EP1669438B1 - Comprimé détergent - Google Patents

Comprimé détergent Download PDF

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Publication number
EP1669438B1
EP1669438B1 EP05077550A EP05077550A EP1669438B1 EP 1669438 B1 EP1669438 B1 EP 1669438B1 EP 05077550 A EP05077550 A EP 05077550A EP 05077550 A EP05077550 A EP 05077550A EP 1669438 B1 EP1669438 B1 EP 1669438B1
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EP
European Patent Office
Prior art keywords
region
tablet
sleeve
solid
smooth
Prior art date
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Not-in-force
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EP05077550A
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German (de)
English (en)
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EP1669438A1 (fr
Inventor
Johannes c/o Unilever R&D Vlaardingen Krieg
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to EP05077550A priority Critical patent/EP1669438B1/fr
Publication of EP1669438A1 publication Critical patent/EP1669438A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid compositions
    • 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

Definitions

  • This invention relates to a process for the preparation of a cleaning composition in the form of tablets.
  • the invention also relates to cleaning compositions in the form of tablets, for use in fabric washing or machine dishwashing.
  • Detergent compositions in tablet form have advantages over powdered products in that they do not require measuring and are thus easier to handle and dispense into the wash load.
  • Tablets of a cleaning composition are generally made by compressing or compacting a quantity of the composition in particulate form.
  • WO 00/61717 describes the preparation of a compressed particulate tablet on top of which a (non compressed) layer is made by pouring a mixture of nonionic and PEG followed by hardening.
  • This formulation and its method of preparation is disadvantageous because it requires a very long hardening step in the tablet mould, during which the tablet-mould cannot be used for further production, therewith significantly increasing the cost of production. In addition, the mould needs cleaning after being used.
  • WO 99/24549 describes a detergent tablet comprising a compressed solid body and a non-compressed gelatinous portion mounted in a mould of said body. This method requires a pre-prepared mould in the tablet surface, involving extra steps in the process and also special equipment to make such moulds are needed.
  • Co-pending European patent application EP 1,516,916 A1 published on 23.3.05 describes a method of making a detergent tablet comprising a compressed phase and a smooth phase.
  • the smooth phase is sprayed on the pre-formed compressed phase.
  • the spraying involves the formation of small droplets of the liquid material and the spraying has to be done accurately in order to avoid leakage and spoilage problems.
  • the spraying sometimes may lead to uneven smooth-phases that make the tablet less attractive to consumers.
  • the present invention aims to provide a process for the production of multi-phase cleaning tablets comprising a compressed phase and a second preferably smooth phase that gives a good adherence of the smooth phase to the compressed phase without the need for an adhesive between said phases, and without the need of a complicated production process and without the need of indents or moulds in the tablet surface and wherein the smooth phase can easily be manufactured and avoiding leakage and spoilage problems.
  • a method of preparing a cleaning tablet which comprises a plurality of discrete regions with different compositions, wherein at least a first region of the tablet is a solid region of compacted particulate material and a second region is a smooth region, characterised in that the method comprises the steps of a)providing a solid region of compacted particulate material thereby forming the first region; b) fitting tightly an outer sleeve around the periphery of the first region wherein said sleeve extends above the surface area of the first region thereby forming a mould; c)introducing a fluid composition into the mould to form said second region; d) solidifying said second region and optionally removing said sleeve.
  • the invention in a second aspect, relates to a cleaning tablet comprising a plurality of discrete regions with different compositions, wherein at least a first region of the tablet is a solid region of compacted particulate material and a second region is a smooth region, wherein the tablet comprises a sleeve which is tightly fitted around the periphery of the tablet, and wherein the sleeve is made of water-soluble film.
  • the sleeve is positioned on the peripheral edges around the solid region of the tablet in such a way that that the sleeve is tightly fitted around the tablet.
  • tightly fitted means that there is essentially no or very little room between the sleeve and the tablet.
  • the tight fitting ensures that normally the tablet is fixed in the sleeve and no movement of the tablet region is possible.
  • the distance between the sleeve and the first region is between 0.1 and 1000 ⁇ m, preferably between 0.1 and 100 ⁇ m.
  • the solid region has a top- and bottom-surface and side-surfaces which are substantially perpendicular to the top- and bottom-surface.
  • the side-surfaces are covered by the sleeve.
  • the sleeve is fitted around the side-surfaces of the solid region whereby the top- and bottom-surface of said region are substantially not covered, such as illustrated in figure 1.
  • the sleeve continues above the surface area, preferably the top-surface, of the first region such that the sleeve extends above the surface area thereby forming a mould, such as illustrated in figure 1.
  • the sleeve extends between 0.1 and 20 mm, more preferably between 1 and 10 mm and most preferably between 1 and 5 mm above the top-surface of the first region. preferably between 1 and 5 mm above the top-surface of the first region.
  • a fluid is introduced into the mould formed by said sleeve to form the second region.
  • a fluid composition may be a liquid or may have a pasty or gel-like consistency. It may for example be poured, dosed, extruded, or sprayed.
  • the sleeve is made from a film material and is a substantially uniform material.
  • film materials may for example be produced by blowing or casting.
  • uniform means that the film has substantially the same composition when comparing one piece of the film with another piece of the film a distance away from the first piece.
  • the film itself may consist of more than one layer. Suitable materials are elastomers, water-soluble material, shrink foil and adhesive tape.
  • Shrink foil is a material that shrinks upon heating.
  • the advantage of using shrink foil is the very tight wrapping of the sleeve around the tablet thereby preventing leakage of the fluid material between the sleeve and solid region.
  • the application of the foil does not have to be accurate as the foil will shrink upon application of heat and thereby tightens itself around the tablet.
  • Adhesive tape may be convenient as the tape sticks to the solid region and is therefore easy applicable.
  • Double adhesive tape has the further advantage that when the tablet is further packed in a wrapper the tape will also stick to the wrapper. When the tablet is used and the wrapper is removed, simultaneously the tape is also removed and no residue of the tape is left in the wash-load or washing-machine.
  • the film is a water-soluble film material.
  • Water-soluble material has the clear advantage that the multi-phase tablet can be directly applied in the washing without leaving a residue after washing.
  • the desired degree of solubilisation and strength can be achieved by matching the type of material and its thickness such that the desired solubilisation time is achieved while still maintaining the desired strength.
  • the film material is deformable under heating conditions.
  • Water soluble materials which may be used to form the water soluble films are widely disclosed in the literature and include, for example, polyester amides, polyvinyl alcohol, copolymers of vinyl alcohol and methacrylate, polyethylene oxide, alginates, cellulose ethers such as carboxymethyl cellulose and methylcellulose, starches and starch derivatives, gelatin and any combination of these. Especially preferred is the use of polyvinyl alcohol
  • the water-soluble material is preferably mainly composed of poly vinyl alcohol (PVA) or of a co-polymer of poly vinyl alcohol and poly methyl acrylate (PVA-PMA).
  • PVA poly vinyl alcohol
  • PVA-PMA poly methyl acrylate
  • the term poly vinyl alcohol as used herein also includes partially hydrolysed poly vinyl acetates.
  • the water-soluble film can also contain minor quantities of plasticizers, anti-foams, anti-oxidants, surfactants, perfumes and the like.
  • the film thickness before application to the tablet is from 30 to 150 micrometer, more preferred from 40 to 100 micrometer, most preferred from 60 to 90 micrometer.
  • the average thickness will be from 10 to 150 micrometers, more preferred from 20 to 100 micrometers, most preferred from 30 to 80 micrometers.
  • the fluid material to be poured into the mould will (just before pouring) have a viscosity of 0.1 Pa.s to 12 Pa.s and a yield stress of 5 to 80 Pa at a sheer rate of 21 s -1 .
  • These viscosities can for example be determined via the method as described in EP 1,032,642 .
  • the material Before the introduction of the smooth phase, preferably the material is pre-heated to an elevated temperature for example from 50 to 150°C, more preferably from 60 to 140°C, most preferably from 70 to 130°C.
  • the fluid, preferably liquid, molten material is then introduced, e.g. poured or dosed into the mould formed by the tightly fitted sleeve.
  • Solidification of the fluid material may be accomplished by any suitable method e.g. cooling, gellation or by removal of shear.
  • the solidification involves the cooling of the fluid phase, preferably to ambient temperature.
  • the solid phase of the cleaning tablets according to the invention are preferably manufactured by a process comprising the steps of inserting a particulate composition into a tablet mould and compression of the particulate composition to form a compressed tablet followed by removal of the compressed tablet from the tablet mould.
  • the particulate composition is compressed at a force of 0.1 to 20 kN/cm 2 . After the compression the compressed tablet is preferably removed from the tablet mould.
  • the upper surface of the compressed composition may be treated with one or more materials e.g. barriers before the application of the second region.
  • the sleeve may remain on the tablet or may be removed. If the sleeve is to be removed, the fluid material preferably is at least partially solidified, sufficiently to have form retention before the removal of the sleeve.
  • the tablet of the invention may be packed into a suitable packaging material after production.
  • Water soluble film may advantageously be used.
  • pouring the liquid composition on top of the solid region generally leads to a good adherence of the smooth phase to the compressed phase and may generally lead to a reduced or even an absence of the need for an adhesive between the compressed phase and the smooth phase.
  • Another advantage of the process of the present invention is that an expensive metal mould is not needed.
  • no cleaning steps of the moulding equipment are necessary between two subsequent tablets and that processing times are shortened as there is no need for a waiting time until the fluid phase solidifies before a next tablet is made.
  • Furthermore the presence of a sleeve around the tablet allows the gripping and handling of said tablet without the need of touching the detergent material.
  • the cleaning tablets produced by a method of the invention generally do not need substantial indentations in its surface (e.g. moulds, indents or cavities) to retain the smooth phase.
  • the upper surface of the compressed phase can be substantially flat, therewith avoiding the need to use complicated equipment to produce said tablet and also avoiding weaknesses in the tablet due to uneven surfaces.
  • the present invention relates to a washing tablet comprising a plurality of discrete regions with different compositions, wherein at least a first region of the tablet is a solid region of compacted particulate material and a second region is a smooth region wherein the tablet comprises a sleeve which is tightly fitted around the periphery of the tablet.
  • the distance between the sleeve and the tablet is between 0.1 and 1000 ⁇ m. Preferably between 0.1 and 100 ⁇ m.
  • the sleeve is made of water-soluble film.
  • the sleeve around the tablet has several benefits.
  • the tablets with a sleeve are very appealing to customers; the sleeve gives the tablet a clean look, direct contact between the materials of the tablet and the consumer can be avoided and the tablet is very stable towards breaking and crumbling.
  • the regions of the cleaning tablet are possibly separate layers within a tablet.
  • the second region covers a substantial part of the upper surface of the solid region, e.g. preferably at least 65%, more preferred at least 75%, most preferred more than 90% or even substantially all of the upper surface of the first region is covered by the second region.
  • the term upper surface refers to one of the main sides of the cleaning tablet which by placing the tablet on a flat surface could be classified as the upper surface.
  • the first region suitably is a layer of compacted particulate material, preferably having a substantially flat upper surface.
  • the first region of the tablet is a solid region prepared by compression of a particulate composition.
  • the first region has a weight of from 10 to 50 grams, more preferred from 15 to 40 grams.
  • the smooth region has a weight of 0.5 to 15 grams, more preferred 1 to 10 grams, most preferred 2 to 6 grams.
  • the solid region of compacted material comprises no or only low levels of surfactants.
  • the level of surfactants in the first region is less than 10 wt%(based on the total weight of the tablet or even less than 10% wt based on the weight of the first region), more preferred from 0 to 9 wt%, most preferred from 1 to 8 wt%.
  • the solid region may comprise surfactant materials
  • this region 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 the solid region.
  • the bleach system is predominantly present in the solid region.
  • the enzymes are predominantly present in the solid region.
  • the term "predominantly present” refers to a situation wherein at least 90 wt% of an ingredient is present in one region, more preferred more than 98 wt%, most preferred substantially 100 wt%.
  • the second region of the tablet is a smooth region.
  • 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. Poured smooth regions however may have small irregularities in their upper surface for example caused by uneven solidification or by the inclusion of small air bubbles into the region. Generally however the region is still smooth in appearance and is clearly distinguishable from the generally uneven appearance of compacted particulate materials.
  • the second region is both a smooth region and a semi-solid region.
  • semi-solid refers to compositions which are on the one hand solid enough to retain their shape at ambient temperature but which are neither completely solid.
  • Semi-solid compositions are characterised by a ratio of F f to E b of less than 1.0, more preferred from 0.1 to 0.9, most preferred from 0.2 to 0.6, while traditional tablets of compacted particulate materials are generally characterised by a ratio of F f to E b of more than 1, more generally more than 1.25 or even more than 1.5 up to say 6.
  • the second region has an average thickness of from 0.5 to 5 mm, more preferred 1 to 4 mm, for example 1.5 to 3 mm.
  • the smooth or semi-solid second region comprises from 40-100 wt% of surfactants (based on the total weight of the second region), more preferred from 50-95 wt%, most preferred the second region is predominantly constituted by surfactants e.g. more than 60 wt% for example 70 to 90 wt%. It has been found that the combination of a separate smooth or semi-solid region and these high surfactant levels provide very good dispersing and cleaning properties to the tablet.
  • the total weight of surfactants in the second region is from 0.5 to 10 grams, more preferred from 1 to 5 grams.
  • the surfactants in the second region comprise a combination of anionic surfactants and non-soap non-ionic surfactants in a weight ratio of from 5 : 1 to 1 : 5, more preferred 3 : 1 to 1 : 3, more preferred 2 : 1 to 1: 2.
  • Further surfactants for example cationic surfactants may equally be present for example at a level of 0.1 to 10 wt% based on the weight of the smooth or semi-solid part.
  • the smooth or semi-solid region may comprise soap for example at a level of 0.1 to 10 wt% based on the weight of the smooth or semi-solid part.
  • the second region of the tablet may comprise diluent materials for example polyethyleneglycol, (mono-)propyleneglycol or di-propylene glycol.
  • diluent materials for example polyethyleneglycol, (mono-)propyleneglycol or di-propylene glycol.
  • the level of these diluents is from 0 to 40 wt%, more preferred 2 to 30, most preferred 10-25 wt% based on the weight of the region.
  • the second phase preferably comprises no or only low levels of water.
  • the level of water is less than 20 wt % based on the weight of the phase, more preferred less than 15 wt%, most preferred from 5 to 12 wt%.
  • the second phase is 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.
  • each of the regions may be composed of a limited number of discrete regions.
  • the cleaning tablets of the invention may optionally comprise further regions, for example the tablet may be partly or wholly coated.
  • a tablet of this invention may be intended for use in machine dishwashing.
  • Such a tablet is likely to contain surfactant in a low concentration such as 0.5 to 2 wt% based on the whole tablet, although higher concentrations ranging up to 10 wt% may be used.
  • Such tablet will typically contain salts, such as over 60 wt%, often over 85 wt% of the tablet.
  • Water-soluble salts typically used in machine dishwashing compositions are phosphates (including condensed phosphates) carbonates and silicates, generally as alkali metal salts.
  • Water soluble alkali metal salts selected from phosphates, carbonates and silicates may provide 60 wt% or more of a dishwashing composition.
  • a tablet of this invention will be intended for fabric washing.
  • the tablet 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 tablets according to the invention may be placed into a dispensing tray, or preferably directly with the washload into the drum of the washing machine.
  • 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 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 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 non-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 of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
  • Suitable 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 wholly 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 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
  • xH 2 O 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 solid region) of a fabric washing tablet preferably includes 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 smooth 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 cleaning tablets of the invention may also contain (preferably in the smooth 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.
  • 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; 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 solid region) a fluorescer (optical brightener), for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba-Geigy AG, 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 solid 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 cleaning 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 first 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 solid region of a cleaning tablet of this invention is preferably a matrix of compacted particles.
  • 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.
  • the starting particulate composition may in principle have any bulk density
  • the present invention is especially relevant to solid regions made by compacting powders of relatively high bulk density, because of their greater tendency to exhibit disintegration and dispersion problems.
  • Such solid regions 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 the solid region 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 15 to 60 g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
  • the tablets may be of any shape. However, for ease of packaging they are preferably blocks of substantially uniform cross-section, such as cylinders or cuboids.
  • the overall density of a tablet preferably lies in a range from 1040 or 1050gm/litre up to 1600gm/litre.
  • the diameter of the solid region is substantially the same as the diameter of the smooth region.
  • substantially the same diameter means that the diameter of the first phase differs less than 5 mm with the diameter of the second phase, more preferably less than 3mm or even less than 1mm.
  • a detergent powder was made of the following composition by pregranulating the granule ingredients, followed by post-dosing the rest of the ingredients Ingredient Parts by weight granules Na-las 1.1 Nonionic 7EO 0.5 Soap (C16-C18) 0.1 Zeolite A24 2.4 NaAc3aq 0.3 Light soda ash 0.4 SCMC (68%) 0.1 Moisture/minors 0.4 Post-dose EAG (17% silicone) 3.0 Fluorescer (15%) 2.2 STP HPA 28.3 STP LV 34.0 Na-disilicate (80%) 3.8 TAED (83%) 4.3 Percarbonate 16.9 Dequest 2047 1.9 Minors/ enzymes/colour to 100
  • the tablets were made as follows: 25 grams of the powder are inserted into a 45 mm die of a tabletting machine, optionally followed by a flattening step, the material is compressed at 6kN/cm 2 into a single tablet, followed by ejection of the tablet.
  • a ribbon-like piece was cut from a sheet of PVA-film.
  • This 'ribbon' has a height which is slightly larger than the height of the solid phase; in this case the height of the ribbon was around 2 cm.
  • the length of the ribbon was a little longer than the circumference or periphery of the tablet to provide an overlap for gluing the ribbon together into a sleeve.
  • the length of the ribbon was around 14.5 cm.
  • the ribbon was folded into a circular shape, like a peripheral sleeve and the ends were glued together with water.
  • the diameter of the sleeve was about 2 mm smaller than the diameter of the tablet to obtain a tight fit of the sleeve around the tablet.
  • the sleeve was stretched, and placed around the tablet in a way that the lower edge of the sleeve was at the same height as the bottom of the tablet, and the top of the sleeve extended 3-6 mm above the top surface of the tablet. After releasing, the sleeve shrank to a smaller diameter and was tightly wrapped around the periphery of the solid phase to form a mould.
  • Fluid compositions were prepared by mixing the following ingredients: Ingredient Parts by weight Na-las 39.1 Nonionic 7EO 33.5 C12 soap 7.3 Monopropyleenglycol to 100
  • the mixture was heated to 80°C to provide a molten liquid composition. 5 gram of the molten liquid was dosed into the mould formed by the sleeve to form a layer of around 3 mm. The molten liquid was left to solidify for 2 to 3 minutes.
  • Tablets prepared according the above methods provide good adherence of the smooth or semi-solid part to the rest of the tablet therewith avoiding the need to use adhesive materials. Furthermore the tablets of the invention show fast dispersing of the compacted powder region during the washing process therewith allowing the early release of e.g. builder components into the washing liquor. The smooth part shows delayed dispersing therewith providing the surfactants at a later stage during the washing process.

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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. Méthode de préparation d'une pastille nettoyante qui comprend une pluralité de régions discrètes avec différentes compositions, dans lesquelles au moins une première région de la pastille est une région solide d'un matériau particulaire compacté et une seconde région est une région lisse, caractérisée en ce la méthode comprend les étapes consistant à
    a) fournir une région solide d'un matériau particulaire compacté formant de ce fait la première région ;
    b) ajuster précisément une enveloppe externe autour de la périphérie de la première région dans laquelle ladite enveloppe se prolonge au-dessus de la zone de surface de la première région formant de ce fait un moule ;
    c) introduire une composition fluide à l'intérieur du moule pour former ladite seconde région ;
    d) solidifier ladite seconde région ;
    e) éventuellement retirer ladite enveloppe.
  2. Méthode selon la revendication 1 dans laquelle la première région est essentiellement exempte d'indentations, moules et cavités.
  3. Méthode selon l'une quelconque des revendications 1 ou 2, dans laquelle la composition fluide qui est introduite à l'intérieur du moule est une composition fondue et de préférence a une température allant de 50 à 150 C, de manière davantage préférée allant de 70 à 150 °C.
  4. Pastille nettoyante comprenant une pluralité de régions discrètes avec différentes compositions, dans laquelle au moins une première région de la pastille est une région solide d'un matériau particulaire compacté et une seconde région est une région lisse, dans laquelle la pastille comprend une enveloppe qui est ajustée précisément autour de la périphérie de la pastille, et dans laquelle l'enveloppe est faite d'un film hydrosoluble.
  5. Pastille nettoyante selon la revendication 4 ou méthode selon l'une quelconque des revendications 1 à 3 dans laquelle la distance entre l'enveloppe et la pastille est entre 0,1 et 1 000 µm.
  6. Pastille nettoyante selon l'une quelconque des revendications 4 ou 5, ou méthode selon l'une quelconque des revendications 1 à 3 dans lesquelles le film hydrosoluble est du poly vinyl alcool (PVA) ou d'un copolymère de poly vinyl alcool et de poly acrylate de méthyle (PVA-PMA).
  7. Pastille nettoyante selon l'une quelconque des revendications 4 à 6, ou méthode selon l'une quelconque des revendications 1 à 3, dans lesquelles la seconde région comprend de 40 à 100 % en poids de tensioactifs.
  8. Pastille nettoyante selon l'une quelconque des revendications 4 à 7, ou méthode selon l'une quelconque des revendications 1 à 3 comprenant une couche barrière entre la première région et la seconde région.
  9. Utilisation d'une pastille nettoyante selon l'une quelconque des revendications 4 à 8 pour le lavage de textiles ou pour le lavage mécanique de la vaisselle.
EP05077550A 2004-12-08 2005-11-09 Comprimé détergent Not-in-force EP1669438B1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012069895A1 (fr) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Comprimé soluble contenant des éléments abrasifs
US9924863B2 (en) 2012-04-05 2018-03-27 Bioptigen, Inc. Optical coherence tomography systems integrated with surgical microscopes
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning
WO2021214408A1 (fr) * 2020-04-20 2021-10-28 Eurotab Operations Ensemble de tablette detergente et procédé d'emballage

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0913808D0 (en) 2009-08-07 2009-09-16 Mcbride Robert Ltd Dosage form detergent products
DE102015213939A1 (de) * 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Mehrphasiges Geschirrspülmittel umfassend einen Tensid-Kern
DE102015213938A1 (de) * 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Einsatz einer Kombination aus Komplexbildner und Tensid zur Verbesserung der Klarspülleistung
DE102018221584A1 (de) * 2018-12-13 2020-06-18 Henkel Ag & Co. Kgaa Verfahren zur Herstellung mehrphasiger Wasch- oder Reinigungsmittelformkörper

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4605509A (en) 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3417649A1 (de) 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
DE3541147A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Reinigungsmittelkompaktate
GB8619634D0 (en) 1986-08-12 1986-09-24 Unilever Plc Antifoam ingredient
US4818426A (en) 1987-03-17 1989-04-04 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
DE3742043A1 (de) 1987-12-11 1989-06-22 Hoechst Ag Verfahren zur herstellung von kristallinen natriumschichtsilikaten
CA2001927C (fr) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
EP0458398B1 (fr) 1990-05-21 1997-03-26 Unilever N.V. Activation du blanchiment
US5383917A (en) 1991-07-05 1995-01-24 Jawahar M. Desai Device and method for multi-phase radio-frequency ablation
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
EP1032643B1 (fr) 1997-11-10 2003-05-21 The Procter & Gamble Company Pastille de detergent faite d'une partie comprimee et d'une partie non comprimee
ES2198768T3 (es) 1997-11-10 2004-02-01 THE PROCTER & GAMBLE COMPANY Procedimiento para fabricar una pastilla detergente.
GB9906172D0 (en) * 1999-03-17 1999-05-12 Unilever Plc A process for producing a water soluble package
EP1043390A1 (fr) 1999-04-09 2000-10-11 The Procter & Gamble Company Détergent sous forme de tablette
DE10215320A1 (de) 2002-04-02 2003-10-23 Metagen Pharmaceuticals Gmbh Verwendungen von TFF3 bindenden Substanzen zur Diagnose und Behandlung von Krebserkrankungen
DE10223266C1 (de) * 2002-05-24 2003-11-20 Henkel Kgaa Verwendung Einspülkammer-dosierbare Tabletten-Portionen
ATE307191T1 (de) 2002-06-11 2005-11-15 Unilever Nv Waschmitteltabletten
ATE391168T1 (de) * 2002-06-11 2008-04-15 Unilever Nv Waschmitteltabletten
ES2301755T3 (es) 2002-06-14 2008-07-01 Unilever N.V. Pastillas detergentes.
DE10233564A1 (de) * 2002-07-24 2003-10-16 Henkel Kgaa Wasch- und Reinigungsmittelportionen mit Umhüllung
EP1405902A1 (fr) 2002-10-01 2004-04-07 Unilever N.V. Compositions détergentes
EP1405901B1 (fr) 2002-10-01 2007-06-13 Unilever N.V. Compositions détergentes
DE60209658T2 (de) 2002-10-01 2006-08-10 Unilever N.V. Waschmittelzusammensetzungen
DE60208493T2 (de) 2002-10-09 2006-07-06 Unilever N.V. Verfahren zur Herstellung einer Reinigungsmitteltablette
DE10253213B3 (de) * 2002-11-15 2004-07-22 Henkel Kgaa Wasserlösliche Portionsverpackung mit Füllung und Verfahren zu deren Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012069895A1 (fr) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Comprimé soluble contenant des éléments abrasifs
DE102010051226A1 (de) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Ausspültablete mit abrasiven Bestandteilen
US9924863B2 (en) 2012-04-05 2018-03-27 Bioptigen, Inc. Optical coherence tomography systems integrated with surgical microscopes
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning
US11596587B2 (en) 2017-02-02 2023-03-07 Water Pik, Inc. Tablet including abrasive for dental cleaning
WO2021214408A1 (fr) * 2020-04-20 2021-10-28 Eurotab Operations Ensemble de tablette detergente et procédé d'emballage

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