AU742565B2 - Detergent compositions - Google Patents

Description

WO 98/42817 PCT/EP98/01770 DETERGENT COMPOSITIONS This invention relates to detergent compositions in the form of tablets for use in fabric washing.

Detergent compositions in tablet form have been described in, for example, GB 911204 (Unilever), US 3953350 (Kao), JP 60-015500A (Lion), and EP-A-711827 (Unilever) and are sold commercially in Spain. Tablets have several advantages over powdered products: they do not require measuring and are thus easier to handle and dispense into the washload, and they are more compact, hence facilitating more economical storage.

Such tablets are generally made by compressing or compacting a quantity of detergent composition in particulate form. It is desirable that tablets should have adequate mechanical strength when dry, before use, yet disintegrate and disperse/dissolve quickly when added to wash water. It has not proved simple to achieve both properties simultaneously. As more pressure is used when a tablet is compacted, so the tablet density and strength rise, but the speed of disintegration/dissolution when the tablet comes into contact with wash water goes down.

During the period from about 1960 to 1970 there was considerable research activity in connection with tablets WO 98/42817 PCT/EP98/01770 2 for use in fabric washing. A number of patents were published by major detergent manufacturers. Detergent tablets were sold commercially in USA and some European countries.

However, tablets disappeared from the market place in nearly all countries (Spain is the apparent exception) even though tablets have apparent advantages and have become known as a product form for machine dishwashing compositions which are characterised by a low content of organic surfactant.

US-A-3018267 (Procter Gamble) taught that the force, and hence pressure, applied when compacting a composition into tablets should be limited, or else the tablets would take too long to dissolve.

The compression pressure used in the Examples of this document was from 180 to 300 psi (approximately 1.2 to 2.1 MPa). Elsewhere in the document it is proposed that the pressure should not exceed 350 psi (approximately 2.5 MPa) to avoid slow disintegration encountered with higher pressures.

A number of proposals have been put forward as ways to improve the compromise between conflicting desiderata, but there still remains a desire to improve tablet strength without loss of speed of disintegration and vice versa.

WO 98/42817 PCT/EP98/01770 3 Some documents have proposed surface treatments or coatings to enhance tablet strength. For instance US-A-3451928 (Colgate) stated that the problem of strength versus speed of dissolution remained unsolved, and proposed a treatment of spraying on water, followed by flash heating.

US-A-3324038 (Procter) proposed the application of a coating containing urea.

It is known to include materials whose function is to enhance disintegration of tablets when placed in wash water. Some tablets which are sold commercially incorporate urea for this purpose. Urea has a very high solubility in water exceeding 100gms per 100ml water at 0 C. EP-A-711827 teaches the use of sodium citrate for the same purpose.

Detergent compositions, including tablet compositions, frequently contain a mixture of anionic and nonionic organic surfactants. It is often desirable to include both of these types of surfactant, for performance of the composition when washing fabrics.

We have now found that an improved compromise between tablet strength and speed of disintegration can be achieved by following certain principles concerning tablet formulation and manufacture.

WO 98/42817 PCT/EP98/01770 4 At the same time it is possible to incorporate materials which are desired to give good washing performance, and it is possible to formulate component ingredients of the tablet so that they are satisfactory in handling during tablet manufacture.

Also, we have found that two different measures of tablet strength are relevant to properties observed by a consumer.

Force to cause fracture is a direct assessment of strength and indicates the tablets' resistance to breakage when handled by a consumer at the time of use. The amount of energy (or mechanical work) put in prior to fracture is a measure of table deformability and is relevant to the tablets' resistance to breakage during transport.

Both properties are relevant to consumers' perception of tablets: consumers will want tablets to be strong enough to handle, to reach them intact, and to disintegrate quickly and fully at the time of use. By following this invention's principles as to formulation, it is possible to achieve a good combination of these properties.

In this invention, we have found it desirable to incorporate most (if not all) of the surfactants in particles which constitute a substantial part but by no means all the composition of a tablet. The organic WO 98/42817 PCT/EP98/01770 surfactant in these particles provides a substantial part, but again by no means all, of their weight.

Secondly, it is desirable that the surfactant is a mixture of non-soap anionic and nonionic detergent surfactants.

(preferably accompanied by soap) where both are present in significant amounts, but anionic is in the majority.

Thirdly, the balance of the composition should then contain material, other than organic surfactant, which is water soluble. This approach to formulation may be applied to the composition of a whole tablet, or to an individual region of a tablet with a plurality of distinct regions, e.g. layers.

So, according to a first aspect of this invention, there is provided a detergent tablet of compressed particulate composition wherein the tablet or a region thereof comprises organic surfactant and water-soluble detergency builder, characterised in that the tablet or region thereof contains from 30 to 65% by weight (of the tablet or region as the case may be) of particles which contain from 25 to 80% by weight (of these particles) of water-soluble detergency builder and from 20 to 50% by weight (of these particles) of non-soap organic surfactant which is anionic and nonionic surfactants in a ratio from 5:1 to 1.5:1 and in that in addition to said particles the tablet or region WO 98/42817 PCT/EP98/01770 6 contains at least 15% by weight (of the tablet or region respectively) of substance which is other than soap or organic surfactant and which has a solubility in water of at least 10gm/litre at 200C.

We believe that concentrating most or all of the surfactant into surfactant-rich particles, and using a substantial proportion of anionic surfactant is beneficial in providing tablets which have both strength and elasticity, while allowing the remainder of the tablet composition to contain a substantial proportion of water-soluble material which assists disintegration of the tablets at the time of use.

It is not necessary to include surfactant as a binder material in the part of the composition outside the surfactant-rich particles. Excluding it from this part of the composition is advantageous, to avoid interference with the prompt dissolution of this part of the composition.

So, it is preferred that the weight of the non-soap anionic surfactant in the particles is at least 1.7 times the weight of the nonionic surfactant in them. More preferably, this weight ratio of anionic surfactant to nonionic surfactant lies in a range from 2:1 up to 5:1, and more preferably from 2:1 to 4:1. Preferably these particles contain at least 80% by weight better at least WO 98/42817 PCT/EP98/01770 7 or even 95% of all the organic surfactant (including any soap) in the tablet or region.

The water-soluble material which is present in the composition, externally to the surfactant-rich particles, preferably comprises from 15 to 40% (better 16 or even up to 35%) by weight (of the tablet or region as the case may be) of one or more materials selected from compounds with a water-solubility exceeding 50 grams per 100 grams water; sodium tripolyphosphate containing at least 50% of its own weight of the phase I anhydrous form, and preferably partially hydrated so as to contain water of hydration in an amount which is at least 1% by weight of the sodium tripolyphosphate; mixtures thereof.

It is strongly preferred that the water-soluble material which is present in the composition, externally to the surfactant-rich particles, is present as particles which are substantially free of surfactant, i.e. contain no more than 5% of their own weight of organic surfactant.

A preferred form of this invention provides a detergent tablet of compressed particulate composition, or a discrete region of such a tablet, containing WO 98/42817 PCT/EP98/01770 8 from 35 to 60 wt% (and probably from 41 to 53, 56 or 60wt%) of particles which contain non-soap anionic surfactant, nonionic surfactant and water-soluble detergency builder, (ii) from 15 to 40 wt%( and probably from 16 or 1.7 to.

wt%) of particles which are substantially free of surfactant, i.e. contain at least 95% of their own weight of water soluble material but contain no more than 5% of their own weight of organic surfactant, and (iii) from 0 to 50 wt% of further particulate ingredients, wherein the first said particles contain at least preferably at least 24% of their own weight of non-soap surfactant and the weight of anionic surfactant therein is from 1.5 to 5 times the weight of nonionic surfactant therein.

In another aspect, this invention a tablet defined by reference to a test procedure described below. In this aspect the invention provides a detergent tablet of compressed particulate composition wherein the tablet or a discrete region of the tablet comprises particles which contain non-soap anionic surfactant, nonionic surfactant, preferably soap and other water-soluble ingredients, characterised in that the particles contain at least 20 wt% in total of the anionic and nonionic surfactants and in that a test tablet consisting of the said non-soap anionic surfactant, nonionic surfactant, and any soap in the same proportions, together with 15% by weight moisture has a breaking strength as herein defined of at least 0.04 MPa and a modulus as herein defined of not more than 10 MPa preferably not more than 8 MPa.

In a yet further aspect, this invention provides the use of particles containing a mixture of non-soap anionic and nonionic surfactants and detergency builder, where the concentration by weight of non-soap anionic surfactant is at least 1.5 times as great as the concentration by weight of nonionic surfactant and the total concentration of these surfactants is at least 20 wt% of the particles to provide improvements in tablet strength and elasticity versus speed of disintegration.

A tablet of the invention may be either homogeneous or Sheterogeneous. In the present specification, the term •oeo homogeneous" is used to mean a tablet produced by compaction 00! 20 of a single particulate composition, but does not imply that all the particles of that composition will necessarily be of identical composition. The term "heterogeneous" is used to mean a tablet consisting of a plurality of discrete regions, 4*:o for example layers,inserts St

S

S..

0e S WO 98/42817 PCT/EP98/01770 or coatings, each derived by compaction from a particulate composition. In a heterogenous tablet according to the present invention, each discrete region of the tablet will preferably have a mass of at least In a heterogeneous tablet, at least one and possibly more of the discrete regions contains the mixed anionic and nonionic surfactants and detergency builder in accordance with the invention.

Drawinqs The accompanying drawings diagrammatically illustrate the testing of a cylindrical tablet: Fig la shows a tablet when first contacted by the platens of a materials testing machine, Fig lb shows the tablet at the point of failure, Fig 2 diagrammatically illustrates the form of a graph obtained during testing.

Tablet testing We have tested the speed of disintegration of tablets by means of a test procedure in which a tablet was placed on a plastic sieve with 2mm mesh size which is immersed in 9 litres of demineralised water at ambient temperature of The water conductivity is monitored until it reached WO 98/42817 PCT/EP98/01770 11 a constant value. The time for dissolution of the tablets is taken as the time (Tg 0 for change in the water conductivity to reach 90% of its final magnitude.

We have tested tablet strength by a procedure illustrated by the accompanying drawings in which a cylindrical tablet is compressed radially between the platens 12,14 of a materials testing machine until the tablet fractures. At the starting position shown in Fig la, the platens 12, 14 contact the tablet but do not apply force to it. Force is applied, as indicated by the arrows 16 to compress the tablet. The testing machine measures the applied force and also the displacement of the platens towards each other as the tablet is compressed. The distance (y) between the platens before force is applied, which is the diameter of the tablet, is also known. At failure, illustrated in Fig Ib the tablet cracks (eg as shown at 18) and the applied force needed to maintain the displacement drops. Measurement is discontinued when the applied force needed to maintain the displacement has dropped by 25% from its maximum value (indicated as point D in Fig 2 below) A graph of force against displacement has the form illustrated by Fig 2. The maximum force is the force at failure (Ff) From this measurement of force a test WO 98/42817 PCT/EP98/01770 12 parameter called diametral fracture stress, which we have used in the past, can be calculated using the equation S= 2 Ff 7rDt where a is the diametral fracture stress in Pascals, Ff is the applied force in Newtons to cause fracture, D is the tablet diameter in metres and t is the tablet thickness in metres.

The force at failure divided by the area of a diametral plane through the tablet (approximately the area of the crack 18) is the breaking strength, with units of Pascals.

The break energy is the area under the graph of force against displacement, up to the point of break. It is shown shaded in Fig 2 and is given by the equation: Eb fF(x)dx 0 where Eb is the break energy in joules, x is the displacement in metres, F is the applied force in Newtons at displacement x and Xf is the displacement at failure.

The displacement at failure relative to the tablet diameter is the relative displacement xf/y.

WO 98/42817 PCT/EP98/01770 13 Breaking strength divided by relative displacement is a modulus, whose value is inverse to tablet elasticity.

Materials and other features Materials which may be used in tablets of this invention will now be discussed in more detail.

Anionic Surfactant Compounds Synthetic non-soap) anionic surfactants are well known to those skilled in the art. The anionic surfactant may comprise, wholly or predominantly, linear alkyl benzene sulphonate of the formula R S0 3

M

where R is linear alkyl of 8 to 15 carbon atoms and M* is a solubilising cation, especially sodium.

Primary alkyl sulphate having the formula ROSO3-

M'

in which R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M* is a solubilising cation, is also commercially significant as an WO 98/42817 PCT/EP98/01770 14 anionic surfactant and may be used in this invention.

Frequently, such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired non-soap anionic surfactant and may provide 75 to 100wt% of any anionic non-soap surfactant in the composition.

Examples of other non-soap anionic surfactants include olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.

One or more soaps of fatty acids may also be included in addition to the required non-soap anionic surfactant.

Examples are sodium soaps derived from the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil. These may be formed by adding fatty acid and a base such as sodium carbonate to a slurry which is spray-dried to form the surfactant-rich base particles.

Nonionic surfactant compounds Nonionic surfactant compounds include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide.

WO 98/42817 PCT/EP98/01770 Specific nonionic surfactant compounds are alkyl (C 8 22 phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C8- 20 primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine.

Especially preferred are the primary and secondary alcohol ethoxylates, especially the C_.

1 and C 12 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.

Detergencv Builder The composition which is compacted to form tablets or tablet regions includes water-soluble detergency builder.

Water-soluble phosphorous-containing inorganic detergency builders include the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates.

Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.

Non-phosphorous water-soluble builders may be organic or inorganic. Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic WO 98/42817 PCT/EP98/01770 16 builders include polycarboxylate polymers, such as polyacrylates and acrylic/maleic copolymers, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.

Tablet compositions preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which can function as builders and also inhibit unwanted deposition onto fabric from the wash liquor.

Proportions Generally, a tablet or a region thereof in accordance with this invention will contain overall from 2 or 5wt% up to or 50wt% non-soap surfactant, and from 5 or 10wt% up to or 80wt% detergency builder.

The concentration of non-soap anionic surfactant in the tablet or a region thereof will generally be at least one and a half times the concentration of nonionic surfactant.

It is preferably at least 3% by weight of the tablet or region, e.g. from 3wt% up to 30 or 40wt%. The concentration of nonionic surfactant is preferably at least 2% by weight of the tablet or region, such as 2 to 15wt% of the tablet or region thereof.

WO 98/42817 PCT/EP98/01770 17 The quantity of soap in the tablet or region thereof is preferably from 0.1 or 0.2 up to 1% or 2% by weight of the tablet or region thereof. Higher proportions such as up to 4% are less preferred.

Where a tablet is heterogenous, these percentage ranges may apply to the overall composition of the tablet, as well as to at least one region of the tablet.

In accordance with this invention, anionic non-soap surfactant, nonionic surfactant water-soluble detergency builder and other materials which preferably include soap are made into particles such that the non-soap surfactant provides from 20 to 50% of the weight of these particles.

Preferably the non-soap surfactant provides at least 22% or 24% of the weight of these particles, and more preferably at least 28%, desirably up to 45% of their weight. When soap is present, it is desirably from 0.2 to and possibly more, up to 3% or 4% by weight of these particles, and in these particles the weight ratio of nonionic detergent to soap is preferably from 5:1 better 10:1 to 30:1.

Such particles may be made by spray drying, or by a granulation process. Preferably they contain water-soluble detergency builder in an amount which is from 30 to 80% of the weight of these particles, better 30 or 40 up to 60% of WO 98/42817 PCT/EP98/01770 18 the weight of these particles.

The surfactant mixture used in these particles can be tested mechanically in directly analogous manner to the testing of tablets, discussed above. To do this a mixture of the non-soap surfactants and any soap is made on a small scale, and cast into cylindrical form or some other shape from which a cylinder can be cut. If necessary this is dried to reduce the water content to 15% by weight (approximating to 5% moisture in the particles which contain this surfactant mixture). Next, it is tested on a materials testing machine in the manner described above for testing of tablets. This mechanical testing procedure can also be applied to tablets made from the surfactant-rich particles alone.

We have found that the effect of anionic surfactant in these particles is to enhance elasticity without much effect on magnitude of the force to cause fracture.

Nonionic surfactant tends to have some opposite effect.

Soap when present, cooperates with the nonionic surfactant to reduce mobility of the nonionic surfactant and to increase tablet strength (as measured by force to cause failure).

By using sufficient quantities of anionic non-soap surfactant, nonionic surfactant and preferably soap we have found that it is possible to achieve adequate strength and WO 98/42817 PCT/EP98/01770 19 elasticity of a test tablet which in turn signifies that the same mixture will give tablets with good strength and elasticity.

Breaking strength is desirably at least 0.04MPa preferably at least 0.05MPa. The modulus is desirably no more than MPa preferably no more than 8 or even 5 MPa.

We have observed that a mixture of alkylbenzene sulphonate and nonionic surfactant in ratio 1.16:1 gave a modulus of about 15 MPa but when the proportions were changed to 2.2:1 (in accordance with this invention) the modulus dropped dramatically to about 4.0 to 4.5 MPa, indicating greater elasticity, with very little change in force at failure.

DisinteQration-promoting particles In addition to the required particles containing surfactants and builder, a tablet or tablet region of this invention contains water-soluble material which serves to promote disintegration. Preferably this is provided as particles which are substantially free of organic surfactant.

One preferredpossibility is that the said particles which promote disintegration are particles containing sodium tripolyphosphate with more than 50% of it (by weight of the particles) in the anhydrous phase I form.

WO 98/42817 PCT/EP98/01770 Sodium tripolyphosphate is very well known as a sequestering builder in detergent compositions. It exists in a hydrated form and two crystalline anhydrous forms.

These are the normal crystalline anhydrous form, known as phase II which is the low temperature form, and phase I.

which is stable at high temperature. The conversion of phase II to phase I proceeds fairly rapidly on heating above the transition temperature, which is about 420iC, but the reverse reaction is slow. Consequently phase I sodium tripolyphosphate is metastable at ambient temperature.

A process for the manufacture of particles containing a high proportion of the phase I form of sodium tripolyphosphate by spray drying below 420:C is given in US-A-4536377.

Particles which contain this phase I form will often contain the phase I form of sodium tripolyphosphate as at least 55% by weight of the tripolyphosphate in the particles. Other forms of sodium tripolyphosphate will usually be present to a lesser extent. Other salts may be included in the particles, although that is not preferred.

A further preference is that the sodium tripolyphosphate is partially hydrated. The extent of hydration should be at least 1% by weight of the sodium tripolyphosphate in the particles. It may lie in a range from 2.5 to or it may be higher.

WO 98/42817 PCT/EP98/01770 21 Suitable material is commercially available. Suppliers include Rhone-Poulenc, France and Albright Wilson, UK.

"Rhodiaphos HPA 3.5" from Rhone-Poulenc has been found particularly suitable. It is a characteristic of this grade of sodium tripolyphosphate that it hydrates very rapidly in a standard Olten test. We have found that it hydrates as quickly as anhydrous sodium tripolyphosphate, yet the prehydration appears to be beneficial in avoiding unwanted crystallisation of the hexahydrate when the material comes into contact with water at the time of use.

Another possibility which can be used instead of tripolyphosphate, or in a mixture with it, is that these disintegration-promoting particles contain at least 50% of their own weight, better at least 80%, of a material which has a solubility in deionised water at 20 0 C of at least grams per 100 grams of water.

The said particles may provide material of such solubility in an amount which is at least 7 wt% or 12 wt% of the whole composition of the tablet or region thereof.

A solubility of at least 50 grams per 100 grams of water at 200C is an exceptionally high solubility: many materials which are classified as water soluble are less soluble than this.

WO 98/42817 PCT/EP98/01770 22 Some highly water-soluble materials which may be used are listed below, with their solubilities expressed as grams of solid to form a saturated solution in 100 grams of water at 0

C:-

Material Water Solubility (c/100q) Sodium citrate dihydrate 72 Potassium carbonate 112 Urea >100 Sodium acetate 119 Sodium acetate trihydrate 76 Magnesium sulphate 7H 2 0 71 Potassium acetate >200 By contrast the solubilities of some other common materials at 200C are:- Material Water Solubility (q/100q) Sodium chloride 36 Sodium sulphate decahydrate 21.5 Sodium carbonate anhydrous Sodium percarbonate anhydrous 12 Sodium perborate anhydrous 3.7 Sodium tripolyphosphate anhydrous Preferably this highly water soluble material is incorporated as particles of the material in a substantially pure form each such particle contains over 95% by weight of the material). However, the said WO 98/42817 PCT/EP98/01770 23 particles may contain material of such solubility in a mixture with other material, provided that material of the specified solubility provides at least 50% by weight of these particles.

Other incredients Detergent tablets according to the invention may contain a bleach system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. If any peroxygen compound is present, the amount is likely to lie in a range from 10 to 25% by weight of the tablet.

Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.

Bleach activators have been widely disclosed in the art.

Preferred examples include peracetic acid precursors, for example tetraacetylethylene diamine (TAED), and perbenzoic acid precursors. The quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 (Lever Brothers Company) are also of interest. Another type of bleach activator which may be used, but which is not a bleach precursor, is a transition metal catalyst as disclosed in EP-A-458397, EP-A-458398 and EP-A-549272. A bleach system may also include a bleach stabiliser (heavy WO 98/42817 PCT/EP98/01770 24 metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.

Bleach activator is usually present in an amount from 1 to 10% by weight of the tablet, possibly less in the case of a transition metal catalyst which may be used as 0.1% or more by weight of the tablet.

The detergent tablets of the invention may also contain one of the detergency enzymes well known in the art for their ability to degrade various soils and stains and so aid in their removal. Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics. Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the tablet.

The detergent tablets of the invention may also contain a fluorescer (optical brightener), for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal DMS is disodium 4,4'bis- (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate; and Tinopal CBS is disodium 2,2'-bis-(phenylstyryl) disulphonate.

WO 98/42817 PCT/EP98/01770 An antifoam material is advantageously included, especially if a detergent tablet is primarily intended for use in front-loading drum-type automatic washing machines.

Antifoam materials in granular form are described in EP 266863A (Unilever). Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbed water-soluble carbonate-based inorganic carrier material.

It may also be desirable that a detergent tablet of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, meta- or disilicate. The presence of such alkali metal silicates may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some detergency building. Preferably the surfactant-rich particles contain from 5 to 15% silicate by weight of the particles. This improves the strength and free flow of these particles prior to tabletting.

Further ingredients which can optionally be employed in fabric washing detergent tablet of the invention include anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabricsoftening agents; heavy metal sequestrants such as EDTA; WO 98/42817 PCT/EP98/01770 26 perfumes; and colorants or coloured speckles.

These various other ingredients may be present in the surfactant-rich particles or in the balance of the composition outside them. It is preferred that any bleach is contained in the balance of the composition outside the surfactant-rich particles.

Particle Size and Distribution A detergent tablet of this invention, or a region of such a tablet, is a matrix of compacted particles.

Preferably the particulate composition has an average particle size before compaction in the range from 200 to 2000 Am, more preferably from 250 to 1400 Am. Fine particles, smaller than 180 Am or 200 pm may be eliminated by sieving before tableting, if desired, although we have observed that this is not always essential.

While the starting particulate composition may in principle have any bulk density, the present invention is especially relevant to tablets made by compacting powders of relatively high bulk density, because of their greater tendency to exhibit disintegration and dispersion problems.

Such tablets have the advantage that, as compared with a tablet derived from a low bulk density powder, a given dose of composition can be presented as a smaller tablet.

WO 98/42817 PCT/EP98/01770 27 Thus the starting particulate composition may suitably have a bulk density of at least 400 g/litre, preferably at least 550 g/litre, and perhaps at least 600 g/litre.

Granular detergent compositions of high bulk density prepared by granulation and densification in a high-speed mixer/granulator, as described and claimed in EP 340013A (Unilever), EP 352135A (Unilever), and EP 425277A (Unilever), or by the continuous granulation/densification processes described and claimed in EP 367339A (Unilever) and EP 390251A (Unilever), are inherently suitable for use in the present invention.

Tableting Tableting entails compaction of the particulate composition. A variety of tableting machinery is known, and can be used. Generally it will function by stamping a quantity of the particulate composition which is confined in a die.

Tableting may be carried out without application of heat, so as to take place at ambient temperature or at a temperature above ambient. In order to carry out the tableting at a temperature which is above ambient, the particulate composition is preferably supplied to the tableting machinery at an elevated temperature. This will of course supply heat to the tableting machinery, but the WO 98/42817 PCT/EP98/01770 28 machinery may be heated in some other way also.

If any heat is supplied, it is envisaged that this will be supplied conventionally, such as by passing the particulate composition through an oven, rather than by any application of microwave energy.

The size of a tablet will suitably range from 10 to 160 grams, preferably from 15 to 60 g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose. The tablets may be of any shape. However, for ease of packaging they are preferably blocks of substantially uniform crosssection, such as cylinders or cuboids. The overall density of a tablet preferably lies in a range from 1040 or 1050gm/litre up to 1300gm/litre. The tablet density may well lie in a range up to no more than 1250 or even 1200gm/litre.

WO 98/42817 PCT/EP98/01770 29 Examples Tablets for use in fabric washing were made, starting with spray-dried base powders of the following compositions: Ingredient Parts by Weight A B C Sodium linear alkylbenzene 6.4 9.6 11.0 sulphonate

C

13 15 fatty alcohol 7EO 4.3 1.1 2.4

C

3 15 fatty alcohol 3EO 3.2 3.2 2.3 Sodium tripolyphosphate* 24.3 24.3 18.0 Sodium silicate 6.4 5.9 Soap 0.3 0.3 0.21 Acrylate/maleate copolymer 1.2 1.2 Sodium sulphate, moisture and balance balance balance minor ingredients to 60 to 55 to Added to the slurry as anhydrous sodium tripolyphosphate containing at least 70% phase II form.

Particulate compositions were made by mixing this powder with other ingredients as tabulated below. These included particles of sodium tripolyphosphate specified to contain phase I form and contain 3.5% water of hydration (Rhodia-Phos HPA 3.5 available from Rhone-Poulenc).

WO 98/42817 PCT/EP98/01770 The compositions contained the following percentages by weight: Ingredient T by weight Ex 1 Ex2 Ex 3 Base powder A Base powder B Base powder C Sodium percarbonate granules 14 15 TAED granules 3.4 3.4 3.4 Anti-foam granules 1.2 1.2 3.2 Perfume, enzymes and other 1.4 2.2 minor ingredients Rhodiaphos HPA3.5 20 20 tripolyphosphate Sodium carbonate 3.2 40g portions of each composition were made into cylindrical tablets of 44 mm diameter, using a Carver hand press, with sufficient applied pressure to produce tablets which dissolved to 90% of complete dissolution within approximately equal times not exceeding four minutes, in water at 20 0 C. Applied forces in a range from 2 to 4 kN have usually been found to be enough when using this hand press.

WO 98/42817 PCT/EP98/01770 31 To test dissolution of tablets, a test procedure was used in which a tablet was placed on a plastic sieve with 2mm mesh size which was immersed in 9 litres of demineralised water at ambient temperature of 20'C. The water conductivity was monitored until it reached a constant value. The time for dissolution of the tablets was taken as the time (Tg 0 for change in the water conductivity to reach 90% of its final magnitude.

The strength of these tablets was measured by compressing them radially, between the platens of a universal materials testing machine until fracture of the tablet occurred.

The force at fracture was measured and also the displacement at fracture. The break energy, which as explained above is the area under a force-over-displacement graph up to failure, was calculated.

The following table gives the results obtained for tablets of Examples 2 and 3 embodying the invention, and comparative tablets of Example 1. It is apparent that tablets embodying the invention were stronger although they dissolved in a similar time. Included in the table are mechanical properties of the surfactant mixture used.

Ex 1 Ex2 Ex 3 Powder features active system 6/7 9/4 9/4 anionic/nonionic level of base powder 60 55 active level in base 23 25 active/tripolyphosphate 0.57 0.57 0.88 in base powder level of disintegrant 20 20 Tablet properties force at failure 30.5 35.0 69.5 break energy [m joules] 5.8 10.5 20.4 Properties of surfactant mix Breaking strength [MPa] 0.06 0.08 0.05 0.07 Modulus [MPa] 15 4.0 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

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Claims (18)

1. A detergent tablet of compressed particulate composition wherein the tablet or a region thereof comprises organic surfactant and water-soluble detergency builder, characterised in that the tablet or region thereof contains from 30 to 65% by weight (of the tablet or region respectively) of particles which contain from 25 to 80% by weight (of these particles) of water-soluble detergency builder and from 20 to 50% by weight (of these particles) of non-soap organic surfactant which is S anionic and nonionic surfactants in a weight ratio from 5:1 to 9* 99 1.5:1 and in that in addition to said particles the tablet or region contains 15% or more by weight (of the tablet or region 9 respectively) of material which is other than soap or organic surfactant and which has a solubility in water of at least l0gm/litre at *99

2. A detergent tablet of compressed particulate 9 composition wherein the tablet or a discrete region of the tablet comprises particles which contain at least 9 of non-soap anionic surfactant and nonionic surfactant and optionally soap, and wherein a test tablet consisting essentially of said non-soap anionic surfactant and nonionic surfactant in a weight ratio of from 5:1 to 1.7:1, and any soap present in the same proportions as in said detergent tablet, together with by weight moisture has a breaking strength as herein defined of at least 0.04 MPa and a modulus as herein defined of not more than 10 MPA.

3. A tablet according to claim 2 wherein the particles contain from 30 to 60 wt% of the mixture of surfactants and soap.

4. A tablet according to either claim 2 or claim 3 wherein the tablet comprises soap and other water-soluble ingredients.

A tablet according to any one of claims 1 to 4 wherein the tablet or region thereof contains the said particles in an amount from 41 to 56% by weight.

6. A tablet according to any one of claims 1 to 5 wherein the weight ratio of anionic surfactant to nonionic surfactant lies in a range from 1.7:1 to 5:1.

7. A tablet according to any one of claims 1 to 6 wherein the e. weight ratio of nonionic surfactant to soap in said particles oooo lies in a range from 10:1 to 30:1. eeoc

8. A tablet according to any one of claims 1 to 7 wherein the amount of non-soap organic surfactant in the said particles is from 22 to 45% by weight of the particles. oo

9. A tablet according to any one of claims 1 to 8 containing oooo soap in the said particles in an amount from 0.2 to 2% by S• weight of the particles.

A tablet according to any one of claims 1 to 9 wherein the said particles contain from 30 to 80% by weight (of the particles) of water-soluble detergency builder which is an alkali metal salt of a condensed phosphate.

11. A tablet according to claim 10 wherein the salt of a condensed phosphate is sodium tripolyphosphate.

12. A tablet according to any one of claims 1 to 11 wherein the water-soluble material present in addition to the said particles comprises 15% or more (by weight of the tablet or region thereof respectively) in the form of further particles which contain no more than 5% of their own weight of organic surfactant.

13. A tablet according to any one of claims 1 to 12 wherein the water-soluble substance present in addition to the said 0 particles comprises 25 to 35% (by weight of the tablet or region thereof respectively) of material with a water e00e co• solubility of at least 50gm/litre at 20 0 C, or sodium 00.o0 0° o tripolyphosphate containing more than 50% of its own weight of the phase I anhydrous form, or a mixture thereof. *.0 0: i

14. A tablet according to claim 13 wherein the water-soluble substance present in addition to the said particles comprises e 15 to 35% (by weight of the tablet or region thereof o• S respectively) of sodium tripolyphosphate containing more than of its own weight of the phase I anhydrous form, which is partially hydrated so as to contain from 1 to 4% by weight of water of hydration.

A tablet according to any one of claims 1 to 14 wherein said anionic surfactant is a majority of sodium alkyl benzene sulphonate, optionally accompanied by a smaller amount of other anionic surfactant..

16. A tablet according to any one of claims 1 to 15 wherein said nonionic surfactant is a majority of ethoxylated fatty alcohol, optionally accompanied by a smaller amount of other nonionic surfactant.

17. A process for making a detergent tablet according to any one of claims 1 to 16 which comprises mixing a) particles which contain from 20 to 65% by weight (of these particles) of non-soap organic surfactant which is anionic and nonionic surfactants in a weight ratio from 5:1 to 1.5:1 with b) material which is other than soap or organic surfactant and which has a solubility in water of at least 10gm/litre at and compacting the mixture into a tablet or a region of a tablet.

18. A detergent tablet as hereinbefore described with reference to the examples. e DATED THIS 28th day of March, 2001. UNILEVER PLC By Its Patent Attorneys DAVIES COLLISON CAVE