GB2342358A - Detergent compositions comprising cationic polymers - Google Patents

Abstract

Detergent compositions or components thereof in solid form comprising water swellable cationic polymers and polyanionic builders. Cationic polymers are employed to increase disintegration rate and may also inhibit fabric greying. The composition may also be provided in the form of a coated particle wherein the cationic polymeric disintegrant is in the coating layer.

Description

2342358 Detergent Compositions

Field of the Invention The present invention relates to detergent compositions, in particular, laundry detergents and their disintegration. In particular, the invention relates to detergent particles or tablets comprising water-swellable cationic polymers such as ion exchange resins. 10 Background 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. In recent years, detergent compositions have tended to have increased densities above 15 650g/1, or above 700g/1 or even above 750g/1, 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. Many methods have been described for improving detergent dissolution, for example, 20 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 25 provide good break-up of solid-form detergent products thereby improving product dispensing and/or dissolution. An additional problem for formulators of detergents is that soap, for example from the surface of soiled laundry, tends to bind to water hardness calcium ions and precipitate. 30 The precipitate tends to adhere to items being washed and produce reduced whiteness by resoiling.

2 The present inventors have now found that the use of cationic polymeric disintegrants can assist in prevention of this effect by binding with the soap. However, in order to ensure that the soap impurities can be removed from the wash liquor, prior to complexation with calcium ions, chelant or buflder is needed to rapidly complex calcium ions. In addition, the cationic polymeric disintegrants have been found to be particularly useful in the disruption of coating layers on detergent components.

Surrimgy of the Invention In accordance with the present invention there is now provided a detergent composition or component thereof in a solid form comprising a disintegrant and a polyanionic builder, characterised in that said disintegrant comprises a water-swellable cationic polymer. In a further aspect of the invention, there is provided a detergent composition or component thereof in solid form at least partially coated with a coating layer, characterised in that the coating layer comprises a disintegrant comprising a water-swellable cationic polymer.

Detailed Description of the Invention The Qisinteerant

The disintegrant comprises a water-swellable cationic polymer. Suitable disintegrants include anion exchanQe 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.

Prefer-red cationic groups are pendent from the polymer backbone. Preferred cationic groups are quaternary anionic groups, such as -(N R, R2R3) wherein R I, R2 and R3 are each individually selected from H and optionally substituted lower alkyl or alkenyl groups, such as methyl or ethyl groups.

- 3 Suitable polymeric backbones include for example polyacrylate and/or polymethacrylate homopolymers. or copolymers and polyvinyl polymers such as polyvinyl pyfidines. Polyvinyl pyridines and polyacrylate polymers have been found to be particularly preferred. 5 The disintegrants for use in the present invention are water-swellable. Waterswellability 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 catioruc 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 quaternised 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 EPR88 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 100pm, preferably at least 150pm. Preferred disintegrants have a particle size of no greater than 2000Lm, most preferably below 1700pm. In practice, the particles obtained may have a size distribution. Therefore, 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 I Wpm, more preferably at least 150gm. Preferably at least 80 wt%, preferably 4 at least 90 wt% and most preferably at least 95 wt% disintegrant particles are below 2000Lrn, most preferably below 1700pm, or even below 15004m., to obtain the maximum disintegrating benefits.

The disintegrants are generally present in the detergent composition in amounts from I 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.

It may be particularly advantageous to use the water-swellable cationic polymer in combination with an additional disintegrant, such as any of those discussed in EP-A466484. In such cases, it may be preferred to from a pre- raix 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 wricking agent. Suitable wicking agents comprises a compound or rnixture 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. Preferably also, the wicking agent has low compressibility and maintains porosity under processing conditions, particularly compaction.

Suitable wicking agents are generally cellulose-based. The cellulosebased compounds may optionafly be rnicrocrystalline 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. 1 MM, or at least 0. 2MM, or even at least 0.4mm. Particularly preferred wicking agents are cross- finked.

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 ceflulosic fibres have primarily intrafibre chemical cross-link bonds. That is, the cross-fink 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.

When used in combination, 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.

Preferably 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. By intimate rr6xture is meant that the at least two components are mixed together to form a pre-mix which is a substantially homogeneous mixture.

TWs may be achieved by dry mixing solid wicking agent and solid waterswellable agent with an optional binder. The pre-rnix 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. However, it has been found that particularly effective results are achieved if the water-swellable agent is present as a coating on the wicking agent.

This is particularly beneficial where the wicking agent is fibrous.

6 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 waterswellable 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 fl---omthe 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.

Polyanionic Builder is The term "builder" is intended to mean all materials which tend to remove calcium ion ftom 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 Preferably 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 ftom 0. 5% to 30% by weight based on the weight of the detergent composition as a whole.

It may be preferred that the detergent composition is substantially free of phosphate, however, if present, 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 polymeric meta-phosphates). Preferred phosphate builders are tetrasodium pyrophosphate or more preferably anhydrous or partially hydrated sodium 7 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 mornomeric or ofigomefic in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing two carboxy groups include the watersoluble 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.

1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1, 1,3propane tricarboxylates described in British Patent No. 1,387,447. 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. 20 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, 1,2,3propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent 25 Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the suffionated 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.

8 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.

It may be preferred that the polymefic or oligomefic 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. Borate builders, as well as builders containing borate-forrning materials that can 10 produce borate under detergent storage or wash conditions are useful watersoluble builders herein. Examples of orgaruc polymefic compounds include the water soluble organic homoor co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid 15 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. Examples of such 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. 20 The polyamino compounds are useful herein including those defived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EPA-351629. Terpolymers containing monomer units selected from maleic acid, acrylic acid, 25 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. By chelant is meant sequester (chelate) metal ions. 30 These components are generally present at a level of from 0.005% to 10%, preferably 9 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 arfno alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triarnine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diarnine tetra (methylene phosphonate) and hydroxy-ethylene 1, 1 diphosphonate, 1, 1 hydroxyethane diphosphonic acid and 1, 1 hydroxyethane dimethylene phosphonic acid.

Other suitable chelants for use herein include rlitrilotriacetic acid and is polyaminocarboxylic acids such as ethyl enediaminotetracetic acid, ethylenedian-ne disuccinic acid, ethylenediarrdne diglutaric acid, 2hydroxypropylenedianline disuccinic acid or any salts thereof Other suitable chelants for use herein are iminodiacetic acid derivatives such as 2 hydroxyethyl diacetic acid or glycery] imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-j'-suifonic acid chelants described in EP-A-516,102 are also suitable herein. The P-alanine-N,M-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and indnodisuccinic acid chelants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based chelants. EP-A-510,331 describes suitable chelants derived from collagen, keratin or casein. EPA528,859 describes a suitable alkyl iminodiacetic acid chelant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. GlycinamideN,M-disuccinic acid (GADS), ethyl enediarnine-N-?P-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Diethylenetriamine pentacetic acid, ethyl enediamine-N,N-disuccirdc 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.

Form of the Composition The detergent composition or component thereof, according to the invention may take a variety of solid physical forms, such as tablet, flake, pastille and bar, and preferably granular or tablet forms. Preferably the detergent composition 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 vanous 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 0 or part of a detergent composition. Thus the disintegrant may be present in a detergent granule or may be intermixed with other detergent components as a discrete particle. For incorporation into a tablet, the disintegrant may be incorporated into the granular detergent composition as described above, prior to compaction, When present as part of a coating, 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.

Coatiniz Detergent Tablets Where 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. Preferably the principal ingredients, are used in particulate form.

In particular for laundry tablets, the ingredients such as builder and surfactant can be spray-dned 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. In the core of the tablet is included 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 Lodigee CB and/or LodigeO 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 rnixer, 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 12 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.

The tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting. Suitable equipment includes a 10 standard single stroke or a rotary press (such as Courtoy0, Korch0, Mariestylo, or BonalsOD). 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/m2, preferably not exceed 3 000 kN/m2, and most preferably not exceed 1000 kN/m2.

According to the present invention, 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. Finally the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock. Furthermore it is advantageous if 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 I g/1) in water.

As defined herein "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 I g/l. Water 13 solubility is measured following the test protocol of ASTM E 1148-87 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 C 12 to C22 and most preferably from C 18 to C22. Preferred dicarboxylic acids are oxalic acid (C2), malonic acid (0), succinic acid (C4), glutaric acid (C5), adipic acid (C6), p1melic acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (C 10), undecanedioic acid (C 11), dodecanedioic acid (C12) and tridecanedioic acid (C13).

Preferred fatty alcohols are those having a carbon chain length of from C 12 to C22 and most preferably from C 14 to C 18. Preferred diols are 1,2octadecanediol and 1,2hexadecanediol. Preferred esters are tristearin, tripalmitin, methylbehenate, ethylstearate. Preferred ethers are diethyleneglycol mono hexadecylether, di ethyl eneglycol mono octadecylether, diethyleneglycol mono Otetradecylether, phenylether, ethyl naphtyl ether, 2 methoxynaphtalene, beta naphtyl methyl ether and glycerol monooct adecyl ether. 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 appfied in the form of a melt. Particularly preferred coating compositions have a melting point of from 40 "C to 200 <C.

In a), the coating material is applied at a temperature above its melting point, and solidifies on the tablet. In b), 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, 14 the rapid cooling again causes rapid solidification of the coating material. Clearly 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. Preferably, the materials melt in the range from 60 'C to 160 'C, more preferably from 70 'C to 120 'C.

By "melting poinC 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.

For most purposes. the coating forms from 1% to 10%, preferably from 1.5% to 5%, 1 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. Generally the disintegrant will be present in the finished coating in a weight ratio of coating material to disintegrant of from 1: 1 to 5Q 1, preferably from 2A to 2Q 1, most preferably from 5 1 to 15: 1. Where the coating is applied as a melt, 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.

Depending on the composition of the starting material, and the shape of the tablets, the used compaction force will be adjusted to not affect the strength (Diametral Fracture Stress), and the disintegration time in the washing machine. TWs process may be used to prepare homogenous or layered tablets of any size or shape.

Diametrical Fracture Stress (DFS) is a way to express the strength of a tablet, it is determined by the following equation 2F p Dt Where 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). (Method Pharmaceutical Dosage Forms: Tablets Volume 2 Page 213 to 217) The rate of disintegration of a detergent tablet can be determined in two ways a) In a "VAINTKEU Friabilator with "Vankel Type" drums. - Put 2 tablets with a known weight and D.F.S in the Friabilator drum. - Rotate the drum for 20 rotations. - Collect all product and remaining tablet pieces from the Friabilator drum, and screen it on 5 mm, and through 1.7 mm - Express as % residue on 5 mm and through 1.7 mm. - The higher the % of material through 1.7 mm the better the disintegration.

b) In a washing machine according to the following method - Take two tablets with a known weight and fracture stress, and put them at the Z bottom of a washing machine (i.e. a Bauknecht WA 950).

- Put a 3 kg mixed load on top of the tablets. - Run a 30 'C short cycle (program 4) with city water.

- Stop the cycle after 5 min and check the wash load for undissolved tablet pieces, collect and weigh them, and record the percent residue left.

In another preferred embodiment of the present invention 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 16 between a soluble acid source and an alkali metal carbonate (effervescent component) to produce carbon dioxide gas, i.e. C6H807 + 3NaF[C03 --> Na3C6H507 + 3C02 1 + 3H20 Further examples of acid and carbonate sources and other effervescent systems may be found in: (Pharmaceutical Dosage Forms: Tablets Volume 1 Page 287 to 29 1) An effervescent may be added to the tablet mix in addition to the detergent ingredients. The addition of this effervescent to the detergent compositions or component thereof, in particular to detergent tablets of the invention, improves the disintegration time. The amount of effervescent component will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.

Preferably the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles. 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. When is 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.

Other Detergent Components Detergent Ingredient The composition or component thereof according to the present invention will contain 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, perffimes, brighteners, photobleaching agents and additional corrosion inhibitors.

17 Detersive Surfactants The compositions of the invention generally contain one or more surfactant. The 5 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 Nonlirriiting examples of surfactants useful herein typically at levels from about 1% to about 5 5%, by weight, include the conventional C I I -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the C I O-C I g secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOS03-M +) CH3 and CH3 (CH2)y(CHOS03-M +) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a watersolubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C I O- C18 alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), CIO-CI8 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C 10- 18 glycerol ethers, the C I O-C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12C 18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-CI8 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12- CI8 betaines and sulf6betaines (" sultaines"), C I O-C 18 arnine oxides, and the like, can also be included in the overall compositions. The CIO- CI8 N-alkyl polyhydroxy fatty acid arnides can also be used. Typical examples include the C I 2-C 18 N-methylglucarnides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid arrdes, such as CIO-Cl8 N-(3-methoxypropyl)glucandde. TheN-propyl through N-hexyl C I 2-C 18 glucarnides can be used for low sudsing. C I O-C20 18 con-ventional soaps may also be used. If high sudsing is desired, the branched-chain Cl O-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. Preferably the quaternary ammonium surfactant is a mono C6-C 16, preferably C6-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 10 bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in the detergent composition of the invention are cationic ester surfactants such as thoses disclosed in US Patents Nos. 4228042, 4239660 and 4260529. 15 FEghly preferred cationic surfactants are cationic mono-alkoxylated amine surfactant preferably of the general formula L R N- p 4 X- R 2,"--- --,, R3 wherein R I 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., R2 and R3 are each independently alkyl groups containing ftom one to about three carbon atoms, preferably methyl, most preferably both R2 and R3 are X- is an methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl, 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 19 group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the -OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are ---CH2CH2OH, --CH2CH2CH2OK CH2CH(CH3)OH and --CH(CH3)CH20H, with --CH2CH2OH being particularly preferred. Preferred R I groups are linear alkyl groups. Linear R I groups having from 8 to 14 carbon atoms are preferred.

Other conventional useful surfactants are listed in standard texts.

Additional Builders In addition to the polyanionic builders present in the detergent compositions of the invention, 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.

Examples of silicate builders which may be incorporated into the detergents of the invention are the alkali metal silicates, particularly those having a Si02:Na2O ratio in the range 1.6:1 to 33.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Fieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate budder does not contain aluminum. NaSKS-6 has the delta- Na2SiO5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaN4Six02x+l -yH20 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. As noted above, the delta-Na2SiO5 (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. 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.

Alun-dnosilicate 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. Alurninosilicate builders include those having the empirical formula-.

Mz(zAI02)yl'xli'-)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. These alurnino silicates can be crystalline or amorphous in structure and can be naturallyoccuMng 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 aluminosillcate ion exchange materials useful herein are available under the designations Zeolite A, Zeollte P (B), Zeolite NLAY and Zeolite X, zeolite MAP may be particularly useful. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula- Nal 2[(AJO2)l2(SI02)121-xH2O 21 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle siZe of about 0. 1-10 microns in diameter.

Fatty acids, e.g., C 12-C 18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with 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. 10 In situations where phosphorus-based builders can be used, and especiafly in the formulation of bars used for hand-laundering operations, 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- I hydroxy- 1, 1 -diphosphonate and other known phosphonates (see, for example, U-S.

Patents 3,159,581, 3,213,03)0; 3,422,02 1; 3,400,148 and 3,422,137) can also be used.

Bleach The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, 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. If present, 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 agentplus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useffil 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 22 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) can also be used.

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. Optionally, 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. 15 Another category of 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-oxoperoxybutyfic acid and 20 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, 19833. Highly preferred bleaching agents also include 6-nonylarnino-625 oxoperoxycaproic acid as described in U.S. Patent 4,634,55 1, issued January 6, 1987 to Bums et al. Nfixtures 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 30 solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S.

23 Patent 4,915,854, issued April 10, 1990 to Mao et a], and U.S. Patent 4, 412,934. The nonanoyloxybenzene suifonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein. Ffighly preferred ando- derived bleach activators are those of the formulae:

RIN(R5)C(O)R2Q0)L or RIC(O)N(R5)R2Q0)L wherein R I is an alkyl group contairing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 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. Preferred examples of bleach activators of the above formulae include (6-octanarnidocaproyl)oxybenzenesulfonate, (6nonanamidocaproyl)oxybenzenesulfonate, (6decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U. S. Patent 4,63 4,5 5 1, 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:

0 11 U, 0 CO N Still another class of preferred bleach activators includes the acyl lactarn activators, especially acyl caprolactams and acy) valerolactams of the formulae:

0 0 11 11 0 C-CH2-CH2 0 C-CH2-CH2 6- 11 1 6- 11 1 R C-N, CH2 R C-N-_, CH2-CH2"' CH2-CH2 24 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from I to about 12 carbon atoms. Mghly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactarr 3,5,5- trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactarn, undecenoyl caprolactam, benzoyl valerolactarn, 5 octanoyl valerolactarn, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and rnixtures 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 caprolactarn, 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 a]. If used, detergent compositions will typically contain from about 0.0250/.D to about 1.251/o, by weight, of such bleaches, especially sulfonate zinc phthalocyanine. If desired, the bleaching compounds can be catalyzed by means of 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. 549,271AI, 549, 272AI, 544,44OA2, and 544,490AI; Preferred examples of these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7- triazacyclo- nonane)2(PF6)2, \Inlll-(u-O)I(u-OAc)2(1,4,7-trimethyl-1,4,7-tr- iazacyclononane)2(CI04)2, NInIV4(u-0)6(1,4,7-triazacyclononane)4(CI04)4, Mn'llMnlV4(uO)I(u- OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CI04)3, MnIV(1,4,7- trirnethyl- 1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof Other 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; 5,284,9441 5,246,612; 5,256,779-, 5,280,117-1 5,274, 147, 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the 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 I ppm to about 500 ppm, of the catalyst species in the laundry liquor.

ELiMes 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 rnixtures. 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 typicafly compnse from about 0. 00 1 % to about 5 %, preferably 0. 0 1 %- I % by weight of a commercial enzyme preparation. Protease enzymes are usually present in such cormnercial preparations at levels sufficient to provide from 0.005 to 0. 1 Anson units (AU) of activity per gram of composition.

Suitable examples of 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 26 ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are cornmercially 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).

Other proteases include Protease A (see European Patent Application 130, 756, published January 9, 1985) and Protease B (see European Patent Appfication Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130, 756, Bott et al, published January 9, 1985). Arnylases include, for example, (x-arnylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE,

International Bio-Synthetics, Inc. and TERMAMYL, Novo Industiries.

The cellulase usable in the present invention include both bacteria] 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 Hurnicola insolens and Humicola strain DSM 1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a mafine mollusk (Dolabella Auncula Solander). suitable cellulases are also disclosed in GB-A-2.075. 028; GB-A 2.095.275 and DE-OS-2.247.8.332. CAREZYME (Novo) is especially useful.

Suitable lipase enzymes for detergent usage include those produced by rrucroorganisms 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 "Arnano-P." Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e. g.

Chromobacter viscosurn var. lipolyticurn NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan, and further Chromobacter viscosum hpases from U.S.

Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex 27 Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) 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 0. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101, 457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261, 868, Hora et al, issued April 14, 198 1. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S.

Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, pubfished October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.

Other components 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.

28 The invention is now exemplified by way of the following examples.

Example 1

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 54mra, 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 16PC 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.

1 In example 1, cationic polymer 1PR 88 (ex. Rohm & Haas) was used as disintegrant, a tablet havincy a total weight of 46g and a diametral fracture stress of 28 kPa was produced. This tablet was immersed in de-ionised water at 2WC and the time taken for the coating to begin to disinterate was measured to be 4 seconds.

Comparative Example A M1hen a ceillulose disintegrant, Nymcel zsbl6Q0 (ex. Metsa Serla), was used as disintegrant in the same proportion in the coating, a tablet having a total weight of 46g and a diametral fracture stress of 30 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 25 seconds.

29 Example 2

The following are examples of detergent compositions according to the invention.

They may be particulate or may be compressed in a tablet press into tablets.

A B C D Base Powder STPP 10.0 - Zeolite A 16.0 - 16.0 C45AS 4.0 - 4.0 5.0 QAS I - 1.0 - - N113AS 17, 2.1 2.0 4.0 - C25 AE3S - 1.0 - 1.0 MA/AA 2.0 1.0 2.0 1.0 LAS 10.0 11.0 8.9 6.6 TAS - 4.0 - - Silicate - 3.0 - 3.0 CMC 1.0 1.0 0.5 1.0 Brightener 2 0.2 0.2 - - Soap 1.0 - - 1.0 DTPMP 0.4 0.4 0.2 0.4 NaSKS-6 9.0 16.0 10.0 6.8 Spray On C45E7 - 2.5 - - C25E3 2.5 - - Silicone antifoam 0.3 0.3 0.3 0.

Perfume 0.3 0.3 0.3 0.3 IPR 88 (Rohm &Haas) 2.0 1.3 3.0 2.5 QEA - 0.5 1.0 - Carbonate 6.0 13.0 15.0 13.0 PB4 18.0 18.0 10.0 - PBI 4-0 4.0 - NOBS 3.0 4.2 1.0 - Photoactivated bleach 0.02 0.02 0.02 0.02 Manganese caLalyt - 0,5 - Protease 1.0 1.0 LO 1.0 Lipase 0.4 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 0.3 D!j mixed sodium sulfate 3.0 3.0 5.0 3.0 Balance (Moisture & 100.0 100.0 100.0 100.0 Mscellaneous Density (g/litre) 630 670 670 670 E F G H Base product:

TAS - 1.0 4.0 MBAS 17,1.9 5.0 10.0 16.0 8.0 C4SAS 4O 4.0 6.0 6O MES 3.0 QAS 11 0.4 - 1.0 - TFAA - 1.0 - - C25E5/C4SE7/C2 2.0 1.0 5E LAS - 18.0 Zeolite 9.0 5.0 8.0 Carbonate 13.0 7.5 5.0 Bicarbonate - 7.5 - DTPN11P 0.7 1-0 - SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 cmc 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Arnylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 - - Photoactivated 70ppm 45ppm - 1 Oppm bleach (ppm) Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 - - NACA - - - 3.0 NAC OBS 2.0 1.0 0.9 3.1 Amberlite CG420 4.0 6.0 3.0 2.0 Agglomerate:

SKS-6 (ly 6.6 6.0 20.0 10.0 LAS 3.0 - 15.0 7.0 C45 AS 6.0 - Balance (Moisture 100 100 100 100 and - Miscellaneous) K Base Powder MEBAS 17.5, 1.8 2.0 Zeolite A - 22.0 6.0 Sodium sulfate 1.0 5.0 - M.A/AA 3.0 3.0 3.0 MES - 5.0 - LAS - - 3.5 C45AS 3.0 4.0 7.0 Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 5.0 Citric acid 2.0 1.5 Spray On C45E5 1.0 1.0 - LASNES 8.0 5.0 5.0 Dry additives NaSKS-6 15.0 6.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.10.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 - NAC OBS - - 4.5 IPR 88 2.5 4.6 1.0 Sodium sulfate - 6.0 - Balance (Moisture and 100 100 100 NEscellaneou 32 L M N Blown Powder Zeolite 15.0 A Sodium sulfate 0.0 5.0 0.0 LAS 9.0 7.0 7.0 C45AS 7.0 2.0 4.0 QAS - - 1.5 DTPX4P 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerate 1.0 - - QAS LAS - 11.0 7.0 TAS 10 2.0 1.0 Silicate 2.0 - 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 7.0 8.0 4.0 Spray On Encapsulated 0.3 0.3 0.3 Perfiime C25E3 2.0 - 2.0 Dry additives NaSKS-6 15.0 12.0 5.0 silicate QEA 1.0 0.5 0.5 Citric/Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate 8.0 15.0 7.0 NAC OBS 6.0 - 5.0 Manganese catalyst - 0.3 NOBS - 2.0 - PBI 14.0 7.0 10.0 Polyethylene oxide of NIIAI 5,000,000 - - 0.2 Bentonite clay 10.0 Citric acid - 0.5 Protease Lo 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 IPR 88 (Rohm & Haas) 5.0 2.0 3.0 Sodium sulfate 0.0 1.0 0.0 Balance oisture and Nfiscellaneous) 100.0 100.0 100.0 Density (gAitre) 850 850 850 33 0 p Q R Agglomerate QAS 2.0 - 2.0 MES - 2.0 - LAS 6.0 - TAS - 2.0 - C45AS 6.0 4.0 2.0 MB AS 16.5, 1.9 4.0 - - Zeolite A 15.0 6.0 - Carbonate 4.0 8.0 4.0 8.0 MA/AA 4.0 2.0 - 2.0 cmc 0.5 0.5 - 0.5 DTPNT 0.4 0.4 - 0.5 Spray On C25E3 1.0 1.0 - - Perfume 0.5 0.5 0.5 0.5 Agglomerate NaSKS-6 7.0 13.0 20.0 9.0 LAS 5.8 9.0 15.0 9.0 Zeolite - 0.9 - C45 AS - 3.0 - Water 0.08 0.1 - 0.2 Dry Adds EDDS/HEDP 0.5 0.3 0.5 0.8 NaSKS 6 (1) or (11) 5.0 - - - Citrate - 1.0 - - Citric acid 2.0 2.0 4.0 NAC OBS 4.1 - 5.0 4.0 TAED 0.8 2.0 - 2.0 Percarbonate 14.0 18.0 13.0 16.0 SRP 1 0.3 0.3 - 0.3 Protease 1-4 1.4 1.0 0-5 Lipase 0.4 0.4 0.3 Cellulase 0.6 0.6 0.5 0.5 Amylase 0.6 0.6 - 0.3 QEA 1.0 - 1.0 1.0 Silicone antifoam 1.0 0.5 0.5 1.5 Brightener 1 0.2 0.2 - 6.2 Brightener 2 0.2 - 0.2 - IPR 88 (Rohm & Haas) 6.0 4.0 2.0 3.0 Density (g/litre) 850 850 goo 775 34 S T u V W X C45AS 11.0 5.0 4.6 6.5 4.1 9.0 C25AES 1.3 1.0 - 1.3 1.0 LAS 10.0 3.0 12.7 10.0 5.0 9.5 C25E3/C25E5 1.5 4.7 3.3 - 4.7 3.3 MEBAS 16.5, 1.7 15.0 12.0 10.0 10.2 7.0 14.1 QAS - 1.15 0.6 - 1.7 - Zeolite A 5.0 16.7 - 7.0 16.7 11.2 Arnberlite CG-420 Citric acid - 1.5 2.5 - 1.5 MA/AA 0.6 - 0.6 - MA/AA 3 - - 7.03 - - 7.03 AA 2.3 - - 2.8 - - EDDS - 0.3 - 0.3 HEDP - 0.5 - - 0.5 - Carbonate 6.0 12.5 14.5 6.0 12.5 14.0 SKS-6/silicate 10.58 0.8 20 10.58 4.8 20 PBI 11.0 - 14.0 - - 4.0 NACA-OBS - 4.7 - - 2.7 - PC 17.3 20.0 17.3 NOBS - - 4.0 - - 4.0 TAED - 2.5 - - 3.5 2.0 Protease 0.25 0.36 0.2 0.26 0.36 0.2 Lipase - - - - - Cellulase 0.1 0.26 0-3 0.26 Amylase - 0.36 - - 0.36 - Brightener 0-17 0.06 0.30 0.17 0.06 0.30 SPIP 1 0.4 0.2 0.5 0.4 0.2 0.5 PEG 1.6 - 0.19 1.6 - 0.19 Sulfate 5.5 6.4 15 5.5 6.4 3.5 CMC - 0.5 0.5 - MgS04 0.13 0.13 Photobleach 0.0026 - - 0.0026 - Agglomerate of example 3 I -3.0 2.0 3.0 4.0 3.0 -3.5 Silicone anti-foam 0.02 0.21 0.17 0.02 0.21 0.17 Perfume 0.42 0.55 0.25 0.42 0.55 0.25 Abbreviations used in the Examrfles In the detergent compositions exemplified above, the abbreviated component identifications have the following meaningsi NYMCELTM: Carboxymethyl cellulose supplied by Metsa-Serla CNT Citric acid intra-cross-linked fibrous cellulose made by Wayerhauser ArbocelTm: NEcronised cellulose supplied by Rettet"MeZY"W" 5 LAS: Sodium linear C I 1- 13 alkyl benzene sulforiate MES: ct-sulpho methylester of Cis fatty acid TAS: Sodium tallow alkyl sulfate CxyAS: Sodium C I x - C I y alkyl sulfate C46SAS- Sodium C 14 - C 16 secondary (2,3) alkyl sulfate CxyEzS: Sodium C I x-C I y alkyl sulfate condensed with z moles of ethylene oxide CxyEz.- C I x-C I y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS-. R2.N+(CH3)2(C2H40H) with R2 C12 - C14 QAS I - R2.N+(CH,-)2(C2H40H) with R2 C8 - C I I SADS: Sodium C14-C22 alkyl disulfate of formula 2-(R).C4 H7.-1,4 (S04-)2 where R = Clo-Cis SADE2S: Sodium C]4-C2,- alkyl disulfate of formula 2-(R).C4 H7--1,4 (SO4-)2, R = Cio-C18, condensed %krith z mol ethylene oxide APA: C8 - C 10 amido propyl dimethyl amine Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS: Sodium toluene sulphonate CFAA: C I 2-C 14 (coco) alkyl N-methyl glucamide TFAA: C16-C I g alkyl N-methyl glucamide TPKFA: C I 6-C 18 topped whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate 36 Zeolite A Hydrated sodium aluminosilicate of formula Nal2(AI02S'02)12. 27H20 having a primary particle size in the range from 0. 1 to 10 micrometers (weight expressed on an anhydrous basis) 5 NaSKS-6 (L Crystalline layered silicate of formula 8- Na2Si2O5 of Clariant Citric acjd Anhydrous citric acid Borate: Sodium borate Carbonate: Anydrous sodium carbonate with a particle size between 200pm and 90opm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400im and 1200pm Silicate: Amorphous sodium silicate (S'02:Na2O = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate Citrate: Tri-sodium citrate dihydrate of activity 96.4% with a particle size distribution between 425pm and 850Vm MA/AA: Copolymer of 1-4 maleic/acrylic acid, average molecular weight about 70,000 MA/AA (1): Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000 AA: Sodium polyacrylate polymer of average m. weight 4,500 CMC: Sodium carboxymethyl cellulose Cellulose ether: Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease 1: Proteoly-tic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.

Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S 37 Cellulase: Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase: Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S tradename Termamyl 120T Amylase 11: Amylolytic enzyme, as disclosed in PCT/ US9703635 Lipase: Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase (1): Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S tradename Lipolase Ultra Endolase: Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4: Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 PB 1: Anhydrous sodium perborate bleach of nominal formula NaB02.H202 Percarbonate: Sodium percarbonate of nominal formula 2Na2CO3.3H2O2 DOBS: Decanoyl oxybenzene sulfonate in the form of the sodium salt DPDA: Diperoxydodecanedioc acid NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate LOBS: Dodecanoyloxybenzene sulfonate in the form of the sodium salt DOBS: Decanoyloxybenzene sulfonate in the form of the sodium salt DOBA: Decanoyl oxybenzoic acid TAED Tetraacetyl ethyl enediarnine DTPA: Diethylene triarnine pentaacetic acid DTPMP:: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060 EDDS: Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.

38 Photoactivated: Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1. Disodium 4,4'-bis(2-sulphostyryl)biphenyI Brightener 22 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2- yl)arnino) stilbene-2:2'-disulfonate HEDP: 1, 1 -hyd roxyethane diphosphonic acid PEGx: Polyethylene glycol, vAth a m. weight of x (typically 4,000) PEO Polyethylene oxide, with an average m. weight of 50,000 TEPAL Tetraethylenepentaamine ethoxylate PVI: Polyvinyl imidosole, with an average m. weight of 20,000 PVP Poly-vinylpyrolidone polymer, av.molecular wt of 60,000 PVNO: Polyvinylpyn dine N-oXide polymer, av. M. weight of 50,000 PvTVI: Copolymer of polyvinylpyrolidone and vinyUrnidazole, with an average molecular weight of 20,000 QEA: bis((C2H50)(C2H40)n)(CH3) -N±C6HI2-N±(CH3) bis((C2H50)-(C2H40))n, wherein n = from 20 to 30 SRP 1: Anionically end capped poly esters SRP 2: Diethoxylated poly (1, 2 propylene terephtalate) short block polymer PEL Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoam- Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of foam controller to said dispersing agent of 10: 1 to 100: 1 Opacifieri Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradenarne Lytron 621 Wax: Paraffin wax 39

Claims (10)

1. A detergent composition or component thereof in a solid form comprising a disintegrant and a polyanionic builder, said disintegrant comprising a waterswellable cationic polymer.

2. A detergent composition according to claim 1 in which the disintegrant comprises an anion exchange resin.

3. A detergent composition according to claim 1 or claim 2 in which the cationic polymer comprises quaternary ammonium cationic groups.

4. A detergent composition according to claim 3 in which the quaternary anunonium cationic groups are pendant from the polymer backbone.

5. A detergent composition according to any preceding claim in the form of a tablet.

6. A detergent composition in a solid form, comprising a core and a coating layer at least partially coating the core, characterised in that the coating layer comprised a disintegrant comprising a water-sweflable cationic polymer.

7. A detergent composition in accordance with claim 6 additionally comprising a polyanionic builder.

8. A detergent composition according to any of claims 1 to 5 or 7 in which the polyanionic builder is selected from di or tri carboxylic acids or their salts, phosphates, polymeric polycarboxylates and chelants. 30

9. A method for making a detergent composition according to any preceding claim comprising forrrUng a core by compressing a particulate material, the particulate material comprising a surfactant and detergent builder and applying a coating material to the core characterised in that the coating material comprises a disintegrant comprising a water-swellable cationic polymer.

10. Use of a water-swellable cationic polymeric material in a detergent composition for reduction of fabric greying.