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EP1574563B1 - Utilisation des comprimés détergents - Google Patents

Utilisation des comprimés détergents Download PDF

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Publication number
EP1574563B1
EP1574563B1 EP05075207A EP05075207A EP1574563B1 EP 1574563 B1 EP1574563 B1 EP 1574563B1 EP 05075207 A EP05075207 A EP 05075207A EP 05075207 A EP05075207 A EP 05075207A EP 1574563 B1 EP1574563 B1 EP 1574563B1
Authority
EP
European Patent Office
Prior art keywords
phase
semi
tablet
soap
solid phase
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
EP05075207A
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German (de)
English (en)
Other versions
EP1574563A1 (fr
Inventor
Felix Marco Van Der Kooij
Gilbert Martin Verschelling
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
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Filing date
Publication date
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Priority to EP05075207A priority Critical patent/EP1574563B1/fr
Publication of EP1574563A1 publication Critical patent/EP1574563A1/fr
Application granted granted Critical
Publication of EP1574563B1 publication Critical patent/EP1574563B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • This invention relates to use of a cleaning composition in the form of a tablet for use in fabric washing.
  • 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 washload.
  • Single phase tablets of a cleaning composition are generally made by compressing or compacting a quantity of the composition in particulate form.
  • WO-A-01/42416 describes the production of multi-phase moulded bodies comprising a combination of core moulded bodies and a particulate premix.
  • WO-A-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-A-00/61717 describes a detergent tablet which is characterised in that at least part of its outer surface is semi-solid. The latter disclosure states that the semi-solid layer can be rubbed onto heavily stained areas of the fabric to pretreat them, thereby assisting removal of the stains in the wash.
  • a multi-phase laundry cleaning tablet comprising a compressed particulate phase and a semi-solid phase for pretreating a region of a fabric prior to washing by rubbing the semi-solid phase on the region, wherein an intermediate phase is at least partly situated between the semi-solid phase and the compressed particulate phase, and wherein the intermediate phase comprises at least 10% by weight of soap.
  • a second aspect of the present invention provides a method of pretreating a region of a fabric prior to washing by rubbing the region with a semi-solid phase of a multi-phase laundry cleaning tablet comprising the semi-solid phase and a compressed particulate phase, wherein an intermediate phase is at least partially situated between the semi-solid phase and the compressed particulate phase and wherein the intermediate phase comprises at least 10% by weight of soap.
  • a third aspect of the present invention provides a method of washing a fabric, comprising washing the fabric in a wash liquor in which a multi-phase laundry cleaning tablet has been dispersed and/or dissolved, a region of the fabric having first been rubbed with a semi-solid phase of the tablet, wherein the tablet further comprises a compressed particulate phase and wherein an intermediate phase is at least partially situated between the semi-solid phase and the compressed particulate phase and wherein the intermediate phase comprises at least 10% by weight of soap.
  • phase refers to a region or a plurality of regions of a tablet having a particular composition and/or physical form such as solid homogeneous mass, compressed particulate mass or semi-solid such as gel. These regions may be arranged as layers or as islands at least partly surrounded by one or more other such regions.
  • the tablets utilised in the present invention may be any suitable shape, e.g. spherical or polyhedral. However, preferably they are of cylindrical shape wherein the two main surfaces (upper side and bottom side) are substantially flat. In another preferred class of embodiments, the surface of the semi-solid layer is dome-shaped to facilitate pre-treatment application.
  • the multi-phase tablets used in the present invention comprise a semi-solid phase, an intermediate phase and additionally one phase of compacted particulates. Suitably, there may be further phases.
  • the intermediate phase is at least partly situated between the semi-solid phase and the compressed particulate phase. That is to say, at least part of the area where the semi-solid phase would be in contact with the compressed particulate phase at an interface therebetween, an intermediate phase intervenes. However, some semi-solid phase could still be in direct contact with compressed particulate phase. Most preferably though, substantially no semi-solid phase is in direct contact with compressed particulate phase.
  • the intermediate phase itself may actually comprise regions of intermediate phase of respective composition and/or physical state which are different from each other. The only requirement is that they each differ from the semi-solid phase and the compressed particulate phase. In the case where the compressed particulate phase and/or semi-solid phase are in the form of a plurality of discrete islands, two or more such islands could be respectively isolated at the interface by a different intermediate phase.
  • One or more other phases than compressed particulate, semi-solid and intermediate may also be present in contact with any one or more of the latter phases.
  • the intermediate phase is intended to reduce bleeding of liquid from the semi-solid phase into the compressed particulate phase.
  • it is sufficient to inhibit liquid transfer to the extent that after 8 weeks storage immediately after manufacture, at 37°C and at 70% relative humidity at 1 atmosphere pressure, less than 10% by weight, more preferably less than 5% by weight of the material in the compressed solid layer consists of liquid from the semi-solid phase.
  • the weight of the compressed particulate phase should preferably increase by less than 10%, more preferably by less than 5%.
  • the intermediate phase comprises at least 10% b weight of soap preferably at least 15%, more preferably at least 20% and even as high as at least 50% by weight of soap.
  • Typical soap levels in the intermediate phase are from 15% to 50%, preferably from 20% to 40%, more preferably from 25% to 40% by weight.
  • soap is meant one or more inorganic or organic salts of one or more fatty acids, which independently may be saturated or unsaturated and optionally may be branched.
  • Suitable soaps preferably have from 12 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms.
  • the intermediate phase is harder than the semi-solid phase and less hard than the compressed particulate phase.
  • the intermediate phase has a weight of from 0.5 to 40 grammes, more preferred from 1 to 20 grammes, most preferred from 2 to 10 grammes.
  • the other phases each have a weight of 2 to 40 grammes.
  • the total weight of the cleaning tablet according to the invention is from 10 to 70 grammes.
  • the intermediate phase is preferably applied by compaction in a tabletting machine and therefore, soap levels substantially higher than 50% by weight (say up to 60% or up to 55% by weight) are less preferred.
  • ingredients may alternatively or additionally be present in the intermediate phase, although preferably, it is substantially free of non-soap surfactants, bleach ingredients and builder materials.
  • a highly soluble material such as sugars, urea, alkali metal salts such as sodium chloride.
  • highly soluble materials will have a solubility of at least 100 grammes per litre water of 20° C, more preferred at least 250 grammes.
  • the intermediate phase may be prepared by any suitable method for example the spraying, applying or brushing of a soap containing formulation, if appropriate followed by hardening e.g. by cooling.
  • the soap-containing layer is obtainable from the compression of a particulate mixture comprising at least 50% by weight of soap containing particles together with solid particles of any other optional ingredient.
  • the soap containing particles preferably comprise at least 10% by weight, preferably at least 25% wt, more preferably at least 50% wt (based on the particles) of soap surfactants.
  • Suitable detergent particles may for example be granules or other particles having high soap levels, for example soap noodles, marumes or granulates with high soap levels.
  • the level of soap surfactants in the soap rich particles is more than 50 wt%, more preferred more than 70 wt%, especially preferred from 75 wt% to 100 wt%.
  • the level of soap rich particles in the soap rich phase is at least 60% wt, more preferred at least 80 % by weight.
  • surfactants for example anionic, nonionic or cationic surfactants may equally be present in the intermediate phase for example at a level of 0.1 to 10 wt% based on the weight of any soap containing part. However, normally, a soap containing phase will be substantially free from non-soap surfactants.
  • the intermediate soap rich phase may comprise other materials, for example soluble materials such as electrolyte materials, meltable organic materials and sugars, at a level of 2 to 70 %wt, more preferably from 3 to 50 wt%, most preferably 5 to 40 % by weight, based on the weight of the smooth part.
  • soluble materials such as electrolyte materials, meltable organic materials and sugars
  • water-soluble materials such as the sodium and potassium citrates, sodium chloride, sodium sulphate, acetates and carbonates, urea and sugar.
  • the water solubility at 20° C of these materials is preferably at least 10 grammes per 100 ml of water, more preferred more than 15 grammes, most preferably more than 20 grammes.
  • these soluble materials are present, their particle size could be chosen such that the intermediate phase may form as a continuous matrix having dispersed therein particles of the water soluble material.
  • the semi-solid phase is one which has a consistency which enables some of it to be applied to a fabric by rubbing. Phases with a waxy or soapy or gel-like consistency are especially suitable.
  • a preferred semi-solid phase is one which is termed herein, a "smooth phase".
  • Other suitable semi-solid phases are any described in WO-A-00/61717 .
  • the semi-solid phase preferably contains one or more ingredients which prior to incorporation are liquid at 25°C and 1 atmosphere pressure.
  • This may be selected from one or more aliphatic or aromatic, polar or non-polar organic liquids (particularly organic solvents) such as liquid alkanols, diols and polyols.
  • organic solvents are polyethyleneglycol, dipropyleneglycol, isopropanol or (mono-)propyleneglycol.
  • liquid non-soap surfactants such as liquid nonionic surfactants, eg liquid (poly)alkoxylated aliphatic alcohols.
  • the level of such organic liquids is from 0 to 40 wt%, more preferred 1 to 20, most preferred from 4 to 15 wt% based on the weight of the semi-solid phase.
  • the semi-solid phase preferably, however, 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, more preferred less than 15 wt%, most preferred from 5 to 12 wt%.
  • the smooth phases are substantially free from water, which means that apart from low levels of moisture (e.g. for neutralisation or as crystal water) no additional added water is present.
  • smooth phase 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 porous and particulate appearance of a compacted particulate material.
  • the semi-solid is transparent or translucent.
  • this means that the composition has an optical transmissivity of at least 10%, most preferably 20%, still more preferably 30%, through a path length of 0.5 cm at 25° C.
  • These measurements may be obtained using a Perkin Elmer UV/VIS Spectrometer Lambda 12 or a Brinkman PC801 Colorimeter at a wavelength of 520nm, using water as the 100% standard.
  • the transparency or translucency of a semi-solid phase does not preclude the composition being coloured, e.g. by addition of a dye, provided that it does not detract substantially from clarity.
  • the semi-solid phase comprises from 30-100 wt% of non-soap surfactants, more preferred 40 to 90 wt% (based on the total weight of said smooth phase), more preferred from 50 to 80 wt%.
  • the total weight of surfactants in the semi-solid phase, especially when it is a smooth phase is from 2 to 20 grammes, more preferred from 3 to 10 grammes.
  • the tablet may be a multi-phase tablet wherein the phases other than the semi-solid phase as described above comprise no or only low levels of non-soap surfactants.
  • the level of non-soap surfactants in the compressed particulate phase is less than 10 wt%(based on the total weight of said phases), more preferred from 0 to 9 wt%, most preferred from 1 to 8 wt%.
  • a compressed particulate phase is a matrix of compacted particles.
  • the compressed particulate phase is essentially a tablet portion comprising granular and/or simple powder material compressed into a solid mass.
  • it will comprise surfactant, preferably also detergency builder and more preferably one or more other ingredients selected from the classes of ingredients used in solid cleaning compositions, especially laundry wash compositions (although other cleaning composition types such as mechanical wavewashing compositions are also possible).
  • Such other optional classes of ingredients may for example be selected from enzymes, bleaches and bleach systems, fluorescers, antifoams, anti-dye transfer agents, anti-redeposition agents, disintegrants and coloured speckles.
  • the compressed particulate phase may comprise surfactant materials
  • this phase preferably comprises ingredients of the tablet other than surfactants.
  • these ingredients are for example builders, bleach system, enzymes etc.
  • the builders in the tablet are predominantly present in this first compressed particulate phase.
  • the first compressed particulate phase is from 5 to 50 grams, for example 10 to 40 grams.
  • the regions are present as layers in the cleaning tablet.
  • the particulate composition 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, although we have observed that this is not always essential.
  • Tableting to make a compressed particulate phase entails compaction of a particulate composition.
  • phase has to be bonded together and/or formed as a unitary mass.
  • a variety of tableting machinery is known, and can be used. Generally it will function by stamping a quantity of the particulate composition which is confined in a die.
  • Manufacture of a tablet with two layers of differing composition may be carried out by placing a predetermined quantity of one composition in a mould, then adding a second composition on top, and next driving a die into the mould to cause compression.
  • a predetermined quantity of a first composition may be placed in a mould and compacted by driving a die into the mould, followed by removing the die, adding a second composition and compacting again.
  • Tableting machinery able to carry out such operations is known.
  • suitable tablet presses are available from Fette and from Korsch.
  • a two phase tablet comprising the compressed particulate phase and the intermediate phase may be formed such as described above and then the semi-solid phase applied over the intermediate phase, eg by melt adhesion or by bonding with a separate adhesive such as a hot-melt adhesive.
  • 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.
  • 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 (gm), preferably from 15 to 60 gm, depending on the conditions of intended use, and whether the tablet represents a dose for an average load in a fabric washing 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 is preferably 1040 or 1050 gm/litre, better 1100 gm/litre, up to 1300 or 1350 gm/litre or even more. The tablet density may well lie in a range up to no more than 1250 or even 1200 gm/litre.
  • 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, because of their greater tendency to exhibit disintegration and dispersion problems.
  • 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 g/litre, preferably at least 500 g/litre, and advantageously at least 700 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 , EP-A-352 135 , and EP-A-425 277 , or by the continuous granulation/densification processes described and claimed in EP-A-367 339 and EP-A-390 251 are inherently suitable for use in the present invention.
  • Preferred embodiments of the invention will now be described by way of example only. Further modification within the scope of the present invention will be apparent to the person skilled in the art.
  • Tablets for use according to the invention are preferably manufactured by a process involving the application of pressure to a particulate mixture.
  • the preparation of the soap containing phase may involve the dosing of a particulate mixture comprising ingredients of the intermediate phase, i.e. soap rich particles, preferably in combination with other materials as described above, followed by the exertion of pressure, preferably above the yield stress of the intermediate phase components. It has been found that the exertion of pressure to a particulate mixture comprising significant levels of soap rich particles leads to a certain flow behaviour of the mixture leading to the formation of an intermediate phase.
  • the semi-solid phase can then be applied by melt-bonding or by use of a suitable adhesive.
  • the first 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 intermediate and the particulate region(s) 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- 10 kN/cm 2 , more preferred 0.5 to 5 kN/cm 2 .
  • the co-compression preferably takes place at a force of 1- 100 kN/cm 2 ., more preferred 2-50 kN/cm 2 ., most preferred 2-10 kN/cm 2 .
  • the intermediate phase may also be manufactured separately by compression of a suitable composition such as a particulate soap rich material e.g. at the compation forces as indicated above.
  • a suitable composition such as a particulate soap rich material e.g. at the compation forces as indicated above.
  • the intermediate phase may be prepared by other methods for example the spraying of a suitable composition such as a soap rich composition, for example onto the (pre) compressed compacted tablet phase on which the intermediate phase layer is formed or adhered.
  • a suitable composition such as a soap rich composition
  • Another suitable method for the preparation of an intermediate phase may involve casting or extrusion of a suitable composition such as a soap containing composition.
  • the semi-solid phase may also be prepared e.g. by extrusion, casting or other shaping methods.
  • Separately prepared intermediate phase and semi-solid phase can then be adhered to other part(s) of the tablet for example by gentle pressing or by usage of an adhesive material.
  • a separately prepared solid phase of compressed particulate materials can be combined with one ore more pre-prepared intermediate phases e.g. by gentle co-compression, followed by body of the semi-solid phase.
  • a fabric washing tablet as a whole will be likely to contain at least 2 wt%, probably at least 5 wt%, up to 40 or 50 wt% surfactant based on the whole tablet, and from 5 to 80 wt% detergency builder, based on the whole tablet.
  • the compressed particulate phase comprises one or more disintegrants.
  • Preferred disintegrants are materials which have a solubility in (preferably deionised) water at 20°C of at least 50 grams per 100 grams of water.
  • This disintegrant may be present in an amount which is at least 5wt%, 7 wt% or 12 wt% of the tablet. Some of the disintegrant may be present in the base powder used to make the complete tablet formulation used for the compressed particulate phase, whilst the remainder, preferably the majority, is added as a post-dosed ingredient to the base powder before tableting in the compressed particulate phase. It is preferred that at least 75wt% or even 85wt% of the material is not in the base powder, but is added as a post-dosed ingredient.
  • a solubility of at least 50 grams per 100 grams of water at 20°C is an exceptionally high solubility: many materials which are classified as water soluble are less soluble than this.
  • this highly water-soluble disintegrant is incorporated as particles of the material in a substantially pure form (i.e. the majority of such particles contain 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.
  • the preferred disintegrant of high water-solubility are sodium citrate dihydrate, potassium carbonate, urea, sodium acetate in its anhydrous or trihydrate form, sodium acetate which is partially hydrated - as can be the case when it is spray dried, magnesium sulphate 7H 2 O and potassium acetate. Mixtures of these can also be used.
  • the most preferred of the aforementioned materials are sodium citrate dihydrate, sodium acetate in either its anhydrous, trihydrate or partially hydrated form. Mixtures of these most preferred materials can also be used.
  • Another suitable class of disintegrants comprises cellulose disintegrants.
  • compositions which are used in tablets of the invention will contain one or more detergent surfactants.
  • these preferably provide from 5 to 50% by weight of the overall tablet composition, more preferably from 8 or 9% by weight of the overall composition up to 40% or 50% by weight.
  • Surfactant may be anionic (soap or 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 40% by weight of the tablet composition.
  • Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art.
  • 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.
  • Primary alkyl sulphate having the formula ROSO 3 - M + in which R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M + is a solubilising cation, is commercially significant as an anionic surfactant.
  • Linear alkyl benzene sulphonate of the formula where R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium, 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 soap surfactant in the composition.
  • the amount of non-soap anionic surfactant lies in a range from 5 to 20 wt% of the tablet composition.
  • Soaps for use in accordance to the invention are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
  • soaps are selected from C 12 to C 22 soaps for example from C 12 to C 18 soaps.
  • 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.
  • the primary and secondary alcohol ethoxylates especially the C 9-11 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 whole tablet.
  • nonionic surfactants are liquids. These may be absorbed onto particles of the composition.
  • the surfactant may be wholy nonionic, in an amount below 5 wt% of the whole tablet although it is known to include some anionic surfactant and to use up to 10 wt% surfactant in total.
  • a composition which is used in 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 wholly 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 strongly favoured as environmentally acceptable water-insoluble builders for fabric washing.
  • Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O.Al 2 O 3 . 0.8-6 SiO 2 . xH 2 O
  • xH2O xH2O
  • xH2O calcium ion exchange capacity
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble ).
  • the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, the novel zeolite P described and claimed in EP 384070 (Unilever ) and mixtures thereof.
  • a water-insoluble detergency builder could be a layered sodium silicate as described in US 4664839 .
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6").
  • KSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as described in DE-A-3,417,649 and DE-A-3,742,043 .
  • layered silicates 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 can be used.
  • 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 be organic or inorganic.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
  • alkali metal generally sodium
  • organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dip
  • At least one region (preferably the second region) of a fabric washing tablet preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which can function as builders and also inhibit unwanted deposition onto fabric from the wash liquor.
  • Tablets according to the invention may contain a bleach system in at least one region of a tablet, preferably in the second region.
  • 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.
  • 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 perbenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • perbenzoic acid precursors perbenzoic acid precursors.
  • the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 are also of interest.
  • bleach activator which may be used, but which is not a bleach precursor, is a transition metal catalyst as disclosed in EP-A-458397 , EP-A-458398 and EP-A-549272 .
  • a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
  • a bleach is present and is a water-soluble inorganic peroxygen bleach, the amount may well be from 10% to 25% by weight of the composition.
  • the detergent tablets of the invention may also contain (preferably in the second region) one of the detergency enzymes well known in the art for their ability to degrade and aid in the removal of various soils and stains.
  • Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics. Examples of suitable proteases are Alcalase (Trade Mark), and Savinase (Trade Mark), as supplied by Novo Industri Als, Copenhagen, Denmark.
  • Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the composition; and these granules or marumes present no problems with respect to compaction to form a tablet.
  • the detergent tablets of the invention may also contain (preferably in the second region) a fluorescer (optical brightener), for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba Ceigy AC, Basel, Switzerland.
  • a fluorescer optical brightener
  • 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 (preferably in the second region), 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 266863A (Unilever).
  • 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.
  • 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 tablet for fabric washing will generally not contain more than 15 wt% silicate.
  • a tablet for machine dishwashing will often contain more than 20 wt% silicate.
  • the silicate is present in the second region of the tablet.
  • ingredients which can optionally be employed in a region of a fabric washing detergent of the invention tablet include anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents; heavy metal sequestrants such as EDTA; perfumes; and colorants or coloured speckles.
  • anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents
  • heavy metal sequestrants such as EDTA
  • perfumes and colorants or coloured speckles.
  • dispersing aids are water-swellable polymers (e.g. SCMC) highly soluble materials (e.g. sodium citrate, potassium carbonate or sodium acetate) or sodium tripolyphospate with preferably at least 40% of the anhydrous phase I form.
  • SCMC water-swellable polymers
  • highly soluble materials e.g. sodium citrate, potassium carbonate or sodium acetate
  • sodium tripolyphospate preferably at least 40% of the anhydrous phase I form.
  • the intermediate phase When the intermediate phase is embodied as a soap rich region of the tablet, it may advantageously be prepared by compacting particles with a high soap content as described above. Preferably these particles have a mean particle size of from 100 to 1000 ⁇ m.
  • the intermediate phase is of course a separate phase from the compressed particulate phase which is preferably a matrix of compacted particles.
  • any particulate composition has a mean 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, although we have observed that this is not always essential.
  • 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, because of their greater tendency to exhibit disintegration and dispersion problems.
  • 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 g/litre, preferably at least 500 g/litre, and perhaps at least 600 g/litre.
  • 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.
  • the size of a tablet will suitably range from 10 to 160 grams, preferably from 10 to 70g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
  • the tablets may be of any shape. However, for ease of packaging they are preferably blocks of substantially uniform cross-section, such as cylinders or cuboids.
  • the overall density of a tablet preferably lies in a range from 1040 or 1050gm/litre up to 1600gm/litre.
  • the compressed particulate phase had the following composition: Composition (%wt) P1 Na-LAS 4.15 Nonionic 7EO 1.82 Soap 0.33 zeolite A24 (anhydrous) 9.30 Na Acetate.3aq 1.18 Na Carbonate 1.38 SCMC (68%) 0.18 Moisture, salts, NDOM 1.67 Antifoam granule 1.01 Fluorescer granule (15 % active) 2.31 STP HPA 48.1 Nabion/Disilicate co granule. 2.50 TAED (as granule 83%) 4.52 Coated Percarbonate 17.2 Dequest 2047 (43%) 2.70 Enzymes 0.94 Perfume 0.71 TOTAL 100.0
  • compositions were used for the intermediate phase Composition wt% I1 I2 Soap granules (Prisavon 1878 ex Uniqema) 25 50 Granular sodium sulphate 75 50
  • the semi-solid phase had the following composition: Composition wt% S1 Na-LAS 32.90 Nonionic 5EO 27.35 Na soap (C16/C18) 2.96 Tween 40 12.05 DiPropyleneGlyc ol 17.77 Dye 0.011 Water 6.96 Total 100
  • a tablet consisting of a compressed particulate phase, an intermediate phase and a semi-solid phase was produced by first compressing 25 gr of composition P1 in a Fette tabletting machine. An intermediate phase was then formed on top of this particulate phase, by compressing 2 gr of composition I1 in the same Fette tabletting machine.
  • the semi-solid phase was produced by casting 5 gr of liquid composition S1 at 90°C into a mould, after which the phase was let to solidify. The semi-solid phase was then glued onto the intermediate phase with 0.3 gr of a hot melt water soluble glue, to form the complete tablet.
  • Example 2 Tablets were made in the same manner as in Example 1, but now using composition I2 for the intermediate layer (Example 2) and a tablet which did not contain an intermediate layer (comparative Example A).
  • the loss in weight (in % of the original gel weight) is a measure of the amount leaked into the compacted particulate phase.
  • the compacted particulate phase was examined visually for changes in colour.
  • Example 1 A Weight loss of gel (wt%) 4 6 28 Colour of compacted particulate phase white white Yellow spots

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Utilisation d'une pastille de nettoyage de blanchisserie multi-phase comprenant une phase particulaire compressée et une phase semi-solide pour le traitement avant lavage d'une zone d'un textile avant lavage, par frottement de la phase semi-solide sur la zone, dans laquelle une phase intermédiaire est au moins en partie située entre la phase semi-solide et la phase particulaire compressée, et dans laquelle la phase intermédiaire comprend au moins 10 % en poids de savon.
  2. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la phase intermédiaire comprend au moins 15 %, de manière davantage préférée au moins 20 %, de manière préférée entre toutes au moins 50 % en poids de savon.
  3. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite phase intermédiaire peut être obtenue par compression d'un mélange particulaire comprenant au moins 50 % en poids de particules détergentes, dans laquelle lesdites particules détergentes comprennent au moins 10 % en poids de tensioactif savon.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite phase semi-solide comprend jusqu'à 40 %, de préférence de 1 % à 20 %, de manière davantage préférée de 4 % à 15 % en poids de liquide organique.
  5. Utilisation selon la revendication 4, dans laquelle le liquide organique comprend un ou plusieurs solvants organiques choisis parmi les alcanols, les diols et les polyols liquides.
  6. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la phase semi-solide comprend au moins 50 % en poids (basée sur le poids de ladite phase) de tensioactifs de type non savon.
  7. Utilisation selon l'une ou plusieurs des revendications précédentes, dans laquelle la phase semi-solide comprend moins de 20 % en poids d'eau, de préférence de 5 à 12 % en poids.
  8. Procédé de prétraitement d'une zone d'un textile avant lavage, par frottement de la zone avec une phase semi-solide d'une pastille de nettoyage de blanchisserie multi-phase comprenant la phase semi-solide et une phase particulaire compressée, dans lequel une phase intermédiaire est au moins en partie située entre la phase semi-solide et la phase particulaire compressée, et dans lequel la phase intermédiaire comprend au moins 10 % en poids de savon.
  9. Procédé de lavage d'un textile, comprenant le lavage du textile dans une liqueur de lavage dans laquelle une pastille détergente de blanchisserie multi-phase a été de nettoyage et/ou dissoute, une zone du textile ayant été, tout d'abord, frottée avec une phase semi-solide de la pastille et dans lequel la pastille comprend en outre une phase particulaire compressée et dans lequel une phase intermédiaire est au moins en partie située entre la phase semi-solide et la phase particulaire compressée, et dans lequel la phase intermédiaire comprend au moins 10 % en poids de savon.
EP05075207A 2004-03-12 2005-01-26 Utilisation des comprimés détergents Not-in-force EP1574563B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05075207A EP1574563B1 (fr) 2004-03-12 2005-01-26 Utilisation des comprimés détergents

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04075807 2004-03-12
EP04075807 2004-03-12
EP05075207A EP1574563B1 (fr) 2004-03-12 2005-01-26 Utilisation des comprimés détergents

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EP1574563B1 true EP1574563B1 (fr) 2007-06-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111757926A (zh) * 2018-02-23 2020-10-09 荷兰联合利华有限公司 具有透明固体部分的单位剂量洗涤剂产品

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112023001052A2 (pt) 2020-08-12 2023-03-07 Unilever Ip Holdings B V Método para formação de uma composição detergente estável para lavagem de roupas
WO2022033857A1 (fr) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Composition de détergent à lessive
WO2022033851A1 (fr) 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Composition de détergent à lessive

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Publication number Priority date Publication date Assignee Title
US6551981B1 (en) * 1998-07-17 2003-04-22 Patrizio Ricci Detergent tablet
EP1043390A1 (fr) * 1999-04-09 2000-10-11 The Procter & Gamble Company Détergent sous forme de tablette
DE60320062D1 (de) * 2002-06-11 2008-05-15 Unilever Nv Waschmitteltabletten

Non-Patent Citations (1)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111757926A (zh) * 2018-02-23 2020-10-09 荷兰联合利华有限公司 具有透明固体部分的单位剂量洗涤剂产品
CN111770985A (zh) * 2018-02-23 2020-10-13 荷兰联合利华有限公司 具有有光泽的固体部分的单位剂量洗涤剂产品
CN111770985B (zh) * 2018-02-23 2021-10-15 联合利华知识产权控股有限公司 具有有光泽的固体部分的单位剂量洗涤剂产品
US12134749B2 (en) 2018-02-23 2024-11-05 Conopco Inc. Shaped detergent product composition comprising aminopolycarboxylate

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