CN1329662A - detergent composition - Google Patents

Abstract

This invention relates to detergent compositions or components thereof in solid form and methods for increasing the disintegration rate of the detergent composition while simultaneously inhibiting fabric graying. Suitable detergent compositions contain water-swellable cationic polymers and polyanionic builder agents. The invention also relates to detergent compositions or components thereof in solid form, which are at least partially coated with a coating containing a cationic polymeric disintegrant.

Description

detergent composition

field of invention

The present invention relates to detergent compositions, especially laundry detergents, and their disintegration. In particular the invention relates to detergent granules or tablets comprising water-swellable cationic polymers, such as ion exchange resins.

background

Especially desirable are detergent compositions which provide detergent actives to the wash water upon contact with the water. In recent years, there has been a tendency for detergent compositions to have increased densities of more than 650 g/l, or more than 700 g/l or even more than 750 g/l, or to be provided in tablet form, which has the effect of inhibiting dispersion and/or distribution, thus contributing to the wash water Trend to rapidly deliver detergent actives.

A number of methods have been described for improving the dissolution of detergents, for example EP-A-466484 describes the use of disintegrants and their mechanism, which suggests 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 remains a need for disintegrants that provide good dispersion of solid form detergent products to improve product dispersion and/or dissolution.

Another problem faced by detergent formulators is that soap, for example on soiled laundry surfaces, tends to bind hydraulic calcium ions and precipitate, which tends to stick to the items washed, resulting in reduced whiteness due to resoiling.

The inventors have now found that the use of a cationic polymeric disintegrant can help avoid this effect by combining it with the soap. However, to ensure that soap impurities are removed from the wash liquor prior to complexing with calcium ions, chelating agents or builders are required to rapidly complex calcium ions. Furthermore, cationic polymeric disintegrants have been found to be particularly suitable for the breakdown of coatings on detergent components.

Summary of the invention

According to the present invention there are provided detergent compositions or components thereof in solid form comprising a disintegrant and a polyanionic builder, characterized 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, characterized in that the coating contains a disintegrant comprising a water-swellable cation polymer. Detailed Description of the Invention Disintegrant

The disintegrant comprises a water-swellable cationic polymer, suitable disintegrants include anion exchange resins such as IPR 88 (Rohm & Haas).

The disintegrant comprises a cationic polymer, wherein the cationic groups may be pendant to or on pendant chains from the polymer backbone.

Preferred cationic groups are side groups of the polymer backbone, preferred cationic groups are quaternary ammonium cationic groups such as -(NR ₁ R ₂ R ₃ ) ⁺ , wherein R ₁ , R ₂ and R ₃ are each selected from H and optionally substituted lower alkyl or alkenyl such as methyl or ethyl.

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

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

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

The disintegrant is preferably added to the detergent composition in the form of a dry added granule. It has been found that the particle size of the disintegrant can be selected to obtain disintegration properties which are particularly beneficial 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 greater than 2000 microns, most preferably less than 1700 microns. 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%, most preferably at least 95 wt% of the disintegrating components or particulate disintegrants are at least 100 microns, more preferably at least 150 microns. 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 disintegrant effect.

Disintegrants are typically present in detergent compositions in an amount of 1-20 wt%, preferably 2-15 wt%, most preferably 2-10 wt%, by weight of the detergent composition.

It is especially advantageous to use water-swellable cationic polymers 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 pre-mix of the water-swellable cationic polymer and other disintegrants prior to addition to the detergent composition.

The disintegrant of the present invention can also be used in combination with a wicking agent. Suitable water-absorbing agents comprise compounds or mixtures of compounds which are capable of rapidly penetrating water into the detergent composition containing disintegrating components when the detergent composition comes into contact with water during washing. The water-absorbing agent is generally substantially insoluble in cold water at 15° C., and it is also preferred that the water-absorbing agent has a low compressibility and remains porous under processing conditions, especially upon compaction.

Suitable water-absorbing agents are generally cellulose-based, the cellulose-based compound optionally being microcrystalline or mechanically comminuted and processed cellulose, eg Arbocel ^™ .

The water-absorbing agent may be in the form of a powder obtainable by mechanical grinding, a microcrystalline powder or may be in granular form, for example agglomerates of fine-grained water-absorbing agent or as fibers or mixtures thereof. Especially preferred water-absorbing agents are fibrous, for example fibers having an aspect ratio of at least 3:1, preferably at least 5:1 or even at least 10:1. Suitable fibers include fibers having a length of at least 0.1 mm, or at least 0.2 mm, or even at least 0.4 mm, and it is especially preferred that the water absorbing agent is cross-linked.

Especially preferred water absorbents are crosslinked cellulose fibers as described in US5137537, US5183707, US5190563, US5562740, US5549791, US5549863, US5709774 or US5716703. These especially preferred cellulosic fibers are crosslinked in an essentially individual fashion, ie the cellulosic fibers have predominantly interfiber chemical crosslinks. That is, the crosslinks are primarily between individual cellulose molecules rather than between cellulose molecules of separate fibers. The method of preparing the crosslinked fibers may be, for example, the dry crosslinking method described in US3224926 or the aqueous solution as described in US3241553 or the non-aqueous solution crosslinking as described in US4035147.

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, usually 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 two components and optionally with other components and/or binders, intimate mixture means that at least two components are mixed together to form a substantially homogeneous A premix of a mixture.

This can be achieved by dry blending the solid water absorbing and solid water swelling agents with optional binders. The premix can be in particulate form, which can 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 a water-swelling agent is present as a coating of the water-absorbing agent. This is especially advantageous when the water-absorbing agent is fibrous.

The coating of the water-swelling agent provided on the surface of the water-absorbing agent can be achieved by any conventional method, such as by mixing the water-absorbing agent and the water-swellable polymer with the solvent for the water-swelling agent in any order of addition, forming a gel or a solution or containing a part Swelling slurry of water swelling agent. Preferably mixing is continued until a substantially homogeneous mixture is obtained. The mixture of the water-absorbing agent and the water-swelling agent is subsequently recovered by any conventional technique such as separation from the solvent by evaporation of the solvent or by addition of a non-solvent for the water-swelling agent to form a mixture which is then precipitated by any conventional technique such as subsequent Filter or decant off the solvent to separate from the solvent. polyanionic builder

The term "builder" refers to any substance which tends 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, chelating agents or the corresponding acids of any of these materials and mixtures thereof.

Water-soluble builders are preferably present in amounts of 0.05% to 50% by weight, preferably 0.1% to 40% by weight, most preferably 0.5% to 30% by weight, based on the weight of the total detergent composition.

It is preferred that the detergent composition be substantially free of phosphates, however, where present, suitable phosphate-containing detergent builders include, but are not limited to, polyphosphates (e.g., tripolyphosphate, pyrophosphate, and glassy polymeric Alkali metal, ammonium and alkanolammonium salts of metaphosphate). A preferred phosphate builder is tetrasodium pyrophosphate or more preferably anhydrous or partially hydrated sodium tripolyphosphate at a level of from 0.5% to 50% by weight, more preferably from 5% to 45% by weight, based on the total detergent composition. %.

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

Suitable polycarboxylates containing two carboxy groups include water soluble polycarboxylates of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid salts and ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups especially include water-soluble citrate, itaconate and citraconate and succinate derivatives, such as carboxymethoxysuccinate described in GB1379241, in GB1389732 The lactyloxysuccinates described and the aminosuccinates described in Dutch application 7205873 and the oxypolycarboxylate substances described in GB1387447, such as 2-oxo-1,1,3-propanetricarboxylate salt. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in GB1261829 and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in GB1398421 and 1398422 and US3936448, and the sulfonated pyrolyzed citrates described in GB1439000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more preferably citrates.

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

Preferably the polymeric or oligomeric polycarboxylates are present at a level 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 generate borate under detergent storage or wash conditions are water-soluble builders useful herein.

Examples of organic polymers include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid includes 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 polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, the copolymers having a molecular weight of 2000-100000, especially 40000-80000.

The 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 maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having a molecular weight of 5000-10000, are also suitable.

Chelating agents are also effective as polyanionic builders in the detergent compositions employed herein. 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 .

Preferred among the above species are diethylenetriaminepenta(methylenephosphonate), ethylenediaminetris(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate) and hydroxyl - Ethylene-1,1-diphosphonate, 1,1-hydroxyethanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other suitable chelating agents for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedi Succinic acid or any salt thereof.

Other suitable chelating agents for use in the present invention are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid described in EP-A-317542 and EP-A-399133. Iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516102 can also be used . β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinate described in EP-A-509382 Acid sequestrants are also 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 alkyliminodiacetic acid sequestrants. Also suitable are dipicolinic acid and 2-phosphinobutane-1,2,4-tricarboxylic acid. Glycylamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS ) is also suitable.

Diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or their alkali metal, alkaline earth metal, ammonium or substituted Ammonium salts or their mixtures. form of composition

According to the invention, the detergent compositions or components thereof may take various solid physical forms such as tablets, flakes, lozenges and bars, preferably in the form of granules or tablets. Preferably the detergent composition is in tablet form. Detergent compositions can be manufactured by various methods including dry blending, agglomeration, compaction or spray drying of the various compounds contained in the detergent composition, or combinations of these techniques.

The disintegrant is added to the detergent composition in any conventional manner, eg it may be added in any of the above mentioned processing steps, but is preferably dry blended into the particulate detergent mixture. Alternatively or additionally, the disintegrant may be provided as a coating of all or part of the detergent composition. Thus, the disintegrant can be present in the detergent granule or mixed with other detergent ingredients as individual granules. For incorporation into tablets, the disintegrant may be added to the granular detergent composition as described above prior to compaction. Disintegrants are especially useful in detergent tablet coatings when present as part of the coating. The coating aspect of the present invention is described in the context of detergent tablet coatings where a detergent composition core is first formed and subsequently coated. However, the coating can equally well be applied to detergent granules or other solid detergent forms. Coating Detergent Tablets

When the detergents of the present invention are in tablet form, they can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press. Any liquid components, such as surfactants or suds suppressors, may be added to the solid particulate component in a conventional manner, preferably the main component is used in particulate form.

Particularly for laundry tablets, the ingredients, such as builders and surfactants, can be spray-dried in a conventional manner and subsequently compacted under suitable pressure. Detergent tablets can be manufactured in any size or shape and can be surface treated if desired. In the tablet core, surfactants and builders are included, which generally provide the major part of the tablet's detergency power.

The particulate material used to prepare the tablets of the present invention may be prepared by any granulation 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 of 600 g/l or less. Higher density particulate matter can be prepared by granulation and densification in a high shear batch mixer/granulator or a continuous granulation and densification process (eg using Lodige® CB and/or Lodige® KM mixers). Other suitable methods include fluidized bed methods, compaction methods (such as roller compaction), extrusion, and any particulate matter prepared by any chemical method, such as flocculation, crystallization, sintering, etc. The individual particles can also be any other particles , particles, spheres or grains.

The particulate matter can be mixed together by any conventional means. Batch processes are suitable in eg concrete mixers, Nauta mixers, ribbon mixers and the like. Alternatively, the mixing process can be performed continuously by weighing each component onto a conveyor belt and mixing in one or more drums or mixers. Liquid spraying on mixtures of particulate matter such as non-ionic surfactants can be performed. Other liquid components can be sprayed on to the mixture of particulate materials individually or premixed, for example a slurry of perfume and fluorescer can be sprayed. Finely divided flow aids (separators such as zeolites, carbonates, silicas) may be added to the particulate matter after spraying of the nonionic surfactant, preferably towards the end of the process, to make the mixture less viscous.

Tablets may be prepared by using any compression process, such as tabletting, briquetting or extrusion, tabletting being preferred. Suitable equipment includes standard single stroke or rotary presses (eg Courtoy®, Korch®, Manesty® or Bonals®). Tablets prepared according to the invention preferably have a diameter of 40mm-50mm and a weight of 25-60g. The required compaction pressure for the preparation of these tablets does not exceed 5000 kN/m ² , preferably does not exceed 3000 kN/m ² , most preferably does not exceed 1000 kN/m ² .

According to the invention, the tablet is subsequently coated with a coating such that the tablet does not absorb moisture or absorbs moisture only at a very slow rate. The coating is also robust so that the tablets suffer no more than a very low degree of breakage or loss when subjected to moderate mechanical shock during handling, packaging and shipping. Finally, the coating is preferably friable so that the tablet breaks up when subjected to strong mechanical vibrations. Furthermore, it is advantageous that the coating material dissolves under alkaline conditions or is easily emulsified by surfactants. This avoids the deposition of undissolved particles or clumps of coating substance on the laundry load, which is important when the coating substance is completely insoluble in water (eg less than 1 g/l).

"Essentially insoluble" as defined herein means having very low solubility in water. This is understood to mean having a solubility in water at 25°C of less than 20 g/l, preferably less than 5 g/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, diols, esters and ethers. Preferred fatty acids are those containing C12-C22, most preferably C18-C22 carbon chain lengths. 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 C12-C22, most preferably C14-C18 carbon chain length. Preferred diols are 1,2-octadecanediol and 1,2-hexadecanediol. Preferred esters are glyceryl tristearate, tripalmitin, methyl behenate, ethyl stearate. Preferred ethers are diethylene glycol monocetyl ether, diethylene glycol monostearyl ether, diethylene glycol monotetradecyl ether, phenyl ether, ethyl naphthyl ether, 2-methanol Oxynaphthalene, Beta Naphthyl Methyl Ether and Glyceryl Monostearyl Ether. Other preferred coating substances include dimethyl-2,2-propanol, 2-hexadecanol, 2-octadecyl alcohol, 2-hexadecanone, 2,15-hexadecanedione and 2-hydroxybenzyl alcohol.

Preformed detergent tablet cores can then be coated according to the invention. The coating can be applied in a number of ways, but typically 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°C to 200°C.

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 an adherent coating. Substantially insoluble material can be provided to tablets by, for example, spraying or dipping. Usually when a molten substance is sprayed on a tablet, it will quickly solidify to form an adherent coating. When the tablet is dipped in the molten mass and then removed, the rapid cooling again causes rapid solidification of the coating mass. Apparently, substantially insoluble materials having melting points below 40°C do not solidify sufficiently at room temperature, and materials having melting points in excess of about 200°C have been found to be impractical for practical use. The material preferably melts at 60°C to 160°C, more preferably 70 to 120°C.

"Melting point" refers to the temperature at which a substance becomes a clear liquid when heated slowly, eg, in a capillary tube.

Coatings of any desired thickness can 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 the desired degree of disintegration of the coating upon contact with water in the wash liquor to facilitate delivery of the detergent composition to the wash water and to improve dissolution. Typically the disintegrant will be present in the final coating in a coating material:disintegrant 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 generally 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 (diametrical crushing stress), and the disintegration time in the washing machine. The method can be used to prepare uniform or layered tablets of any size or shape.

Diameter Fracture Stress (DFS) is a way of expressing tablet strength and is determined by the following formula: $=\frac{2f}{\mathrm{\μDt}}$ where F is the maximum force (in Newtons) to cause tensile failure (crushing), as measured by a VK200 Tablet Hardness Tester supplied by Van Kellindustries, Inc. D is the diameter (mm) of the tablet, and t is the tablet thickness (mm). (Method Pharmaceutical Dosage Forms: Tablets Vol. 2, pp. 213-217).

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

a) In a "VAN KEL" Friabilator with a "Vankel Type" drum.

- Place 2 tablets of known weight and DFS in the Friabilator drum.

- Rotate the drum 20 revolutions.

- Collect all product and residual flakes by Friabilator drum, on 5 mm, and sieve through 1.7 mm.

- Residue in % over 5 mm and through 1.7 mm.

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

b) in the washing machine as follows

- Take 2 tablets of known weight and breaking stress and place them in the bottom of the washing machine (ie Bauknecht WA950).

- Place a 3 kg mixed load on top of the tablet.

- Run short cycle at 30°C with tap water (Program 4).

- Stop cycle after 5 minutes, check wash load for undissolved flakes, collect and weigh, record percent residue remaining.

In another preferred embodiment of the present invention, the detergent composition also contains an effervescent component. Effervescence is defined herein as the release of gas bubbles from a liquid as a result of a chemical reaction between a water-soluble acid source and an alkali metal carbonate (the effervescent component) to generate carbon dioxide gas,

Right now,

Other examples of acid and carbonate sources and other effervescent systems can be found in: (Pharmaceutical Dosage Forms: Tablets Vol. 1, pp. 287-291). In addition to detergent ingredients, effervescent agents can be added to the tablet mix. The disintegration time is improved by adding the effervescent agent to detergent compositions or components thereof, especially detergent tablets according to the invention. The amount of effervescent component is preferably 5-20%, most preferably 10-20% by weight of the tablet. The effervescent agent is preferably added as an agglomerate of different particles or as a compacted mass rather than as individual particles. Due to the gas generated by the effervescent component, detergent tablets can have a higher DFS and still have the same disintegration time compared to tablets without the effervescent component. When the DFS of the tablet with the effervescent component is the same as the tablet without the effervescent component, the disintegration of the tablet with the effervescent component will be faster. Other Detergent Components Detergent Components

The compositions of the present invention, or components thereof, may contain additional detergent ingredients, the exact nature and amount of which will depend upon the application of the component or composition and the physical form of the component and composition.

The detergent compositions of the present invention preferably contain one or more additional detergent ingredients selected from bleaches, bleach catalysts, alkaline systems, additional builders, organic polymers, enzymes, suds suppressors, calcium soaps , dispersants, soil-suspending and anti-redeposition agents, detergents, fragrances, brighteners, photo-bleaches and additional preservatives. detergent surfactant

Compositions of the invention generally 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 and mixtures thereof as discussed below.

Non-limiting examples of surfactants useful herein at levels of from about 1% to about 55% by weight include conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS") and primary, branched and Random C ₁₀ -C ₂₀ Alkyl Sulfate (“AS”), Formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ )CH C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates of ₂ CH ₃ , wherein x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-soluble cation, especially sodium, unsaturated Sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfate ("AE _x S"; especially EO1-7 ethoxy sulfate), C ₁₀ -C ₁₈ alkyl alkoxy Carboxylates (especially EO1-5 ethoxy carboxylates), C ₁₀ -C ₁₈ glyceryl ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₂ -C ₁₈ alpha - Sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including so-called narrow-peak alkyl ethoxylates, may also be included in the overall composition. and C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ₁₂ -C ₁₈ betaines and sultaines, C ₁₀ -C ₁₈ amine oxide etc. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides, see WO9206154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can be used for low sudsing. _C10 - _C20 conventional soaps can also be used. If high sudsing is desired, branched C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful.

Suitable cationic surfactants for incorporation into the detergent compositions of the present invention include quaternary ammonium surfactants. Quaternary ammonium surfactants are preferably mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. 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 US Patents 4,228,042, 4,239,660 and 4,260,529.

More preferred cationic surfactants are cationic mono-alkoxylated amine surfactants, preferably having the general formula I: wherein ^R is 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; R ^{and R} are each an alkyl or alkenyl moiety containing 1-Alkyl of about 3 carbon atoms, preferably methyl, most preferably ^R2 and ^R3 are both methyl; ^R4 is selected from hydrogen (preferred), methyl and ethyl; X ^- is an anion, such as chloride , bromide, methyl sulfate, sulfate, etc., to provide electrical neutrality; A is alkoxy, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably in formula I the A _p R ⁴ group has p = 1 and is a hydroxyalkyl group having not more than 6 carbon atoms so that the -OH group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms open. Especially preferred _ApR4 are _{-CH2CH2OH , -CH2CH2CH2OH , -CH2CH} ( _CH3 )OH and -CH _{( CH3} ) _CH2OH ^, especially preferably _{-CH2CH 2} OH. Preferably the ^R1 group is a straight chain alkyl group, straight chain ^R1 groups containing 8 to 14 carbon atoms are preferred.

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

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

Examples of silicate builders which may be added to the detergents of the present invention are alkali metal silicates, especially those having a SiO2: _Na2O ratio of 1.6 _: 1 to 3.2:1 and layered silicic acid. Salts such as layered sodium silicates as described in US 4,664,839, HP Rieck, issued May 12,1987. NaSKS-6 is a trademark for a crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has _the delta- _Na2SiO5 morphology of layered silicates. It can be prepared, for example, by the methods described in DE-A-3417649 and DE-A-3742043. SKS-6 is a more preferred phyllosilicate for use in the present invention, but other such phyllosilicates may also be used, such as silicic acid having the general formula _{NaMSixO2x +1 yH2O} Salt, wherein M is sodium or hydrogen, x is a number between 1.9-4, preferably 2, and y is a number between 0-20, preferably 0 here. Various other phyllosilicates available from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in the alpha, beta and gamma forms, respectively. As _noted 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 crisping agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component in suds control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates described in GP-A-2321001, published November 15,1973.

Aluminosilicate builders are useful herein. Aluminosilicate builders are of great importance in recently marketed heavy duty granular detergent compositions and can also be an important builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the following empirical formula:

[M _z (zAlO ₂ ) _y ] xH ₂ O

wherein z and y are integers of at least 6, the molar ratio of z to y is 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 can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetic. US 3,985,669, Krummel et al., issued October 12, 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 designations Zeolite A, Zeolite P(B), Zeolite MAP and Zeolite X, with Zeolite MAP being especially useful. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O,

wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) are useful in the present invention. The particle size of the aluminosilicate is preferably about 0.1-10 microns in diameter.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be added to the composition alone, or in combination with the aforementioned builders, especially citrate and/or succinate builders, to provide additional builder activity . This use of fatty acids generally results in reduced foam, which should be taken into account by the formulator.

Where phosphorus-based builders can be used, and especially in the formulation of soap bars for use in handwashing operations, the various alkali metal phosphates such as the known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate. Phosphonate builders can also be used, such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, eg, US Pat. bleach

The detergent compositions of the present invention may also optionally comprise a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. If present, bleaching agents will generally be present at levels of from about 1% to about 30%, more usually from about 5% to about 20%, of the detergent compositions, especially for fabric laundering. Bleach activators, if present, will generally be present in amounts of from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleaching compositions containing the bleach and bleach activators.

The bleaching agent for use in the present invention may be any bleaching agent useful for detergent compositions in fabric laundering, hard surface cleaning or other known or to become known laundering applications. These include oxygen bleaches as well as other bleaches. Perborate bleaches, such as sodium perborate (eg, mono- or tetra-hydrated sodium perborate), can be used in the present invention. Other suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and the corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleaches (such as OXONE commercially available from DuPont) may also be used.

Preferred percarbonate bleaches contain dry particles having an average particle size in the range of about 500 microns to about 1000 microns, wherein not more than about 10% by weight of said particles are smaller than about 200 microns, and not more than About 10% by weight of the particles are larger than about 1250 microns. The percarbonate can optionally be coated with silicates, borates or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Another class of bleaches which may be used without limitation includes percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxyperoxybutyric acid, and dodecanedioic acid diperoxide . US4483781 issued November 20, 1984 to Hartman, Burns et al. US Patent Application 740446 filed June 3, 1985, EP-A-0133354 published February 20, 1985 to Banks et al., and November 1983 Such bleaching agents are disclosed in US 4,412,934, Chung et al. More preferred bleaching agents also include 6-nonylamino-6-oxyperoxydecanoic acid, which is described in US Patent 4,634,551, Burns et al., issued January 6,1987. A bleach mixture can also be used.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably mixed with the bleach activator, which results in the in situ formation of the peroxyacid corresponding to the bleach activator in aqueous solution (ie during the wash). Various non-limiting examples of activators are disclosed in US4915854 and US4412934, Mao et al., issued April 10, 1990. Nonanoylbesylate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. See also US4634551 for other typical bleaches and activators useful in the present invention. More preferred amido-derived bleach activators are those of the formula:

R ¹ N(R ⁵ )C(O)R ² C(O)L or R ¹ C(O)N(R ⁵ )R ² C(O)L

还有另外一种优选的漂白活化剂包括酰基内酰胺活化剂，特别是具有如下结构式的酰基己内酰胺和酰基戊内酰胺，：

其中R⁶为H或含有1-约12个碳原子的烷基、芳基、烷氧基芳基或烷芳基。更优选的内酰胺活化剂包括苯甲酰基己内酰胺、辛酰基己内酰胺、3，5，5-三甲基己酰基己内酰胺、壬酰基己内酰胺、癸酰基己内酰胺、十一烷酰基己内酰胺、苯甲酰基戊内酰胺、辛酰基戊内酰胺、癸酰基戊内酰胺、十一烷酰基戊内酰胺、壬酰基戊内酰胺、3，5，5-三甲基己酰基戊内酰胺及其混合物。也参见1985年10月8日颁布的Sanderson的US4545784，列为本文参考文献，它披露了吸附到过硼酸钠中的包括苯甲酰基己内酰胺在内的酰基己内酰胺。除了氧漂白剂之外的其它漂白剂也是现有技术已知的，且可用于本发明。一种具有特殊价值的非氧漂白剂包括光活化漂白剂，如磺化的锌和/或铝酞菁。参见1977年7月5日颁布的Holcombe等的US4033718。如果使用的话，洗涤剂组合物一般含有按重量计约0.025％-约1.25％的这种漂白剂，特别是磺化的锌酞菁。如果需要，漂白化合物可用锰化合物催化。这种化合物在现有技术中是已知的，并且包括例如披露于US5246621、US5244594、US519 4416、US5114606，和EP549271A1、549272A1、544440A2和544490A1中的锰基催化剂。这种催化剂的优选实例包括Mn^IU ₂(u-O)₃(1，4，7-三甲基-1，4，7-三氮杂环壬烷)₂(PF₆)₂、Mn^III ₂(u-O)₁(u-OAc)₂(1，4，7-三甲基-1，4，7-三氮环杂壬烷)₂(ClO₄)₂、Mn^IV ₄(u-O)₆(1，4，7-三氮杂环壬烷)₄(ClO₄)₄、Mn^IIIMn^IV ₄(u-O)₁(u-OAc)₂(1，4，7-三甲基-1，4，7-三氮杂环壬烷)₂(ClO₄)₃、Mn^IV(1，4，7-三甲基-1，4，7-三氮杂环壬烷)₂-(OCH₃)₃(PF₆)及其混合物。其它的金属基漂白催化剂包括US4430243和US5114611中所披露的那些。以下US4728455、5284944、5246612、5256779、5280117、5274147、5153161和5227084，也报道了使用带有各种络合配位体的镁以提高漂白性能。wherein ^R is an alkyl group containing about 6 to about 12 carbon atoms, ^R is an alkylene group containing 1 to about 6 carbon atoms, R is H or an alkyl group containing about ¹ to about 10 carbon atoms , aryl or alkaryl, and L is any suitable leaving group. A leaving group is any group which is displaced from the bleach activator following 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 formula include (6-octanoylamino-caproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, (6-decanoylamino-caproyl)oxybenzenesulfonate, (6-decanoylamino-caproyl) ) dobesylates and mixtures thereof, which are described in US4634551, which is incorporated herein by reference. Another class of bleach activators includes the benzoxazine-type activators disclosed in US Patent 4,966,723, Hodge et al., issued October 30, 1990, incorporated herein by reference. More preferred benzoxazine type activators are:

Yet another preferred bleach activator includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formula:

wherein R is H or an ^alkyl , aryl, alkoxyaryl or alkaryl group containing 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 US Patent 4,545,784, Sanderson, issued October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and may be used in the present invention. A class of non-oxygen bleaches of particular value includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718, Holcombe et al., issued July 5,1977. If used, detergent compositions will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines. The bleaching compounds can, if desired, be catalyzed with manganese compounds. Such compounds are known in the prior art and include, for example, manganese-based catalysts disclosed in US5246621, US5244594, US5194416, US5114606, and EP549271A1, 549272A1, 544440A2 and 544490A1. Preferred examples of such catalysts include Mn ^IU ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4 , 7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal-based bleach catalysts include those disclosed in US4430243 and US5114611. The following US Pat.

In practice, and without limitation, the compositions and methods of the present invention can be adjusted to provide at least one part per ten million active bleach catalyst species in the wash solution, and preferably from about 0.1 ppm to about 700 ppm in the wash solution. , more preferably from about 1 ppm to about 500 ppm of catalyst species. enzyme

Enzymes may be included in the formulations herein for a variety of fabric laundering applications including, for example, the removal of protein-based, carbohydrate-based or triglyceride-based stains, and to prevent fugitive dye transfer during washing, and for fabric restoration . Enzymes added include proteases, amylases, lipases, cellulases and peroxidases and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. However, their choice is influenced by certain factors, such as optimum pH-activity and/or stability, thermostability and stability to active detergents, builders, etc. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

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

Suitable examples of proteases are the subtilisins obtained from special strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is obtained from a special strain of Bacillus having maximal activity throughout the pH range of 8-12, which is developed and sold under the tradename ESPERASE by Novo Industries A/S. The preparation of this and similar enzymes is described in GB1243784 to Novo. Commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the trademarks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and under the trademark MAXATASE by International Bio-Synthetics, Inc. (Netherlands). Other proteases include Protease A (see EP130756A published January 9, 1985) and Protease B (see European Patent Application 87303761.8, filed April 28, 1987 and EP130756A, Bott et al., published January 9, 1985). Amylases include, for example, α-amylases described in GB1296839 (Novo); RAPIDASE from International Bio-Synthetic, Inc. and TERMAMYL from Novo Industries.

The cellulases used in the present invention include bacterial and fungal cellulases, preferably they have a pH optimum of 5-9.5. Suitable cellulases are disclosed in US 4,435,307, Barbesgoard et al., issued March 6, 1984, which discloses cellulase 212-producing fungi from Humicola insolens or Humicola niger strain DSM1800 or from a fungus belonging to the genus Aeromonas. Suitable fungal cellulases, as well as cellulases extracted from the hepatopancreas of the marine mollusk (Dolabella Auricula Solander). GB-A-2075028, GB-A-2095275 and DE-OS-2247832 also disclose suitable cellulases. CAREZYME (Novo) is especially useful,

Lipases suitable for use in detergents include microorganisms of the genus Pseudomonas, such as those obtained from Pseudomonas stutzeri ATCC 19.154 as disclosed in GB1372034. See also lipases in Japanese Patent Application No. 53,20487, published February 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd. (Nagoya, Japan) under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, a lipase from Chromobacter viscosum such as Chromobacter viscosum var. lipolyticum commercially available from Toyo Jozo Co. (Tagata, Japan), NRRLB 3673; available from U.S. Biochemical Corp. (UAS ) and Chromobacter viscosum lipase from Disoynth Co. (Netherlands); and lipase 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 an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used as "solution bleaches", ie to prevent the transfer of dyes or pigments removed from a substrate during wash operations to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Detergent compositions containing peroxidases are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.

US Patent 3,553,139, McCarty et al., issued January 5, 1971, discloses a wide range of enzyme materials and their incorporation into synthetic detergent compositions. Enzymes are further disclosed in US 4,101,457, Place et al., issued July 18, 1978, and US 4,507,219, Hughes, issued March 26, 1985. US Patent 4,261,868, Hora et al., issued April 14, 1981, discloses enzyme materials for use in liquid detergent formulations, and their incorporation into such formulations. Enzymes for use in detergents can be stabilized in a variety of ways. US3600319 issued by Gedge et al. on August 17, 1971 and EP0199405 issued by Venegas on October 29, 1986 (application number 86200586.5) disclosed and listed enzyme stabilization techniques. Enzyme stabilization systems are also described eg in US3519570.

Other ingredients commonly used in detergent compositions and which may be added to the detergent tablets of the present invention include soil release agents, soil anti-redeposition agents, dispersants, brighteners, suds suppressors, fabric softeners, dye transfer inhibiting agents potions and spices.

The present invention is illustrated by the following implementation examples. Example 1

Commercially available granular detergents were placed in a 54mm diameter ring mold and compressed using a Lloyd Instruments LR 50 test apparatus to form detergent tablets containing surfactants, builders, enzymes, perfume and other detergent ingredients. The compressive load was optimized to give a tablet with a round tablet strength of 12 kPa diameter crushing stress (expressed in kPa), calculated as above.

Heat adipic acid (du Pont) to 163°C under slow stirring in a constant temperature bath until it melts. The disintegrant was then added under continuous stirring to obtain a homogeneous 10% w/w suspension in adipic acid. The tablet prepared as above is dipped in the liquid to obtain the final coated tablet.

In Example 1, the cationic polymer IPR88 (available from Rohm & Haas) was used as a disintegrant, yielding a tablet with a total weight of 46 g and a diameter breaking stress of 28 kPa. The tablet was dipped in deionized water at 20°C and the time to start disintegration of the coating was measured to be 4 seconds.

Comparative Example A

When a cellulose disintegrant, Nymcel zsb16® (from Metsa Serla) was used in the coating in the same proportion as the disintegrant, a tablet with a total weight of 46 g and a diameter breaking stress of 30 kPa was produced. The tablet was dipped in deionized water at 20°C and the time to start disintegration of the coating was measured to be 25 seconds.

Example 2

The following are examples of detergent compositions of the present invention. They can be granulated or can be compressed into tablets in a tablet machine.

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 - - 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 C45E7 - 2.5 - - C25E3 2.5 - - -       Silicone defoamer 0.3 0.3 0.3 0.3 Spices 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 - PB1 4.0 4.0 - - NOBS 3.0 4.2 1.0 -           Photoactivated Bleach 0.02 0.02 0.02 0.02 Manganese catalyst - - 0.5 - Protease 1.0 1.0 1.0 1.0                      0.4 0.4 0.4 0.4                     0.25 0.30 0.15 0.3 Sodium Sulfate Dry Mix 3.0 3.0 5.0 3.0 Balancer (moisture and trace components) 100.0 100.0 100.0 100.0 Density (g/l) 630 670 670 670

E F G H base 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/C _{2 5} E ₃ - 2.0 - 1.0 LAS - 18.0 - - Zeolite 9.0 5.0 - 8.0 carbonate 13.0 7.5 - 5.0 Bicarbonates - 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 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 cellulase 0.15 0.05 - - Photoactivated Bleach (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 (moisture and trace components) 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 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 3.0 2.0 1.5 spray C45E5 1.0 1.0 - LAS/MES 8.0 5.0 5.0 dry additive NaSKS-6 15.0 6.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0                   0.4 0.4 0.4             Amylase 0.1 0.1 0.1                        0.1 0.1 0.1 NOBS - 6.1 -                             - - 4.5 IPR 88 2.5 4.6 1.0 Sodium Sulfate - 6.0 - Balancing substances (moisture and trace components) 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 Silicate 2.0 - 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 7.0 8.0 4.0 Spray Capsule Fragrance 0.3 0.3 0.3 C25E3 2.0 - 2.0   Dry Additives            NaSKS-6 Silicate 15.0 12.0 5.0 QEA 1.0 0.5 0.5         Citric Acid/Citrate 5.0 - 2.0 Bicarbonates - 3.0 - Carbonate 8.0 15.0 7.0                                         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 - - 10.0 Citric acid - - 0.5 Protease 1.0 1.0 1.0                              0.4 0.4 0.4                       0.6 0.6 0.6 Cellulase 0.6 0.6 0.6                                       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 (moisture and trace components) 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 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 C25E3 1.0 1.0 - - Spices 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 0.08 0.1 - 0.2 dry additive 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 14.0 18.0 13.0 16.0 SRP1 0.3 0.3 - 0.3 Protease 1.4 1.4 1.0 0.5                  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 defoamer 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/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 AAA 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 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 0.25 0.36 0.2 0.26 0.36 0.2 Lipase - - - - - - cellulase 0.3 0.26 - 0.3 0.26 - Amylase - 0.36 - - 0.36 - brightener 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 Sulfate 5.5 6.4 3.5 5.5 6.4 3.5 CMC - 0.5 - - 0.5 - MgSO4 - 0.13 - - 0.13 - photobleach - 0.0026 - - 0.0026 - Agglomerates of Example 3 3.5 3.0 2.0 3.0 4.0 3.0 Silicone defoamer 0.02 0.21 0.17 0.02 0.21 0.17 spices 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: NYMCEL™: carboxymethylcellulose CMF supplied by Metsa-Serla: citric acid internally crosslinked fibrous cellulose Arbocel ^™ manufactured by Wayerhauser: Micronized cellulose supplied by Rettesmeyer LAS: Sodium linear _C11-13 alkylbenzene sulfonate MES: Alpha-sulfomethyl ester of _C18 fatty acid TAS: Sodium tallow alkyl sulfate _CXY AS: _C1X -C _1Y sodium alkyl sulfate C46SAS: C ₁₄ -C ₁₆ secondary (2,3) alkyl sodium sulfate C _XY E _Z S : C _1X -C _1Y alkyl sodium sulfate C _XY E _Z condensed with z moles of ethylene oxide : C _1X -C _1Y major linear primary alcohols QAS condensed with an average z moles of ethylene oxide: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ QAS1 : R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₈ -C ₁₁ SADS : Formula 2-(R).C ₄ H ₇ -1, 4-(SO ₄ -) ₂ C ₁₄ -C ₂₂ Alkyl disulfuric acid

Sodium where R = C ₁₀ -C ₁₈ SADE2S : C ₁₄ -C ₂₂ alkane of formula 2-(R).C ₄ H ₇ -1,4-(SO ₄ -) ₂ condensed with z moles of ethylene oxide Sodium Disulfate, where R = C ₁₀ -C ₁₈ APA: C ₈ -C ₁₀ Amidopropyl Dimethylamine Soap: Sodium Linear Alkyl Carboxylate, 80/20 of tallow and coconut fatty acids

The mixture gives STS: Sodium toluenesulfonate CFAA: _C12 - _C14 (coconut) alkyl N-methylglucamide TFAA: _C16 - _C18 alkyl N-methylglucamide TPKFA: _C16 - _C18 Topped whole-fraction fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O, main particles

Particle size 0.1-10 microns (weight on dry basis ₎ NaSKS-6(I) _: Clariant's crystalline layered silicate of formula δ- _Na2Si2O5 Citric acid: anhydrous citrate borate : sodium borate carbonate: anhydrous sodium bicarbonate with a particle size of 200-900 microns; bicarbonate: anhydrous sodium bicarbonate with a particle size distribution of 400-1200 microns _{; Na2O} ratio=2.0:1) Sulfate: Anhydrous sodium sulfate Magnesium sulfate: Anhydrous magnesium sulfate Citrate: Trisodium citrate dihydrate, active 86.4%, particle size distribution

425-850 micron MA/AA : 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000MA/AA(1): 4:6 maleic acid/acrylic acid copolymer, average molecular weight about 10000AA : Sodium polyacrylate polymerization The average molecular weight is about 4500CMC : sodium carboxymethyl cellulose cellulose ether : methyl cellulose ether with a degree of polymerization of 650, by Shin Etsu

Protease obtained by Chemicals : Sold under the tradename Savinase by Novo Industries A/S

Protease containing 3.3% by weight active enzyme Protease I: as described in WO95/01591, ex Genencor Int. Inc.

Protease sold by Novo Industries A/S containing 4% active Enzyme Alcalase: Proteolytic enzyme sold by Novo Industries A/S containing

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

A cellulase containing 0.23% by weight active enzyme amylase: marketed by Novo Industries A/S under the tradename Termamyl 120T

Sold amylase containing 1.6% by weight active enzyme Amylase II: amylase lipase as described in PCT/US9703635: sold under the tradename Lipolase by Novo Industries A/S

A lipase containing 2.0% by weight active enzyme Lipase (1): marketed by Novo Industries A/S under the tradename Lipolase Ultra

Sold lipase containing 2.0% by weight of active enzyme Endolase: Endoglucose, marketed by Novo Industries A/S, containing

1.5 _% active by weight Enzyme PB4: Anhydrous sodium perborate _{tetrahydrate of} formula _{NaBO2.3H2OH2O2} PB1: _Anhydrous sodium _perborate percarbonate of formula _NaBO2.H2O2 : Formula Sodium percarbonate of Na ₂ CO ₃ .3H ₂ O ₂ DOBS: Decanoyl hydroxybenzene sulfonate in sodium salt form DPDA: Peroxydodecanedioic acid NOBS: Nonanoyl hydroxybenzene sulfonate in sodium salt form NACA- OBS: (6-Nonanoylhexanoyl)hydroxybenzenesulfonate LOBS: Dodecanoylhydroxybenzenesulfonate, sodium salt form NOBS: Nonanoylhydroxybenzenesulfonate, sodium salt form DOBA: Nonanoylhydroxybenzoic acid TAED: Tetraacetylethylenediamine DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta(methylene phosphonate), commercially available from Monsanto

 Dequest 2060 Sales EDDS : Ethylamine-N,N'-disuccinic acid, (S,S) isomer, its sodium salt form

Formula photoactivated bleach: Zinc sulfonate encapsulated in a polymer dissolved in bleach (1) dextrin

Phthalocyanine photoactivated bleach: aluminum sulfonate encapsulated in polymer dissolved in bleach (2) dextrin

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

Amino)stilbene-2: 2'-disodium disulphonate HEDP : 1,1-hydroxy-ethanediphosphonic acid PEGX : polyethylene glycol, average molecular weight X (usually 4000) PEO : polyethylene oxide, Average molecular weight 50,000TEPAE : Tetraethylenepentamine ethoxylate PVI : Polyvinylimidazole, average molecular weight 20,000PVP : Polyvinylpyrrolidone polymer, average molecular weight 60,000PVNO : Polyvinylpyridine N-oxide polymer, average molecular weight 50,000PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole, average

Subquantity 20000QEA: ((C ₂ H ₅ O)(C ₂ H ₄ O)N)(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ ) double

((C ₂ H ₅ O)(C ₂ H ₄ O) _n ), where n=20-30 SRP1: anion-terminated polyester SRP2: diethoxylated poly(1,2-propylene phthalo Ester) short block

Polymer) PEI : Polyethylenediamine, with an average molecular weight of 1800 and an average of 7 ethylene per nitrogen

Average degree of ethoxylation of oxygen residues Polysiloxane antifoam: polydimethylsiloxane foam control agent with polysiloxane-agent oxyalkylene copolymer as dispersant, said foam control agent with The ratio of the dispersant is

                                                                                                                                               

Lytron 621 Sales Wax : Paraffin

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.