CN1349557A - Detergent compositions - Google Patents

Abstract

A softening laundry detergent tablet comprises clay and laundry surfactant. The tablet is a compressed mass of particles including granules which consist largely of clay.

Description

Detergent composition

Technical Field

The present invention relates to softening laundry detergent tablets containing high levels of softening clay, and in particular to such compositions in tablet form.

Background

It is known to provide detergent compositions in tablet form prepared by compressing granular detergent compositions. A small amount of adhesive is typically included in the composition to keep the sheet intact.

While it is desirable that the tablets should have good integrity before use, it is also desirable that they should disintegrate quickly in use when in contact with wash water. It is known to include a disintegrant which will facilitate disintegration of the tablet. Various types of disintegrating agents are known, including a type in which disintegration is caused by swelling of the disintegrating agent. Various swelling and disintegrating agents have been proposed in the literature, preferably mainly starch, cellulose and water-soluble organic polymers. Inorganic swelling-decomposing agents such as bentonite are also mentioned, for example, in EP-A-466484.

In the disclosure, the same material is used as the binder and the disintegrant. It is also mentioned that the disintegration agents may give rise to building aid, anti-redeposition or fabric softening properties. The amount of the decomposer is preferably 1% to 5%. It is also mentioned in EP- ｃA-466484 that the sheet may have ｃA non-uniform structure comprising ｃA plurality of discrete regions, such as layers, inserts or coatings.

In WO98/40463, the disintegrant is a material such as starch or cellulose, which is added substantially only in the form of granules.

JP-A-9/87696 relates to tablets containing ｃA nonionic detergent composition and ｃA nonionic surfactant as essential components, and particularly relates to the suppression of the deposition of ｃA nonionic surfactant from ｃA tablet during storage of the tablet, and also relates to the case where the nonionic surfactant causes the expected loss of softening action when ｃA softening clay is included. It describes the formation of tablets containing a comminuted clay mineral together with a comminuted oil-absorbing carrier and a disintegrant.

It would be desirable to provide soft laundry tablets containing sufficient clay to provide significant softening. While low amounts of clay can produce a decomposition effect, unfortunately the amount of clay that produces a useful softening effect can tend to retard the decomposition rather than promote it. This is because at the high amounts of clay required for the softening action there is a tendency for the clay of the tablet to gel when in contact with water, so that a gel layer forms around the tablet which hinders penetration of water into the tablet and thus hinders dispersion of the tablet.

It is therefore desirable to incorporate clay in the tablets in such a way that at high concentrations of clay, the gelling tendency is minimized and the disintegration of the clay tablets is maximized.

Summary of The Invention

According to one embodiment of the present invention there is provided a softening laundry detergent tablet comprising clay and laundry surfactant, wherein the tablet is a compressed mass of particles, at least 50% by weight of the clay being present as particles having a size of at least 100 μm. The clay is generally the major component of the particle and is generally present in an amount of at least 30%, generally at least 50%, preferably at least 75% by weight of the particle. The particles are preferably formed from at least 90% by weight clay.

Preferably at least 60%, usually at least 75%, and most preferably at least 90% of the clay is present as particles of at least 100 μm, but usually below 1700 μm.

The tablet may contain at least 5%, preferably at least 8%, most preferably at least 10% by weight of clay, based on the weight of the tablet. The amount may be less than 25%, typically less than 20%, preferably not more than 15% by weight of the tablet.

Preferably at least 70%, preferably at least 90% by weight of the clay is present as particles having a size of 150-850 μm. Preferably, substantially all (e.g., at least 90% or 95% by weight) of the particles used to prepare the tablet have a size of at least 100 μm, typically 100-1700 μm.

According to a second aspect of the present invention there is provided a process for the preparation of a softening laundry detergent tablet comprising clay and laundry surfactant, which comprises providing at least 50% by weight of the clay as clay particles having a size of at least 100 μm, mixing the clay particles with other particulate components of the tablet, and compressing the mixture into a tablet.

Detailed Description

Preferably at least 50%, preferably 70%, most preferably at least 90% by weight of the clay is in the form of particles having a size of 100-1700 μm, preferably 100-1180 μm, most preferably 150-850 μm. Fine powders, i.e. clay particles having a size below 20 μm, preferably below 10% by weight of the total clay, most preferably below 5% by weight of the total clay, typically below 1% by weight.

As a result of the addition of the particulate clay (instead of fines), the amount of clay that can be included can be increased without causing gelling. Additionally, the inclusion of particulate clay instead of fines increases the disintegration of the clay.

The granules may be formed by conventional clay granulation techniques whereby clay fines are granulated, for example by agglomeration or extrusion. Granulation is carried out in the presence of a binder, generally promoting granule formation. Preferably the binder comprises, or most typically consists essentially of, water. Thus, the particles may consist essentially of clay alone (e.g., greater than 90% by weight clay).

However, if desired, other materials may be incorporated as binders, such as water-soluble polyols (e.g. glycerol) or other conventional clay binders, which are preferably readily water-soluble. The total amount of binder is generally less than 10% by weight of the particles, typically less than 5% by weight. If desired, other materials may be included in the particles, which materials are incorporated into the sheet using convenient methods. However, the amount of clay is typically at least 50%, preferably at least 70% or 80% by weight of the particles.

The clay particles may be substantially homogeneously distributed in the tablet whereby such high concentrations promote a softening effect, such concentrations and particle forms will promote disintegration of the entire tablet. Additionally, the particle concentration may be higher in one or more first regions of the sheet than in one or more second regions of the sheet. For example, in one embodiment, the first region may contain clay particles in an amount at least 1.5 times, and typically 2 to 5 times, the amount of clay in the second region. This means that the first area can be arranged to disperse faster than the second area. The amount of clay in the first zone is typically at least 5%, typically at least 10% by weight of the first zone. The amount of clay in the second zone is typically at least 0.1%, for example 1-5%, of the or each second zone. Typically at least 60% by weight of the total clay content, typically from 70% or 75% to 80% or 90% is in the or each first region, with the balance being present in the or each second region.

The tablets typically contain at least 5% by weight of a laundry detergent, typically comprising nonionic and/or anionic surfactants. If desired, the surfactant may also be present in some regions at a higher concentration (e.g., at least 1.5 times, typically 2-5 times) than other regions. Typically at least 5% by weight of nonionic and/or anionic surfactant is present in any first region of the tablet, which has a higher clay concentration than the remainder of the tablet.

Laundry enzymes are typically included in the tablets. When the clay is present in a higher concentration in one or more of the first zones, it is preferred that more enzyme is present in these zones than in the other zones, e.g. the amount in the first zone should generally be at least 1.5 times, usually at least 2 or at least 5 times the amount in the other zones, so that as the first zone disperses into the wash water quickly, the enzyme disperses therein as quickly as possible.

Tablets typically contain laundry bleach. If the clay is more concentrated in one or more of the first regions than in the second region, it is preferred that the concentration of bleaching agent is higher in the second region than in the first region. Preferably the concentration of bleach in the or each second region is at least 1.5 times the concentration in the or each first region, preferably substantially all of the bleach is in the or each second region.

It is generally preferred that the wash sheet should also contain a clay flocculating agent to aid in the deposition of clay onto the fabric surface. This facilitates the construction of the tablet so that the clay disperses more rapidly than the flocculating agent. For example, the flocculant and clay may remain physically separated from each other, to some extent, by the clay being enclosed in discrete particles, even with the flocculant being uniformly distributed throughout the tablet. However, when the clay particles are concentrated in one or more first zones, it is generally preferred to include a flocculating agent in one or more second zones, which disperse more slowly than the first zones. Preferably, substantially all of the flocculating agent is in the or each second zone.

It is not necessary that all of the second regions have the same composition, and there may be one or more of the second regions having a different composition from the other second regions.

The discrete first and second regions (when present) may be some extent or other zone within the tablet, for example resulting from the formation of tablets from clay particles and other coarse particulate materials, typically greater than 1mm, some or all of which have one volume and the remainder having another volume, thereby forming first and second regions in the compressed tablet. Preferably, however, each zone is a layer and the wash tablet is a multi-layer tablet having at least two layers. It is generally preferred that there should be three layers, the sheet generally being a sandwich sheet between similar and different central layers on each outer surface. The different layers may be differently coloured.

Typically the first region is 20-80%, usually about 40-60%, usually about 50% by weight of the sheet, with the remainder of the sheet being the second region.

The tablets of the invention have dimensions that facilitate metering in a washing machine. The preferred dimensions are 10-150g, which can be selected according to the intended wash load and the design of the washing machine used. Preparation of tablets

The detergent tablets of the invention may be prepared simply by mixing the solid components together and compressing the mixture using a conventional tablet press as used in the pharmaceutical industry, for example. Preferably, the major component, especially the gelling surfactant, is used in particulate form. Any liquid component, such as a surfactant or suds suppressor, can be incorporated into the solid particulate component in a conventional manner.

Such as builder and surfactant components, may be spray dried by conventional means and then compressed at an appropriate pressure. Preferably, the tablets of the invention are compressed with a force of less than 100000N, more preferably less than 50000N, even more preferably less than 5000N, most preferably less than 3000N. In fact, the most preferred embodiment is a tablet compressed with a force of less than 2500N.

The particulate material used to make the tablets of the present invention may be prepared by any granulation or prilling method. An example of such a process is spray drying (at concurrent flow)Or in a countercurrent spray-drying tower) which generally results in a low bulk density of 600g/l or less. In a high shear batch mixer/granulatorBy granulation and densification or by continuous granulation and densification processes (e.g. using Lodige)^(R)CB and/or Lodige^(R)KM mixer) can produce higher density particulate materials. Other suitable processes include fluidized bed processes, compression processes (e.g., roller compression), extrusion, and the preparation of any particulate material by chemical processes such as flocculation, crystallization (crystallization), and the like. The particles may also be any other particulate, granular, prill or granule.

The components of the particulate material may be mixed together using any conventional apparatus, and a batch process is suitable, for example, for a concrete mixer, Nauta mixer, ribbon mixer or any other apparatus. Alternatively, the mixing process may be carried out continuously by metering the weight of the components onto a moving belt and mixing them by stirring in one or more drums or mixers. A non-gelling binder may be sprayed onto some or all of the mixture of particulate material components. Other liquid components may also be sprayed onto the mixture of the individual or premixed components. For example, perfume and optical brightener slurries can be sprayed. Preferably, near the end of the process, the binder is sprayed to make the mixture low viscous, after which the comminuted flow aid (release agent, e.g. zeolite, carbonate, silica) is added to the particulate material.

The tablets may be prepared by any compression method, for example tabletting, briquetting or extrusion, preferably tabletting. Suitable equipment includes standard single stroke or rolling presses (e.g., Courtoy)^(R)，Korch^(R)，Manesty^(R)Or Bonals^(R)). The tablets prepared according to the invention preferably have a diameter of 20mm to 60mm, preferably at least 35 and up to 55mm, and a weight of between 25 and 100 g. The ratio of the height to the diameter (or width) of the tablet is preferably greater than 1: 3, more preferably greater than 1: 2. The pressure used for preparing the tablets should not exceed 100000kN/m²Preferably not more than 30000kN/m²More preferably not more than 5000 kN/m²And even more preferably not more than 3000 kN/m²Most preferably not more than 1000 kN/m². In the preferred embodiment of the present inventionIn one embodiment, the tablets have a density of at least 0.9g/cc, more preferably at least 1.0g/cc, preferably less than 2.0g/cc, more preferably less than 1.5g/cc, even more preferably less than 1.25g/cc, and most preferably less than 1.1 g/cc.

The multilayer tablets may be prepared by known techniques. Coating layer

The robustness of the tablets of the invention can be further improved by preparing coated tablets, the coating covering the uncoated tablets of the invention, thereby further improving the mechanical properties of the tablets while maintaining or further improving the dispersion.

In one embodiment of the invention, the sheet may then be coated so that the sheet does not absorb water or only absorbs water at a very slow rate. The coating is also strong such that the tablets are subjected to moderate mechanical impact during use, packaging and shipping resulting in no more than a very low amount of breakage or wear. Finally, the coating is preferably frangible so that the sheet breaks when subjected to strong mechanical impact. In addition, it is advantageous if the coating material is dispersible under alkaline conditions or easily emulsified by surfactants. This helps to avoid the problem of residues visible during the washing stage adhering to the window of the front-loading washing machine and also avoids the deposition of particles or lumps of coating material on the washed load.

Water solubility is determined using the following ASTM E1148-87, test protocol entitled "Standard test methods for determining Water solubility".

Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof. The coating material has a melting point preferably in the range of 40 ℃ to 200 ℃.

The coating may be applied in a variety of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material.

In a), the coating material is applied and cured on the sheet at a temperature above its melting point. In b), the coating material is applied as a solution and the solvent is dried, leaving a coherent coating. The substantially insoluble material may be applied to the sheet by, for example, spraying or dipping. Typically, when the molten material is sprayed onto the sheet, it quickly solidifies to form an adherent coating. Rapid solidification of the coating material can be caused when the sheet is dipped into the molten material, then removed, and rapidly cooled. It is clear that substantially insoluble materials having a melting point below 40 c are not sufficiently curable at room temperature and that materials having a melting point above about 200 c have not been found to be practical. Preferably, the melting point of the material is between 60 ℃ and 160 ℃, more preferably between 70 ℃ and 120 ℃.

By "melting point" is meant the temperature at which the material becomes a transparent liquid when heated slowly in, for example, a capillary.

Any desired thickness of the coating may be applied according to the present invention. For most purposes, the coating will comprise from 1% to 10%, preferably from 1.5% to 5% by weight of the tablet.

The tablet coating is preferably very hard and provides additional strength to the tablet.

In a preferred embodiment of the invention, the cracking of the coating in the wash is improved by the addition of a disintegrant to the coating. The disintegrant swells upon contact with water and breaks the coating into small pieces. This will improve the dispersion of the coating in the wash solution. The amount of disintegrant suspended in the coating melt is up to 30%, preferably 5% to 20%, most preferably 5% to 10% by weight. Possible disintegrants are described in the handbook of pharmaceutical excipients (1986). Examples of suitable disintegrants include starch; native, modified or pregelatinized starches; starch sodium gluconate; a gum; agar gum; guar gum; locust bean gum; karaya gum; pectin; gum tragacanth; croscarmylosesodium, polyvinylpolypyrrolidone, cellulose, carboxymethylcellulose, alginic acid and salts thereof, including sodium alginate, silica, clay, polyvinylpyrrolidone, soybean polysaccharide, ion exchange resins, and mixtures thereof. Tensile strength

Depending on the composition of the raw material and the shape of the tablet, the pressure used can be adjusted without affecting the tensile strength and the disintegration time in the washing machine. The process can be used to prepare uniform or layered tablets of any size or shape.

For cylindrical sheets, tensile strength is equivalent to radial fracture stress (DFS), which is one way to express sheet strength, determined by the following equation:

tensile strength 2F/pi Dt

Measured with a VK 200-piece hardness tester supplied by Van Kell industries, inc, where F is the maximum force (newtons) that causes loss of tension (cracking). D is the diameter of the sheet and t is the thickness of the sheet.

(pharmaceutical dosage form method: tablets (Tabelets), Vol.2, p.213-217). Sheets having a radial rupture stress below 20kPa are considered brittle and may result in some breakage of the sheet to the consumer. Preferably the radial rupture stress is at least 25 kPa.

The same applies to non-cylindrical sheets where the cross-section perpendicular to the height of the sheet is not circular and where forces are applied in a direction perpendicular to the height of the sheet and perpendicular to the side of the sheet that is perpendicular to the non-circular cross-section to determine tensile strength. Foaming agent

In another preferred embodiment of the invention, the detergent tablet may further comprise a foaming agent.

Foaming, as defined herein, means that carbon dioxide gas is generated as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate, resulting in gaseous bubbles emanating from the liquid,

namely:

additional examples of acid and carbonate sources and other blowing agent systems can be found in: (Pharmaceutical Dosage Forms: tablets, Vol. 1, p. 287-291).

In addition to the detergent component, a sudsing agent may be added to the tablet mixture. The addition of sudsing agents to detergent tablets improves the disintegration time of the tablets. Preferably in an amount of from 5% to 20%, most preferably from 10% to 20% by weight of the tablet. Preferably, the blowing agent should be added as an agglomerate of different particles or as a compact, rather than as a separate particle.

Because blistering in the sheet generates gases, the sheet may have a higher d.f.s., but still have the same disintegration time as a non-blistering sheet. The foamed sheet decomposed faster when the d.f.s. of the foamed sheet remained the same as the non-foamed sheet.

Additional dispersing aids may be provided by using compounds such as sodium acetate or urea. A list of suitable dispersing aids can also be found in the pharmaceutically metered forms: sheets, volume 1, version 2, compiled by H.A. Lieberman et al, ISBN 0-8247-. Adhesive agent

To further facilitate dispersion, a non-gelling binder may be incorporated into the particles to form a tablet.

If a non-gelling binder is used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates, and water-soluble polyacrylate copolymers. The pharmaceutical excipients handbook, second edition, lists the following types of binders: gum arabic, alginic acid, Carbomer, sodium carboxymethylcellulose, dextrin, ethylcellulose, gelatin, guar gum, hydrogenated vegetable oil type 1, hydroxyethyl cellulose, hydroxypropyl methylcellulose, liquid glucose, magnesium aluminum silicate, maltodextrin, methylcellulose, polyisobutylene salts, polyvinylpyrrolidone, sodium alginate, starch, and zein. Most preferred binders also have a cleaning action active in laundry, for example cationic polymers, i.e. ethoxylated hexamethylenediamine quaternary ammonium compounds, dihexaethylenetriamine or other substances such as pentamines, ethoxylated polyethyleneamines, maleic acrylic polymers.

Preferably sprayed with a non-gelling binder material, whereby it has a suitable melting point below 90 c, preferably below 70 c, even more preferably below 50 c, so as not to destroy or degrade the other active components in the matrix. Most preferred are non-aqueous liquid binders (i.e., not in aqueous solution) which can be sprayed in molten form. However, they may also be solid adhesives which are incorporated into the matrix by dry addition, but which have adhesive properties in the sheet.

The non-gelling binder material is preferably used in an amount of from 0.1% to 15%, more preferably less than 5%, especially less than 2% by weight of the tablet if it is a non-laundry active.

The use of gelling binders, such as nonionic surfactants, in liquid or molten form is preferably avoided. Nonionic surfactants and other gelling binders are not excluded from the composition, but preferably they are processed into the detergent tablet as a component of the particulate material, rather than as a liquid. Clay clay

The clay minerals used to provide the softening properties to the compositions of the present invention may be described as swellable, three-layer clays, i.e. aluminium-silicates and magnesium silicates, having an ion exchange capacity of at least 50meq/100 g. The term "swellable", as used to describe clays, refers to the ability of the layered clay structure to be swelled or expanded when the clay is contacted with water. The three-layer swelling clays used herein are those materials that are geologically classified as smectites.

There are two different types of smectite-type clays; first, alumina is present in the silicate lattice; the second type of smectite, magnesium oxide, exists in silicate lattices. The general formula of these smectites is Al for the alumina and magnesia type clays, respectively₂(Si₂O₅)₂(OH)₂And Mg₃(Si₂O₅)(OH)₂. It is recognized that the range of water of hydration in the above formula may vary with the processing to which the clay is subjected. This is not important to the use of the smectite in the present invention, in that the swellable nature of the hydrated clay is determined by the silicate lattice structure. In addition, substitution by atoms of iron and magnesium may occur in the lattice of the smectite, with metal cations such as Na⁺、Ca⁺⁺And H⁺Can coexist with the hydration water to provide electric neutrality. Except as described below, such cationic substitution is not important for the use of the clays of the present invention, as the desired physical properties of the clay do not substantially change.

Useful tri-layer expanded aluminosilicates of the present invention are also characterized by a dioctahedral lattice, whereas expanded tri-layer magnesium silicate has a trioctahedral lattice.

As noted herein above, the clay used in the compositions of the present invention contains cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions, and the like. It is customary to distinguish clays by one cation which is predominantly or exclusively adsorbed. For example, a sodium clay is one in which the cation adsorbed is predominantly sodium. Such adsorbed cations may be accommodated in an exchange reaction with cations present in the aqueous solution. The general exchange reaction involving the smectite is represented by the following equation:

clay (Na) + NH₄OH-smectite clay (NH)₄)+NaOH

Since 1 equivalent weight of ammonium ion is substituted for 1 equivalent weight of sodium in the above equilibrium reaction, it is customary to measure the cation exchange capacity (sometimes referred to as "basic exchange capacity") in terms of milliequivalents per 100g of clay (meq/100 g). The cation exchange capacity of Clays is determined by several methods, including electrodialysis, exchange with ammonium ions, followed by titration, or by The methylene blue method, which is fully listed in Grimshaw "chemistry and Physics of Clays" (The chemistry and Physics of clay), page 264-265, Interscience (1971). The cation exchange capacity of clay minerals is related to such factors as the swellable nature of the clay, the charge of the clay, which in turn is determined at least by the lattice structure, etc. The cation exchange capacity of the clay ranges from about 2meq/100g for kaolin to about 150meq/100g and more for certain smectite clays. Illite clays have ion exchange capacities sometimes in the lower portion of the range, i.e., about 26meq/100g for the average illite clay.

Illite and kaolin, which have relatively low ion exchange capacity, are preferred clays that are not used in the compositions of the present invention. In fact, this illite and kaolin constitute the main components of clay scales, which, as mentioned above, are removed from the surface of the fabric by means of the composition according to the invention. However, smectites such as nontronite, having an ion exchange capacity of about 70meq/100g, and montmorillonites, having an ion exchange capacity greater than 70meq/100g, have been found useful in the compositions of the present invention in that they deposit onto the fabric to provide the desired softening effect. Thus, the clay minerals useful in the present invention can be characterized as swellable, three-layer smectite-type clays having an ion exchange capacity of at least about 50meq/100 g.

While not intending to be bound by theory, it is clear that the advantageous softening (and possibly dye scavenging, etc.) effect of the compositions of the present invention is obtained and is due to the physical and ion exchange properties of the clays used therein. That is, the experiments illustrate that non-swelling clays such as kaolin and illite, which are two types of clays having an ion exchange capacity of less than 50meq/100g, do not provide the advantageous aspects of clays used in the compositions of the present invention.

The smectites used in the compositions of the present invention are completely commercially available. Such clays include, for example, montmorillonite, volkonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite. The clays herein are available under various trade names, such as Thixogel #1 and Gelwhite GP, available from Georgia Kaolin, Elizabeth, N.J.; volclay BC and Volclay #325 available from American colloid, Skokie, Illinois; black hills Bentonite BH450 available from International Minerals and Chemicals and Veegum Pro and Veegum F available from R.T. Vanderbilt. It is recognized that such smectite-type minerals available under the trade names described above can comprise a mixture of discrete mineral bodies. Such mixtures of smectite minerals are suitable for use in the present invention.

Although smectite-type clays having a cation exchange capacity of at least about 50meq/100g are suitable for use in the present invention, certain clays are preferred. For example, Gelwhite GP is a smectite in an extremely white form, and is therefore preferred when formulating white granular detergent compositions. Volclay BC is a crystal lattice containing at least 3% iron (expressed as Fe)₂O₃) The smectite-type clay mineral of (1), which has a very high ion exchange capacity, is one of the most effective clays for use in laundry compositions, and is preferred from the viewpoint of product properties.

Suitable clay minerals for use in the present invention can be selected based on the fact that the smectite clay exhibits a true 14 Å x-ray diffraction pattern, this characteristic pattern, in combination with the exchange capacity measurement performed by the method described above, provides the basis for selecting a particular smectite-type mineral for use in the disclosed granular detergent composition.

The clay is preferably predominantly particulate, at least 50% (preferably at least 75% or at least 90%) being in the form of particles having a size of at least 100-. Preferably the amount of clay in the particles is at least 50%, typically at least 70% or 90% by weight of the particles. Detersive surfactant

Non-limiting examples of surfactants suitable for use in the present invention are generally anionic surfactants such as sulfonates, sulfates and ether sulfates at levels of from about 1% to about 55% by weight. These include conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS"), and branched primary and random C₁₀-C₂₀Alkyl sulfates ("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, particularly sodium, an unsaturated sulfate such as oleyl sulfate, C₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS "; in particular EO 1-7 ethoxy sulfate), C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylates), C_10-C₁₈Glycerol ethers, C₁₀-C₁₈Alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈α -sulfonated fatty acid ester if desired, conventional nonionic and amphoteric surfactants such as C may also be included in the overall composition of the invention₁₂-C₁₈Alkyl ethoxylates ("AE") including so-called narrow peak alkyl ethoxylates and C₆-C₁₂Alkylphenol alkoxylates (in particular ethoxylates and mixed ethoxy/propoxylates), C₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxides, and the like. Also usable are C₁₀-C₁₈N-alkyl polyhydroxy fatty acid amides, typical examples include C₁₂-C₁₈N-methylglucamide. See WO 92/06154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides,e.g. C₁₀-C₁₈N- (3-methoxypropyl) glucamide. When low foaming is desired, N-propyl to N-hexyl C may be used₁₂-C₁₈A glucamide. Also usable are C₁₀-C₂₀Conventional soaps. If high foaming is desired, it is possible to use branches C₁₀-C₁₆Soap. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventionally useful anionic, amphoteric, nonionic or cationic surfactants are listed in standard textbooks.

In a preferred embodiment, the tablet comprises at least 5 wt% surfactant, more preferably at least 15 wt%, even more preferably at least 25 wt%, most preferably from 35% to 55 wt% surfactant. The amount of anionic surfactant is preferably at least 1.5 times, generally at least 2 or 3 times the total amount of other surfactants. Builder

Detergent builders may optionally be included in the compositions of the present invention to assist in controlling mineral hardness. Inorganic and organic builders can be used. Builders are commonly used in compositions for laundering fabrics to aid in the removal of particulate soils.

The level of builder may vary over a wide range depending on the end use of the composition.

Inorganic or phosphorous containing builders include, but are not limited to: the following alkali metal, ammonium and alkanolammonium salts: polyphosphates (exemplified by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. However, in some areas, non-phosphorous builders are required. Importantly, the efficacy of the compositions of the present invention is unexpectedly good even in the presence of so-called "weak" builders (as compared to phosphates), such as citrate, or in so-called "low built" situations which can occur when zeolite or layered silicate builders are used.

Examples of silicate builders are alkali metal silicates, especially those having SiO₂∶Na₂Silicates and phyllosilicates with O ratios in the range of 1.6: 1 to 3.2: 1, e.g. in 1987Layered sodium silicate as described in US patent US4664839 issued on day 5, 12, h.p.rieck. NaSKS-6 is a trademark of layered crystalline silicates sold by Hoechst (generally abbreviated herein as "SKS-6"). Unlike zeolite builders, Na SKS-6 silicate builders are free of aluminum. NaSKS-6 is a compound having delta-Na₂SiO₅A layer silicate in a morphological form. They can be prepared by processes such as those described in DE-A-3417649 and DE-A-3742043. SKS-6 is the highly preferred layered silicate for use herein, but other layered silicates, such as those having the general formula NaMSi, can be used in the present invention_xO2_x+1·yH₂Layered silicates of O, where M is sodium or hydrogen, x has a value of 1.9 to 4, preferably 2, and y has a value of 0 to 20, preferably 0 various other layered silicates available from Hoechst include NaSKS-5, NaSKS-7, and NaSKS-11, in the form of α, β, and γ₂SiO₅(NaSKS-6 form) is most preferred for use herein. Other silicates are also useful, such as magnesium silicate, as a crispening agent for granule formulations, as a stabilizer for oxygen bleaches, and as a component of foam control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates of German patent application 2321001 published on 11/15/1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of primary importance in the most commonly marketed heavy-duty granular detergent compositions, and can also be an important builder component in liquid detergent formulations. Aluminosilicate builders include builders having the empirical formula:

Mz(zAlO₂)y].xH₂o wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, and x is an integer of about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring aluminosilicates or synthetically derived. A process for preparing aluminosilicate ion exchange materials is disclosed in U.S. Pat. No. 3,3985669 to Krummel et al, issued 10/12/1976. Preferred synthetic crystalline aluminosilicate ion exchange materials for use herein are commercially available as registered zeolite a, zeolite p (b), zeolite MAP and zeolite X. 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 referred to as zeolite a. Dehydrated zeolites (x ═ 0 to 10) may also be used herein. The aluminosilicate preferably has a particle size of about 0.1 to 10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to: various polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having multiple carboxylic acid groups, preferably at least 3 carboxylic acid groups. Polycarboxylate builders can generally be added to the compositions in the acid form, but can also be added in the form of neutralized salts. When used in the form of a salt, alkali metal salts such as sodium, potassium and lithium or alkanolammonium salts are preferred.

A variety of useful materials are included in polycarboxylate builders. One important class of polycarboxylate builders includes the ether polycarboxylates, including oxydisuccinates, such as those disclosed in U.S. Pat. No. 4,7 to Berg, 1964, and U.S. Pat. No. 3,3128287 to Lamberti et al, 1972, 1,8. See also U.S. patent US4663071 to Bush et al entitled "TMS/TDS" builder on 5.5.1987. Suitable ether polycarboxylates also include cyclic compounds, particularly cycloaliphatic compounds, as described in US 3923679; US 3835163; US 4158635; those described in US4120874 and US 4102903.

Other useful builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid, and carboxymethoxysuccinic acid, alkali metal, ammonium and substituted ammonium salts of various polyacetic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3, 5-tricarboxylic acid, carboxymethoxysuccinic acid, and water-soluble salts thereof.

Citrate builders, for example, citric acid and its water-soluble salts (especially the sodium salt) are polycarboxylate builders of particular importance in heavy-duty liquid detergent formulations because they are available from renewable resources and because of their biodegradability. Citrate salts may also be used in granular compositions, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

Also suitable for use in the detergent compositions of the present invention are 3, 3-dicarboxy-4-oxa-1, 6-adipate salts and related compounds disclosed in U.S. patent number US4566984 to Bush, issued on 28.1.1986. Useful succinic acid builders include C₅-C₂₀Alkyl and alkenyl succinic acids and their salts. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, etc. Lauryl succinate is a preferred builder in this group and is described in European patent application 86200690.5/0,200,263 published on 5.11.1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,44226 to Crutchfield et al, granted on 3/13 1979, and U.S. Pat. No. 3308067 to Diehl, granted on 3/7 1967. See also US 3723322.

Fatty acids, e.g. C₁₂-C₁₈Monocarboxylic acids may also be incorporated into the composition either alone or in combination with the aforementioned builders, especially citrate and/or succinate builders, to provide additional builder activity. The use of fatty acids generally reduces foaming, which the formulator should consider.

Where phosphorus containing builders can be used, especially in bar formulations for hand washing operations, various alkali metal phosphates such as the well known sodium tripolyphosphates, pyrophosphates and orthophosphates can be used. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other well known phosphonates may also be used (see, for example, U.S. Pat. Nos. 3159581; 3213030; 3422021; 3400148 and 3422137). Bleaching agent

The detergent compositions of the present invention may contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. When present, bleaching agents are generally present at levels of from about 1% to about 30%, more typically from about 5% to about 20% of the detergent composition, especially for laundering fabrics. If included, the bleach activator is typically present at a level of from about 0.1% to about 60%, more preferably from about 0.5% to about 40%, of the bleach composition comprising bleach plus bleach activator.

The bleaching agent used herein may be any bleaching agent suitable for use in detergent compositions for cleaning fabrics, cleaning hard surfaces, or other cleaning applications now known or to be known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches such as sodium perborate (e.g., monohydrate or tetrahydrate) may be used herein.

Another class of bleaching agents that can be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaches include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, magnesium 4-nonylamino-4-oxoperoxybutyrate and magnesium diperoxydodecanedioate. These bleaches are disclosed in U.S. patent No. US4483781 to Hartman, issued on 20/11/1984, U.S. patent application 740446 to Burns et al, issued on 3/6/1985, european patent application 0133354 to Banks et al, issued on 20/2/1985, and U.S. patent No. US4412934 to Chung et al, issued on 1/11/1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxo-peroxyhexanoic acid as described in U.S. patent No. 4,34551 to Burns et al, 6.1.7.

Peroxygen bleaching agents may also be used in the present invention. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and its equivalent, "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, commercially produced by DuPont) can also be used.

Preferred percarbonate bleach compositions comprise dry particles having an average particle size in the range of from about 500 to about 1000 microns, no more than about 10% by weight of said particles being less than about 200 microns and no more than about 10% by weight of said particles being greater than about 1250 microns. The percarbonate may optionally be coated with silicate, borate or water soluble surfactants. Percarbonate is available from various suppliers such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be used.

Peroxygen bleaches, perborates, percarbonates, etc., are preferably used in combination with bleach activators, which result in the in situ generation of peroxyacids corresponding to the bleach activators in aqueous solution (i.e., during the wash). Various non-limiting examples of activators are disclosed in U.S. patent No. 4915854, and U.S. patent No. 4412934, issued to Mao et al at 4/10 1990. Nonoyloxybenzene sulfonate (NOBS) and Tetraacetylethylenediamine (TAED) activators are typical activators, and mixtures thereof may also be used. Other typical bleaching agents and activators useful herein are also described in US 4634551.

Highly preferred amido-derived bleach activators are those of the formula:

R1N (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L wherein R¹Is 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 as a result of nucleophilic attack of the perhydrolytic anion on the bleach activator. A preferred leaving group is benzenesulfonate.

Preferred examples of bleach activators of the above formula include (6-octanoylamino-hexanoyl) oxybenzene-sulfonate, (6-nonanoylamino hexanoyl) oxybenzene-sulfonate, (6-decanoylamino-hexanoyl) oxybenzene-sulfonate, and mixtures thereof, as described in U.S. patent No. 4634551, which is incorporated herein by reference.

Another class of bleach activators includes the benzoxazines disclosed in U.S. Pat. No. 4,4966723 to Hodge et al, granted at 30.10.1990 (which is incorporated herein by reference). Highly preferred activators of the benzoxazine class are:

another class of preferred bleach activators include acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula:

wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl, or alkylaryl group having from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3, 5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3, 5, 5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Pat. No. 4,45784 to Sanderson, issued on 8/10/1985, which is incorporated herein by reference, and which discloses acyl caprolactams, including benzoyl caprolactam, which are adsorbed into sodium perborate.

Those bleaching agents other than oxygen bleaching agents are also well known in the art and may be used in the present invention. One particularly preferred class of non-oxygen bleaching agents includes photosensitizing bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718 issued to Holcombe et al, 7/5 in 1977. If desired, detergent compositions will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially zinc phthalocyanine sulfonates.

If desired, the bleaching compound may be catalyzed by a manganese compound. Such compounds are well known in the art and include, for example, those described in U.S. Pat. Nos. US-A-5246621, US-A-5244594Manganese-based catalysts as disclosed in US-A-5194416, US-A-5114606 and EP-A-549271, EP-A-549272, EP-A-544440 and EP-A-544490; preferred examples of these catalysts include Mn^IV 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) (OCH₃)₃(PF₆) And mixtures thereof. Other metal-containing bleach catalysts include those disclosed in US4430243 and US 5114611. Using a mixture with various complexesManganese of ligands for improving bleaching are also reported in the following U.S. patents: 4728455, 5284944, 5246612, 5256779, 5280117, 5274147, 5153161 and 5227084.

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

Enzymes may be included in the formulations of the present invention for a variety of purposes in the laundering of fabrics, including, for example, the removal of protein, carbohydrate or triglyceride containing stains, and for the inhibition of dye migration by shedding, and for fabric restoration. Enzymes to be incorporated include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof. Other types of enzymes may also be included. They may be derived from any suitable source, for example plant, animal, bacterial, mould and yeast sources. However, their selection is governed by several factors, such as pH-activity and/or optimum stability, thermostability, and stability towards active detergents, builders, etc. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Enzymes are generally incorporated in sufficient amounts 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 comprise from about 0.001% to about 5%, preferably from 0.01% to 1%, by weight of the commercial enzyme preparation. Proteases are typically present in such commercial preparations at levels sufficient to provide 0.005 to 0.1Anson Units (AU) of activity per gram of composition.

Examples of suitable proteases are subtilisins, which are obtained from particular strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is obtained from a strain of Bacillus having maximum activity in the pH range 8-12, which has been developed and sold by the company Novo Industries A/S under the registered trade name ESPERASE. The preparation of this and similar enzymes is described in British patent Specification GB1243784 to Novo. Commercially available proteolytic enzymes suitable for removal of proteinaceous soils include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthesis, Inc. (the Netherlands). Other proteases include protease A (see EP-A-130756 published on 9.1.1985); protease B (see European patent application 87303761.8 filed on 28.4.1987 and EP-A-130756 by Bott et al published on 9.1.1985).

Amylases include, for example, the amylases described in GB-A-1296839(Novo), RAPIDASE from International Bio-Synthesis, Inc., and TERMAMYL from Novo industries.

Cellulases useful in the present invention include bacterial and fungal cellulases. Preferably, they have an optimum pH of 5 to 9.5. Suitable cellulases are disclosed in U.S. patent No. 4435307 issued on 3/6 of 1984 to Barbesgoard et al, which discloses mold cellulases produced by humicola insolens and the strain humicola DSM1800 or cellulases 212 produced by molds belonging to the genus aeromonas, and 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 which may be used in detergents include those produced by a microorganism of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British patent 1372034. See also the lipase of Japanese patent application 5320487, published for public inspection on 24.2.1978. This lipase is commercially available from Amano Pharmaceutical Co.Ltd, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other commercially available lipases include Amano-CES, a lipase derived from Chromobacterium viscosum, e.g., Chromobacterium viscosum NRRLB 3673, available from Toyo Jozo Co., Tagata, Japan; there are also Chromobacterium viscosus lipases from Disoynth, USA and the Netherlands, and lipases from Pseudomonas gladioli. Lipase derived from Humicola lanuginosa and commercially available from Novo (see also EP0341947) is a preferred lipase for use herein.

Peroxidases are used in combination with oxygen sources, e.g., percarbonates, perborates, persulfates, hydrogen peroxide, etc., for "solution bleaching," i.e., to prevent dyes or pigments that are released from a substrate during a washing operation from migrating to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro-or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in, for example, PCT International application WO89/099813 to O.Kirk, published 10/19 1989, assigned to Novo Industries A/S.

Various enzymatic materials and methods for their incorporation into synthetic detergent compositions are also disclosed in U.S. patent No. US3553139 to McCarty et al, issued on 5.1.1971. Enzymes are also disclosed in Place et al, US4101457, issued on 7/18 1978, and in Hughes, US4507219, issued on 3/26 1985. Enzymatic materials for liquid detergent formulations and methods for their incorporation into these formulations are disclosed in US4261868 to Hora et al, issued 4/14 in 1981. Enzymes used in detergents can be stabilized using a variety of techniques. Techniques for stabilizing enzymes are disclosed and exemplified in U.S. Pat. No. 4,142,39,1971 issued to Gedge et al, U.S. Pat. No. 3,031,031, and European patent application publication No. 0199405, 86200586.5 to Venegas published at 10,29 in 1986. Enzyme stabilization systems are also described, for example, in US patent No. US 3519570. Flocculating agent

Most clay flocculating polymers are rather long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and piperazine (ethylene imine). Gums such as guar gum are also suitable.

Polymers of ethylene oxide, acrylamide or acrylic acid are preferred. If their molecular weight is from 100000 to 10 million, these polymers greatly enhance the deposition of fabric softening clays. Preferably, such polymers have an average molecular weight of 150000 to 5 million.

The most preferred polymer is poly (ethylene oxide). The molecular weight distribution can be readily determined using gel permeation chromatography with relatively narrow molecular weight distribution poly (ethylene oxide) standards.

The amount of flocculating agent is preferably from 0.5 to 10%, most preferably from about 2 to 6% by weight of the tablet.

The flocculant is preferably predominantly particulate, at least 50% by weight (preferably at least 75%, most preferably at least 90%) being in the form of particles having a size of at least 100-. Preferably, the amount of flocculating agent in the granule is at least 50%, typically at least 70% or 90% by weight of the granule.

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

It will be appreciated that improved disintegration or dispersibility can be obtained when the clay material is compressed prior to incorporation into the tablet or cleaning composition. For example, a tablet comprising clay that is compressed prior to incorporation into the tablet disintegrates faster than a tablet comprising the same clay material that was not compressed prior to incorporation into the tablet. In particular, the amount of pressure used to compact the clay is important to obtain clay particles that aid in disintegration or dispersion.

In addition, when the softening clay is compressed and then incorporated into a cleaning composition or tablet, not only is improved disintegration or dispersion obtained, but also good fabric softness is achieved.

Preferably, the clay component is obtained by compressing a clay material. Preferred methods include the step of subjecting the clay material to a pressure of at least 10MPa, or even at least 20MPa or even 40 MPa. This may be done, for example, by tableting or rolling the clay material, optionally in combination with one or more other components, to form clay tablets or flakes, preferably followed by size reduction, e.g., milling the compressed clay tablets to form compressed clay particles. The particles may then be incorporated into a tablet or a cleaning composition.

The tabletting and rolling processes are known from the prior art. For example, clay compaction may be performed in a Lloyd 50K tablet press or with a Chilsonator roller compaction apparatus available from Fitzpatrick, Inc.

In the examples, detergent base powders of the compositions in table 1 were prepared as follows. All of the particulate materials of the base composition are mixed together in a mixing drum to form a homogeneous particulate mixture. In this mixing, the binder is sprayed.

95 parts of the base powder were mixed in a mixing drum and diluted with 5 parts of montmorillonite clay.

Then, tablets were prepared as follows. 42.8g of the mixture was charged into a circular mold having a diameter of 5.4cm, and pressed to give a sheet having a tensile strength (or radial rupture stress) of 15 kPa.

The amount of residue in the washing machine feed compartment was assessed by means of a "tablet dispensing experiment": two laundry sheets were placed in a Baucknecht WA9850 dosing chamber. Clothes washing machineThe machine was supplied with water at a set temperature of 8 deg.C and a hardness of 21 grains/gram, the water inlet flow rate to the feeding chamber was set at 4L/min, and the flow time was 78 seconds. The washing machine was powered on and the wash cycle was set at wash program 4 (white/color, short cycle), checking the amount of tablet residue remaining in the dosing chamber. The residue was determined as follows:

TABLE 1

			(％)
Anionic agglomerates 1	21.45
		Anionic agglomerates 2	12
Cationic agglomerates	5.45
		Layered silicate	10.8
Sodium percarbonate	11.19
		Bleach activator agglomerates	5.49
Sodium carbonate	10.64
		EDDS/sulfate particles	0.47
Hydroxy ethane diphosphonic acid tetrasodium salt	0.73
		Soil release agent polymers	0.33
Fluorescent agent	0.18
		Zinc phthalocyanine sulfonate capsule	0.025
Soap powder	1.4
		Suds suppressor	1.87
Citric acid	7.1
		Protease enzyme	0.79
Lipase enzyme	0.28

Cellulase enzymes	0.22
		Amylase	1.08
Diisopropylbenzene sulfonate	0.75
		Adhesive agent
Cationic polymers	0.42
		PEG 4000	0.725
PEG 1000	0.365

The anionic agglomerate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate.

The anionic agglomerate 2 consists of 40% anionic surfactant, 28% zeolite and 32% carbonate.

The cationic agglomerate consisted of 20% cationic surfactant, 56% zeolite and 24% sulfate.

The layered silicate consists of 95% SKS 6 and 5% silicate.

The bleach activator agglomerate consists of 81% TAED, 17% acrylic acid/maleic acid copolymer (acid form) and 2% water.

Ethylenediamine N, N-disuccinic acid sodium salt/sulfate particles consisted of 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor consists of 11.5% silicone oil, 59% zeolite and 29.5% water.

Table 2 summarizes ten different embodiments.

TABLE 2

	1	Examples 2	Examples 3	Examples 4	Examples 5	Examples 6	Examples 7	Examples 8	Examples 9	Examples 10
											Base powder	95	95	95	95	95	95	95	95	95	95
											Clay A powder	5
Water-binding Clay A Agglomerates (150-1700μm)		5
											With water/glycerol/paraffin binding Clay A agglomerates (100-1700μm)			5
											Clay B powder				5
Water-binding Clay B Agglomerates 150-850μm					5
											Clay B extrudates (150-1700μm)						5
Clay B extrudates (850-1400μm)							5

Clay B extrudates (425-850μm)								5
											Clay B extrudates (150-425μm)									5
Clay B extrudates (100-150μm)										5

In examples 1-3, a primary montmorillonite clay (labeled clay A) was used. In examples 4-10a, different grades of montmorillonite clay (labeled clay B) were used.

In example 2, granules were prepared as follows.

450g of clay A was added to a Braun mixer, model 4262, with the blade set at 3000 rpm. While the clay was being mixed by the blade, 84g of distilled water was gradually mixed into the clay within 15 seconds. After the addition of water, the water and clay mixture was mixed for an additional 2 minutes. The prepared agglomerates were then dried in a Sherwood Scientific fluidized bed dryer set at 90 ℃ for 30 minutes. The dried agglomerates are sieved to remove oversized particles (particles larger than 1700 μm) and particles smaller than 150 μm from the mixture.

In example 5, the same procedure was used except that particles smaller than 100 μm were removed.

In example 3, particles smaller than 100 μm were removed from the mixture using the same method as in example 1 except that 84g of 23g of a paraffin solution, 15g of glycerin and 32g of water were used instead of 84g of distilled water.

In each of examples 6-10, extrudates were prepared using the following method.

500g of clay B were mixed with 250g of distilled water. The resulting mixture was fed to a Dome extruder with the screw set at 80 rpm. The resulting mixture was then sieved using an ASTM sieving apparatus. The prepared extrudates were then dried in a Sherwood Scientific fluid bed dryer set at 90 ℃ for 30 minutes. The dried extrudate is sieved to obtain a defined particle size distribution and oversized particles and fines are removed from the mixture.

When clay a powder and clay B powder were used (examples 1 or 4), the agglomerates and extrudates of clay a and B gave a considerably lower% residue (and hence better dispersion). The minimum residue (and therefore the best dispersion) was obtained in examples 5, 8 and 9. This illustrates the advantageous effect of clay addition as particles in the size range 150-.

Other examples include tablets prepared from the following composition powders:

examples A and B

Table a: detergent-based powder composition

	Ex A	Ex B
				(％)	(％)
Clay extrudates	14.00	14.00
			Flocculant agglomerates	3.8	3.8
Anionic agglomerates 1	32	38
			Anionic particles 2	2.27	2.27
Cationic agglomerates	4.0
			Sodium percarbonate	8.0	10.0
Bleach activator agglomerates	2.31	2.8
			Sodium carbonate	21.066	16.57
EDDS/sulfate particles	0.19	0.19
			Hydroxy ethane diphosphonic acid tetrasodium salt	0.34	0.34

Fluorescent agent	0.15	0.15
			Zinc phthalocyanine sulfonate capsule	0.027	0.027
Soap powder	1.40	1.40
			Suds suppressor	2.6	2.6
Citric acid	4.0	4.0
			Protease enzyme	0.45	0.45
Cellulase enzymes	0.20	0.20
			Amylase	0.20	0.20
Perfume	1.00	1.00
			Adhesive agent
Pluriol 1000	2.0	2.0

The clay extrudate contained 97% CSM Quest 5A clay and 3% water.

The flocculant raw material was polyethylene oxide with an average molecular weight of 300000.

The anionic agglomerate 1 comprises 40% anionic surfactant, 27% zeolite and 33% carbonate.

The anionic agglomerate 2 comprises 40% anionic surfactant, 28% zeolite and 32% carbonate.

The cationic agglomerate comprises 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate comprises 95% SKS 6 and 5% silicate.

The bleach activator agglomerate comprises 81% TAED, 17% acrylic acid/maleic acid copolymer (acid form) and 2% water.

Ethylenediamine N, N-disuccinic acid sodium salt/sulfate particles comprised 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor comprises 11.5% silicone oil (available from Dow Corni0g), 59% zeolite, and 29.5% water. Example C (micronized citric acid)

In the composition of example B, the citric acid used was replaced by micronized citric acid. Before use, the citric acid used was ground with a coffee grinder to the following psd.

	Of particles larger than 1.4mm Maximum amount of	Particles smaller than 150 μm Maximum amount of (2)
			Examples B	8％	12％

	Minimum amount of particles smaller than 150 μm
		Examples C	80％

Examples D-F (phosphorylated compositions)

	Example D	Example E	Example F
					(％)	(％)	(％)
Clay extrudates	13.00	13.00	13.00
				Flocculating agent Agglomerates	3.5	3.5	3.5
Anionic particles	38.2	38.2	38.2
				Sodium percarbonate	8.0

Sodium perborate monohydrate		8.0
				Sodium perborate tetrahydrate			8.0
Bleach activator agglomerates	2.3	2.3	2.3
				HPA sodium tripolyphosphate	15.4	15.4	15.4
Sodium carbonate	10.043	10.043	10.043
				EDDS/sulfate particles	0.19	0.19	0.19
Hydroxy ethane diphosphonic acid Tetrasodium salt	0.34	0.34	0.34
				Fluorescent agent	0.15	0.15	0.15
Zinc phthalocyanine sulfonate capsule	0.027	0.027	0.027
				Soap powder	1.40	1.40	1.40
Suds suppressor	2.6	2.6	2.6
				Citric acid	1.0	1.0	1.0
Protease enzyme	0.45	0.45	0.45
				Cellulase enzymes	0.20	0.20	0.20
Amylase	0.20	0.20	0.20
				Perfume	1.00	1.00	1.00
Adhesive agent
				Pluriol 1000	2.0	2.0	2.0

The clay extrudate contained 97% CSM Quest 5A clay and 3% water. The flocculant raw material was polyethylene oxide with an average molecular weight of 300000. The layered silicate comprises 95% SKS 6 and 5% silicate. The bleach activator agglomerate comprises 81% TAED, 17% acrylic acid/maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinic acid sodium salt/sulfate particles comprised 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. Zinc phthalocyanine sulfonate capsules are 10% active. The suds suppressor comprises 11.5% silicone oil (available from Dow Corning), 59% zeolite and 29.5% water. The anionic particles are blown powders having the following composition:

(%) sodium Linear alkyl benzene sulfonate 17.7 nonionic C357 EO 2.0.0 nonionic C353 EO 5.9.9 soap 0.5 sodium tripolyphosphate (Rhodia-Phos HPA3.5 from 47.8Rhone Poulenc)10.8 sodium carboxymethyl cellulose 0.4 acrylic acid/maleic acid copolymer 2.1 salt, water 12.9Examples G and H

		Ex G	Ex H
						(％)	( ％ )
Clay extrudates		14.00	1 4. 0 0
				Flocculant agglomerates		3.8	3. 8
Anionic agglomerates 1		32	3 2
				Anionic particles 2		2.27	2. 2 7
Cationic agglomerates		4.0	4. 0
				Sodium percarbonate		8.0	8. 0
Bleach activator agglomerates		2.31	2. 3 1
				Sodium carbonate		18.066	1 8. 0 6 6
EDDS/sulfate particles		0.19	0.

			1 9
				Hydroxy ethane diphosphonic acid tetrasodium salt		0.34	0. 3 4
Fluorescent agent		0.15	0. 1 5
				Zinc phthalocyanine sulfonate capsule		0.027	0. 0 2 7
Soap powder		1.40	1. 4 0
				Suds suppressor		2.6	2. 6
Arbocel TF-30-HG		5.0
				Vivapur G22			5. 0
Citric acid		2.0	2. 0
				Protease enzyme		0.45	0. 4 5
Cellulase enzymes		0.20	0. 2 0
				Amylase		0.20	0. 2 0

Perfume		1.00	1. 0 0
				Adhesive agent
Pluriol 1000		2.0	2. 0

The clay extrudate contained 97% CSM Quest 5A clay and 3% water. The flocculant raw material was polyethylene oxide with an average molecular weight of 300000. The anionic agglomerate 1 comprises 40% anionic surfactant, 27% zeolite and 33% carbonate.

The anionic agglomerate 2 comprises 40% anionic surfactant, 28% zeolite and 32% carbonate.

The cationic agglomerate comprises 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate comprises 95% SKS 6 and 5% silicate.

The bleach activator agglomerate comprises 81% TAED (tetraacetylethylenediamine), 17% acrylic acid/maleic acid copolymer (acid form) and 2% water.

Ethylenediamine N, N-disuccinic acid sodium salt/sulfate particles comprised 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor comprises 11.5% silicone oil (available from Dow Corning), 59% zeolite and 29.5% water. Arbocel TF-30-HG and Vivapur G22 are celluloses containing a disintegrant available from Rettenmaier corporation.

Examples I to N

Examples a-G were repeated, and tablets prepared from the indicated compositions were immersed in a bath containing 80 parts adipic acid mixed with 18.5 parts CSM Quest 9 clay and 1.5 parts Coasol (Coasol is diisobutyl adipate).

The tablet may also contain high molecular weight poly (ethylene oxide), a cellulolytic agent and/or an acetate salt. It should also contain highly soluble salts.

Claims (10)

1. A softening laundry detergent tablet comprising clay and laundry surfactant, wherein the tablet is a compressed body of particles, at least 50% by weight of the clay being present as particles of at least 100 μm in size.

2. A tablet according to claim 1 wherein the clay content of the tablet is at least 5% by weight of the tablet.

3. A tablet according to claim 1 wherein the clay content of the tablet is at least 8%, preferably at least 10% by weight of the tablet.

4. A tablet according to any preceding claim wherein at least 75% by weight of the clay is present as particles having a size of 100-.

5. A tablet according to any preceding claim wherein the clay particles comprise at least 50% by weight clay.

6. A tablet according to claim 5 wherein the clay particles comprise at least 70%, preferably at least 90% by weight of clay.

7. A tablet according to any preceding claim wherein the clay particles consist essentially of clay alone or clay with up to 10% by weight of a binder for the clay particles.

8. A tablet according to any preceding claim, wherein the tablet further comprises a clay flocculating agent.

9. A tablet according to any preceding claim wherein the particles are substantially all particles having a size of at least 100 μm.

10. A process for the preparation of a softening laundry detergent tablet comprising clay and laundry surfactant, which comprises providing at least 50% by weight of the clay as particles having a size of at least 100 μm, mixing the clay particles with other particulate components of the tablet, and compressing the mixture into a tablet.