolyphosphate in the particles.
  • these disintegration- promoting particles can also contain other forms of 10 tripolyphosphate or other salts within the balance of their composition.
  • the material in such water-soluble disintegration- promoting particles can function as a detergency builder, 15 (as is the case with sodium tripolyphosphate) then of course it contributes to the total quantity of detergency builder in the tablet composition.
  • a solubility of at least 50 g/lOOg of deionised water at 2020°C is an exceptionally high solubility: many materials which are classified as water soluble are less soluble than this.
  • this highly water soluble material is incorporated as particles 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.
  • Preferred water-soluble materials having a solubility exceeding 50 grams/100 grams of deionised water at 20°C are sodium citrate dihydrate, urea, and sodium acetate.
  • the sodium acetate may be in a partially or fully hydrated form (trihydrate) .
  • Sodium acetate trihydrate is especially preferred.
  • the highly water-soluble material is a salt which dissolves in water in an ionised form. As such a salt dissolves it leads to a transient local increase in ionic strength which can assist disintegration of the tablet by preventing nonionic surfactant from swelling and inhibiting dissolution of other materials.
  • tablets of this invention may contain water- soluble salt, with a solubility exceeding 50g/100g of deionised water at 20°C, both as a small percentage within the said granulated particles and as separate particles which are mixed with them.
  • such highly water soluble salt may be present in an amount of from 0 to 30% by weight of those particles, preferably of from 3 to 10% or 15% thereof, while the materials added to those particles before tabletting may be such highly soluble salts in an amount of from 2 or 5% up to 15% by weight of the whole tablet formulation.
  • the said particles which promote disintegration are particles which contain sodium tripolyphosphate with more than 50% (by weight of the particles) of the anhydrous phase I form, and, which is partially hydrated so as to contain water of hydration in an amount which is at least 1% by weight of the sodium tripolyphosphate .
  • 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.
  • a process for the manufacture of particles containing a high proportion of the phase I form of sodium tripolyphosphate by spray drying below 420°C is given in US-A-4 536 377.
  • These particles should also contain sodium tripolyphosphate which 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 1 to 4%, or it may be higher. Indeed fully hydrated sodium tripolyphosphate may be used to provide these particles.
  • the remainder of the tablet composition used to form the tablet or region thereof may include additional sodium tripolyphosphate.
  • This may be in any form, including sodium tripolyphosphate with a high content of the anhydrous phase II form. Suitable material is commercially available. Suppliers include Rhone-Poulenc, France and Rhodia, UK.
  • a zero-phosphate tablet in accordance with this invention may utilise a suitable amount, e.g. 15% by weight or more of disintegration-promoting material with solubility of at least 50gm/100gm at 20°C.
  • Other countries permit the use, or at least some limited use, of phosphates, making it possible to use some sodium tripolyphosphate .
  • Optional water-soluble organic polymer Tablets of the present invention may include a water- soluble organic polymer which is solid at 25°C to act as a binder for the particulate composition when compacted. This may be included in granulated particles containing organic surfactant and/or detergency builder.
  • solid is used here to denote materials which have the appearance of an immobile solid at 25°C and can be handled as solids. They contrast with liquids which, even if viscous, can be seen to be capable of fluid flow.
  • Organic polymers are in general amorphous materials which are strictly classified as supercooled liquids - but of such high viscosity that for practical purposes they are solid.
  • water-soluble is used here in relation to this organic polymer to indicate that when the polymer is placed in water it appears, on visual inspection, to dissolve. Whether the solution is a true isotropic solution or has some colloidal character is not important to this invention.
  • the polymer material should melt at a temperature of at least 35°C, better 40°C or above, which is above ambient temperatures in many temperate countries.
  • the melting temperature is somewhat above 40°C, so as to be above the ambient temperature .
  • Some polymers which may be used are solids at temperatures up to 100°C, that is to say they retain a solid appearance even though they are in an amorphous state . They may soften and melt to a mobile liquid on heating further, or may decompose without melting on heating sufficiently in excess of 100°C. Such polymers will generally be added as a powder during the course of granulation. Another possibility would be addition as a solution in a volatile organic solvent, but that is not preferred.
  • polymers which may be used melt to liquid form at temperatures not exceeding 80°C and may be sprayed as molten liquid onto the surfactant and builder mixture during the course of granulation.
  • Organic polymers are in general amorphous solids.
  • a significant parameter characterising amorphous solids is their glass transition temperature.
  • an amorphous hydrophilic polymer absorbs moisture, the moisture acts as a plasticiser and lowers the glass transition temperature of the polymer.
  • Suitable polymers may have a glass transition temperature, when anhydrous, which is from 300 to 500K (i.e. approximately 25°C to 225°C) but may be incorporated in a moisture-containing state so that their glass transition temperature is lower.
  • Preferred polymer materials are synthetic organic polymers especially polyethylene glycol .
  • Polyethylene glycol of average molecular weight 1500 melts at 45°C and has proved suitable.
  • Polyethylene glycol of higher molecular weight can also be used (PEG 4000 melts at 56°C and PEG 6000 at 58°C) .
  • Other possibilities are polyvinylpyrrolidone, and polyacrylate and water-soluble acrylate copolymers .
  • the amount of water-soluble polymer included in particles which may also contain organic surfactant and detergency builder is preferably between 0.2% or 0.5% or 1% and 15% by weight of the particles, possibly at least 1.5 or 3%. Further preferred is that the amount is not over 7 or 10% by weight.
  • the amount of water-soluble polymer present may be defined in terms of the whole composition of the tablet or region thereof, in which case, it is desirably present in an amount of between 0.5% and 5% by weight, more preferably 0.5 to 4% by weight. In some cases the addition of the polymer has been found to hinder slightly, the disintegration of the tablet.
  • the level of the water-soluble polymer is preferably in the range 0.5 to 2% by weight.
  • Optional bleach system is preferably in the range 0.5 to 2% by weight.
  • Tabletted compositions 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 composition of the tablet or region thereof.
  • 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
  • Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED) , now in widespread commercial use in conjunction with sodium perborate and sodium percarbonate; and perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the quaternary ammonium and phosphonium bleach activators disclosed in US 4 751 015 and US 4 818 426 (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-458 397, EP-A-458 398 and EP-A-549 272.
  • a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate .
  • a bleach stabiliser such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate .
  • Tablets according to the second aspect of the invention comprise one or more detergency enzymes.
  • the enzyme is selected from amylase, protease, cellulase, lipase and mixtures thereof.
  • the aforementioned enzymes are designed to remove a variety of soils and stains from fabrics.
  • Detergent tablets according to the first aspect of the invention may also comprise one or more detergency enzymes .
  • Detergency enzymes are well known in the art for their ability to degrade and aid in the removal of, various soils and stains.
  • suitable proteases are Maxatase (Trade Mark), as supplied by Gist-Brocades N.V. , Delft, Holland, and Alcalase (Trade Mark) , and Savinase (Trade Mark) , as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the composition of the tablet or region thereof; and these granules or marumes present no problems with respect to compaction to form a tablet.
  • the 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.
  • An antifoam material is advantageously included if organic surfactant is present, 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 863A (Unilever) .
  • Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbed water-soluble carbonate-based inorganic carrier material.
  • Antifoam granules may be present in an amount up to 5% by weight of the composition of the tablet or region thereof.
  • a tablet of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, eta- or disilicate.
  • an alkali metal silicate particularly sodium ortho-, eta- or disilicate.
  • the presence of such alkali metal silicates at levels, for example, of 0.1 to 10 wt%, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits in manufacture of the particulate material which is compacted into tablets.
  • a composition for fabric washing will generally not contain more than 15wt% silicate.
  • a tablet for machine dishwashing will frequently contain at least 20wt% silicate.
  • the starting particulate composition from which the tablets are produced may in principle have any bulk density
  • the present invention may be especially relevant to tablets of detergent composition made by compacting powders of relatively high bulk density, because of their greater tendency to exhibit disintegration and dispersion problems.
  • Such tablets have the advantage that, 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 g/litre, preferably at least 500 g/litre, and possibly at least 600 g/litre.
  • Granular detergent compositions of high bulk density prepared by granulation and densification in a high-speed mixer/granulator, as described and claimed in EP-A-340 013 (Unilever) , EP-A-352 135 (Unilever) , and EP-A-425 277 (Unilever) , or by the continuous granulation/densification processes described and claimed in EP-A-367 339 (Unilever) and EP-A-390 251 (Unilever) , are inherently suitable for use in the present invention.
  • WO- A-98/11193 Another particularly suitable process for the preparation of a high-bulk density detergent powder is described in WO- A-98/11193 (Unilever) .
  • a feedstock of the starting acid for production of the anionic surfactant is partially neutralised, for example by sodium hydroxide, before being fed into a high-speed mixer densifier (e.g. Lodige CB 30 Recycler) where the partially neutralised acid feedstock is completely neutralised, whilst being mixed with the majority of other components of the detergent base powder granule.
  • This powder can be further densified by treating in a moderate speed mixer (e.g. Lodige KM 300 mixer) , before which stage further detergency builder may be added.
  • a moderate speed mixer e.g. Lodige KM 300 mixer
  • the water-soluble polymer material is preferably added before the further densification step, although it may be added in the first mixer.
  • the water-soluble polymer material may be heated to a temperature considerably above its melting point to obtain a free-flowing liquid.
  • the resulting powder can be cooled and dried using a fluid bed, after which any desired particle size control can be exercised.
  • any separate particles containing further components of the finished formulation can be mixed with the base powder prior to compaction.
  • Particle size control Particle sizes can be controlled in the manufacturing process of any particles included in the composition. Oversize particles are usually removed by sieving (for example by a Mogensen screen) at the end of the production process, followed by milling and recycling of the removed oversize fraction. Undersize particles can also be removed by sieving, or if the manufacturing process employs a fluidised bed then undersized particles may be entrained in the air stream and subsequently recovered from it for recycling to the granulation stage. It is preferred that the average particle size of granulated particles forming the particulate composition from which the tablet is formed is between 400 and 1100 micrometers, preferably between 500 and 1000 micrometers. Preferably no more than 5% of these particles are smaller than 200 micrometers while no more than 5% are larger than 1400 micrometers.
  • Materials which are mixed with the granulated particles may also comply with these requirements concerning particle size. These materials (post-added) typically comprise from 5% - 60% by weight of the total weight of the final composition, more usually 35 to 55% by weight.
  • Tabletting entails compaction of a particulate composition.
  • tabletting machinery is known, and can be used. Generally it will function by stamping a quantity of the particulate composition which is confined in a die. Tabletting 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 tabletting machinery at an elevated temperature. This will of course supply heat to the tabletting machinery, but the machinery may be heated in some other way also. If 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 grams, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
  • the tablets may be of any shape. However, for ease of packaging they are preferably blocks of substantially uniform cross- section, such as cylinders or cuboids.
  • the overall density of a tablet for fabric washing preferably lies in a range from 1040 or 1050g/litre preferably at least HOOg/litre up to 1400g/litre.
  • the tablet density may well lie in a range up to no more than 1350 or even 1250g/litre.
  • the overall density of a tablet of some other cleaning composition such as a tablet for machine dishwashing or as a bleaching additive, may range up to 1700g/litre and will often lie in a range from 1300 to 1550g/litre.
  • the detergent tablet may be made by a process which comprises mixing the disintegrant granules with either the water-soluble disintegration-promoting particles or with the aluminosilicate builder material and one or more detergency enzymes, and with the other constituents of the composition, placing a quantity of the resultant particulate composition within a mould and compacting the composition within the mould to produce the tablet. Tablet testing - disintegration
  • the speed of disintegration of the tablets in the examples was measured by means of a test procedure under static conditions in which a pre-weighed tablet was placed on a metal grid with 1 X 1 cm mazes and the tablet and grid was then immersed in a suitable amount of 15° FH (French Hardness) tap water at 10°C or 20°C so that the tablet when immersed is covered by 2cm of water. After 60 seconds the metal grid is carefully taken out of the water and the wet tablet residue is weighed. If the tablet had fully disintegrated in this time then the time taken for 100% disintegration is recorded.
  • FH Frnch Hardness
  • the tablets exhibit 50% or more disintegration in the above test, more preferably 60% or more, most preferably 70% or more.
  • DFS diametrical fracture stress in Pascals
  • F max is the applied load in Newtons to cause fracture
  • D is the tablet diameter in metres
  • t is the tablet thickness in metres.
  • 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 tablets when used as fabric washing tablets in an automatic washing machine, may be added either to the powder dispensing draw, or, directly in to the washing drum. This may occur either manually or automatically.
  • the detergent/cleaning tablets of the invention are suitable for use in what is known in the art as ⁇ homecare' applications. That is, detergent tablets which are suitable for use in cleaning and maintainance operations typically carried out around the home. It does not include operations carried out directly on a human or animal body which are known as personal care' applications.
  • ⁇ homecare' detergent tablets include; laundry tablets, (machine) dishwashing tablets, hard-surface cleaning tablets, toilet-cleaning tablets, bleaching tablets, water- softening tablets etc.
  • NDOM non detergent organic matter
  • SOKALAN HP23 is a grafted co-polymer of polyethylene oxide and polyvinylacetate ex BASF, Germany.
  • DEQUEST 2047 is ethylene diamine tetra methylene phosphonate ex Monsanto.
  • SOKALAN CP5 is a co-polymer of acrylic acid and maleic acid ex BASF, Germany.
  • Disintegrant granules used either a zeolite or silica as the water-insoluble inorganic material.
  • the water-swellable agent was chosen from one of four types of water-swellable agents.
  • the granules had the compositions given in table 2 and were sieved to collect the fraction having a particle size of 250 to 700um or 700 to 1200 urn. Unless otherwise stated the particle size is or 700 to 1200 urn.
  • the amounts given in Table 2 are the percentages of each ingredient in the disintegrant granule and add up to 100% by weight based on the total weight of the granule .
  • Comparative example CI contains no disintegrant granule.
  • Comparative example C2 also contains no disintegrant granule but contains Aquasorb A500 cross- linked CMC added as a separate ingredient as well as some additional zeolite powder.
  • the amounts in Table 3 add up to 100% by weight .
  • each comparative composition 40g portions of each comparative composition were made into cylindrical tablets of 44.5 mm diameter and height 18-22 mm using a Graseby Specac laboratory tabletting machine.
  • the compaction pressure used for each tablet was adjusted so that the tablets were all compacted to the same diametrical fracture stress of 30 kPa.
  • the strength of the tablets, in their dry state as made on the press, was determined as their diametrical fracture stress DFS by the method detailed in the description of the invention above.
  • Examples 1 to 11 The 'stock 1' composition of table 1 was mixed with varying amounts of disintegrant granule and in some examples additional sodium acetate trihydrate/zeolite blend (99:1 parts by weight) as shown in table 4 to produce examples 1 to 11 which are examples according to the invention.
  • the amounts in Table 4 add up to 100% by weight.
  • a to E below refer to the disintegrant granule for which details are given above .
  • compositions were compacted on a Graseby Laboratory Tablet Press as detailed above for comparative examples CI and C2 above .
  • Example 3 shows improved disintegration over comparative example CI (which comprises no disintegrant granule and no acetate) . This is observed for both the smaller and larger disintegrant granule particle sizes (compare examples 3 & 7 and 4 & 8) . By increasing the particle size of the disintegrant granule, the disintegration result can be improved (compare examples 3 and 4) .
  • Examples 9 to 11 show that the following water-swellable polymers are effective as part of the disintegrant granule in the descending order; Ac-Di-Sol > Arbocel FT40 > National Starch 78-1551. This demonstrates that the cross- linked CMC disintegrants are more effective than the pre- gelatinised starch. Comparative example CI demonstrates that in the absence of either a swellable polymer or the disintegrant granule the tablet does not disintegrate but instead takes in water. Comparative example C2 demonstrates that limited disintegration is achieved when the inorganic carrier and swellable polymer are added in a non-granulated form.
  • Examples 12 to 19 The 'stock 2' composition of table 1 was mixed with varying amounts of disintegrant granule and in some examples additional sodium acetate trihydrate/zeolite blend (99:1 parts by weight) and/or PEG 1500 powder as shown in table 7 to produce examples 12 to 19 which are examples according to the invention.
  • the amounts in Table 7 add up to 100% by weight.
  • C to G in the table refers to the disintegrant granule.
  • compositions were compacted on a Graseby Laboratory Tablet Press as detailed above for comparative examples CI and C2 above.
  • Example 13 demonstrates that fully hydrating the zeolite* 1 (as used in disintegrant granules A and C-E) results in lower disintegration values.
  • Example 14 demonstrates that the zeolite known as Zeolite A4 is also not as effective as the zeolite* 1 as a carrier. Examples 17 to 19 show good results for high levels of the disintegrant granule in the absence of post-added acetate. Comparative example C3 demonstrates that disintegration is not achieved in the absence of the disintegrant granule.
  • Examples 20 to 22 were prepared by preparing a base powder by granulation as described above for the stock compositions to obtain a composition having the overall compositions given in table 9.
  • compositions were compacted on a Graseby Laboratory Tablet Press as detailed above for comparative examples CI and C2 above.

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Abstract

La présente invention concerne une pastille de composition de détergent en particules compactées qui comprend un tensioactif sans savon et un agent de détergence. Cette composition comprend: (a) des granules désintégrantes comprenant un matériau inorganique non soluble dans l'eau et un agent gonflant à l'eau qui, à l'état anhydre comprend au moins 20 % en masse de la masse combinée du matériau inorganique et de l'agent gonflant à l'eau et, soit (b) des particules favorisant la désintégration solubles dans l'eau contenant au moins 40 % en masse de ces particules de matériaux sélectionnées parmi des composés dont la solubilité dans l'eau est supérieure à 50 grammes pour 100 grammes d'eau à 200C, ou un tripolyphosphate de sodium contenant au moins 50 % de sa propre masse de la forme anhydre de phase I ou étant partiellement hydraté, soit (c) 10 % à 60 % en masse d'un agent aluminosilicate et au moins une enzyme de détergence. Ces pastilles présentent de bonnes propriétés de désintégration.
PCT/EP2002/000945 2001-02-05 2002-01-29 Compositions de nettoyage WO2002062939A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1418226A1 (fr) * 2002-11-07 2004-05-12 Unilever N.V. Composition détergente

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022268657A1 (fr) 2021-06-24 2022-12-29 Unilever Ip Holdings B.V. Composition de nettoyage monodose

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1029263A (en) * 1963-05-17 1966-05-11 Procter & Gamble Ltd Manufacture of detergent briquettes
WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
WO1998055582A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions de nettoyage sous forme de tablette
WO2000032741A1 (fr) * 1998-11-27 2000-06-08 Unilever Plc Compositions detergentes
DE19932569A1 (de) * 1999-07-13 2001-01-18 Henkel Kgaa Wasch- und Reinigungsmittelformkörper, insbesondere für das maschinelle Geschirrspülen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1029263A (en) * 1963-05-17 1966-05-11 Procter & Gamble Ltd Manufacture of detergent briquettes
WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
WO1998055582A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions de nettoyage sous forme de tablette
WO2000032741A1 (fr) * 1998-11-27 2000-06-08 Unilever Plc Compositions detergentes
DE19932569A1 (de) * 1999-07-13 2001-01-18 Henkel Kgaa Wasch- und Reinigungsmittelformkörper, insbesondere für das maschinelle Geschirrspülen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1418226A1 (fr) * 2002-11-07 2004-05-12 Unilever N.V. Composition détergente

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EP1358311A1 (fr) 2003-11-05
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EP1358311B1 (fr) 2011-08-17

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