CN1329662A - Detergent compositions - Google Patents

Abstract

The invention relates to detergent compositions or components thereof in solid form and for methods of increasing the disintegration rate of such detergent compositions whilst inhibiting fabric greying. Suitable detergent compositions comprise water-swellable cationic polymers and polyanionic builder. The invention also relates to detergent compositions or components thereof in the solid form which are at least partially coated with a coating layer comprising cationic polymeric disintegrants.

Description

Detergent composition

Technical Field

The present invention relates to detergent compositions, especially laundry detergents, and their disintegration. In particular, the present invention relates to detergent granules or tablets containing a water-swellable cationic polymer, such as an ion exchange resin.

Background

Especially desirable are detergent compositions that provide detergent active to the wash water upon contact with the water. In recent years, detergent compositions have a tendency to be provided in the form of tablets or increased densities in excess of 650g/l, or in excess of 700g/l or even in excess of 750g/l, which has a tendency to inhibit dispersion and/or distribution and thus provide detergent active rapidly to the wash water.

ｃA number of methods for improving detergent dissolution have been described, for example EP- ｃA-466484 describes the use of disintegrants and their mechanism, which indicates that disintegrants which act by swelling on contact with water are preferred. Examples of known disintegrants are crosslinked polyvinylpyrrolidone, montmorillonite or bentonite, sodium carboxymethylcellulose and acrylate/maleic anhydride copolymers. However, there is still a need to provide well dispersed disintegrants for detergent products in solid form to improve product dispersion and/or dissolution.

Another problem faced by detergent formulators is that soaps, for example, on the surface of soiled clothes tend to bind water hard calcium ions and precipitate which tends to adhere to the items being washed, resulting in reduced whiteness due to re-staining.

The present inventors have now found that the use of a cationic polymeric disintegrant can help to avoid this effect by combining with a soap. However, to ensure that soap impurities can be removed from the wash liquor prior to complexing with calcium ions, a sequestrant or builder is required to rapidly complex the calcium ions. Furthermore, the cationic polymeric disintegrants have been found to be particularly useful in the breaking of coatings on detergent parts.

Summary of The Invention

According to the present invention there is provided a detergent composition or component thereof in solid form comprising a disintegrant and a polyanionic builder, characterised in that the disintegrant comprises a water-swellable cationic polymer. In another aspect of the present invention there is provided a detergent composition or component thereof in solid form at least partially coated with a coating characterised in that the coating contains a disintegrant which comprises a water swellable cationic polymer. Detailed description of the invention disintegrants

Disintegrants contain water swellable cationic polymers and suitable disintegrants include anion exchange resins such as IPR88 (Rohm & Haas).

Disintegrants include cationic polymers in which the cationic groups may be pendant from the polymer backbone or on a side chain of the polymer backbone.

Preferred cationic groups are pendant groups of the polymer backbone, and preferred cationic groups are quaternary ammonium cationic groups, e.g., - (NR)₁R₂R₃)⁺Wherein R is₁、R₂And R₃Each selected from H and optionally substituted lower alkyl or alkenyl, for example methyl or ethyl.

Suitable polymer backbones include, for example, polyacrylate and/or polymethacrylate homopolymers or copolymers and polyvinyl polymers, such as polyvinyl pyridine. Polyvinylpyridine and polyacrylate polymers have been found to be particularly preferred.

The disintegrants for use in the present invention are water swellable, which is obtained by conventional methods known to those skilled in the art, such as cross-linking and/or selection of substituents on the polymer backbone to reduce water solubility and provide swellability. Crosslinking can be carried out by conventional methods, for example by using from 0.5 to 20% by weight, based on the weight of the polymer, of a crosslinking agent, for example divinylbenzene. Particularly preferred cationic polymers for use as disintegrants in the present invention are partially crosslinked poly (4-vinylpyridine hydrochloride) and partially crosslinked polyacrylates esterified with partially quaternized N, N-dimethylethanolamine, divinylbenzene crosslinked with 2% by weight based on the polymer. Suitable polymers are commercially available as ion exchange resins, for example IRP 88 and Amberlite CG-420.

Suitable polymers should be thermally stable up to at least the temperatures used for suitable detergent processing.

The disintegrant is preferably added to the detergent composition in the form of dry-added granules. It has been found that the particle size of the disintegrant can be selected to give particularly beneficial disintegration properties when used in detergent compositions. The disintegrant in particulate form preferably has a particle size of at least 100 microns, preferably at least 150 microns. Preferred disintegrants have a particle size of no more than 2000 microns, most preferably less than 1700 microns. In practice, the resulting granules may have a size distribution, and therefore the granule size is preferably such that at least 80 wt%, preferably at least 90 wt%, most preferably at least 95 wt% of the disintegrant component or particulate disintegrant is at least 100 microns, more preferably at least 150 microns. Preferably at least 80 wt%, preferably at least 90 wt% and most preferably at least 95 wt% of the disintegrant particles are below 2000 microns, most preferably below 1700 microns or even below 1500 microns for maximum disintegration effect.

The disintegrant is typically present in the detergent composition in an amount of from 1 to 20 wt%, preferably from 2 to 15 wt%, most preferably from 2 to 10 wt%, by weight of the detergent composition.

It is particularly advantageous to use the water-swellable cationic polymer in combination with other disintegrants, for example any of the disintegrants discussed in EP-A-466484. In this case, it is preferred to form a premix of the water-swellable cationic polymer and the other disintegrant before addition to the detergent composition.

The disintegrating agent of the present invention may also be used in combination with a water absorbing agent (packaging agent). Suitable water-absorbing agents comprise a compound or mixture of compounds which is capable of allowing rapid penetration of water into the detergent composition comprising the disintegrating component when the detergent composition is contacted with water in the wash. The water-absorbing agent is generally substantially insoluble in cold water at 15 ℃, and it is also preferred that the water-absorbing agent has a low compressibility and retains porosity under processing conditions, particularly under compression.

Suitable water absorbents are typically cellulose based, which may optionally be microcrystalline or mechanically comminuted and processed cellulose, such as Arbocel^TM。

The water-absorbing agent may be in the form of a powder obtainable by mechanical grinding, a microcrystalline powder or may be in the form of particles, for example agglomerates of fine-grained water-absorbing agent or as fibres or mixtures thereof. Particularly preferred water-absorbing agents are fibrous, e.g. fibres having an aspect ratio of at least 3: 1, preferably at least 5: l or even at least 10: 1. Suitable fibres include fibres having a length of at least 0.1mm, or at least 0.2mm, or even at least 0.4mm, particularly preferred water-absorbing agents are cross-linked.

Particularly preferred water absorbents are cross-linked cellulosic fibres as described in US5137537, US5183707, US5190563, US5562740, US5549791, US5549863, US5709774 or US 5716703. These particularly preferred cellulosic fibers are crosslinked in a substantially individualized form, i.e., the cellulosic fibers have predominantly interfiber chemical crosslinks. I.e. the cross-links are mainly between single cellulose molecules rather than between cellulose molecules of separate fibres. The process for making the crosslinked fibers may be a dry crosslinking process as described in US3224926 or an aqueous solution as described in US3241553 or a non-aqueous solution crosslinking as described in US4035147, for example.

When used in combination, the water absorbing agent and the water swellable cationic polymer are preferably present in a weight ratio of less than 2: 1, preferably less than 1: 1, and the weight ratio is generally not less than 1: 20, preferably not less than 1: 10.

Preferably, the water swellable cationic polymer and any water absorbing agent are mixed to form an intimate mixture of the two components and optionally other components and/or binders, by which is meant a pre-mixture in which at least two of the components are mixed together to form a substantially homogeneous mixture.

This can be achieved by dry blending the solid water absorbing agent and the solid water swelling agent with an optional binder. The premix may be in particulate form, which may be achieved, for example, by granulation, for example, by agglomeration, extrusion or dry compaction. However, we have found that particularly effective results are obtained if the water-swellable agent is present as a coating on the water-absorbing agent. This is particularly advantageous when the water-absorbing agent is fibrous.

The provision of a coating of water-swellable agent on the surface of the water-absorbing agent may be achieved by any conventional means, for example by mixing the water-absorbing agent and water-swellable polymer with a solvent for the water-swellable agent in any order of addition to form a gel or solution or slurry containing partially swollen water-swellable agent. Preferably, the mixing is continued until a substantially homogeneous mixture is obtained. The mixture of water-absorbing agent and water-swellable agent is then recovered by any conventional technique, for example by separation from the solvent by evaporation of the solvent or by addition of a non-solvent for the water-swellable agent to form a precipitate of the mixture which is then separated from the solvent by any conventional technique, for example by subsequent filtration or decantation of the solvent. Polyanion builders

The term "builder" refers to all substances which tend to remove calcium ions from solution. Polyanionic builders are present to rapidly bind calcium ions in the wash liquor. Suitable polyanionic builders include water-soluble builders selected from the group consisting of water-soluble polycarboxylates, phosphates, borates, polymeric polycarboxylates, chelants or the corresponding acids of any of these and mixtures thereof.

The water-soluble builder is preferably present in an amount 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 entire detergent composition.

Preferably the detergent composition is substantially free of phosphate, however, if present, suitable phosphate-containing detergent builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (e.g., 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 total detergent composition.

Carboxylate or polycarboxylate builders can be monomeric or oligomeric in type, although monomeric polycarboxylates are generally preferred for cost and performance reasons.

Suitable polycarboxylates containing two carboxyl 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 ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups include in particular the water-soluble citrates, itaconates and citraconates and succinate derivatives, for example carboxymethoxysuccinates as described in GB1379241, lactyloxy succinates as described in GB1389732 and aminosuccinates as described in Netherlands application 7205873 and oxypolycarboxylate materials as described in GB1387447, for example 2-oxo-1, 1, 3-propanetricarboxylate. The most preferred polycarboxylic acid containing three carboxyl 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, 1, 2, 2-ethane tetracarboxylates, 1, 3, 3-propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates as disclosed in GB 1261829. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in GB1398421 and 1398422 and US3936448, and the sulfonated pyrolytic citrates described in GB 1439000. Preferred polycarboxylates are hydroxycarboxylic acid salts containing up to three carboxyl groups per molecule, more preferably citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or their mixtures with their salts, for example citric acid or citrate/citric acid mixtures, can also be used as builder components.

Preferably the polymeric or oligomeric polycarboxylate is present in a content of less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the composition.

Borate builders and builders containing borate-forming materials which produce borates under detergent storage or wash conditions are useful water-soluble builders of the present invention.

Examples of organic polymers include water-soluble organic homo-or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl groups separated by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1596756. Examples of such salts are the polyacrylates of MWt1000-5000 and their copolymers with maleic anhydride having a molecular weight of 2000-.

Polyamino compounds useful in the present invention include those derived from aspartic acid as disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomer units selected from the group consisting of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having a molecular weight of 5000-10000, are also suitable.

Chelants are also effective as polyanionic builders in the detergent compositions used in the present invention. Chelating agents refer to chelating metal ions. These components are generally present at 0.005% to 10%, preferably 0.1% to 5%, more preferably 0.25% to 7.5%, most preferably 0.3% to 2% by weight of the composition.

Suitable chelating agents for use in the present invention include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, and nitrilotriethylene phosphonates.

Among the above species, preferred are diethylenetriaminepenta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxy-ethylene-1, 1-diphosphonate, 1-hydroxyethane diphosphonic acid and 1, 1-hydroxyethane dimethylene phosphonic acid.

Other suitable chelating agents for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids, such as ethylenediamine tetraacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropanediamine disuccinic acid or any salts thereof.

Other suitable chelants for use in the present invention are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl iminodiacetic acid as described in EP-A-317542 and EP-A-399133 the iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelants described in EP-A-516102 also β -alanine-N, N' -diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid chelants as described in EP-A-509382 are suitable.

EP-A-476257 describes suitable amino-based chelating agents. EP-A-510331 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528859 describes suitable alkyl iminodiacetic acid chelating agents. Dipicolinic acid and 2-phosphinobutane-1, 2, 4-tricarboxylic acid are also suitable. glycinamide-N, N ' -disuccinic acid (GADS), ethylenediamine-N-N ' -disuccinic acid (EDDG) and 2-hydroxypropanediamine-N-N ' -disuccinic acid (HPDDS) are also suitable.

Diethylene triamine pentaacetic acid, ethylenediamine-N, N' -disuccinic acid (EDDS) and 1, 1-hydroxyethane diphosphonic acid or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof may also be used. Form of the composition

According to the present invention, the detergent composition or components thereof may take various solid physical forms such as tablets, flakes, pastilles and bars, preferably in the form of granules or tablets. Preferably the detergent composition is in the form of a tablet. The detergent composition may be manufactured by various processes, including dry blending, agglomeration, compaction or spray drying of the various compounds contained in the detergent composition, or a combination of these techniques.

The disintegrant is incorporated into the detergent composition by any conventional means, for example it may be incorporated in any of the above-described processing steps, but is preferably dry-blended into the particulate detergent mixture. Alternatively or additionally, the disintegrant may be provided as a coating on all or part of the detergent composition. Thus, the disintegrant may be present in the detergent granule or mixed with other detergent components as individual granules. For incorporation into tablets, the disintegrant may be incorporated into the granular detergent composition as described above prior to compaction. When present as a partial coating, disintegrants are particularly suitable for use in coating detergent tablets. The coating aspect of the invention is described in the context of a detergent tablet coating wherein a detergent composition core is first formed and subsequently coated. However, the coating can be applied equally well to detergent particles or other solid detergent forms. Coated detergent tablets

When the detergents of the invention are in tablet form, they may be prepared simply by mixing the solid components together and compressing the mixture in a conventional tablet press. Any liquid component, such as a surfactant or suds suppressor, can be added to the solid particulate component in a conventional manner, preferably with the principal component being used in particulate form.

Especially for laundry tablets, the components, e.g. builders and surfactants, can be spray-dried in a conventional manner and subsequently compacted under suitable pressure. The detergent tablets may be manufactured in any size or shape and may be surface treated if desired. In the tablet core, surfactants and builders are included, which generally provide a major portion of the tablet's detergency.

The particulate material used to prepare the tablets of the present invention may be prepared by any granulation or prilling process. An example of such a process is spray drying (in co-current or counter-current spray drying towers), which generally gives low bulk densities of 600g/l or less. Particulate material of higher density may be prepared by granulation and densification in a high shear batch mixer/granulator or a continuous granulation and densification process for example using Lodige CB and/or Lodige KM mixers. Other suitable methods include fluidized bed processes, compaction processes (e.g., roller compaction), extrusion, and any particulate matter prepared by any chemical process, such as flocculation, crystal sintering, and the like, and the individual particles can also be any other particle, granule, sphere, or grain.

The particulate matter may be mixed together by any conventional method. Batch processes are suitable, for example, in concrete mixers, Nauta mixers, ribbon mixers, etc. In addition, the mixing process can be carried out continuously by weighing each component into a conveyor and mixing in one or more drums or mixers. Liquid spraying on a mixture of particulate matter (e.g., nonionic surfactant) may be performed. The other liquid components may be sprayed on the mixture of particulate materials, either separately or pre-mixed, for example a slurry of sprayable perfume and optical brightener. After spraying the nonionic surfactant, finely divided flow aids (release agents, such as zeolites, carbonates, silica) can be added to the particulate material, preferably towards the end of the process, to render the mixture less viscous.

Tablets may be prepared by using any compression process, such as tabletting, briquetting or extrusion, preferably tabletting. Suitable apparatus comprises a standard single stroke or rotary press (e.g. Courtoy, Korch, Manesty or Bonals ® A @. Tablets prepared according to the invention preferably have a diameter of 40mm to 50mm, a weight of 25 to 60 g. The required compaction pressure for preparing these tablets does not exceed 5000kN/m²Preferably not more than 3000kN/m²Most preferably not more than 1000kN/m²。

According to the invention, the tablets are subsequently coated with a coating, so that the tablets do not absorb moisture or absorb moisture only at a very slow rate. The coating is also strong so that the tablets do not break or wear to any great extent when subjected to moderate mechanical vibrations during handling, packaging and transport. Finally, the coating is preferably friable, so that the tablet breaks when subjected to strong mechanical vibration. Furthermore, it is advantageous that the coating substance is dissolved under alkaline conditions or easily emulsified by a surfactant. This avoids deposition of undissolved particles or lumps of coating material on the laundry load, which is important when the coating material is completely insoluble in water (e.g. less than 1 g/l).

"substantially insoluble" as defined herein means having a very low solubility in water. This is understood to mean having a solubility in water at 25 ℃ of less than 20g/l, preferably less than 5g/l, most preferably less than 1 g/l. Water solubility is measured according to the test method of ASTM E1148-87 entitled "Standard test method for measuring Water solubility".

Suitable coating substances are fatty acids, C2-C13 dicarboxylic acids, fatty alcohols, glycols, esters and ethers, preferred fatty acids are fatty acids having a carbon chain length of C12-C22, most preferably C18-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 (C13), preferred fatty alcohols are fatty alcohols having a carbon chain length of C12-C22, most preferably C14-C18 preferred glycols are 1, 2-octadecanediol and 1, 2-hexadecanediol, preferred esters are glycerol tristearate, glycerol tripalmitate, methylbehenate, ethyl behenate, preferably dioctadecyl alcohol, ethylene glycol monobutyl ether, hexadecyl ether, ethylene glycol monobutyl ether.

The preformed detergent tablet core may then be coated according to the present invention. The coating can be applied in a number of ways, but is usually applied 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 40 ℃ to 200 ℃.

In a), the coating substance is applied at a temperature above its melting point and solidifies on the tablet. In b), the coating is applied as a solution and the solvent is dried off to leave a coherent coating. The substantially insoluble material may be provided to the tablet by, for example, spraying or dipping. Typically, when the molten material is sprayed onto the tablet, it will rapidly solidify to form a coherent coating. When the tablets are immersed in the molten mass and then removed, rapid cooling again results in rapid solidification of the coating mass. It is clear that substantially insoluble materials having a melting point below 40 c do not solidify sufficiently at room temperature and that materials having a melting point above about 200 c have not been found to be practical. The material is preferably melted at 60 ℃ to 160 ℃, more preferably 70 ℃ to 120 ℃.

"melting point" refers to the temperature at which a substance becomes a transparent liquid when heated slowly, for example, in a capillary.

Coatings of any desired thickness may be used in the present invention. For most applications, the coating will comprise from 1% to 10%, preferably from 1.5% to 5% by weight of the tablet or detergent component.

The disintegrant is present in the coating in an amount sufficient to produce a desired degree of coating disintegration upon contact with water in the wash liquor to facilitate providing the detergent composition to the wash water and to improve dissolution. Typically the disintegrant will be present as the coating material: the disintegrant is present in the final coating in a weight ratio of 1: 1 to 50: 1, preferably 2: 1 to 20: 1, most preferably 5: 1 to 15: 1. When the coating is applied as a melt, the disintegrant is typically suspended in the coating melt at a level of up to 30%, preferably 5-20%, and most preferably 5-10% by weight.

Depending on the composition of the raw material and the shape of the tablet, the compaction force used can be adjusted so as not to affect the strength (diametral crushing stress), and the disintegration time in the washing machine. The process can be used to prepare homogeneous or layered tablets of any size or shape.

The Diametral Fracture Stress (DFS) is a way of expressing the strength of a tablet and is determined by the following equation: $=\frac{2F}{\mathrm{\μDt}}$ where F is the maximum force (newtons) that results in tensile failure (fracture) as measured by the VK200 tablet hardness tester supplied by Van kellndustries, inc. D is the diameter (mm) of the tablet, and t is the tablet thickness (mm). (Method Pharmaceutical DosageForm: tablets volume 2, 213-.

The disintegration rate of detergent tablets can be determined by two methods:

a) in a "VAN KEL" fribilator with a "Vankel Type" drum.

Placing 2 tablets of known weight and DFS in a fribilator drum.

Rotating drum 20 revolutions.

All products and residual plate-like material were collected by a fribilator drum, on 5mm, and sieved through 1.7 mm.

Residual in% over 5mm and passing 1.7 mm.

The higher the% passing through 1.7mm of material, the better the disintegration.

b) In a washing machine, the method is as follows

Taking 2 tablets of known weight and crushing stress and placing them at the bottom of the washing machine (i.e. Bauknecht WA 950).

A 3kg mixing load was placed on top of the tablet.

Run with tap water for a short period of 30 ℃ (procedure 4).

After 5 minutes the cycle was stopped, the washing load was checked for undissolved pieces, collected and weighed, and the percentage of residue remaining was recorded.

In another preferred embodiment of the present invention, the detergent composition further comprises an effervescent component. Effervescence, as defined herein, refers to the result of carbon dioxide gas generation due to a chemical reaction between a water soluble acid source and an alkali metal carbonate (effervescence component), the release of gas bubbles from a liquid,

that is to say that the first and second electrodes,

other examples of acid and carbonate sources and other effervescent systems may be found in: (pharmaceutical dosage Forms: Tablets volume 1, pp.287-291). In addition to the detergent components, effervescent agents may be added to the tablet mixture. The addition of the effervescent agent to detergent compositions or components thereof, especially the detergent tablets of the invention, improves disintegration time. The amount of effervescent ingredient is preferably from 5 to 20%, most preferably from 10 to 20% by weight of the tablet. The effervescent agent is preferably added as an agglomerate of different particles or as a compact mass, rather than as a separate particle. Due to the gas generated by the effervescent component, the detergent tablet may have a higher DFS, still having the same disintegration time as compared to a tablet without the effervescent component. The disintegration of tablets containing an effervescent component will be faster when the DFS of the tablet containing the effervescent component is the same as the tablet without the effervescent component. Other detergent ingredients

The compositions of the present invention or components thereof may contain additional detergent ingredients, the exact nature and amount of these additional ingredients added will depend on the use of the ingredient or composition and the physical form of the ingredient and composition.

The detergent compositions of the present invention preferably contain one or more additional detergent components selected from the group consisting of bleaching agents, bleach catalysts, alkaline systems, additional builders, organic polymers, enzymes, suds suppressors, lime soaps, dispersants, soil suspension and anti-redeposition agents, soil release agents, perfumes, brighteners, photobleaches and additional preservatives. Detergent surfactant

The compositions of the present invention typically contain one or more surfactants. The surfactant may comprise any surfactant known in the art selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants discussed below and mixtures thereof.

Non-limiting examples of surfactants for use herein at levels of about 1% to about 55% by weight include conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and primary, branched and random C₁₀-C₂₀Alkyl sulfate ('AS'), formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀-C₁₈Secondary (2, 3) alkyl sulfates wherein x and (y + 1) are integers of at least about 7, preferably at least about 9, M is a water soluble cation, especially sodium, unsaturated sulfates, e.g. oleyl sulfate, C₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS "; especially EO1-7 ethoxy sulfate), C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylates), C₁₀-C₁₈Glyceryl ether, C₁₀-C₁₈Alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈α -sulfonated fatty acid esters if desired, conventional nonionic and amphoteric surfactants, such as C, may also be included in the overall composition₁₂-C₁₈Alkyl ethoxylates ("AE") including so-called narrow peak alkyl ethoxylates and C₆-C₁₂Alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxides, and the like. C may also be used₁₀-C₁₈N-alkyl polyhydroxy fatty acid amides. Typical examples include C₁₂-C₁₈N-methylglucamides, see WO 9206154. Other saccharide-derived surfactants include N-alkoxy polyhydroxy fatty acid amides, e.g. C₁₀-C₁₈N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C₁₂-C₁₈Glucamides may be used for low foaming. C₁₀-C₂₀Conventional soaps may also be used. If high foaming is desired, a branched chain C may be used₁₀-C₁₆Soap. Mixtures of anionic and nonionic surfactants are particularly useful.

Suitable cationic surfactants for incorporation in the detergent compositions of the present invention include quaternary phosphonium surfactantsAn ammonium surfactant. The quaternary ammonium surfactant is preferably mono C₆-C₁₆Preferably C₆-C₁₀N-alkyl or alkenyl ammonium surfactants in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups. Also preferred are mono-alkoxylated and di-alkoxylated amine surfactants.

Other suitable cationic surfactants which may be used in the detergent compositions of the present invention are cationic ester surfactants such as those disclosed in US4228042, 4239660 and 4260529.

More preferred cationic surfactants are cationic mono-alkoxylated amine surfactants, preferably having the general formula I:wherein R is¹Is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; r²And R³Each is an alkyl group containing from 1 to about 3 carbon atoms, preferably methyl, most preferably R²And R³Are both methyl; r⁴Selected from hydrogen (preferred), methyl and ethyl; x^-Is an anion, such as chloride, bromide, methyl sulfate, and the like, to provide electrical neutrality; a is alkoxy, especially ethoxy, propoxy or butoxy; p is from 0 to about 30, preferably from 2 to about 15, most preferably from 2 to about 8.

Preferably in formula I A_pR⁴The group has p ═ 1, and is a hydroxyalkyl group having no more 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 is A_pR⁴is-CH₂CH₂OH、-CH₂CH₂CH₂OH、-CH₂CH(CH₃) OH and-CH (CH)₃)CH₂OH, particularly preferably-CH₂CH₂And (5) OH. Preferably R¹The radicals being straight-chain alkyl radicals, straight-chain R containing from 8 to 14 carbon atoms¹The radical is preferred.

Other conventionally useful surfactants are listed in standard texts. Other builders

In addition to the polyanionic builders present in the detergent compositions of the present invention, other builders may be present to help control mineral hardness. Inorganic and organic builders can be used. Builders are commonly used in fabric washing compositions to aid in the removal of particulate soils. The level of additional builder can vary widely depending on the end use of the composition.

Examples of silicate builders which may be incorporated in the detergents of the invention are alkali metal silicic acidsSalts, especially those of SiO₂∶Na₂Silicates and layered silicates with an O ratio of 1.6: 1 to 3.2: 1, such as the layered sodium silicate described in US4664839 to h.p. rieck, issued 5.12.1987. NaSKS-6 is a trademark of crystalline layered silicate sold by Hoechst (generally abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6. delta. -Na with layered silicate₂SiO₅Form is shown. It can be prepared, for example, by the processes described in DE-A-3417649 and DE-A-3742043. SKS-6 is a more preferred layered silicate for use in the present invention, but other such layered silicates, such as those having the general formula NaMSi, can also be used_xO_2x+1·yH₂O, where M is sodium or hydrogen, x is a number between 1.9 and 4, preferably 2, and y is a number between 0 and 20, preferably 0 here, other various layered silicates obtained from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in α, β and γ forms, respectively.As described above, delta-Na₂SiO₅(SKS-6 form) is most preferred for use in the present invention. Other silicates are also useful, such as magnesium silicate, which can be used as a crispening agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component in foam control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates described in GP-A-2321001 published in 11/15 of 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are very important in the recently marketed heavy-duty granular detergent compositions, and also as an important builder component in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

[M_z(zAlO₂)_y]·xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y is 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 aluminosilicates may be crystalline or amorphous in structure, and may be naturally occurring aluminosilicates or synthetic. US3985669 to Krummel et al, issued 10/12 in 1976, discloses a process for producing aluminosilicate ion exchange materials. Preferred synthetic crystalline aluminosilicate ion exchange materials for use in the present invention are available under the trade designations zeolite a, zeolite p (b), zeolite MAP and zeolite X, zeolite MAP being particularly useful. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O，

wherein x is from about 20 to about 30, especially about 27. This material is known as zeolite a. Dehydrated zeolites (x ═ 0 to 10) can be used in the present invention. The particle size of the aluminosilicate is preferably from about 0.1 to 10 microns in diameter.

Fatty acids, e.g. C₁₂-C₁₈The monocarboxylic acids may also be added alone or in admixture with the aforementioned builders, especially citrate and/or succinate buildersTo produce additional builder activity in the composition. Such use of fatty acids generally results in reduced foam, which the formulator should consider.

Where phosphorus-based builders can be used, and particularly during the formulation of soap bars for use in hand washing operations, various alkali metal phosphates, such as the known sodium tripolyphosphates, pyrophosphates and orthophosphates, can be used. Phosphonate builders, such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates may also be used (see, for example, US3159581, 3213030, 3422021, 3400148 and 3422137). Bleaching agent

The detergent compositions of the present invention may optionally further comprise a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. If present, especially for fabric laundering, the bleaching agent is generally present at levels of from about 1% to about 30%, more usually from about 5% to about 20% of the detergent composition. If present, the amount of bleach activator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising bleach and bleach activator.

The bleaching agent used in the present invention may be any bleaching agent useful for detergent compositions in fabric washing, hard surface cleaning or other known or to be known laundry applications. These include oxygen bleaches as well as other bleaching agents. Perborate bleaching agents, such as sodium perborate (e.g., sodium perborate mono-or tetra-hydrate) may be used in the present invention. Other suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, commercially produced by DuPont) may also be used.

Preferred percarbonate bleach compositions contain dry particles having an average particle size in the range of from about 500 microns to about 1000 microns, wherein no more than about 10% by weight of said particles are smaller than about 200 microns and no more than about 10% by weight of said particles are larger than about 1250 microns. The percarbonate may optionally be coated with a silicate, borate or water soluble surfactant. Percarbonate is available from various commercial sources, such as FMC, Solvay and Tokai Denka.

Another class of bleaching agents that may be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxyperoxybutyric acid and diperoxydodecanedioic acid. Such bleaches are disclosed in U.S. patent application 4483781 to Hartman, issued on 20.11.1984, Burns, EP-A-0133354 to Bank et al, published on 2.20. 740446,1985, filed on 3.6.1985, and U.S. patent application 4412934 to Chung et al, issued on 1.11.1983. More preferred bleaching agents also include 6-nonanamido-6-oxyperoxydecanoic acid, which is described in US4634551 to Burns et al, issued on 6.1.1987. Mixtures of bleaching agents may also be used.

Peroxygen bleaches, perborates, percarbonates, and the like are preferably mixed with bleach activators, which can result in the in situ generation of the peroxyacid corresponding to the bleach activator in aqueous solution (i.e., during the wash). Various non-limiting examples of activators are disclosed in US4915854 and US4412934 to Mao et al, issued 4, 10, 1990. Nonoyl Oxybenzenesulfonate (NOBS) and Tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. For other typical bleaches and activators used in the present invention, see also US 4634551. More preferred amido-derived bleach activators are those having the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C(O)L

Wherein R is¹Is an alkyl group containing from about 6 to about 12 carbon atoms, R²Is an alkylene radical having from 1 to about 6 carbon atoms, R⁵Is H or an alkyl, aryl or alkaryl group 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 upon nucleophilic attack of the bleach activator by the perhydrolytic anion. A preferred leaving group is phenyl sulfonate. Preferred examples of bleach activators of the above formula include (6-octanoylamino-hexanoyl) oxybenzenesulfonate, (6-nonanoylamino hexanoyl) oxybenzenesulfonate, (6-decanoylamino-hexanoyl) oxybenzenesulfonateAcid esters and mixtures thereof, as described in US4634551, which is incorporated herein by reference. Another class of bleach activators includes the benzoxazine-type activators disclosed in US4966723 to Hodge et al, issued 10, 30, 1990, and incorporated herein by reference. More preferred benzoxazine type activators are:

yet another preferred bleach activator comprises acyl lactam activators, particularly acyl caprolactams and acyl valerolactams, of the formula:

wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl or alkylaryl group containing from 1 to about 12 carbon atoms. More preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3, 5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecanoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecanoyl valerolactam, nonanoyl valerolactam, 3, 5, 5-trimethylhexanoyl valerolactam, and mixtures thereof. See also Sanderson, US 454545784, issued on 8/10/1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. Other bleaching agents besides oxygen bleaching agents are also known in the art and may be used in the present invention. One non-oxygen bleaching agent of particular value includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718 to Holcombe et al, issued 7/5 in 1977. If used, detergent compositions typically contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines. If desired, the bleaching compound may be catalyzed by a manganese compound. Such compounds are known in the art and include, for example, manganese-based catalysts as disclosed in US5246621, US5244594, US 5194416, US5114606, and EP549271a1, 549272a1, 544440a2 and 544490a 1. Preferred examples of such catalysts include Mn^IU ₂(u-O)₃(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(PF₆)₂、Mn^III ₂(u-O)₁(u-OAc)₂(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₂、Mn^IV ₄(u-O)₆(1, 4, 7-triazacyclononane)₄(ClO₄)₄、Mn^IIIMn^IV ₄(u-O)₁(u-OAc)₂(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃、Mn^IV(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include those disclosed in US4430243 and US 5114611. The use of magnesium with various complexing ligands to improve bleaching performance is also reported in the following US4728455, 5284944, 5246612, 5256779, 5280117, 5274147, 5153161 and 5227084.

In practice, and not by way of limitation, the compositions and methods of the present invention can be modified to provide an aqueous wash solution containing at least one part in ten million of active bleach catalyst species, and preferably from about 0.1ppm to about 700ppm, more preferably from about 1ppm to about 500ppm, of catalyst species in the wash liquor. Enzyme

Enzymes may be included in the formulations herein for various fabric laundering applications, including, for example, the removal of protein-based, carbohydrate-based, or triglyceride-based stains, and for the prevention of fugitive dye transfer during laundering, as well as for fabric restoration. The enzymes added include protease, amylase, lipase, cellulase and peroxidase and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as plants, animals, bacteria, fungi and yeasts. However, their selection is influenced by certain factors, such as optimum pH-activity and/or stability, thermostability and stability towards active detergents, builders and the like. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

The enzyme is typically added at a level sufficient to provide up to about 5mg, more typically from about 0.01mg to about 3mg, of active enzyme by weight per gram of detergent composition. In other words, the compositions of the present invention typically contain from about 0.001% to about 5%, preferably from 0.01% to 1%, by weight of a commercial enzyme preparation. Proteases are generally present in such commercial preparations in an amount sufficient to provide 0.005-0.1Anson Units (AU) of activity per gram of composition.

Suitable examples of proteases are subtilisins from particular strains of Bacillus subtilis and Bacillus licheniformis, another suitable protease is obtained from a particular strain of Bacillus having the greatest activity over the entire pH range of 8-12, which is developed and sold under the trade name ESPERASE by Novo Industica A/S.A method for the preparation of this and similar enzymes is described in GB1243784 to Novo.commercially available proteolytic enzymes suitable for removal of protein-based stains include those sold under the trade names ALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthesis, Netherlands.other proteases include protease DASA (see EP130756A published on 1.9.198) and protease B (see EP130756,756,83 to Bo 9 et al published on 4.28.1987 and EP130756,639 to starch.

Cellulases usable in the present invention include bacterial and fungal cellulases, preferably having an optimum pH of 5 to 9.5. Suitable cellulases are disclosed in US4435307 by Barbesgoard et al, issued 3/6 1984, which discloses suitable fungal cellulases obtained from Humicola insolens or Humicola lanuginosa strain DSM1800 or a fungus belonging to the genus aeromonas which produces cellulase 212, as well as cellulases extracted from the hepatopancreas of marine mollusks (dolabella auricula Solander). Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832. CAREZYME (Novo) is particularly useful,

suitable lipases for use in detergents include those derived from microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 as disclosed in GB 1372034. See also lipase in japanese patent application 53,20487 published on 24.2.1978. 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 suitable commercial lipases include Amano-CES, lipases from Chromobacterium viscosum, e.g., commercially available from Toyo Jozo Co. (Tagata, Japan), Chromobacterium viscosum var. lipolyticum, NRRLB 3673; chromobacter viscosum lipases from U.S. Biochemical Corp. (UAS) and Disoynth Co. (Netherlands); and lipase derived from Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP0341947) is a preferred lipase for use in the present invention.

Peroxidases are used in combination with oxygen sources such as percarbonates, perborates, persulfates, hydrogen peroxide, and the like. They are used as "solution bleaches," i.e., to prevent dyes or pigments removed from a substrate during a washing operation from transferring to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chlorine and bromoperoxidase. Detergent compositions comprising peroxidase enzymes are disclosed in e.g. PCT International application WO89/099813, published by O.Kirk on 19.10.1989, assigned to Novo Industriassi/S.

US3553139 to McCarty et al, issued on 5.1.1971, discloses a broad range of enzyme feedstocks and their incorporation into synthetic detergent compositions. Enzymes are further disclosed in US4101457 by Place et al, published 1978 at 18 and US4507219 by Hughes, published 1985 at 26. US4261868 to Hora et al, issued 4, 14, 1981, discloses raw base materials for liquid detergent formulations, and methods for their incorporation into such formulations. Enzymes used in detergents can be stabilized in various ways. Enzyme stabilization techniques are disclosed and exemplified by US3600319 by Gedge et al, published 8/17 1971, and by EP0199405 by Venegas, published 10/29 1986 (application No. 86200586.5). Enzyme stabilization systems are also described, for example, in US 3519570.

Other components commonly used in detergent compositions and which may be incorporated into detergent tablets of the invention include soil release agents, soil antiredeposition agents, dispersants, brighteners, suds suppressors, fabric softeners, dye transfer inhibitors and perfumes.

The invention is illustrated by the following examples of embodiments. Example 1

Commercially available granular detergents were placed in an annular mould 54mm in diameter and compressed using a Lloyd Instruments LR 50 test apparatus to form detergent tablets containing surfactant, builder, enzyme, perfume and other detergent components. The compression load was optimized to give tablets with a circular tablet strength of 12kPa diameter crushing stress (expressed in kPa) calculated as described above.

Adipic acid (du Pont) was heated to 163 ℃ in a thermostatic bath with slow stirring until molten. The disintegrant was then added under continuous stirring to give a 10% w/w homogeneous suspension in adipic acid. The tablets prepared as above were immersed in a liquid to obtain the final coated tablets.

In example 1, the cationic polymer IPR88 (obtained from Rohm & Haas) was used as a disintegrant, yielding a tablet with a total weight of 46g and a diameter crushing stress of 28 kPa. The tablet was immersed in deionized water at 20 ℃ and the time to onset of disintegration of the coating was measured to be 4 seconds.

Comparative example A

When the cellulose disintegrant, Nymcel zsb16 @ (available from Metsa Serla), was used in the coating in the same proportions as the disintegrant, tablets were produced having a total weight of 46g and a diameter crush stress of 30 kPa. The tablets were immersed in deionized water at 20 ℃ and the time to onset of disintegration of the coating was measured to be 25 seconds.

Example 2

The following are examples of detergent compositions of the present invention. They may be microgranules or may be compressed into tablets in a tablet press.

Raw powder	A	B	C	D
STPP		-	10.0	-
					Zeolite A	16.0	-	-	16.0
C45AS	4.0	-	4.0	5.0
					QASI	-	1.0	-	-
MBAS 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	-	-
					Silicates of acid or alkali	-	3.0	-	3.0
CMC	1.0	1.0	0.5	1.0
					Whitening agent 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 mist
C45E7	-	2.5	-	-
					C25E3	2.5	-	-	-
Silicone antifoam agent	0.3	0.3	0.3	0.3
					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 salt	6.0	13.0	15.0	13.0
					PB4	18.0	18.0	10.0	-
PB1	4.0	4.0	-	-
					NOBS	3.0	4.2	1.0	-
Photoactivated bleaching agents	0.02	0.02	0.02	0.02
					Manganese catalyst	-	-	0.5	-
Protease enzyme	1.0	1.0	1.0	1.0
					Lipase enzyme	0.4	0.4	0.4	0.4
Amylase	0.25	0.30	0.15	0.3
					Dry mixed sodium sulfate	3.0	3.0	5.0	3.0
BalancingSubstance (moisture) And micro-components)	100.0	100.0	100.0	100.0
					Density (g/l)	630	670	670	670

	E	F	G	H
					Base material product
TAS	-	1.0	4.0	-
					MBAS17，1.9	5.0	10.0	16.0	8.0
C45AS	4.0	4.0	6.0	6.0
					MES	3.0	-	-	-
QASII	0.4	-	1.0	-
					TFAA	-	1.0	-	-
C25E5/C45E7/C2 5E3	-	2.0	-	1.0
					LAS	-	18.0	-	-
Zeolite	9.0	5.0	-	8.0
					Carbonate salt	13.0	7.5	-	5.0
Bicarbonate salt	-	7.5	-	-
					DTPMP	0.7	1.0	-	-
SRP1	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 enzyme	0.8	1.0	0.5	0.5
Amylase	0.8	0.4	-	0.25
					Lipase enzyme	0.2	0.1	0.2	0.1
Cellulase enzymes	0.15	0.05	-	-
					Photoactivated bleaching agents (ppm)	70ppm	45ppm	-	10ppm
Brightener 1	0.2	0.2	0.08	0.2
					PB1	6.0	2.0	-	-
NACA	-	-	-	3.0
					NACOBS	2.0	1.0	0.9	3.1
Amberlite CG420	4.0	6.0	3.0	2.0
					Agglomerates
SKS-6(I)	6.6	6.0	20.0	10.0
					LAS	3.0	-	15.0	7.0
C45 AS	3.0	6.0	-	-
					Balance (water and micro component)	100	100	100	100

	I	J	K
				Raw powder
MBAS17.5，1.8	-	-	2.0
				Zeolite A	-	22.0	6.0
Sodium sulfate	1.0	5.0	-
				MA/AA	3.0	3.0	3.0
MES	-	5.0	-
				LAS	-	-	3.5
C45AS	3.0	4.0	7.0
				Silicates of acid or alkali	-	1.0	5.0
Soap	-	-	2.0
				Brightener 1	0.2	0.2	0.2
Carbonate salt	8.0	16.0	5.0
				Citric acid	3.0	2.0	1.5
Spray mist
				C45E5	1.0	1.0	-
LAS/MES	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 enzyme	1.0	1.0	1.0
				Lipase enzyme	0.4	0.4	0.4
Amylase	0.1	0.1	0.1
				Cellulase enzymes	0.1	0.1	0.1
NOBS	-	6.1	-
				NACOBS	-	-	4.5
IPR 88	2.5	4.6	1.0
				Sodium sulfate	-	6.0	-
Balance (water and micro component)	100	100	100

	L	M	N
				Blown powder zeolite A	-	-	15.0
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
DTPMP	0.4	0.4	0.4
				CMC	0.4	0.4	0.4
MA/AA	4.0	2.0	2.0
				Agglomerates QAS	1.0	-	-
LAS	-	11.0	7.0
				TAS	2.0	2.0	1.0
Silicates of acid or alkali	2.0	-	4.0
				Zeolite A	8.0	8.0	8.0
Carbonate salt	7.0	8.0	4.0
				Spray encapsulation Encapsulated fragrances	0.3	0.3	0.3
C25E3	2.0	-	2.0
				Dry additive NaSKS-6 Silicates of acid or alkali	15.0	12.0	5.0
QEA	1.0	0.5	0.5
				Citric acid/citrate salt	5.0	-	2.0
Bicarbonate salt	-	3.0	-
				Carbonate salt	8.0	15.0	7.0
NACOBS	6.0	-	5.0
				Manganese catalyst	-	-	0.3
NOBS	-	2.0	-
				PB1	14.0	7.0	10.0
Polyethylene oxide MW 5,000,000	-	-	0.2
				Bentonite clay	-	-	10.0
Citric acid	-	-	0.5
				Protease enzyme	1.0	1.0	1.0
Lipase enzyme	0.4	0.4	0.4
				Amylase	0.6	0.6	0.6
Cellulase enzymes	0.6	0.6	0.6
				Silicone antifoam agent	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 (water and micro component)	100.0	100.0	100.0
				Density (g/l)	850	850	850

	O	P	Q	R
					Agglomerates
QAS	2.0	-	2.0	-
					MES	-	2.0	-	-
LAS	6.0	-	-	-
					TAS	-	2.0	-	-
C45AS	6.0	4.0	2.0	-
					MBAS16.5，1.9	4.0	-	-	-
Zeolite A	15.0	6.0	-	-
					Carbonate salt	4.0	8.0	4.0	8.0
MA/AA	4.0	2.0	-	2.0
					CMC	0.5	0.5	-	0.5
DTPMP	0.4	0.4	-	0.5
					Spray mist
C25E3	1.0	1.0	-	-
					Perfume	0.5	0.5	0.5	0.5
Agglomerates
					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 (W)	0.08	0.1	-	0.2
Dry additives
					EDDS/HEDP	0.5	0.3	0.5	0.8
NaSKS 6(I)or(II)	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 salts	14.0	18.0	13.0	16.0
SRP1	0.3	0.3	-	0.3
					Protease enzyme	1.4	1.4	1.0	0.5
Lipase enzyme	0.4	0.4	0.3	-
					Cellulase enzymes	0.6	0.6	0.5	0.5
Amylase	0.6	0.6	-	0.3
					QEA	1.0	-	1.0	1.0
Silicone antifoam agent	1.0	0.5	0.5	1.5
					Brightener 1	0.2	0.2	-	6.2
Whitening agent 2	0.2	-	0.2	-
					IPR 88(Rohm & Haas)	6.0	4.0	2.0	3.0
Density (g/l)	850	850	800	775

	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
							MBAS 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
Amberlite CG-420	-	-	-	-	-	-
							Citric acid	-	1.5	2.5	-	1.5	-
MA/AA	-	0.6	-	-	0.6	-
							MA/AA3	-	-	7.03	-	-	7.03
AA	2.3	-	-	2.8	-	-
							EDDS	-	0.3	-	-	0.3	-
HEDP	-	0.5	-	-	0.5	-
							Carbonate salt	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
							PB1	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 enzyme	0.25	0.36	0.2	0.26	0.36	0.2
							Lipase enzyme	-	-	-	-	-	-
Cellulase enzymes	0.3	0.26	-	0.3	0.26	-
							Starch (A)Flour enzyme	-	0.36	-	-	0.36	-
Whitening agent	0.17	0.06	0.30	0.17	0.06	0.30
							SRP1	0.4	0.2	0.5	0.4	0.2	0.5
PEG	1.6	-	0.19	1.6	-	0.19
							Sulfates of sulfuric acid	5.5	6.4	3.5	5.5	6.4	3.5
CMC	-	0.5	-	-	0.5	-
							MgSO4	-	0.13	-	-	0.13	-
Photobleaches	-	0.0026	-	-	0.0026	-
							Agglomerate of example 3	3.5	3.0	2.0	3.0	4.0	3.0
Silicone antifoam agent	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 examples

In the detergent compositions exemplified above, the abbreviated components have the following meanings: NYMCELTM: provided by Metsa-SerlaCMF of carboxymethyl cellulose: citric acid internally crosslinked fibrous cellulose Arbocel manufactured by Wayerhauser^TM: micronized cellulose LAS supplied by Rettesmeyer: straight chain C_11-13Sodium alkyl benzene sulfonate MES: c₁₈α -sulfomethyl ester of fatty acid TAS sodium tallow alkylsulfate C_XYAS ： C_1X-C_1YSodium alkyl sulfate C46 SAS: c₁₄-C₁₆Sodium secondary (2, 3) alkylsulfate C_XYE_ZS: c condensed with z moles of ethylene oxide_1X-C_1YSodium alkyl sulfate C_XYE_Z: c condensed with an average of z moles of ethylene oxide_1X-C_1YPrimary alcohol QAS: r₂N⁺(CH₃)₂(C₂H₄OH)，R₂＝C₁₂-C₁₄QAS1 ： R₂N⁺(CH₃)₂(C₂H₄OH)，R₂＝C₈-C₁₁SADS: formula 2- (R) C₄H₇-1，4-(SO₄-)₂C of (A)₁₄-C₂₂Alkyl disulfuric acid

Sodium, wherein R ═ C₁₀-C₁₈SADE 2S: condensed with z moles of ethylene oxide, formula 2- (R). C₄H₇-1，4- (SO₄-)₂C of (A)₁₄-C₂₂Sodium alkyl disulfate, where R ═ C₁₀-C₁₈APA ： C₈-C₁₀Amidopropyl dimethyl amine soap: sodium linear alkyl carboxylates from tallow and coconut oil fatty acids 80/20

The mixture yielded STS: sodium toluenesulfonate CFAA: c₁₂-C₁₄(coconut) alkyl N-methylglucamide TFAA: c₁₆-C₁₈Alkyl N-methylglucamide TPKFA: c₁₆-C₁₈Topped whole fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite a: formula Na₁₂(AlO₂SiO₂)₁₂.27H₂Hydrated sodium aluminosilicate of O, mainly granular

Particle size 0.1-10 microns (weight expressed on a dry basis) NaSKS-6 (I): clariant of the formula delta-Na₂Si₂O₅Citric acid, crystalline layered silicate of (2): anhydrous citric acid borate salt: sodium borateCarbonate salt: anhydrous sodium carbonate bicarbonate with particle size of 200-: anhydrous sodium bicarbonate silicate with particle size distribution of 400-: amorphous sodium Silicate (SiO)₂∶Na₂O ratio 2.0: 1) sulfate: anhydrous sodium sulfate magnesium sulfate: anhydrous magnesium sulfate citrate: trisodium citrate dihydrate, 86.4% activity, particle size distribution

425 and 850 micron MA/AA: 1: 4 maleic/acrylic copolymer having an average molecular weight of about 70000MA/AA (1): 4: 6 maleic/acrylic copolymer, average molecular weight about 10000 AA: sodium polyacrylate polymer, average molecular weight about 4500 CMC: sodium carboxymethylcellulose cellulose ether: a methyl cellulose ether having a degree of polymerization of 650, produced by Shin Etsu

Chemicals obtain protease: sold under the trade name Savinase by Novo Industries A/S

Contains 3.3% by weight of the active enzyme protease I: as described in WO95/01591, ex Genencor int

A commercially available protease containing 4% by weight of the active enzyme Alcalase: proteolytic enzymes sold by Novo Industries A/S containing

5.3% by weight active enzyme cellulase: sold under the name Carezyme by Novo Industries A/S

Containing 0.23% by weight of the active enzyme amylase: from Novo Industries A/S under the trade name Termamyl 120T

A commercial amylase containing 1.6% by weight of the active enzyme amylase II: amylase lipase as described in PCT/US 9703635: sold under the trade name Lipolase by Novo Industries A/S

Containing 2.0% by weight of active enzyme lipase (1): under the trade name Lipolase Ultra from Novo Industries A/S

A lipase sold containing 2.0% by weight of the active enzyme endosase: endoglucanase, sold by Novo Industries A/S, comprising

1.5% by weight of active enzyme PB 4: formula NaBO₂.3H₂O.H₂O₂Anhydrous sodium perborate tetrahydrate PB 1: formula NaBO₂.H₂O₂Anhydrous sodium perborate ofPercarbonate salts: formula Na₂CO₃.3H₂O₂Sodium percarbonate DOBS: decanoyl hydroxybenzenesulfonate salt DPDA in sodium salt form: peroxydodecanedioic acid NOBS: nonanoyl hydroxybenzenesulfonate, sodium salt form NACA-OBS: (6-nonanoylhexanoyl) hydroxybenzenesulfonate LOBS: dodecanoyl hydroxybenzenesulfonate, sodium salt form NOBS: nonanoyl hydroxybenzenesulfonate, sodium salt form DOBA: TAED nonanoyl hydroxybenzoic acid: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylene triamine penta (methylene phosphonate) commercially available from Monsanto

EDDS is sold under the name Dequest 2060: ethylamine-N, N' -disuccinic acid, (S, S) isomer, sodium salt form thereof

Photoactivated bleaching agents of formula: encapsulated zinc sulfonate in bleach (1) dextrin-solubilized polymers

Phthalocyanine photoactivated bleaching agents: encapsulated aluminum sulfonate in bleach (2) dextrin-dissolved polymers

Phthalocyanine brightener 1: 4, 4' -bis (2-sulfostyryl) biphenyl disodium brightener 2: 4, 4' -bis (4-phenylamino-6-morpholino-1, 3, 5-triazin-2-yl)

Amino) stilbene-2: 2' -disodium disulfonate HEDP: 1, 1-hydroxy-ethane diphosphonic acid PEGX: polyethylene glycol, average molecular weight X (typically 4000) PEO: polyethylene oxide, average molecular weight 50000 TEPAE: tetraethylenepentamine ethoxylate PVI: polyvinylimidazole, average molecular weight 20000 PVP: polyvinylpyrrolidone polymer, average molecular weight 60000 PVNO: polyvinylpyridine N-oxide polymer, average molecular weight 50000 PVPVI: copolymers of polyvinylpyrrolidone and vinylimidazole, average fraction

Quantum 20000 QEA: ((C)₂H₅O)(C₂H₄O)N)(CH₃)-N⁺-C₆H₁₂-N⁺-(CH₃) Double is

((C₂H₅O)(C₂H₄O)_n) Wherein n is 20-30SRP 1: anionic end-capped polyester SRP 2: diethoxylated poly (1, 2-propylene phthalate) short blocks

Polymer) PEI: polyethylene diamine, average molecular weight 1800, average 7 ethylene per nitrogen

Average degree of ethoxylation of oxy residues polysiloxane defoaming: a polydimethylsiloxane foam control agent and a polysiloxane-agent oxyalkylene copolymer as a dispersing agent, wherein the proportion of the foam control agent to the dispersing agent is

10: 1-100: 1 sunscreen agent: water-based mixture of monostyrene latexes, under the trade name BASF

Lytron 621 sells wax: paraffin wax

Claims (10)

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

2. The detergent composition of claim 1, wherein the disintegrant comprises an anion exchange resin.

3. A detergent composition according to claim 1 or 2, wherein the cationic polymer contains quaternary ammonium cationic groups.

4. A detergent composition according to claim 3, wherein the quaternary ammonium 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 solid form comprising an inner core and a coating at least partially coating the inner core, characterised in that the coating comprises a disintegrant comprising a water-swellable cationic polymer.

7. A detergent composition according to claim 6, further comprising a polyanionic builder.

8. A detergent composition according to any one of claims 1 to 5 or 7 wherein the polyanionic builder is selected from di-or tri-carboxylic acids or salts thereof, phosphates, polymeric polycarboxylates and chelants.

9. A process for the preparation of a detergent composition as claimed in any preceding claim, which comprises forming a core by compressing a particulate material comprising surfactant and detergent builder, 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 polymer in a detergent composition to reduce fabric greying.