WO2007007037A1 - Article and method - Google Patents

Article and method Download PDF

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Publication number
WO2007007037A1
WO2007007037A1 PCT/GB2006/002412 GB2006002412W WO2007007037A1 WO 2007007037 A1 WO2007007037 A1 WO 2007007037A1 GB 2006002412 W GB2006002412 W GB 2006002412W WO 2007007037 A1 WO2007007037 A1 WO 2007007037A1
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WO
WIPO (PCT)
Prior art keywords
tablets
tablet
load
washing
dishwashing machine
Prior art date
Application number
PCT/GB2006/002412
Other languages
French (fr)
Inventor
Andreas Wegner
Laurence Geret
Original Assignee
Reckitt Benckiser N.V.
Reckitt Benckiser (Uk) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser N.V., Reckitt Benckiser (Uk) Limited filed Critical Reckitt Benckiser N.V.
Publication of WO2007007037A1 publication Critical patent/WO2007007037A1/en

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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
    • C11D17/0091—Dishwashing 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

Definitions

  • the present invention relates to cleaning tablets, including dishwashing tablets, laundry cleaning tablets and wa- ter softening tablets used in cleaning methods.
  • the invention further relates to cleaning methods using such tablets.
  • detergents in tablet form. These tablets are usually manufactured from the same ingredients as the known powders or granules, with the addition of tabletting aids. The problems with the formation of lumps which are known with powders and granules are avoided by such tablets.
  • the known detergent tablets also have the advantage that they avoid the need to measure out powder or granules which can sometimes be somewhat complicated and tiresome.
  • such tablets have a disadvantage compared to the use of powder or granules which is that they reduce the flexibility in measuring out the required quantity of de- tergent .
  • Known detergent tablets may comprise a detergent composition together with other cleaning aid compositions.
  • known multi-benefit automatic dishwasher tablets comprise three major components: a detergent composition, a water softening function ("salt function”) and a rinse aid function. These components may be provided in separate conjoined layers of the tablet and arranged to dissolve into the wash water during different stages of the washing operation.
  • Such an automatic dishwasher tablet comprising a detergent, dishwasher salt function and rinse aid function to weigh between 20 and 25g.
  • a tablet may comprise around 1Og of detergent composition, around 1Og of water softening function composition and around Ig to 2g of rinse aid function.
  • dishwasher detergent in the form of smaller tablets is known from EP 0 318 204 Al.
  • this document relates to difficulties associated with incompatible components. In this case it is necessary to use a combination of at least two types of tablet with incompatible components being distributed among the tablet types in such a way that substantially only compatible ingredients are formulated in the same tablet type.
  • the different types can either be offered separately and mixed in the correct proportions by the user or provided as a pre-mixed product.
  • both cases have their own difficulties.
  • the difficulty arises of maintaining the correct proportions between the various tablet types when measuring out the amount required.
  • problems occur if the tablet types become unevenly distributed in the mixture or if they are separated during transport or storage .
  • the present invention aims to address at least one disadvantage associated with the prior art whether discussed herein or otherwise.
  • a multi-benefit cleaning tablet for use in a washing operation, characterised in that the tablet has a mass of between Ig and 15g such that it can be used singularly or with one or more other like tablets depending upon a required washing performance.
  • the term multi-benefit is intended to encompass cleaning tablets which serve more than one function in use.
  • the multi-benefit comprises detergent plus rinse aid (3-in-l) functions or detergent plus rinse aid plus water-softening (3-in-l) functions.
  • the cleaning tablet comprises a detergent compo- sition.
  • the cleaning tablet may comprise a water-softening tablet which comprises a cleaning composition comprising a water-softening composition.
  • the cleaning tablet comprises a tablet for use in an automatic ware washing machine .
  • the cleaning tablet comprises a tablet for use in an automatic dishwashing machine.
  • a tablet for use in an automatic dishwashing machine the term multi-benefit is intended to encompass the expressions of w 2-in-l" (detergent plus rinse aid function) and "3-in-l"
  • the tablet may not normally need to be used in com- bination with separately added rinse aid and/or dishwasher salt (although of course one or more of these formulations may be added should the washing conditions require) .
  • the rinse aid function is preferably provided by the presence of a surfactant and the water softening function may be provided by the presence of a builder.
  • the tablet comprises detergent composition and rinse aid and suitably water-softener composition.
  • the tablet comprises detergent composition and surfactant to provide a rinse aid function.
  • the tablet comprises detergent composition and builder to provide a water-softener function.
  • the tablets may be enhanced to provide further functions in use.
  • the further functions are generally selected from glass / decor/ enamel/ ceramic / metal (e.g. stainless steel and / or aluminium) protection and dishwasher machine protection.
  • the glass / decor / enamel / ceramic protection is generally provided by inclusion of a source of zinc and / or bismuth.
  • the dishwasher machine protection is generally provided by en- suring that the dishwasher wash liquor has a high pH and / or by the inclusion of protective metal salts such as phosphonates .
  • cleaning composition is understood in the broad sense in the present application, namely as comprising all those substances and mixtures of substances which can be used in connection with cleaning processes. These include not only the compositions which are actually active in cleaning, such as detergents, for example dishwasher de- tergents, and washing substances, but all compositions which support cleaning functions concerned, such as water softeners, or which have the effect of providing protective care, such as fabric treaters or final rinses.
  • cleaning composition are mixtures of ingredients selected from: surfactant, builder, filler, bleach (optionally containing also bleach activator and/or a bleach catalyst) , water-softening composition and en- zymes.
  • the cleaning composition may contain other minor ingredients such as dye, fragrance and optical bright- eners .
  • water-softening composition we mean a mixture of a water-softening active (s) with other compounds selected from those mentioned in the previous paragraph, or elsewhere in this specification.
  • detergent composition is understood to comprise all those substances and mixtures of substances which are active in cleaning, such as detergents and washing substances.
  • detergent composition mixtures of ingredients selected from: surfactant, builder, filler, bleach (optionally containing also bleach activator and/or a bleach catalyst) and enzymes.
  • the tablet according to the present invention may comprise a multi zone tablet to aid the consumer to recognise that the tablet provides multi-functional ability.
  • the different zoning may be required because of incompatibility between the components of each of the func- tions. This incompatibility could either be in terms of chemical incompatibility / antagonism or physical incompatibility in that the arrangement of the zones is influenced by (for example) the order of release of the functions into the wash liquor.
  • the zoning may take a variety of forms.
  • the zoning may take the form of a multilayer tablet, with each zone having a distinct composition.
  • the zoning may take the form of one or more inserts / appendices in / on a single / multilayer tablet.
  • the functions may be arranged in a concentric fashion, such as a block hav- ing successive layers.
  • the zones dissolve in the wash liquor at differential rates or even at different stages of the wash cycle.
  • one or more function of the tablet may contain a delaying agent or a scattering agent .
  • Preferred forms of delaying agents are water soluble coatings. If the aim of the delay is, for example, for the ingredients to be released in a certain phase of the washing cycle, as is the case with formulations for the final rinse for machine rinsing in the form of the invention, pH-dependent coating materials can be used. Alternatively temperature-dependent coatings can be used.
  • the coating may also provide greater stability during storage and handling as well as a certain delay in dissolution in the wash liquor.
  • Preferred forms of scattering agents include swelling components (such as cellulose) or effervescent systems, such as a combination of bicarbonate of soda and citric acid, in order to support the rapid dissolution of the tablets, especially when poorly soluble ingredients are included.
  • swelling components such as cellulose
  • effervescent systems such as a combination of bicarbonate of soda and citric acid
  • the tablet may typically comprise, for example, a bleach, stain remover, water-softener, enzyme or fabric conditioner, in addition to the cleaning composition.
  • the tablet may be designed to release components at different times during the laundry ⁇ wash.
  • a bleach or fabric conditioner is generally released at the end of a wash
  • a water-softener is generally released at the start of a wash.
  • An enzyme may be released at the start or the end of a wash.
  • the tablet may comprise, for, example, a water-softener, salt function, enzyme, rinse aid function, bleach or bleach activator.
  • the tablet may be designed to release the components at different times during the wash cycle. For example, a rinse aid, bleach or bleach activator is generally released at the end of a wash, and a water-softener, salt or enzyme is generally released at the start of a wash.
  • the tablet has a mass of no more than 14g, more preferably no more than 13g, more preferably no more than 12g, more preferably no more than Hg, still more prefera- bly no more than 1Og.
  • the tablet may have a mass of no more than 9g, for example of no more than 8g, 7g, ⁇ g, or 5g.
  • the tablet has a mass of at least 2g, more preferably at least 3g.
  • the tablet may have a mass of at least 4g, for example at least 5g, 6g, 7g or 8g.
  • the tablet comprises a detergent composition in an amount of from Ig to 12g, preferably an amount of from 2g to 8g, for example an amount of from 3g to 6g.
  • the tablet comprises detergent composition in an amount of no more than 12g, preferably no more than Hg, more preferably no more than 1Og, for example no more than 9g# 8g, 7g, 6g, 5g, 4g, 3g or 2g.
  • the tablet comprises a detergent composition in an amount of at least Ig, preferably at least 2g, for example at least 3g,' 4g, 5g, 6g, 7g or 8g.
  • the tablet has a mass of between Ig and 7g, preferably of between 2g and 6g, more preferably between 3g and 5g, for example around 4g.
  • the tablet has a mass of between 5g and 13g, preferably between 7g and Hg, more preferably between 8g and 1Og, for example around 9g.
  • the cleaning composition comprises detergent composition which comprises a substantially complete formulation for its respective use. Accordingly, it is suitably not necessary to employ a number of tablets ac- cording to the present invention comprising different compositions. Difficulties associated with a consumer having to count out a selection of different tablets may thus be avoided.
  • the tablet is free from phosphorus-containing compounds .
  • the cleaning tablets of the present invention may have a number of advantages compared to known larger tablets.
  • the tablet As the tablet is smaller than known tablets it comprises less detergent and thus if a single tablet is used in a wash cycle of an automatic dishwashing machine there will be less release of detergent composition into the waterways.
  • the use of a single ' tablet in a ware washing machine of the floor standing type may be appropriate to wash a small load or if the load is lightly soiled and thus the use of tablets accordingly to the present invention may provide significant environmental benefits.
  • Tablets according to the present invention may also be "multi-dosed" .
  • one tablet could be used with the environmental advantage as described above.
  • two tablets may be used.
  • For a particularly heavily soiled load three tablets may be used.
  • a consumer may be provided with the flexibility to vary the amount of detergent used in an automatic dishwashing machine, particularly in a machine of the floor standing type, without having to expend the time and energy associated with using powder or granular detergents .
  • the use of two like tablets of the present invention may be more effective than the use of a known tablet having the same formulation as the tablets of the present invention and a weight equal to the combined weight of said two tablets of the present invention.
  • the tablets according to the present invention may also retain the benefits that those known tablets have over powder or granular detergent compositions.
  • Tablets according to the present invention may be less susceptible to breakage and may be more easily removed from a machine chamber and distributed in a dish washing machine than known tablets.
  • a problem which occasionally occurs with known dishwasher detergent tablets, namely that the tablets become stuck between pieces of crockery and do not dissolved correctly as a result, may also be substantially avoided.
  • the tablet is such that it need not be used in combination with other tablets of differing type.
  • the starting material for the cleaning tablets of the in- vention may be formulated in the same way as conventional powders, granules or tablets.
  • a suitable formulation for a tablet composition may therefore comprise a large number of different ingredients, which may include any of the following: builders, surfactants, enzymes, bleaches, bleach activators, sources of alkalinity, dyes, perfumes, disintegrants, dispersants for lime soaps, organic polymers, including polymers to inhibit colour transfer, crystal growth inhibitors, complexing agents for heavy metal ions, salts, enzyme stabilisers, corrosion inhibitors, solvents, fabric softeners, optical brighteners, hydro- tropic agents, etc.
  • the tablet composition may contain suitable fillers, such as sulphates and chlorides, and tabletting aids, such as polyethylene glycol, starch or starch derivatives, etc.
  • water-softening particulates which may be 1 used in tablets according to the present invention include:
  • citrate salts for example alkali metal citrates, and especially sodium citrate.
  • a compound of class A) and a compound of class B) are both present in a water-softening composition.
  • Additional beneficial compounds in a water-softening com- position include one or more of:
  • ion exchange agents including alkali metal (preferably sodium) aluminosilicates, either crystalline, amorphous or a mixture of the two;
  • ion capture agents - agents which prevent metal ions from forming insoluble salts or reacting with surfactants, such ⁇ as polyphosphate, monomeric polycarbonates, such as citric acid ⁇ or salts thereof, EDTA, algins, alginates; and
  • anti-nucleating agents - agents which prevent seed crystal growth such as polycarbonate polymers, such as polyacfylates, acrylic/maleic copolymers, and acrylic phosphonates, and sulfonates.
  • a cleaning tablet may contain surface active agents such as an anionic, non-ionic, cationic, amphoteric or zwitterionic surface active agents or mixtures thereof.
  • anionic surfactants are straight-chained or branched alkyl sulfates and alkyl polyalkoxylated sulfates, also known as alkyl ether sulfates. Such surfactants may be produced by the reaction of sulfates with higher (e.g. C 8 -C 2 O) fatty alcohols.
  • Examples of primary alkyl sulfate surfactants are those of formula:
  • R is a linear C 8 -C 2 O hydrocarbyl group and M is a water-solubilising cation.
  • R is Ci 0 -Ci 6 alkyl, for example Ci 2 -Ci 4
  • M is alkali metal such as lithium, sodium or potassium.
  • secondary alkyl sulfate surfactants are those which have the sulfate moiety on a "backbone" of the molecule, for example those of formula:
  • n and n are independently 2 or more, the sum of m+n typically being 6 to 20, for example 9 to 15, and M is a water-solubilising cation such as lithium, sodium or potassium.
  • Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants of formulae:
  • x is at least 4, for example 6 to 20, preferably 10 to 16.
  • M is cation, such as an alkali metal, for example lithium, sodium or potassium.
  • alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the formula:
  • R is a C 8 -C 20 alkyl group, preferably Ci 0 -Ci 8 such as a C 12 -Ci 6
  • n is at least 1, for example from 1 to 20, preferably 1 to 15, especially 1 to 6
  • M is a salt- forming cation such as lithium, sodium, potassium, aramo- nium, alkylammonium or alkanolammonium.
  • alkyl sulfates and alkyl ether sulfates will generally be used in the form of mixtures comprising varying alkyl chain lengths and, if present, varying degrees of alkoxy- lation.
  • Other anionic surfactants which may be employed are salts of fatty acids, for example C 8 -C 18 fatty acids, especially the sodium or potassium salts, and alkyl, for example C 8 - Ci 8 , benzene sulfonates.
  • non-ionic surfactants are fatty acid alkoxy- lates, such as fatty acid ethoxylates, especially those of formula:
  • R is a straight or branched C 8 -Ci S alkyl group, preferably a C 9 -C 15 , for example Ci 0 -C 14 , alkyl group and n is at least 1, for example from 1 to 16, preferably 2 to 12, more preferably 3 to 10.
  • the alkoxylated fatty alcohol non-ionic surfactant will frequently have a hydrophilie-lipophilic balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, most preferably from 10 to 15.
  • HLB hydrophilie-lipophilic balance
  • fatty alcohol ethoxylates are those made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials are commercially marketed under the trademarks NEODOL 25-7 and NEODOL 23-6.5 by Shell Chemical Company.
  • Other useful compounds of this type include NEODOL 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide,- NEODOL 23-9, an ethoxylated primary Ci 2 -C 13 alcohol having about 9 moles of ethylene oxide; and NEODOL 91-10, an ethoxylated C 9 -Ci 1 primary alcohol having about 10 moles of ethylene oxide.
  • DOBANOL 91-5 is an ethoxylated C 9 -Ci 1 fatty alcohol with an average of 5 moles ethylene oxide
  • DOBANOL 25-7 is an ethoxylated Ci 2 -Ci 5 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol .
  • Suitable ethoxylated alcohol non-ionic surfactants include TERGITOL 15-S-7 and TERGITOL 15-S-9, both of which are linear secondary alcohol ethoxylates available from Union Carbide Corporation.
  • TERGITOL 15-S-7 is a mixed ethoxylated product of a C 11 -Ci 5 linear secondary alkanol with 7 moles of ethylene oxide and TERGITOL 15-S-9 is the same but with 9 moles of ethylene oxide.
  • Suitable alcohol ethoxylated non-ionic surfactants are NEODOL 45-11, which is a similar ethylene oxide condensation products of a fatty alcohol having 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also available from Shell Chemical Company.
  • non-ionic surfactants are, for example, C 10 -C 18 al- kyl polyglycosides, such as C 12 -C 16 alkyl polyglycosides .
  • surfactants are polyhydroxy fatty acid amides, such as Ci 0 -C 18 N- (3-methoxypropyl) glycamides and ethylene oxide-propylene oxide block polymers of the Pluronic type.
  • cationic surfactants are those of the quaternary ammonium type.
  • the total content of surfactants in the tablet is desirably 60 to 95 wt%, especially 75 to 90 wt%.
  • an anionic surfactant is present in an amount of 50 to 75 wt%
  • the nonionic surfactant is present in an amount of 5 to 50 wt%
  • the cationic surfactant is present in an amount of from 0 to 20 wt%, by weight of tablet.
  • the tablets may also independently comprise enzymes, such as protease, lipase, amylase, cellulase and peroxidase enzymes.
  • enzymes are commercially available and sold, for example, under the registered trade marks ESPERASE, ALCALASE and SAVINASE by Nova Industries A/S and MAXATASE by International ' Biosynthetics, Inc.
  • the enzymes are independently present in the tablets in an amount of from 0.5 to 3 wt%, especially 1 to 2 wt%, when added as commercial preparations they are not pure and this represents an equivalent amount of 0.005 to 0.5 wt% of pure enzyme. As mentioned above they can be incorporated after extrusion if wished.
  • the tablets may, if desired, comprise a thickening agent or gelling agent.
  • Suitable thickeners are polyacrylate polymers such as those sold under the trade mark CARBOPOL, or the trade mark ACUSOL by Rohm and Haas Company.
  • Other suitable thickeners are xanthan gums.
  • the thickener if present, is generally present in an amount of from 0.2 to 4 wt%, especially 0.5 to 2 wt%.
  • Tablets used in dishwashing independently usually comprise a detergency builder.
  • the builders counteract the effects of calcium, or other ion, water hardness.
  • examples of such materials are citrate, succinate, malonate, carboxy- methyl succinate, carboxylate, polycarboxylate and polya- cetyl carboxylate salts, for example with alkali metal or alkaline earth metal cations, or the corresponding free acids.
  • Specific examples are sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, Ci 0 -C 2 S fatty acids and citric acid.
  • organic phosphonate type sequestering agents such as those sold by Monsanto under the trade mark DEQUEST and alkylhydroxy phosphonates .
  • Citrate salts and C 12 -C 18 fatty acid soaps are preferred.
  • Further builders are: phosphates such as sodium, potassium or ammonium salts of mono-, di- or tri-poly or oligo-phosphates; zeolites; silicates, amorphous or structured, such as sodium, potassium or ammonium salts.
  • Suitable builders are polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic and copolymers and their salts, such as those sold by BASF under the trade mark SOKALAN.
  • the builder is desirably present in an amount of up to 90 wt%, preferably 15 to 90 wt%, more preferably 15 to 75 wt%, relative to the total weight of the tablet. Further details of suitable components are given in, for example, EP-A-694,059, EP-A-518,720 and WO 99/06522.
  • the tablets can also optionally comprise one or more additional ingredients.
  • additional ingredients include conventional cleaning composition components such as further surfactants, bleaches, bleach enhancing agents, builders, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, organic solvents, co-solvents, phase stabilisers, emulsifying agents, preservatives, soil suspending agents, soil release agents, germicides, pH adjusting agents or buffers, non-builder alkalinity sources, chelating agents, clays such as smectite clays, enzyme stabilizers, anti- limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting agents, brighteners, and perfumes'. If used, such optional ingredients will generally constitute no more than 10 wt%, for example from 1 to 6 wt%, of the total weight of the tablets.
  • Tablets which comprise an enzyme may optionally contain materials which maintain the stability of the enzyme.
  • enzyme stabilizers include, for example, polyols such as propylene glycol, boric acid and borax. Combinations of these enzyme stabilizers may also be employed. If utilized, the enzyme stabilizers generally constitute from 0.1 to 1 wt% of the tablets.
  • Preferred dishwashing tablets are adapted to be used in automatic dish washing machines. Due to their specific requirements specialised formulation is required and these are illustrated below.
  • Amounts of the ingredients can vary within wide ranges, however preferred automatic dishwashing cleaning composition tablets herein (which typically have a 1% aqueous solution pH of above 8, more preferably from 9.5 to 12, most preferably from 9.5 to 10.5) are those wherein there is present: from 5% to 90%, preferably from 5% to 75%, of builder; from 0.1% to 40%, preferably from 0.5% to 30%, of bleaching agent; from 0.1% to 15%, preferably from 0.2% to 10%, of the surfactant system; from 0.0001% to 1%, preferably from 0.001% to 0.05%, of a metal-containing bleach catalyst; and from 0.1% to 40%, preferably from 0.1% to 20% of a water-soluble silicate.
  • Such fully-formulated embodiments typically further comprise from 0.1% to 15% of a polymeric dispersant, from 0.01% to 10% of a chelant, and from 0.00001% to 10% of a detersive enzyme, though further additional or adjunct ingredients may be present.
  • Non-ionic surfactants useful in ADW (Automatic Dish Washing) tablets of the present invention desirably include surfactant (s) at levels of from 1% to 10% of the composition.
  • surfactant s
  • bleach-stable surfactants are preferred.
  • Non-ionic surfactants generally are well known, being described in more detail in Kirk Othmer ' s Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Sur- factants and Detersive Systems", incorporated by reference herein.
  • an ADW tablet comprises at least one non-ionic surfactant.
  • non-ionics are ethoxylated non- ionic surfactants prepared by the reaction of a monohy- droxy alkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 16 moles, and still more preferably at least 20 moles of ethylene oxide per mole of alcohol or alkylphe- nol .
  • non-ionic surfactants are formed from a linear chain fatty alcohol with 16-20 carbon atoms and at least 12 moles, particularly preferably at least 16 moles, and still more preferably at least 20 moles, of ethylene oxide, per mole of alcohol.
  • the non-ionic surfactant may additionally comprise propylene oxide (PO) units in the molecule.
  • PO propylene oxide
  • the PO units constitute up to 25% by weight, preferably up to 20% by weight and still more preferably up to 15% by weight of the overall molecular weight of the non-ionic surfactant.
  • Particularly preferred surfactants are ethoxylated mono- hydroxy alkanols or alkylphenols, which additionally comprises polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol portion of such surfac- tants constitutes more than 30%, preferably more than 50%, more preferably more than 70% by weight of the overall molecular weight of the non-ionic surfactant.
  • non-ionic surfactants includes reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane .
  • Another preferred non-ionic surfactant can be described by the formula:
  • R 1 represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof
  • R 2 represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms or mixtures thereof
  • x has a value between 0.5 and 1.5
  • y has a value of at least 15.
  • nonionic surfactants are the end-capped polyoxyalkylated non-ionics of formula: R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2
  • R 1 and R 2 represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocar- bon groups with 1-30 carbon atoms
  • R 3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n- butyl, 2-butyl or 2-methyl-2 -butyl group
  • x has a value between 1 and 30 and
  • k and j have values between 1 and 12, preferably between 1 and 5.
  • R 1 and R 2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where groups with 8 to 18 carbon atoms are particularly preferred.
  • group R 3 H methyl or ethyl are particularly preferred.
  • Particularly preferred values for x are from 1 and 20, preferably from 6 to 15.
  • each R 3 in the formula can be different.
  • (R 3 methyl) units which can be used in every single order for example (PO) (EO) (EO) , (EO) (PO) (EO) , (EO) (EO) (PO) ,
  • the value 3 for x is only an example and bigger values can be chosen whereby a higher number of variations of (EO) or (PO) units would arise.
  • a tablet disintegrant could be present in the tablets, for example a water-swellable cellulosic compound.
  • the cleaning tablets of the present invention can suitably be manufactured using a variety of processes; for example by pressing under pressure. Depending on the demands placed on the dissolution behaviour and stability in storage and transport, and depending on the nature of the ingredients, the appropriate pressing pressure can be set accordingly.
  • a further preferred manufacturing process is compacting, which is understood in this application to mean pressing agglomeration without the use of binders, which is usually performed by rollers rotating in opposite directions and possessing grooves of the appropriate dimensions.
  • binders which is usually performed by rollers rotating in opposite directions and possessing grooves of the appropriate dimensions.
  • Tablets accordingly to the invention may be manufactured using procedures other than compacting (e.g. extrusion / injection moulding) , and non-compacting methods may pro- vide greater flexibility with regard to the manufacturing process .
  • a cleaning tablet of the invention may be used in a variety of ways.
  • Other fields of use in the detergent sector are conceivable and possible, such as use as a detergent composition for dissolution in water, for cleaning hard surfaces, such as floors.
  • the tablet is arranged such that N tablets can be employed in a washing method to wash a load which substantially corresponds to a full load of a ware washing machine, and which load has a normal level of soiling, wherein N is 1, 2, 3 or 4.
  • N is 2 for an automatic dishwasher of the floor standing type.
  • the tablet is arranged such that the number of tablets employed in the washing method can be adjusted as detailed in the second aspect which follows.
  • a method of performing a washing operation characterised in that the method employs one or more tablets according to the first aspect and a quantity of water.
  • the tablets comprise a detergent composition.
  • the tablets are substantially identical.
  • the method only employs substantially identical tablets according to the first aspect . It may thus not be necessary to use a combination of tablets having distinct formulations.
  • the method comprises washing articles in an automatic ware washing machine. More preferably the method comprises washing articles, for example crockery, within an automatic dishwashing machine.
  • the method comprises the step of determining whether one or more tablets are required depending on the level of soiling and the quantity of articles to be washed.
  • the method will use N tablets.
  • N 1 to 4.
  • A 0 to 2.
  • A is > 0 and ⁇ (N - 1).
  • for a domestic dish washer of the floor standing type A 1 or 2 , preferably 1.
  • the method will use N - B tablets.
  • B 0 to 2.
  • B is > 0 and ⁇ (N - 1) .
  • B 1 or 2, preferably 1.
  • the method will use N - C tablets.
  • C 0 to 2.
  • C is > 0 and ⁇ (N - I).
  • N a domestic dishwasher of the floor standing type
  • A, B and C have fixed values.
  • a domestic dishwasher of the floor standing type A, B and C have the same value.
  • variation of the "dose" of tablets may thus be simple for a user to perform.
  • N For a domestic dish washer of the table top type N may be 1 or 2, suitably 1.
  • B and C are 0.
  • A may also be 0. Whilst it may thus not be possible to vary the "dose" in the same manner this may not be problematic since such a dishwasher is, for example, less likely to be operated part loaded.
  • the determination step comprises a user noting the extent of soiling of the articles to be washed, noting the extent to which a machine is loaded and determining whether N tablets should be used or if an adjustment needs to be made.
  • a value for N will be provided with the tablets.
  • a user will use a value for A, B or C provided with the tablets.
  • a packaged product comprising a packet containing one or more tablets according to the first aspect; preferably at least two tablets, more preferably at least three tablets, and most preferably at least four tablets.
  • the packet contains up to ten tablets, preferably up to eight tablets, and most preferably up to six tablets.
  • the tablets are substantially identical.
  • the packet comprises a plastics wrapper providing a water tight container for one or more tablets.
  • the packaged product comprises instructions for varying the "dose" of tablets employed to perform a washing operation.
  • the instructions comprise instructions for performing a method according to the second aspect .
  • the instructions include values for N, A, B and C as described in the second aspect .
  • the packet comprises N tablets.
  • N is 2.
  • Example 1 Cleaning tablets of cuboid shape having a length of 24mm, a width of 16mm and a thickness of 14mm were produced by tabletting a tablet composition to provide a tablet having, a mass of around 9g.
  • the tablets had the following formulation:
  • the tablets were produced according to the following method. Solid raw materials are weighed separately into the mixing vessel. Liquids are weighed and added to the mixture. Raw materials are combined in a commercial mixer for 10 minutes. Mixtures are then emptied into drums and transferred to the storage vessel of a rotary press. A rotary press is used to press the tablets, the final compression forces are on average 34 kN.

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Abstract

The invention provides multi-benefit cleaning tablets for use in a washing operation. The tablets are characterised in that each tablet has a mass of between 1g and 15g such that it can be used singularly or with one or more other like tablets depending upon a required washing performance. Also provided are cleaning methods which use the tablets and packaged products which comprise the tablets.

Description

ARTICLE AND METHOD
The present invention relates to cleaning tablets, including dishwashing tablets, laundry cleaning tablets and wa- ter softening tablets used in cleaning methods. The invention further relates to cleaning methods using such tablets.
It is known to provide cleaning compositions in various forms for use in ware washing machines such as dish and clothes washing machines .
One of the most common forms in which laundry and dish washer detergents are used consists of powder or granules in which the average particle size ranges between 0.1 and 2mm in diameter. In use, such powder or granules are placed in a chamber from which they are washed out during the washing cycle . Because of the hygroscopic nature of the powder or granules lumps occasionally form as a result of which the detergent may not be correctly delivered into the washing chamber of a dishwasher or washing machine. It is known to use additives to alleviate this effect, but these may not always be effective.
Accordingly, as an alternative to powders or granules it is known to use detergents in tablet form. These tablets are usually manufactured from the same ingredients as the known powders or granules, with the addition of tabletting aids. The problems with the formation of lumps which are known with powders and granules are avoided by such tablets. The known detergent tablets also have the advantage that they avoid the need to measure out powder or granules which can sometimes be somewhat complicated and tiresome. However, such tablets have a disadvantage compared to the use of powder or granules which is that they reduce the flexibility in measuring out the required quantity of de- tergent . Instead, it is usual for the same amount of detergent to be added to every washing cycle, which is determined by the size of the tablet, irrespective of whether the crockery or laundry to be cleaned is heavily or lightly soiled and/or whether the machine being oper- ated has a full or reduced load.
Known detergent tablets may comprise a detergent composition together with other cleaning aid compositions.
For example, known multi-benefit automatic dishwasher tablets comprise three major components: a detergent composition, a water softening function ("salt function") and a rinse aid function. These components may be provided in separate conjoined layers of the tablet and arranged to dissolve into the wash water during different stages of the washing operation.
It is typical for such an automatic dishwasher tablet comprising a detergent, dishwasher salt function and rinse aid function to weigh between 20 and 25g. For example, such a tablet may comprise around 1Og of detergent composition, around 1Og of water softening function composition and around Ig to 2g of rinse aid function. In order to clean crockery using a domestic dishwasher a single tablet will be added regardless of the amount of crockery or extent of the soiling of the crockery which is to be washed in the dishwasher. The provision of dishwasher detergent in the form of smaller tablets is known from EP 0 318 204 Al. However, this document relates to difficulties associated with incompatible components. In this case it is necessary to use a combination of at least two types of tablet with incompatible components being distributed among the tablet types in such a way that substantially only compatible ingredients are formulated in the same tablet type.
The different types can either be offered separately and mixed in the correct proportions by the user or provided as a pre-mixed product. However, both cases have their own difficulties. In the first case, the difficulty arises of maintaining the correct proportions between the various tablet types when measuring out the amount required. In the second case, problems occur if the tablet types become unevenly distributed in the mixture or if they are separated during transport or storage .
Accordingly, there remains a need to provide a detergent composition in a form which allows for variable dosage in a simple manner which is convenient for the consumer.
Accordingly, the present invention aims to address at least one disadvantage associated with the prior art whether discussed herein or otherwise.
According to a first aspect' of the present invention there is provided a multi-benefit cleaning tablet for use in a washing operation, characterised in that the tablet has a mass of between Ig and 15g such that it can be used singularly or with one or more other like tablets depending upon a required washing performance. The term multi-benefit is intended to encompass cleaning tablets which serve more than one function in use.
Suitably, the multi-benefit comprises detergent plus rinse aid (3-in-l) functions or detergent plus rinse aid plus water-softening (3-in-l) functions.
Suitably, the cleaning tablet comprises a detergent compo- sition. Alternatively or in addition, the cleaning tablet may comprise a water-softening tablet which comprises a cleaning composition comprising a water-softening composition.
Suitably, the cleaning tablet comprises a tablet for use in an automatic ware washing machine .
Preferably, the cleaning tablet comprises a tablet for use in an automatic dishwashing machine. In the case of tab- lets for use in an automatic dishwashing machine the term multi-benefit is intended to encompass the expressions of w2-in-l" (detergent plus rinse aid function) and "3-in-l"
(detergent plus rinse aid plus water softening functions) .
Thus, the tablet may not normally need to be used in com- bination with separately added rinse aid and/or dishwasher salt (although of course one or more of these formulations may be added should the washing conditions require) . The rinse aid function is preferably provided by the presence of a surfactant and the water softening function may be provided by the presence of a builder.
Suitably, the tablet comprises detergent composition and rinse aid and suitably water-softener composition. Suita- bly, the tablet comprises detergent composition and surfactant to provide a rinse aid function. Suitably, the tablet comprises detergent composition and builder to provide a water-softener function.
For tablets for use in an automatic dishwashing machine it will also be appreciated that the tablets may be enhanced to provide further functions in use. The further functions are generally selected from glass / decor/ enamel/ ceramic / metal (e.g. stainless steel and / or aluminium) protection and dishwasher machine protection. The glass / decor / enamel / ceramic protection is generally provided by inclusion of a source of zinc and / or bismuth. The dishwasher machine protection is generally provided by en- suring that the dishwasher wash liquor has a high pH and / or by the inclusion of protective metal salts such as phosphonates .
The term "cleaning composition" is understood in the broad sense in the present application, namely as comprising all those substances and mixtures of substances which can be used in connection with cleaning processes. These include not only the compositions which are actually active in cleaning, such as detergents, for example dishwasher de- tergents, and washing substances, but all compositions which support cleaning functions concerned, such as water softeners, or which have the effect of providing protective care, such as fabric treaters or final rinses.
Included in the term "cleaning composition" are mixtures of ingredients selected from: surfactant, builder, filler, bleach (optionally containing also bleach activator and/or a bleach catalyst) , water-softening composition and en- zymes. The cleaning composition may contain other minor ingredients such as dye, fragrance and optical bright- eners .
By use of the term "water-softening composition" we mean a mixture of a water-softening active (s) with other compounds selected from those mentioned in the previous paragraph, or elsewhere in this specification.
As used herein the term "detergent composition" is understood to comprise all those substances and mixtures of substances which are active in cleaning, such as detergents and washing substances.
Included in the term "detergent composition" are mixtures of ingredients selected from: surfactant, builder, filler, bleach (optionally containing also bleach activator and/or a bleach catalyst) and enzymes.
The tablet according to the present invention may comprise a multi zone tablet to aid the consumer to recognise that the tablet provides multi-functional ability. Alternatively the different zoning may be required because of incompatibility between the components of each of the func- tions. This incompatibility could either be in terms of chemical incompatibility / antagonism or physical incompatibility in that the arrangement of the zones is influenced by (for example) the order of release of the functions into the wash liquor.
The zoning, where present, may take a variety of forms. For example the zoning may take the form of a multilayer tablet, with each zone having a distinct composition. Al- ternatively / additionally the zoning may take the form of one or more inserts / appendices in / on a single / multilayer tablet. In a further alternative the functions may be arranged in a concentric fashion, such as a block hav- ing successive layers.
It may be desired that the zones dissolve in the wash liquor at differential rates or even at different stages of the wash cycle. To achieve this aim one or more function of the tablet may contain a delaying agent or a scattering agent .
Preferred forms of delaying agents are water soluble coatings. If the aim of the delay is, for example, for the ingredients to be released in a certain phase of the washing cycle, as is the case with formulations for the final rinse for machine rinsing in the form of the invention, pH-dependent coating materials can be used. Alternatively temperature-dependent coatings can be used.
The coating may also provide greater stability during storage and handling as well as a certain delay in dissolution in the wash liquor.
Preferred forms of scattering agents include swelling components (such as cellulose) or effervescent systems, such as a combination of bicarbonate of soda and citric acid, in order to support the rapid dissolution of the tablets, especially when poorly soluble ingredients are included.
If the tablet is for use in laundry washing, it may typically comprise, for example, a bleach, stain remover, water-softener, enzyme or fabric conditioner, in addition to the cleaning composition. The tablet may be designed to release components at different times during the laundry^ wash. For example, a bleach or fabric conditioner is generally released at the end of a wash, and a water-softener is generally released at the start of a wash. An enzyme may be released at the start or the end of a wash.
If the tablet is for use in dishwashing it may comprise, for, example, a water-softener, salt function, enzyme, rinse aid function, bleach or bleach activator. The tablet may be designed to release the components at different times during the wash cycle. For example, a rinse aid, bleach or bleach activator is generally released at the end of a wash, and a water-softener, salt or enzyme is generally released at the start of a wash.
Preferably the tablet has a mass of no more than 14g, more preferably no more than 13g, more preferably no more than 12g, more preferably no more than Hg, still more prefera- bly no more than 1Og. The tablet may have a mass of no more than 9g, for example of no more than 8g, 7g, βg, or 5g.
Preferably, the tablet has a mass of at least 2g, more preferably at least 3g. The tablet may have a mass of at least 4g, for example at least 5g, 6g, 7g or 8g.
Suitably, the tablet comprises a detergent composition in an amount of from Ig to 12g, preferably an amount of from 2g to 8g, for example an amount of from 3g to 6g.
Suitably, the tablet comprises detergent composition in an amount of no more than 12g, preferably no more than Hg, more preferably no more than 1Og, for example no more than 9g# 8g, 7g, 6g, 5g, 4g, 3g or 2g.
Suitably, the tablet comprises a detergent composition in an amount of at least Ig, preferably at least 2g, for example at least 3g,' 4g, 5g, 6g, 7g or 8g.
Suitably the tablet has a mass of between Ig and 7g, preferably of between 2g and 6g, more preferably between 3g and 5g, for example around 4g.
Suitably, the tablet has a mass of between 5g and 13g, preferably between 7g and Hg, more preferably between 8g and 1Og, for example around 9g.
Suitably, the cleaning composition comprises detergent composition which comprises a substantially complete formulation for its respective use. Accordingly, it is suitably not necessary to employ a number of tablets ac- cording to the present invention comprising different compositions. Difficulties associated with a consumer having to count out a selection of different tablets may thus be avoided.
Suitably, the tablet is free from phosphorus-containing compounds .
The cleaning tablets of the present invention may have a number of advantages compared to known larger tablets.
As the tablet is smaller than known tablets it comprises less detergent and thus if a single tablet is used in a wash cycle of an automatic dishwashing machine there will be less release of detergent composition into the waterways. The use of a single' tablet in a ware washing machine of the floor standing type may be appropriate to wash a small load or if the load is lightly soiled and thus the use of tablets accordingly to the present invention may provide significant environmental benefits. '
Tablets according to the present invention may also be "multi-dosed" . For example, for a small load one tablet could be used with the environmental advantage as described above. For a larger load then two tablets may be used. For a particularly heavily soiled load three tablets may be used. Thus, a consumer may be provided with the flexibility to vary the amount of detergent used in an automatic dishwashing machine, particularly in a machine of the floor standing type, without having to expend the time and energy associated with using powder or granular detergents .
The use of two like tablets of the present invention may be more effective than the use of a known tablet having the same formulation as the tablets of the present invention and a weight equal to the combined weight of said two tablets of the present invention.
Accordingly, it may for example be possible to achieve the same cleaning effect provided by a known 2Og tablet by using two 9g tablets, each having a similar composition as the known tablet. Accordingly, it may be possible to use around 10% less detergent to achieve the same cleaning effect. The environmental benefits associated with the use of tablets accordingly to the present invention will thus be readily apparent . Whilst having advantages over known tablets, the tablets according to the present invention may also retain the benefits that those known tablets have over powder or granular detergent compositions.
Tablets according to the present invention may be less susceptible to breakage and may be more easily removed from a machine chamber and distributed in a dish washing machine than known tablets. A problem which occasionally occurs with known dishwasher detergent tablets, namely that the tablets become stuck between pieces of crockery and do not dissolved correctly as a result, may also be substantially avoided.
Suitably, the tablet is such that it need not be used in combination with other tablets of differing type.
The starting material for the cleaning tablets of the in- vention may be formulated in the same way as conventional powders, granules or tablets. A suitable formulation for a tablet composition may therefore comprise a large number of different ingredients, which may include any of the following: builders, surfactants, enzymes, bleaches, bleach activators, sources of alkalinity, dyes, perfumes, disintegrants, dispersants for lime soaps, organic polymers, including polymers to inhibit colour transfer, crystal growth inhibitors, complexing agents for heavy metal ions, salts, enzyme stabilisers, corrosion inhibitors, solvents, fabric softeners, optical brighteners, hydro- tropic agents, etc. In addition, the tablet composition may contain suitable fillers, such as sulphates and chlorides, and tabletting aids, such as polyethylene glycol, starch or starch derivatives, etc.
Examples of water-softening particulates which may be1 used in tablets according to the present invention include:
A) homo or co polymers of the following monomeric units or salts thereof - acrylic acids, maleic acids, sulfonic acids or phosphonics acid; and/or
B) citrate salts, for example alkali metal citrates, and especially sodium citrate.
Preferably a compound of class A) and a compound of class B) are both present in a water-softening composition.
Additional beneficial compounds in a water-softening com- position include one or more of:
(1) ion exchange agents, including alkali metal (preferably sodium) aluminosilicates, either crystalline, amorphous or a mixture of the two;
(2) ion capture agents - agents which prevent metal ions from forming insoluble salts or reacting with surfactants, such ■ as polyphosphate, monomeric polycarbonates, such as citric acid ■ or salts thereof, EDTA, algins, alginates; and
(3) anti-nucleating agents - agents which prevent seed crystal growth, such as polycarbonate polymers, such as polyacfylates, acrylic/maleic copolymers, and acrylic phosphonates, and sulfonates.
The components of a cleaning tablet depend on its intended use. Generally, the tablet may contain surface active agents such as an anionic, non-ionic, cationic, amphoteric or zwitterionic surface active agents or mixtures thereof.
Examples of anionic surfactants are straight-chained or branched alkyl sulfates and alkyl polyalkoxylated sulfates, also known as alkyl ether sulfates. Such surfactants may be produced by the reaction of sulfates with higher (e.g. C8-C2O) fatty alcohols.
Examples of primary alkyl sulfate surfactants are those of formula:
ROS(VM+
wherein R is a linear C8-C2O hydrocarbyl group and M is a water-solubilising cation. Preferably R is Ci0-Ci6 alkyl, for example Ci2-Ci4, and M is alkali metal such as lithium, sodium or potassium.
Examples of secondary alkyl sulfate surfactants are those which have the sulfate moiety on a "backbone" of the molecule, for example those of formula:
CH2 (CH2) n (CHOSO3-M+) (CH2)mCH3
wherein m and n are independently 2 or more, the sum of m+n typically being 6 to 20, for example 9 to 15, and M is a water-solubilising cation such as lithium, sodium or potassium.
Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants of formulae:
CH2 (CH2) x (CHOSO3-M+) CH3 and
CH3 (CH2) x (CHOSO3-M+) CH2CH3
for the 2-sulfate and 3-sulfate, respectively. > In these formulae x is at least 4, for example 6 to 20, preferably 10 to 16. M is cation, such as an alkali metal, for example lithium, sodium or potassium.
Examples of alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the formula:
RO(C2H4O)nSO3-M+
wherein R is a C8-C20 alkyl group, preferably Ci0-Ci8 such as a C12-Ci6, n is at least 1, for example from 1 to 20, preferably 1 to 15, especially 1 to 6, and M is a salt- forming cation such as lithium, sodium, potassium, aramo- nium, alkylammonium or alkanolammonium. These compounds can provide especially desirable fabric cleaning performance benefits when used in combination with alkyl sulfates.
The alkyl sulfates and alkyl ether sulfates will generally be used in the form of mixtures comprising varying alkyl chain lengths and, if present, varying degrees of alkoxy- lation. Other anionic surfactants which may be employed are salts of fatty acids, for example C8-C18 fatty acids, especially the sodium or potassium salts, and alkyl, for example C8- Ci8, benzene sulfonates.
Examples of non-ionic surfactants are fatty acid alkoxy- lates, such as fatty acid ethoxylates, especially those of formula:
R(C2H4O)nOH
wherein R is a straight or branched C8-CiS alkyl group, preferably a C9-C15, for example Ci0-C14, alkyl group and n is at least 1, for example from 1 to 16, preferably 2 to 12, more preferably 3 to 10.
The alkoxylated fatty alcohol non-ionic surfactant will frequently have a hydrophilie-lipophilic balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, most preferably from 10 to 15.
Examples of fatty alcohol ethoxylates are those made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials are commercially marketed under the trademarks NEODOL 25-7 and NEODOL 23-6.5 by Shell Chemical Company. Other useful compounds of this type include NEODOL 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide,- NEODOL 23-9, an ethoxylated primary Ci2-C13 alcohol having about 9 moles of ethylene oxide; and NEODOL 91-10, an ethoxylated C9-Ci1 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the DOBANOL trademark. DOBANOL 91-5 is an ethoxylated C9-Ci1 fatty alcohol with an average of 5 moles ethylene oxide and DOBANOL 25-7 is an ethoxylated Ci2-Ci5 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol .
Other examples of suitable ethoxylated alcohol non-ionic surfactants include TERGITOL 15-S-7 and TERGITOL 15-S-9, both of which are linear secondary alcohol ethoxylates available from Union Carbide Corporation. TERGITOL 15-S-7 is a mixed ethoxylated product of a C11-Ci5 linear secondary alkanol with 7 moles of ethylene oxide and TERGITOL 15-S-9 is the same but with 9 moles of ethylene oxide.
Other suitable alcohol ethoxylated non-ionic surfactants are NEODOL 45-11, which is a similar ethylene oxide condensation products of a fatty alcohol having 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also available from Shell Chemical Company.
Further non-ionic surfactants are, for example, C10-C18 al- kyl polyglycosides, such as C12-C16 alkyl polyglycosides .
These are especially useful when high foaming compositions are desired. Further surfactants are polyhydroxy fatty acid amides, such as Ci0-C18 N- (3-methoxypropyl) glycamides and ethylene oxide-propylene oxide block polymers of the Pluronic type.
Examples of cationic surfactants are those of the quaternary ammonium type. The total content of surfactants in the tablet is desirably 60 to 95 wt%, especially 75 to 90 wt%. Desirably an anionic surfactant is present in an amount of 50 to 75 wt%, the nonionic surfactant is present in an amount of 5 to 50 wt%, and/or the cationic surfactant is present in an amount of from 0 to 20 wt%, by weight of tablet.
The tablets, particularly when used as laundry washing or dishwashing tablets, may also independently comprise enzymes, such as protease, lipase, amylase, cellulase and peroxidase enzymes. Such enzymes are commercially available and sold, for example, under the registered trade marks ESPERASE, ALCALASE and SAVINASE by Nova Industries A/S and MAXATASE by International ' Biosynthetics, Inc. Desirably the enzymes are independently present in the tablets in an amount of from 0.5 to 3 wt%, especially 1 to 2 wt%, when added as commercial preparations they are not pure and this represents an equivalent amount of 0.005 to 0.5 wt% of pure enzyme. As mentioned above they can be incorporated after extrusion if wished.
The tablets may, if desired, comprise a thickening agent or gelling agent. Suitable thickeners are polyacrylate polymers such as those sold under the trade mark CARBOPOL, or the trade mark ACUSOL by Rohm and Haas Company. Other suitable thickeners are xanthan gums. The thickener, if present, is generally present in an amount of from 0.2 to 4 wt%, especially 0.5 to 2 wt%.
Tablets used in dishwashing independently usually comprise a detergency builder. The builders counteract the effects of calcium, or other ion, water hardness. Examples of such materials are citrate, succinate, malonate, carboxy- methyl succinate, carboxylate, polycarboxylate and polya- cetyl carboxylate salts, for example with alkali metal or alkaline earth metal cations, or the corresponding free acids. Specific examples are sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, Ci0-C2S fatty acids and citric acid. Other examples are organic phosphonate type sequestering agents such as those sold by Monsanto under the trade mark DEQUEST and alkylhydroxy phosphonates . Citrate salts and C12-C18 fatty acid soaps are preferred. Further builders are: phosphates such as sodium, potassium or ammonium salts of mono-, di- or tri-poly or oligo-phosphates; zeolites; silicates, amorphous or structured, such as sodium, potassium or ammonium salts.
Other suitable builders are polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic and copolymers and their salts, such as those sold by BASF under the trade mark SOKALAN. The builder is desirably present in an amount of up to 90 wt%, preferably 15 to 90 wt%, more preferably 15 to 75 wt%, relative to the total weight of the tablet. Further details of suitable components are given in, for example, EP-A-694,059, EP-A-518,720 and WO 99/06522.
The tablets can also optionally comprise one or more additional ingredients. These include conventional cleaning composition components such as further surfactants, bleaches, bleach enhancing agents, builders, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, organic solvents, co-solvents, phase stabilisers, emulsifying agents, preservatives, soil suspending agents, soil release agents, germicides, pH adjusting agents or buffers, non-builder alkalinity sources, chelating agents, clays such as smectite clays, enzyme stabilizers, anti- limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting agents, brighteners, and perfumes'. If used, such optional ingredients will generally constitute no more than 10 wt%, for example from 1 to 6 wt%, of the total weight of the tablets.
Tablets which comprise an enzyme may optionally contain materials which maintain the stability of the enzyme. Such enzyme stabilizers include, for example, polyols such as propylene glycol, boric acid and borax. Combinations of these enzyme stabilizers may also be employed. If utilized, the enzyme stabilizers generally constitute from 0.1 to 1 wt% of the tablets.
Preferred dishwashing tablets are adapted to be used in automatic dish washing machines. Due to their specific requirements specialised formulation is required and these are illustrated below.
Amounts of the ingredients can vary within wide ranges, however preferred automatic dishwashing cleaning composition tablets herein (which typically have a 1% aqueous solution pH of above 8, more preferably from 9.5 to 12, most preferably from 9.5 to 10.5) are those wherein there is present: from 5% to 90%, preferably from 5% to 75%, of builder; from 0.1% to 40%, preferably from 0.5% to 30%, of bleaching agent; from 0.1% to 15%, preferably from 0.2% to 10%, of the surfactant system; from 0.0001% to 1%, preferably from 0.001% to 0.05%, of a metal-containing bleach catalyst; and from 0.1% to 40%, preferably from 0.1% to 20% of a water-soluble silicate. Such fully-formulated embodiments typically further comprise from 0.1% to 15% of a polymeric dispersant, from 0.01% to 10% of a chelant, and from 0.00001% to 10% of a detersive enzyme, though further additional or adjunct ingredients may be present.
Non-ionic surfactants useful in ADW (Automatic Dish Washing) tablets of the present invention desirably include surfactant (s) at levels of from 1% to 10% of the composition. In general, bleach-stable surfactants are preferred. Non-ionic surfactants generally are well known, being described in more detail in Kirk Othmer ' s Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Sur- factants and Detersive Systems", incorporated by reference herein.
Preferably an ADW tablet comprises at least one non-ionic surfactant. One class of non-ionics are ethoxylated non- ionic surfactants prepared by the reaction of a monohy- droxy alkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 16 moles, and still more preferably at least 20 moles of ethylene oxide per mole of alcohol or alkylphe- nol .
Particularly preferred non-ionic surfactants are formed from a linear chain fatty alcohol with 16-20 carbon atoms and at least 12 moles, particularly preferably at least 16 moles, and still more preferably at least 20 moles, of ethylene oxide, per mole of alcohol. The non-ionic surfactant may additionally comprise propylene oxide (PO) units in the molecule. Preferably the PO units constitute up to 25% by weight, preferably up to 20% by weight and still more preferably up to 15% by weight of the overall molecular weight of the non-ionic surfactant. Particularly preferred surfactants are ethoxylated mono- hydroxy alkanols or alkylphenols, which additionally comprises polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such surfac- tants constitutes more than 30%, preferably more than 50%, more preferably more than 70% by weight of the overall molecular weight of the non-ionic surfactant.
Another class of non-ionic surfactants includes reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane .
Another preferred non-ionic surfactant can be described by the formula:
R1O [CH2CH (CH3) O] x [CH2CH2O] γ [CH2CH (OH) R2]
wherein R1 represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof, R2 represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms or mixtures thereof, x has a value between 0.5 and 1.5 and y has a value of at least 15.
Another group of preferred nonionic surfactants are the end-capped polyoxyalkylated non-ionics of formula: R1O [CH2CH (R3) O] x [CH2] kCH (OH) [CH2] jOR2
wherein R1 and R2 represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocar- bon groups with 1-30 carbon atoms, R3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n- butyl, 2-butyl or 2-methyl-2 -butyl group, x has a value between 1 and 30 and, k and j have values between 1 and 12, preferably between 1 and 5. When the value of x is >2 each R3 in the formula above can be different . R1 and R2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where groups with 8 to 18 carbon atoms are particularly preferred. For the group R3 H, methyl or ethyl are particularly preferred. Particularly preferred values for x are from 1 and 20, preferably from 6 to 15.
As described above, when x >2 , each R3 in the formula can be different. For example, when x=3 , the group R3 could be chosen to build ethylene oxide (R3=H) or propylene oxide
(R3=methyl) units which can be used in every single order for example (PO) (EO) (EO) , (EO) (PO) (EO) , (EO) (EO) (PO) ,
(EO) (EO) (EO) , (PO) (EO) (PO) , (PO) (PO) (EO) and (PO) (PO) (PO) .
The value 3 for x is only an example and bigger values can be chosen whereby a higher number of variations of (EO) or (PO) units would arise.
Particularly preferred end-capped polyoxyalkylated alcohols of the above formula are those where k=l and j=l originating molecules of simplified formula:
R1O [CH2CH (R3) 0] XCH2CH (OH) CH2OR2 The use of mixtures of different non-ionic surfactants is particularly preferred in ADW formulations for example mixtures of alkoxylated alcohols and hydroxy group containing alkoxylated alcohols.
A tablet disintegrant could be present in the tablets, for example a water-swellable cellulosic compound.
The cleaning tablets of the present invention can suitably be manufactured using a variety of processes; for example by pressing under pressure. Depending on the demands placed on the dissolution behaviour and stability in storage and transport, and depending on the nature of the ingredients, the appropriate pressing pressure can be set accordingly.
A further preferred manufacturing process is compacting, which is understood in this application to mean pressing agglomeration without the use of binders, which is usually performed by rollers rotating in opposite directions and possessing grooves of the appropriate dimensions. With this .production process, it is also possible to use other ingredients, which are usually not suitable for pressing, because the pressures during cormoactinq are considerably lower.
Tablets accordingly to the invention may be manufactured using procedures other than compacting (e.g. extrusion / injection moulding) , and non-compacting methods may pro- vide greater flexibility with regard to the manufacturing process . A cleaning tablet of the invention may be used in a variety of ways. By way of example, we may refer to use as a dishwasher detergent, as a final rinse in dishwashers, as a detergent in a washing machine or for a hand wash, as a water softener or fabric softening rinse in a washing machine, or as a descaling agent. Other fields of use in the detergent sector are conceivable and possible, such as use as a detergent composition for dissolution in water, for cleaning hard surfaces, such as floors.
Suitably, the tablet is arranged such that N tablets can be employed in a washing method to wash a load which substantially corresponds to a full load of a ware washing machine, and which load has a normal level of soiling, wherein N is 1, 2, 3 or 4. Preferably N is 2 for an automatic dishwasher of the floor standing type. Suitably the tablet is arranged such that the number of tablets employed in the washing method can be adjusted as detailed in the second aspect which follows.
According to a second aspect of the present invention there is provided a method of performing a washing operation characterised in that the method employs one or more tablets according to the first aspect and a quantity of water.
Here it has been found that as the tablets of the present invention are much smaller than conventional commercial detergent tablets they can be accommodated much more eas- ily in a tablet dispenser. This has been found to be of particular significance when a high amount of cleaning agent (i.e. a high number of cleaning tablets is required) . A suggested reason for this effect is that a large number of small tablet may be accommodated much more easily in a tablet dispenser than one larger tablet due to flexibility in positioning. For example it has been found to be easier to accommodate three tablets of weight 9g than one large tablet of weight 27g.
This benefit may seem insignificant as the larger tablet could simply be placed in side the operating part of the machine. However, some automatic washing machines (such as dishwashers) operate a pre-wash cycle in which it is not advantageous to dispense any cleaning formulation. The accommodation of the tablets in the dispenser (which typically does not operate until a main wash cycle) overcomes this disadvantage.
Suitably, the tablets comprise a detergent composition.
Suitably, where the method employs a plurality of tablets the tablets are substantially identical.
Suitably, the method only employs substantially identical tablets according to the first aspect . It may thus not be necessary to use a combination of tablets having distinct formulations.
Preferably, the method comprises washing articles in an automatic ware washing machine. More preferably the method comprises washing articles, for example crockery, within an automatic dishwashing machine.
Preferably, the method comprises the step of determining whether one or more tablets are required depending on the level of soiling and the quantity of articles to be washed.
Suitably, for a load having a normal level of soiling and which load substantially corresponds to a full load of a ware washing machine, the method will use N tablets.
Suitably, N = 1 to 4. Suitably for a domestic dish washer of the floor standing type, N = 2, 3 or 4 , preferably 2.
Suitably, for a load having a heavy level of s'oiling and which load substantially corresponds to a full load of the ware washing machine the method will use N + A tablets.
Suitably, A = 0 to 2. Suitably, A is > 0 and ≤ (N - 1). Suitably, for a domestic dish washer of the floor standing type A = 1 or 2 , preferably 1.
Suitably, for a load having a light level of soiling and which load substantially corresponds to a full load of the ware washing machine the method will use N - B tablets.
Suitably, B = 0 to 2. Suitably, B is > 0 and ≤ (N - 1) . Suitably, for a domestic dishwasher of the floor standing type B = 1 or 2, preferably 1.
Suitably, for a load having a normal level of soiling and which load substantially corresponds to a half load of the ware washing machine the method will use N - C tablets.
Suitably, C = 0 to 2. Suitably, C is > 0 and ≤ (N - I). Suitably, for a domestic dishwasher of the floor standing type C = 1 or 2 , preferably 1. Suitably, for a given ware washing machine and tablet combination N, A, B and C have fixed values. Suitably, for a domestic dishwasher of the floor standing type A, B and C have the same value. Thus variation of the "dose" of tablets may thus be simple for a user to perform.
For a domestic dish washer of the table top type N may be 1 or 2, suitably 1. In this case suitably B and C are 0. In this case A may also be 0. Whilst it may thus not be possible to vary the "dose" in the same manner this may not be problematic since such a dishwasher is, for example, less likely to be operated part loaded.
The terms "normal level of soiling", "heavy level of soiling" and "light level of soiling" as well as "full load" and "half load" are somewhat subjective and will, to a degree, be a matter of judgement for a user. Their judgement may depend in part on the efficiency of their machine and on the water characteristics. However, it will be apparent to a user which situation is most likely to apply in any given case and a user can thus make the determination outlined above and calculate the number of tablets to use according to the basic criteria given above.
Suitably, the determination step comprises a user noting the extent of soiling of the articles to be washed, noting the extent to which a machine is loaded and determining whether N tablets should be used or if an adjustment needs to be made. Suitably, a value for N will be provided with the tablets. Suitably, if an adjustment is required a user will use a value for A, B or C provided with the tablets. According to a third aspect of the present invention there is provided a packaged product comprising a packet containing one or more tablets according to the first aspect; preferably at least two tablets, more preferably at least three tablets, and most preferably at least four tablets. Suitably the packet contains up to ten tablets, preferably up to eight tablets, and most preferably up to six tablets.
Suitably, the tablets are substantially identical.
Suitably, the packet comprises a plastics wrapper providing a water tight container for one or more tablets.
Suitably, the packaged product comprises instructions for varying the "dose" of tablets employed to perform a washing operation.
Suitably, the instructions comprise instructions for performing a method according to the second aspect .
Suitably, the instructions include values for N, A, B and C as described in the second aspect .
Suitably, the packet comprises N tablets. Suitably, N is 2.
The present invention will now be illustrated by way of example.
Example 1 Cleaning tablets of cuboid shape having a length of 24mm, a width of 16mm and a thickness of 14mm were produced by tabletting a tablet composition to provide a tablet having, a mass of around 9g.
The tablets had the following formulation:
Total
Ingredients (%w/w)
Na2CO3. H2O2 10-15
Na5P3O10 15-50
NaHCO3 10-15
Na2CO3 10-15
Polyethylene glycol 2-6
Phosphonate 0-1.5
Polymer 0-5
TAED 0-5
Amylase 0-2
Protease 0-2
Dye 0-0.5
Nonionic 1-5
Anti -Corrosion Agent 0-1
Perfume 0-0.5
Water Balance
Total (%w/w) 100.00
The tablets were produced according to the following method. Solid raw materials are weighed separately into the mixing vessel. Liquids are weighed and added to the mixture. Raw materials are combined in a commercial mixer for 10 minutes. Mixtures are then emptied into drums and transferred to the storage vessel of a rotary press. A rotary press is used to press the tablets, the final compression forces are on average 34 kN.

Claims

Claims
1. A multi-benefit cleaning tablet for use in a washing operation, characterised in that the tablet has a mass of between Ig and 15g such that it can be used singularly or with one or more other like' tablets depending upon a required washing performance.
2. A tablet according to claim 1, comprising a deter- gent composition.
3. A tablet according to Claim 1 or 2 , wherein the multi-benefit comprises detergent plus rinse aid
(2-in-l) functions or detergent plus rinse aid plus water softening (3-in-l) functions.
4. A tablet according to Claim 1 or 2, comprising a water-softening composition.
5. A tablet according to Claim 1 or 2, comprising rinse aid
6. A tablet according to any preceding Claim, wherein the tablet is for a ware washing machine.
7. A tablet according to Claim 6, wherein the tablet is for an automatic dish washing machine.
8. A tablet according to any preceding Claim, wherein the tablet has a mass of between Ig and 7g.
9. A tablet according to any of Claims 1 to 6, wherein the tablet has a mass of between 5g and 13g.
10. A method of performing a washing operation characterised in that the method employs one or more tablets according to any of the preceding claims and a quantity of water.
11. A method according to Claim 11, wherein, where the method employs a plurality of tablets the tablets are substantially identical.
12. A method according to Claim 10 or 11, wherein the method comprises the step of determining whether one or more tablets are required depending on the level of soiling and the quantity of articles to be washed.
13. A method according to any of Claims 10 to 12, wherein the method comprises the step of determining whether one or more tablets are required de- pending on the level of water hardness.
14. A method according to any of Claims 10 to 13, wherein the method comprises washing articles in an automatic ware washing machine.
15. A method according to Claim 14, wherein the tablets comprise detergent composition and the method comprises washing articles in an automatic dishwashing machine .
16. A method according to Claim 15, wherein the dishwashing machine comprises a domestic dishwasher of the floor standing type, and for a load having a normal level of soiling and which load substantially corresponds to a full load of the dishwashing machine the method uses N tablets where N = 2, 3, or 4.
17. A method according to Claim 15 or 16, wherein the dishwashing machine comprises a domestic dishwasher of the floor standing type, and for a load having a heavy level of soiling and which load substantially corresponds to a full load of the dishwashing machine the method uses N + A tablets where N = 2, 3, or 4 and A is > 0 and ≤ (N - 1) .
18. A method according to any of Claims 15 to 17, wherein the dishwashing machine comprises a domestic dishwasher of the floor standing type, and for a load having a light level ' of soiling and which load substantially corresponds to a full load of the dishwashing machine the method uses N - B tab- lets where N = 2, 3, or 4 and B is > 0 and ≤ (N - 1).
19. A method according to any of Claims 15 to 18, wherein the dishwashing machine comprises a domes- tic dishwasher of the floor standing type, and for a load having a normal level of soiling and which load substantially corresponds to a half load of the dishwashing machine the method uses N - C tablets where N = 2, 3, or 4 and C is > 0 and ≤ (N - 1) .
20. A packaged product comprising one or more tablets according to any of Claims 1 to 9.
21. A packaged product according to Claim 20 and further comprising instructions for varying the dose of tablets to perform a method according to any of claims 10 to 19.
22. A packaged product according to Claim 20 or 21, wherein the tablets are substantially identical.
PCT/GB2006/002412 2005-07-08 2006-06-29 Article and method WO2007007037A1 (en)

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Citations (9)

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Publication number Priority date Publication date Assignee Title
US4253842A (en) * 1974-05-15 1981-03-03 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components
EP0224129A2 (en) * 1985-11-21 1987-06-03 Henkel Kommanditgesellschaft auf Aktien Uniformly composed detergent tablets for mechanical dish-washing
EP0318204A1 (en) * 1987-11-19 1989-05-31 Unilever Plc Machine dishwashing compositions
WO2000006684A1 (en) * 1998-07-29 2000-02-10 Reckitt Benckiser N.V. Composition for use in a dishwasher
US6057281A (en) * 1996-06-05 2000-05-02 Amway Corporation Tableted household cleaner comprising carboxylic acid, (Bi)carbonate and polyvinyl alcohol
EP1239026A1 (en) * 2001-03-05 2002-09-11 Unilever Plc Detergent tablets
US20040116317A1 (en) * 2001-04-20 2004-06-17 Burt Diane Joyce Effervescent cleaning tablets
EP1524313A1 (en) * 2003-10-01 2005-04-20 Dalli-Werke GmbH & Co. KG Machine dishwadhing composition with improved rinsing properties
WO2005061689A1 (en) * 2003-12-22 2005-07-07 Danlind As Solid cleaning composition for tabletting

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10110199A (en) * 1996-10-08 1998-04-28 Kao Corp Tablet type detergent composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4253842A (en) * 1974-05-15 1981-03-03 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components
EP0224129A2 (en) * 1985-11-21 1987-06-03 Henkel Kommanditgesellschaft auf Aktien Uniformly composed detergent tablets for mechanical dish-washing
EP0318204A1 (en) * 1987-11-19 1989-05-31 Unilever Plc Machine dishwashing compositions
US6057281A (en) * 1996-06-05 2000-05-02 Amway Corporation Tableted household cleaner comprising carboxylic acid, (Bi)carbonate and polyvinyl alcohol
WO2000006684A1 (en) * 1998-07-29 2000-02-10 Reckitt Benckiser N.V. Composition for use in a dishwasher
EP1239026A1 (en) * 2001-03-05 2002-09-11 Unilever Plc Detergent tablets
US20040116317A1 (en) * 2001-04-20 2004-06-17 Burt Diane Joyce Effervescent cleaning tablets
EP1524313A1 (en) * 2003-10-01 2005-04-20 Dalli-Werke GmbH & Co. KG Machine dishwadhing composition with improved rinsing properties
WO2005061689A1 (en) * 2003-12-22 2005-07-07 Danlind As Solid cleaning composition for tabletting

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GB2428248A (en) 2007-01-24
GB0514004D0 (en) 2005-08-17
GB0613024D0 (en) 2006-08-09
DE202006010475U1 (en) 2006-12-21
DE102006031327A1 (en) 2007-01-11
AT502082A1 (en) 2007-01-15
LU91260B1 (en) 2007-01-09

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