EP1119610B1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP1119610B1
EP1119610B1 EP99954680A EP99954680A EP1119610B1 EP 1119610 B1 EP1119610 B1 EP 1119610B1 EP 99954680 A EP99954680 A EP 99954680A EP 99954680 A EP99954680 A EP 99954680A EP 1119610 B1 EP1119610 B1 EP 1119610B1
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EP
European Patent Office
Prior art keywords
acid
detergent
detergent composition
water
disintegrant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99954680A
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English (en)
French (fr)
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EP1119610A1 (de
Inventor
Neil Joseph Lant
Stephen Wayne Heinzman
Robin Gibson Hall
Paul James Campbell
Darren Rees
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP1119610A1 publication Critical patent/EP1119610A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to detergent compositions, in particular, laundry detergents and their disintegration.
  • the invention relates to detergent particles or tablets comprising water-swellable cationic polymers such as ion exchange resins.
  • detergent compositions It is a particular requirement of detergent compositions that they should deliver the detergent actives to the wash water as soon as possible on contact with water.
  • detergent compositions have tended to have increased densities above 650g/l, or above 700g/l or even above 750g/l, or are even provided in the form of tablets. This has tended to inhibit dispensing and/or distribution and consequently rapid delivery of the detergent actives to the wash water.
  • EP-A-466484 describes the use of disintegrants and their mechanisms. It is stated that disintegrants which act by swelling on contact with water are preferred. Examples of disintegrants given are cross-linked polyvinyl pyrrolidones, montmorillonite or bentonite clay, sodium carboxymethyl cellulose and acrylate / maleic anhydride copolymers. However, there is still a need for disintegrants which provide good break-up of solid-form detergent products thereby improving product dispensing and/or dissolution.
  • soap for example from the surface of soiled laundry, tends to bind to water hardness calcium ions and precipitate.
  • the precipitate tends to adhere to items being washed and produce reduced whiteness by resoiling.
  • cationic polymeric disintegrants can assist in prevention of this effect by binding with the soap.
  • chelant or builder is needed to rapidly complex calcium ions.
  • the cationic polymeric disintegrants have been found to be particularly useful in the disruption of coating layers on detergent components.
  • a detergent composition or component thereof in a tablet form comprising a disintegrant and a polyanionic builder, characterised in that said disintegrant comprises a water-swellable cationic polymer.
  • a detergent composition or component thereof in tablet form at least partially coated with a coating layer, characterised in that the coating layer comprises a disintegrant comprising a water-swellable cationic polymer.
  • the disintegrant comprises a water-swellable cationic polymer.
  • Suitable disintegrants include anion exchange resins such as IPR 88 (Rohm & Haas).
  • the disintegrant comprises a cationic polymer wherein the cationic groups may be pendent from the polymeric backbone or on side-chains to the polymeric backbone.
  • Preferred cationic groups are pendent from the polymer backbone.
  • Preferred cationic groups are quaternary anionic groups, such as -(N R 1 R 2 R 3 ) + wherein R1, R2 and R3 are each individually selected from H and optionally substituted lower alkyl or alkenyl groups, such as methyl or ethyl groups.
  • Suitable polymeric backbones include for example polyacrylate and/or polymethacrylate homopolymers or copolymers and polyvinyl polymers such as polyvinyl pyridines. Polyvinyl pyridines and polyacrylate polymers have been found to be particularly preferred.
  • the disintegrants for use in the present invention are water-swellable.
  • Water-swellability is achieved by the conventional methods available to those skilled in the art, for example, by cross-linking and/or selection of substituents on the polymer backbone to reduce water-solubility and provide swellability.
  • Cross-linking may be by a conventional method, for example by the use of from 0.5 to 20% by weight based on the weight of polymer, of a cross-linker such as divinylbenzene.
  • Particularly preferred cationic polymers for use as disintegrants in the present invention are partially cross-linked poly (4-vinyl pyridine hydrochloride) and partially cross-linked polyacrylate esterified with partially quatemised N,N dimethyl ethanolamine, cross-linked with 2% by weight based on the polymer, of divinyl benzene.
  • Suitable polymers are commercially available as ion exchange resins, for example IPR88 and Amberlite CG-420.
  • Suitable polymers should be heat stable up to at least the temperature for the appropriate detergent processing.
  • the disintegrant is preferably added to the detergent composition in the form of a dry added particle. It has been found that the particle size of the disintegrant may be selected to give particularly beneficial disintegrating properties in use in a detergent composition. Disintegrants in particulate form preferably have a particle size of at least 100 ⁇ m, preferably at least 150 ⁇ m. Preferred disintegrants have a particle size of no greater than 2000 ⁇ m, most preferably below 1700 ⁇ m. In practice, the particles obtained may have a size distribution.
  • the particle size is preferably such that at least 80 wt%, preferably at least 90 wt% and most preferably at least 95 wt% of the components of the disintegrating component or a particulate disintegrants is at least 100 ⁇ m, more preferably at least 150 ⁇ m.
  • at least 80 wt%, preferably at least 90 wt% and most preferably at least 95 wt% disintegrant particles are below 2000 ⁇ m, most preferably below 1700 ⁇ m, or even below 1500 ⁇ m, to obtain the maximum disintegrating benefits.
  • the disintegrants are generally present in the detergent composition in amounts from 1 to 20 wt%, preferably in amounst of 2 to 15 wt%, most preferably from 2 to 10 wt% based on the weight of the detergent composition.
  • water-swellable cationic polymer in combination with an additional disintegrant, such as any of those discussed in EP-A-466484. In such cases, it may be preferred to from a pre-mix of the water-swellable cationic polymer and additional disintegrant prior to incorporation into a detergent composition.
  • the disintegrants of the invention may also be used in combination with a wicking agent.
  • Suitable wicking agents comprises a compound or mixture of compounds which enables fast water penetration into the detergent composition containing the disintegrating component, when the detergent composition is contacted with water in the wash.
  • the wicking agent is generally substantially water-insoluble in cold water at 15°C.
  • the wicking agent has low compressibility and maintains porosity under processing conditions, particularly compaction.
  • Suitable wicking agents are generally cellulose-based.
  • the cellulose-based compounds may optionally be microcrystalline or mechanically ground and processed cellulose such as ArbocelTM.
  • the wicking agent may be in the form of a powder, which may be obtained by mechanical grinding, a microcrystalline powder or it may be in the form of a granule e.g. an agglomerate of fine particle size wicking agent, or as a fibre, or mixtures thereof.
  • Particularly preferred wicking agents are fibrous, for example, those having a length to diameter ratio of at least 3:1, preferably at least 5:1 or even at least 10:1.
  • Suitable fibres include those having a length of at least 0.1mm, or at least 0.2mm, or even at least 0.4mm.
  • Particularly preferred wicking agents are cross-linked.
  • Particularly preferred wicking agents are cross-linked cellulose fibres as described in US 5 137 537, US 5 183 707, US 5 190 563, US 5 562 740, US 5 549 791, US 5 549 863, US 5 709 774 or US 5 716 703.
  • These particularly preferred cellulosic fibres are cross-linked in substantially individualized form i.e. the cellulosic fibres have primarily intrafibre chemical cross-link bonds. That is, the cross-link bonds are primarily between cellulose molecules of a single fibre rather than between cellulose molecules of separate fibres.
  • Processes for making such cross-linked fibres may be either dry cross-linking processes such as is described in US 3 224 926, or aqueous solution, as described in US 3 241 553 or non-aqueous solution cross-linking, as described in US 4 035 147.
  • the wicking agent and water-swellable cationic polymer are preferably present in weight ratios of less than 2:1, preferably less than 1:1.
  • the weight ratio is generally no less than 1:20, preferably no less than 1:10.
  • the water-swellable cationic polymer and any wicking agent are mixed to form an intimate mixture of the two components optionally with additional components and/or binder.
  • intimate mixture is meant that the at least two components are mixed together to form a pre-mix which is a substantially homogeneous mixture.
  • This may be achieved by dry mixing solid wicking agent and solid water-swellable agent with an optional binder.
  • the pre-mix may be in the form of a particle and this can be achieved for example by granulation , such as by agglomeration, extrusion or dry compaction.
  • granulation such as by agglomeration, extrusion or dry compaction.
  • water-swellable agent is present as a coating on the wicking agent. This is particularly beneficial where the wicking agent is fibrous.
  • Providing a coating of the water-swellable agent on the wicking agent may be achieved in any convenient way, for example by mixing the wicking agent and water-swellable polymer with a solvent for the water-swellable agent, in any order of addition, such that a gel or solution is formed or a slurry comprising partially swollen water-swellable agent. Preferably mixing is continued until a substantially homogeneous mixture is obtained.
  • the mixture of wicking agent and water-swellable agent is then recovered by separating out from the solvent by any conventional technique, such as by evaporating off the solvent or by addition of a non-solvent for the water-swellable agent to form a precipitate of the mixture, such mixture is then separated from the solvent by any conventional technique such as by subsequent filtration or decanting off the solvent.
  • builder is intended to mean all materials which tend to remove calcium ion from solution.
  • the polyanionic builder is present to rapidly build calcium ions in the wash liquor.
  • Suitable polyanionic builders include water-soluble builders selected from water-soluble poly-carboxylates, phosphates, borates, polymeric polycarboxylates, chelants, or the corresponding acids of any of these, and mixtures thereof.
  • the water-soluble builder will be present in amounts of from 0.05% to 50% by weight, preferably from 0.1 % to 40 % by weight, most preferably from 0.5% to 30% by weight based on the weight of the detergent composition as a whole.
  • suitable phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates).
  • Preferred phosphate builders are tetrasodium pyrophosphate or more preferably anhydrous or partially hydrated sodium tripolyphosphate at levels of from 0.5% to 50%, more preferably from 5% to 45% by weight based on the detergent composition as a whole.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No.
  • the most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • polymeric or oligomeric polycarboxylates are present at levels of less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • Chelants are also useful as the polyanionic builder for use in the detergent compositions of the invention.
  • chelant is meant sequester (chelate) metal ions.
  • These components are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions.
  • Suitable chelants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
  • Suitable chelants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Suitable chelants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based chelants.
  • EP-A-510,331 describes suitable chelants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid chelant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • Diethylenetriamine pentacetic acid ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof may also be used.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof may also be used.
  • the detergent composition or component thereof, according to the invention is in the form of a tablet.
  • the detergent compositions may be made by a variety of methods, including dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent composition, or mixtures of these techniques.
  • the disintegrant is incorporated into the detergent composition in any conventional way. For example it may be added into any of the processing steps described above, but is preferably dry-added into a particulate detergent mix.
  • the disintegrant may alternatively or additionally be provided in a coating for all or part of a detergent composition.
  • the disintegrant may be present in a detergent granule or may be intermixed with other detergent components as a discrete particle.
  • the disintegrant may be incorporated into the granular detergent composition as described above, prior to compaction.
  • the disintegrant is particularly useful in a detergent tablet coating.
  • the coating aspect of the invention is described below in the context of a detergent tablet coating where a core of detergent compostion is firstly formed and then coated. However, the coating could equally well be applied to a detergent particle or other solid detergent form.
  • the detergent of the present invention is in the form of a tablet
  • these can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press.
  • Any liquid ingredients for example the surfactant or suds suppressor, can be incorporated in a conventional manner into the solid particulate ingredients.
  • the principal ingredients are used in particulate form.
  • the ingredients such as builder and surfactant can be spray-dried in a conventional manner and then compacted at a suitable pressure.
  • the detergent tablets can be made in any size or shape and can, if desired, be surface treated.
  • a surfactant and a builder which normally provides a substantial part of the cleaning power of the tablet.
  • the particulate material used for making the tablet of this invention can be made by any particulation or granulation process.
  • An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600g/l or lower.
  • Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige® CB and/or Lodige® KM mixers).
  • Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
  • Individual particles can also be any other particle, granule, sphere or grain.
  • the particulate materials may be mixed together by any conventional means. Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s). A liquid spray-on to the mix of particulate materials (e.g. non-ionic surfactants) may be carried out. Other liquid ingredients may also be sprayed on to the mix of particulate materials either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed. A finely divided flow aid (dusting agent such as zeolites, carbonates, silicas) can be added to the particulate materials after spraying the non-ionic, preferably towards the end of the process, to make the mix less sticky.
  • a finely divided flow aid dusting agent such as zeolites, carbonates, silicas
  • the tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting.
  • Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy®, Korch®, Manesty®, or Bonals®).
  • the tablets prepared according to this invention preferably have a diameter of between 40mm and 50mm, and a weight between 25 and 60 g.
  • the compaction pressure used for preparing these tablets need not exceed 5000 kN/m 2 , preferably not exceed 3000 kN/m 2 , and most preferably not exceed 1000 kN/m 2 .
  • the tablets are then coated with a coating so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
  • the coating is also strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and shipping result in no more than very low levels of breakage or attrition.
  • the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock.
  • the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants. This avoids the deposition of undissolved particles or lumps of coating material on the laundry load. This may be important when the coating material is completely insoluble (for example less than 1 g/l) in water.
  • substantially insoluble means having a very low solubility in water. This should be understood to mean having a solubility in water at 25°C of less than 20 g/L, preferably less than 5 g/l, and more preferably less than 1 g/l. Water solubility is measured following the test protocol of ASTM E1148-87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
  • Suitable coating materials are fatty acids, C2-C13 dicarboxylic acids, fatty alcohols, diols, esters and ethers.
  • Preferred fatty acids are those having a carbon chain length of from C12 to C22 and most preferably from C18 to C22.
  • Preferred dicarboxylic acids are oxalic acid (C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid (C6), pimelic acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tridecanedioic acid (C 13).
  • Preferred fatty alcohols are those having a carbon chain length of from C12 to C22 and most preferably from C14 to C18.
  • Preferred diols are 1,2-octadecanediol and 1,2-hexadecanediol.
  • Preferred esters are tristearin, tripalmitin, methylbehenate, ethylstearate.
  • Preferred ethers are diethyleneglycol mono hexadecylether, diethyleneglycol mono octadecylether, diethyleneglycol mono 0tetradecylether, phenylether, ethyl naphtyl ether, 2 methoxynaphtalene, beta naphtyl methyl ether and glycerol monooctadecylether.
  • Other preferred coating materials include dimethyl 2,2 propanol, 2 hexadecanol, 2 octadecanone, 2 hexadecanone, 2, 15 hexadecanedione and 2 hydroxybenzyl alcohol.
  • Pre-formed detergent tablet core may then be coated according to the present invention.
  • the coating may be applied in a number of ways, but generally as a liquid, either a) as a melt, or b) as a solution.
  • Preferred coating materials are applied in the form of a melt.
  • Particularly preferred coating compositions have a melting point of from 40 °C to 200 °C.
  • the coating material is applied at a temperature above its melting point, and solidifies on the tablet.
  • the coating is applied as a solution, the solvent being removed e.g. by drying dried to leave a coherent coating.
  • the substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally when the molten material is sprayed on to the tablet, it will rapidly solidify to form a coherent coating. When tablets are dipped into the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material.
  • substantially insoluble materials having a melting point below 40 °C are not sufficiently solid at ambient temperatures and it has been found that materials having a melting point above about 200 °C are not practicable to use.
  • the materials melt in the range from 60 °C to 160 °C, more preferably from 70 °C to 120 °C.
  • melting point is meant the temperature at which the material when heated slowly in, for example, a capillary tube becomes a clear liquid.
  • a coating of any desired thickness can be applied according to the present invention.
  • the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet or detergent component weight.
  • the disintegrant will be present in the coating layer in an amount sufficient to generate the desired degree of disruption of the coating layer on contact with water in the wash liquor to promote delivery of the detergent composition to the wash and improve dissolution.
  • the disintegrant will be present in the finished coating in a weight ratio of coating material to disintegrant of from 1:1 to 50:1, preferably from 2:1 to 20:1, most preferably from 5:1 to 15:1.
  • the disintegrant is generally suspended in the coating melt at a level of up to 30%, preferably between 5 and 20%, and most preferably between 5 and 10% by weight.
  • the used compaction force will be adjusted to not affect the strength (Diametral Fracture Stress), and the disintegration time in the washing machine.
  • This process may be used to prepare homogenous or layered tablets of any size or shape.
  • F is the maximum force (Newton) to cause tensile failure (fracture) measured by a VK 200 tablet hardness tester supplied by Van Kell industries, Inc.
  • D is the diameter of the tablet (mm), and t the thickness of the tablet (mm).
  • the rate of disintegration of a detergent tablet can be determined in two ways :
  • the detergent compositions further comprise an effervescent component.
  • Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate (effervescent component) to produce carbon dioxide gas, i.e. C 6 H 8 O 7 + 3NaHCO 3 ⁇ Na 3 C 6 H 5 O 7 + 3CO 2 ⁇ + 3H 2 O
  • effervescent may be added to the tablet mix in addition to the detergent ingredients.
  • the amount of effervescent component will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.
  • the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles.
  • the detergent tablets Due to the gas created by the effervescent component, the detergent tablets can have a higher D.F.S. and still have the same disintegration time as a tablet without effervescent component.
  • the D.F.S. of the tablet with effervescent component is kept the same as a tablet without, the disintegration of the tablet with effervescent component will be faster.
  • composition or component thereof according to the present invention will contain additional detergent ingredients.
  • additional detergent ingredients The precise nature of these additional ingredients, and levels of incorporation thereof will depend on the application of the component or compositions and the physical form of the components and the compositions.
  • the detergent compositions of the invention preferably contain one or more additional detergent components selected from bleaches, bleach catalysts, alkalinity systems, additional builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brighteners, photobleaching agents and additional corrosion inhibitors.
  • compositions of the invention generally contain one or more surfactant.
  • the surfactant may comprise any surfactant known in the art, selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants such as those discussed below and mixtures thereof.
  • Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10- C 20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3- M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3- M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10 -C 18 alkyl alkoxy sulfates (“AE x S”; especially EO 1-7 ethoxy sulfates), C 10 -C 18 alkyl alkoxy carboxylates
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
  • Suitable cationic surfactants for incorporation into the detergent composition of the invention include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • Highly preferred cationic surfactants are cationic mono-alkoxylated amine surfactant preferably of the general formula I: wherein R 1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R 2 and R 3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R 3 are methyl groups; R 4 is selected from hydrogen (preferred), methyl and ethyl; X - is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
  • Particularly preferred ApR 4 groups are -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CH 2 CH(CH 3 )OH and-CH(CH 3 )CH 2 OH, with -CH 2 CH 2 OH being particularly preferred.
  • Preferred R 1 groups are linear alkyl groups. Linear R 1 groups having from 8 to 14 carbon atoms are preferred.
  • additional builders may be present to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of additional builder can vary widely depending upon the end use of the composition.
  • silicate builders which may be incorporated into the detergents of the invention are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6"
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such 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 herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • magnesium silicate which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders may be useful in the present invention.
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ) y ] ⁇ xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Useful aluminosilicate ion exchange materials are commercially available.
  • aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X, zeolite MAP may be particularly useful.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Further suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • OXONE manufactured commercially by DuPont
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Bums et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al. Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • amido-derived bleach activators are those of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is: Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
  • Patent 4,545,784 issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV -(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH 3 ) 3 (PF 6 ), and mixtures thereof
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • Patent 3,600,319 issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
  • compositions which are commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
  • Detergent tablets comprising surfactants, builder, enzymes, perfume and other detergent ingredients was formed by placing 42.75g of a commercially available granular detergent into a mould of circular shape with a diameter 54mm, and compressed using a Lloyd Instruments LR50 testing apparatus. The compression load was optimised so as to obtain a tablet with cylindrical tablet strength of 12kPa diametral fracture stress s (expressed in kPa). Diametral fracture stress was calculated as set out above.
  • Adipic acid (du Pont) was heated in a thermostatic bath to 163°C with gentle stirring until molten. The disintegrant was then added with continuous stirring so as to obtain a 10% w/w homogeneous suspension in the adipic acid. The tablets prepared as above were then dipped into the liquid to give the final coated tablet.
  • cationic polymer IPR 88 (ex. Rohm & Haas) was used as disintegrant, a tablet having a total weight of 46g and a diametral fracture stress of 28 kPa was produced. This tablet was immersed in de-ionised water at 20°C and the time taken for the coating to begin to disintegrate was measured to be 4 seconds.
  • detergent compositions are compressed in a tablet press into tablets.

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Claims (9)

  1. Waschmittelzusammensetzung oder Bestandteil davon in einer Tablettenform umfassend einen zersetzenden Wirkstoff und einen polyanionischen Builder, wobei der zersetzende Wirkstoff ein wasserquellfähiges kationisches Polymer umfasst.
  2. Waschmittelzusammensetzung nach Anspruch 1, worin der zersetzende Wirkstoff ein Anionenaustauschharz umfasst.
  3. Waschmittelzusammensetzung nach Anspruch 1 oder Anspruch 2, worin das kationische Polymer quartäre kationische Ammoniumgruppen umfasst.
  4. Waschmittelzusammensetzung nach Anspruch 3, worin die quartären kationischen Ammoniumgruppen an die Ploymer-Hauptkette angehängt sind.
  5. Waschmittelzusammensetzung in einer Tablettenform, umfassend einen Kern und eine Überzugsschicht, die wenigstens teilweise den Kern bedeckt, dadurch gekennzeichnet, dass die Überzugsschicht einen zersetzenden Wirkstoff umfasst, der ein wasserquellfähiges kationisches Polymer umfasst.
  6. Waschmittelzusammensetzung nach Anspruch 5, die ferner einen polyanionischen Builder umfasst.
  7. Waschmittelzusammensetzung nach einem der Ansprüche 1 bis 4 oder 6, worin der polyanionische Builder ausgewählt ist aus Di- oder Tricarbonsäuren oder ihren Salzen, Phosphaten, polymeren Polycarboxylaten und Chelanten.
  8. Verfahren zur Herstellung einer Waschmittelzusammensetzung nach einem der vorgenannten Ansprüche, umfassend die Bildung eines Kerns durch Komprimieren eines teilchenformigen Materials, wobei das teilchenförmige Material ein Tensid und einen Waschmittelbuilder umfasst, und das Auftragen eines Überzugsmaterials auf den Kern, dadurch gekennzeichnet, dass das Überzugsmaterial einen zersetzenden Wirkstoff umfasst, der ein wasserquellfähiges kationisches Polymer umfasst.
  9. Verwendung eines wasserquellfähigen kationischen Polymermaterials in einer Waschmittelzusammensetzung zum Verringern von Gewebegraufärbung.
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DE10044472A1 (de) * 2000-09-08 2002-03-21 Cognis Deutschland Gmbh Waschmittel
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GB2376692A (en) * 2001-06-22 2002-12-24 Reckitt Benckiser Nv Fabric softening laundry tablet
EP1275371A1 (de) * 2001-07-13 2003-01-15 Johnson and Johnson GmbH Trockene, eine Folie und zwei Phasen enthaltende, Produkte
MXPA05004942A (es) * 2002-11-15 2005-07-22 Unilever Nv Composicion de detergente mejorada.
EP2473590B2 (de) * 2009-09-02 2018-01-17 Unilever N.V. Verfahren zur behandlung von textilien
JPWO2016043257A1 (ja) * 2014-09-17 2017-06-29 ライオン株式会社 衣料用粉末洗浄剤

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DE2911857A1 (de) * 1979-03-26 1980-10-16 Henkel Kgaa Appretierend wirkendes textilwaschmittel
DE3380259D1 (en) * 1982-12-23 1989-08-31 Procter & Gamble Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
DE3545990A1 (de) * 1985-12-23 1987-06-25 Henkel Kgaa Neue schmutz sammelnde reinigungsverstaerker in waessrigen wasch- und reinigungsloesungen
DE3605716A1 (de) * 1986-02-22 1987-09-03 Henkel Kgaa Verwendung von unloeslichen schmutzsammlern zur regenerierung von wasch- und reinigungsloesungen
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
US5478501A (en) * 1994-04-07 1995-12-26 The Andrew Jergens Company Bathing composition containing coated cationic polymer
GB2318799A (en) * 1996-10-31 1998-05-06 Procter & Gamble Detergent compositions

Also Published As

Publication number Publication date
GB9822023D0 (en) 1998-12-02
AU1097100A (en) 2000-05-01
CA2346187A1 (en) 2000-04-20
DE69929223D1 (de) 2006-02-02
WO2000022091A1 (en) 2000-04-20
DE69929223T2 (de) 2006-08-31
GB2342358A (en) 2000-04-12
BR9914354A (pt) 2001-06-26
ATE314455T1 (de) 2006-01-15
ES2255312T3 (es) 2006-06-16
AR020747A1 (es) 2002-05-29
EP1119610A1 (de) 2001-08-01
JP2002527580A (ja) 2002-08-27
CN1329662A (zh) 2002-01-02

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