CN1309691A - Detergent tablet with high mechanical and dissolution characteristics - Google Patents

Abstract

The present invention relates to a tablet formed by compressing a particulate material, the particulate material comprising a surfactant and a highly soluble compound, the highly soluble compound having a cohesive effect on the particulate material. In a further aspect of the invention there is provided a method of preparing an aqueous solution of a laundry detergent for use in a washing machine, wherein the aqueous solution of laundry detergent is formed by dissolving in water a tablet formed by compressing a particulate material, the tablet comprising a surfactant and a highly soluble compound, the highly soluble compound having a cohesive effect on the particulate material.

Description

Detergent tablets with high mechanical and dissolution properties

The present invention relates to detergent tablets, especially those suitable for laundering.

While sheet cleansing compositions are often mentioned, they have not achieved any substantial success (except for personal wash bars), although there are some advantages to the product in unit dispensing form. One reason may be that tablet detergents generally dissolve more slowly than the powdered ingredients from which they are made, simply because these powdered ingredients are forced close together in the tablet, with relatively little chance for water to penetrate between them. This leads to the problem that slowly dissolving tablets produce residue, eg visible through the washing machine door during the wash cycle, or adhered to fabrics at the end of the wash cycle, or both.

EP-A-0 711 827 published on May 5, 1996 discloses laundry detergent tablets comprising a highly water-soluble substance which improves the disintegration of the entire tablet and the dissolution of its soluble components.

However, especially in some front loading washing machines, the problem of flaky residues visible in the washing machine window is still encountered.

It is an object of the present invention to provide tablets formed by compressing granular material comprising a surfactant which are suitable for storage, transport and handling without breakage, while being readily and rapidly soluble in washing liquids, dissolving the active The ingredients are released into the wash liquor and completely disintegrate and disperse in alkaline or surfactant-rich solutions such as wash liquor.

Summary of the invention

The object of the present invention is achieved by providing a tablet of the above-mentioned type, whereby the granular material also comprises a highly soluble compound which has a binding effect on the granular material.

In another aspect, the present invention provides a process for preparing an aqueous laundry detergent solution for a washing machine, wherein the aqueous laundry detergent solution is formed by dissolving a tablet formed of compressed granular material in water, the tablet Contains a surfactant and a highly soluble compound that has a binding effect on the particulate material.

Detailed description of the invention

The present invention relates to a highly soluble compound having a binding effect on said particulate material.

highly soluble compounds

The present invention relates to a highly soluble compound. Such compounds are formed as mixtures or as single compounds. According to the invention, highly soluble compounds are defined as follows:

A solution containing deionized water and 20 grams per liter (g/l) of a particular compound was prepared as follows:

1 - Put 20 g of the specific compound in a Sotax beaker. The beaker was placed in a constant temperature bath set at 10°C. A stirrer with a marine propeller was placed in the beaker so that the bottom of the stirrer was 5 mm above the bottom of the Sotax beaker. The rotational speed of the stirrer was set at 200 rpm.

2-Add 980 g of deionized water to the Sotax beaker.

3 - 10 seconds after adding water, measure the conductivity of the solution with a conductivity meter.

4- Repeat step 3 after 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 5 minutes and 10 minutes after step 2.

5-Take the measurement result at 10 minutes as the stable value or the maximum value.

According to the present invention, a particular compound is highly soluble when the conductivity of the solution reaches 80% of its maximum value in less than 10 seconds from the time the deionized water is fully added to the compound. Indeed, when the conductivity is monitored in this way, the conductivity plateaus after a period of time and this plateau is considered a maximum. For ease of handling the compound is preferably in the form of a flowable material consisting of solid particles at a temperature between 10 and 80°C, but other forms such as pastes or liquids may also be used.

Examples of highly soluble compounds include sodium di-isoalkylbenzenesulfonate or sodium toluenesulfonate.

Adhesion

For the present invention, the binding effect to the detergent matrix particulate material is characterized by the force required to rupture a tablet based on the tested detergent matrix compressed under controlled compression conditions. For a given compression force, a high tablet strength indicates that the granules adhere strongly together when compressed so that a strong cohesion occurs. A method for assessing tablet strength (also known as radial breaking stress) is given in "Pharmaceutical dosage forms: tablets" Volume 1, eds. H.A. Lieberman et al. (1989).

According to the present invention, the viscosity caused by the highly soluble compound is measured by comparing the tablet strength of the original base powder without the highly soluble compound to the tablet strength of a powder blend comprising 97 parts of the original base powder and 3 parts of the highly soluble compound. Knot effect. The highly soluble compound is added to a substantially anhydrous (water content below 10%, preferably below 5%) matrix. The addition temperature is between 10 and 80°C, more preferably between 10 and 40°C.

According to the present invention, under a given pressure of 3000N, there are 50g of detergent granular material, a tablet with a diameter of 55mm, to make the tablet tensile strength by the presence of 3% of highly soluble compounds that have a binding effect on the matrix granular material When the increase is above 30% (preferably 60%, more preferably 100%), it is defined as that the highly soluble compound has a binding effect on the granular material.

An example of a binding compound is sodium di-isoalkylbenzenesulfonate.

It has been found that when a highly soluble compound of the invention binding to the particulate material is incorporated into a tablet formed by compression of the surfactant-containing particulate material, the dissolution of the tablet in aqueous solution is significantly increased. In a preferred embodiment, at least 1% by weight of said tablet is formed by said highly soluble compound, more preferably at least 2%, even more preferably at least 3%, most preferably at least 5% by weight of said highly soluble compound. Formation of highly soluble compounds that act. It should be noted that in EP-A-0 524 075 a composition comprising a highly soluble compound and a surfactant is disclosed, which is a liquid composition.

According to the present invention, it has been found that a highly soluble compound having a binding effect on the granular material results in a tablet with higher tensile strength at constant pressure or at lower pressure than conventional tablets Tablets with the same tensile strength were obtained. Typically, the tablet has a tensile strength greater than 5 kPa, preferably greater than 10 kPa, more preferably (especially for laundry use) greater than 15 kPa, even more preferably greater than 30 kPa, most preferably (especially for dishwashing or automatic dishwashing) greater than 50 kPa and the tensile strength is lower than 300kPa, preferably lower than 200kPa, more preferably lower than 100kPa, even more preferably lower than 80kPa, most preferably lower than 60kPa. Indeed, in the case of laundry applications, the tablet should be compressed lower than in the case of automatic dishwashing applications to dissolve more easily, so in laundry applications the tensile strength is preferably below 30 kPa.

This can produce tablets that are comparable in firmness or force resistance to conventional tablets, but are less compact and thus more soluble. In addition, since the compound is highly soluble, the dissolution of the tablet is further promoted, resulting in a synergistic effect to promote the dissolution of the tablet of the present invention.

tablet manufacturing

The present invention can obtain a tablet which is not as dense and dense as traditional tablet detergents under the condition of constant pressure.

Tablets according to the invention can be prepared simply by mixing the solid ingredients and compressing the mixture in a conventional tablet press, such as used in the pharmaceutical industry. Preferably the main ingredient, especially the gelling surfactant, is used in the form of granules. Any liquid ingredients such as surfactants or suds suppressors may be incorporated into the solid particulate ingredients in a conventional manner. Particularly for laundry tablets, ingredients such as builders and surfactants can be spray dried in a conventional manner and then compacted under suitable pressure. Preferably, the tablet of the invention is compressed with a force of less than 100000N, more preferably less than 50000N, even more preferably less than 5000N, most preferably less than 3000N. Indeed, the most preferred embodiment is to compress laundry-suitable tablets with a force of less than 2500N, but automatic dishwashing tablets are also contemplated, which are generally more compressed than laundry tablets. tight.

Granular material suitable for use in the preparation of tablets of the present invention may be prepared by any granulation or granulation method. An example of such a process is spray drying (in a co-current or counter-current spray drying tower), typically yielding bulk densities of 600 g/l or less. Higher density granular materials can be granulated and thickened in a high shear batch mixer/granulator or by continuous granulation and thickening (e.g. using Lodige® CB and/or Lodige® KM mixers) preparation. Other suitable methods include fluidized bed methods, compaction methods (such as rolling), extrusion, and any particulate material prepared by any chemical method such as flocculation, crystallization settling, and the like. Individual particles may also be any other particles, granules, spheres or microparticles.

The components of the particulate material may be mixed together by any conventional means. The batch method is suitable for example in concrete mixers, Nauta mixers, ribbon mixers or any other mixers. Alternatively the mixing process can be carried out continuously by metering the components on a conveyor belt, blending in one or more drums or mixers. A non-gelling binder may be sprayed onto some or all of the mixture of particulate materials. Other liquid ingredients may also be sprayed onto the mixture of components individually or premixed. For example, slurries of fragrances and optical brighteners can be sprayed. Finely divided flow aids (separators such as zeolites, carbonates, silica) can be added to the particulate material after spraying the binder, preferably towards the end of the process, to make the mixture less viscous.

The tablets may be manufactured by any compression method such as tableting, briquetting or extrusion (tabletting is preferred). Suitable equipment includes standard single pass or rotary presses (such as Courtoy®, Korch®, Manesty® or Bonals®). Tablets prepared according to the invention preferably have a diameter between 20 and 60 mm, preferably at least 35 and at most 55 mm, and a weight between 25 and 100 g. The height/diameter (or width) ratio of the tablet is preferably greater than 1:3, more preferably greater than 1:2. The pressure used to prepare these tablets does not exceed 100000 kN/m ² , preferably does not exceed 30000 kN/m ² , more preferably does not exceed 5000 kN/m ² , even more preferably does not exceed 3000 kN/m ² , most preferably does not exceed 1000 kN/m ² . In a preferred embodiment of the invention, the tablet has a density of at least 0.9 g/cc, more preferably at least 1.0 g/cc, and preferably less than 2.0 g/cc, more preferably less than 1.5 g/cc, even more preferably Less than 1.25 g/cc, most preferably less than 1.1 g/cc.

Hydrotrope Compounds

In a preferred embodiment of the present invention, said highly soluble binding compound is a hydrotrope compound, a specific compound being a hydrotrope as defined below (see S.E. Friberg and M.Chiu, J. "Dispersion Science and Technology" ( Dispersion Science and Technology) 9(5&6), pages 443-457 (1988-1989)):

1. A solution was prepared comprising 25% by weight of the specified compound and 75% by weight of water.

2. Octanoic acid was then added to the solution in a ratio of 1.6 times the weight of the specific compound in the solution, which was at a temperature of 20°C. The solutions were mixed in a Sotax beaker fitted with a stirrer with a boat propeller positioned about 5 mm above the bottom of the beaker and the stirrer was set at 200 rpm.

3. If the octanoic acid is completely dissolved, ie if the solution contains only one phase, which is the liquid phase, then the particular compound is a hydrotrope.

It should be noted that in a preferred embodiment of the invention said hydrotrope compound is a flowable material made of solid particles at operating conditions between 15 and 60°C.

Hydrotrope compounds include those listed below:

A list of commercial hydrotropes can be found in McCutcheon's Emulsifiers and Detergents, published by the McCutcheon Division of Manufacturing Confectioners. Compounds of concern also include:

1. Nonionic hydrotropes having the following structures:

Wherein R is a C ₈ -C ₁₀ alkyl chain, x is in the range of 1 to 15, and y is 3 to 10.

2. Anionic hydrotropes such as alkali metal aryl sulfonates. These include the alkali metal salts of benzoic acid, salicylic acid, benzenesulfonic acid and its many derivatives, naphthoic acid and various hydrogenated aromatic acids. Examples of these are derived from toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, tetralinsulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid Derivatized sodium, potassium and ammonium benzenesulfonates. Other examples include dialkylbenzenesulfonates such as diisopropylbenzenesulfonic acid, ethylmethylbenzenesulfonic acid, alkylbenzenesulfonic acids with an alkyl chain length of 3 to 10 (preferably 4 to 9), alkanes Salts of linear or branched chain alkyl sulfonic acids having a base chain of 1 to 18 carbons.

其中l、m和n均为0至约20的数，l+m+n=约2至约60、优选约10至约45,R代表H、CH₃或C₂H₅。3. Solvent-borne hydrotropes such as alkoxylated glycerols and alkoxylated glycerol esters, alkoxylated glycerol esters, alkoxylated fatty acids, glycerol esters, polyglycerol esters. Preferred alkoxylated glycerols have the following structures:

Where l, m and n are all numbers from 0 to about 20, l+m+n=about 2 to about 60, preferably about 10 to about 45, and R represents H, CH ₃ or C ₂ H ₅ .

其中R₁和R₂均为C_nCOO或-(CH₂CHR₃-O)₁-H，其中R₃=H、CH₃或C₂H₅,l为1至约60的数，n为约6至约24的数。Preferred alkoxylated glycerides have the following structures:

Wherein R ₁ and R ₂ are both C _n COO or -(CH ₂ CHR ₃ -O) ₁ -H, wherein R ₃ =H, CH ₃ or C ₂ H ₅ , l is a number from 1 to about 60, and n is A number from about 6 to about 24.

其中E为亲水性官能团，R为H或C₁-C₁₀烷基或者为亲水性官能团；R₁为H、低级烷基或芳基，R₂为H、环烷基或芳基。4. Polymeric hydrotropes such as those disclosed in EP636687:

Wherein E is a hydrophilic functional group, R is H or C ₁ -C ₁₀ alkyl or a hydrophilic functional group; R ₁ is H, lower alkyl or aryl, R ₂ is H, cycloalkyl or aryl.

The molecular weight of the polymer is typically between about 1,000 and 1,000,000.

5. Hydrotropes with unusual structures such as 5-carboxy-4-hexyl-2-cyclohexen-1-yloctanoic acid (Diacid®).

The use of such compounds in the present invention further increases the dissolution rate of the tablet, since the hydrotrope compound facilitates the dissolution of, for example, surfactants. Such compounds are formed as mixtures or as single compounds.

coating

The robustness of the tablets of the invention can be further improved by making coated tablets which cover the uncoated tablets of the invention, thereby further improving the mechanical properties of the tablets while maintaining or further improving dissolution.

In one embodiment of the invention, the tablet may be coated so that it does not absorb moisture or absorbs moisture only at a very slow rate. The coating is also so robust that moderate mechanical shocks to which the tablets are subjected during handling, packaging and shipping result in very low levels of breakage or abrasion. Finally, the coating is preferably brittle so that the tablet will break when subjected to strong mechanical shock. Furthermore, it would be advantageous if the coating material was soluble under alkaline conditions or easily emulsified by surfactants. This helps to avoid the problem of visible residue in the window of a front loading washing machine during the wash cycle and also avoids undissolved particles or clumps of coating material being deposited on the washing machine charge.

Water solubility is measured by ASTM E1148-87 test protocol entitled "Standard Test Method for Measuring Water Solubility".

Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecane Diacids, tridecanedioic acid and mixtures thereof.

The melting point of the coating material is preferably from 40°C to 200°C.

The coating can be applied in various 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 at a temperature above its melting point and then cured on the tablet. In b), the coating is applied in solution and then the solvent is dried to leave an adherent coating. A substantially insoluble material can be applied to the tablets by, for example, spraying or dipping. Typically the molten material, when sprayed onto the tablet, solidifies rapidly to form a cohesive coating. When the tablet is immersed in the molten material and then removed, the rapid cooling allows the coating material to solidify rapidly. It is clear that substantially insoluble materials with melting points below 40°C do not solidify adequately at ambient temperatures, and materials with melting points above about 200°C have been found to be impractical. Preferably, the material melts in the range of 60°C to 160°C, more preferably 70°C to 120°C.

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

Coatings of any desired thickness can be applied in accordance with the present invention. In most cases, the coating comprises 1 to 10%, preferably 1.5 to 5%, by weight of the tablet.

The tablet coating of the present invention is very hard and provides additional strength to the tablet.

In a preferred embodiment of the invention, the breakage of the coating during washing is improved by adding a disintegrant to said coating. This disintegrant swells upon contact with water and breaks the coating into small pieces. This will improve the solubility of the coating in the wash liquor. The disintegrant is suspended in the coating melt at a content of up to 30%, preferably between 5 and 20%, most preferably between 5 and 10% by weight. Possible disintegrants are described in the "Handbook of Pharmaceutical Excipients" (1986). Examples of suitable disintegrants include starches: native, modified or pregelatinized starches, sodium starch gluconate; gums: agar gum, guar gum, locust bean gum, karaya gum, pectin , tragacanth gum; croscarmylose Sodium, polyvinylpolypyrrolidone, cellulose, carboxymethylcellulose, alginic acid and its salts including sodium alginate, silicon dioxide, clay, polyvinylpyrrolidone, soybean polysaccharide, ion exchange resin and its mixture.

tensile strength

Depending on the composition of the starting material and the shape of the tablet, the pressure used can be adjusted so as not to affect the tensile strength and disintegration time in the washing machine. This method can be used to prepare uniform or layered tablets of any size or shape.

For cylindrical tablets, tensile strength corresponds to the radial fracture stress (DFS), which is a way of expressing tablet strength, and is determined by: $=\frac{2f}{\mathrm{\μDt}}$

Wherein F is the maximum force (Newton) that causes breaking (breaking) measured by the VK 200 tablet hardness tester provided by Van Kell Industries, Inc., D is the diameter of the tablet, and t is the thickness of the tablet.

(Methods of Pharmaceutical Formulation: Tablets Vol. 2, pp. 213-217).

Tablets with a radial breaking stress below 20 kPa are considered friable, possibly resulting in some broken tablets being delivered to the user. Preferably the radial fracture stress is at least 25 kPa.

The same applies to non-cylindrical tablets to determine tensile strength, the cross-section perpendicular to the height of the tablet is not circular, the force is applied in a direction perpendicular to the direction of the height of the tablet and perpendicular to the sides of the tablet which perpendicular to the non-circular cross-section.

Dosing of tablets

The dispensing rate of the tablet detergent can be determined as follows:

Weigh two tablets, nominally 50g each, and place in the hopper of a Baucknecht® WA9850 washing machine. The water supply to the washing machine was set at a temperature of 20°C and a hardness of 21 grains per gallon. The feeder water inlet flow was set at 8 l/min. Turn on the washing machine and set the wash cycle to wash program 4 (white/coloured, short cycle) and check for the amount of tablet residue left in the hopper. The residual percentage of the feedstock was determined as follows:

% Feeding = Residue Weight x 100/Original Tablet Weight

The steps are repeated 10 times to determine the residual amount, and the average residual amount is calculated based on the measurement results of the ten times. A residue of 40% of the starting tablet weight was considered acceptable in this test. Preferably the residual level is below 30%, more preferably below 25%.

It should be noted that water hardness measurements are given in traditional "grains/gallon" units, 0.001 mol/l = 7.0 grains/gallon, which represents the concentration of Ca2 ⁺ ions in solution.

Foaming agent

In another preferred embodiment of the present invention, said tablet further comprises an effervescent agent.

Foaming as defined herein means the evolution of gas bubbles from a liquid as a result of the chemical reaction between a soluble acid source and an alkali metal carbonate to produce carbon dioxide gas,

Right now

Examples of acid and carbonate sources and other effervescent systems can be found in: Pharmaceutical Dosage Forms: Tablets, Vol. 1, pp. 287-291.

In addition to detergent ingredients, effervescent agents may also be added to the tablet mix. Adding this foaming agent to tablet detergent can improve the disintegration time of the tablet. The amount is preferably between 5 and 20% by weight of the tablet, most preferably between 10 and 20%. The blowing agent is preferably added as an agglomerate of different particles or as compact rather than separated particles.

Due to gas generation by effervescence in the tablet, the tablet can have a higher D.F.S. and still have the same disintegration time as a non-effervescent tablet. The disintegration of the effervescent tablet will be faster while the D.F.S. of the effervescent tablet remains the same as that of the non-effervescent tablet.

Additional dissolution aids can be provided by using compounds such as sodium acetate or urea. A list of suitable dissolution aids can also be found in: Pharmaceutical Dosage Forms: Tablets, Volume 1, 2nd Edition, edited by H.A. Lieberman et al., ISBN 0-8247-8044-2.

detersive surfactant

A surfactant is included in the tablet of the present invention. The addition of the highly soluble compound facilitates the dissolution of the surfactant.

Non-limiting examples of surfactants typically used in the present invention at levels of from about 1 to about 55% by weight include conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS") and primary branched and non- C ₁₀ -C ₂₀ alkyl sulfate (“AS”); C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfate of the formula: CH ₃ (CH ₂ ) _x (CHOSO ₃ ⁻ M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^{−M +} )CH ₂ CH ₃ , wherein x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-soluble cation, especially sodium; Unsaturated sulfates such as oleyl sulfate; C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AExS"; especially EO1-7 ethoxy sulfates); C ₁₀ -C ₁₈ alkyl alkoxycarboxylates acid salts (especially EO1-5 ethoxy carboxylates); C ₁₀ -C ₁₈ glyceryl ethers; C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides; and C ₁₂ -C ₁₈ α- Sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including so-called narrow peak alkyl ethoxylates, may also be included in the overall composition. and C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ₁₂ -C ₁₈ betaines and sultaines, C ₁₀ -C ₁₈ Amine oxide etc. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides are also useful. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides. See WO 92/06154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can be used for low sudsing. Conventional _C10 - _C20 soaps may also be used. For high sudsing, branched C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly suitable. Other suitable conventional surfactants are listed in standard texts. In a preferred embodiment, the tablet comprises at least 5% by weight of surfactant, more preferably at least 15% by weight, even more preferably at least 25% by weight, most preferably between 35% and 45% by weight of surfactant.

non-gelling adhesive

A non-gelling binder can be combined with the granules to form tablets to further facilitate dissolution.

If a non-gelling binder is used, suitable non-gelling binders include synthetic organic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylates and water-soluble acrylate copolymers. The Handbook of Pharmaceutical Excipients (2nd Edition) has the following classifications of binders: Gum Arabic, Alginic Acid, Acrylic Polymers, Sodium Carboxymethylcellulose, Dextrin, Ethylcellulose, Gelatin, Guar Gum, Type I Hydrogenated Vegetable Oil, Hydroxyethylcellulose, Hydroxypropylmethylcellulose, Liquid Glucose, Magnesium Aluminum Silicate, Maltodextrin, Methylcellulose, Polymethacrylate, Povidone, Sodium Alginate, Starch and zein. Most preferred binders also have an active cleaning function in laundry washing such as cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary compounds, bis-hexamethylene triamine, or others such as pentaamine , Ethoxylated Polyvinylamine, Maleic Acrylic Polymer.

The non-gelling adhesive material is preferably sprayed on and thus has a suitable melting point below 90°C, preferably below 70°C, even more preferably below 50°C so as not to damage or weaken the other active ingredients in the matrix. Most preferred are anhydrous liquid binders that can be sprayed in the molten state (ie, not aqueous solutions). However, they can also be solid binders which are incorporated into the matrix by the dry process but are cohesive within the tablet.

The amount of non-gelling binder material is preferably within 0.1 to 15% of the composition, more preferably less than 5%, especially if it is not a laundry active material, preferably less than 2% by weight of the tablet.

Avoiding the use of gelling binders such as nonionic surfactants in liquid or molten form is preferred. Nonionic surfactants and other gelling binders are not excluded from the composition, but are preferably incorporated into the tablet as a component of the particulate material rather than in liquid form.

builder

Builders may optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric washing compositions to aid in the removal of particulate soils.

The level of builder can vary widely depending on the end use of the composition.

Inorganic or P-containing builders include, but are not limited to, the following alkali metal, ammonium, and alkanolammonium salts: polyphosphates (such as tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphate), phosphonic acid Salt, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. But in some places non-phosphate builders are required. Importantly, the compositions of the present invention unexpectedly occur even in the presence of so-called "weak" builders (compared to phosphates) such as citrates or when zeolite or layered silicate builders are used. Works well with "insufficient additives" ("low compounding").

Examples of silicate builders are alkali metal silicates, especially those with a _SiO2 / _Na2O ratio in the range of 1.6:1 to 3.2:1, and layered silicates such as US 4 664 839 (1987 Granted on May 12 to HP Rieck) described in layered sodium silicate. NaSKS-6 is a trademark for a crystalline layered silicate sold by Hoechst (often abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na ₂ SiO ₅ form of layered silicate. It can be prepared by the methods described in DE-A-3 417 649 and DE-A-3 742 043. SKS-6 is a very preferred phyllosilicate for use in the present invention, but other such phyllosilicates may also be used such as those of the general formula: _{NaMSixO2x +1} · _yH2O , where M is sodium or hydrogen, x is a number from 1.9 to 4 (preferably 2), and y is a number from 0 to 20 (preferably 0). Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, in the alpha, beta and gamma forms. As previously stated _, the most preferred for use in the present invention is delta- _Na2SiO5 (NaSKS-6 type). Other silicates can also be used, such as magnesium silicate, which can be used in granular formulations as embrittlement agents, as oxygen bleach stabilizers, and as a component of suds control systems.

Examples of carbonate builders are alkaline earth and alkali metal carbonates, as disclosed in German Patent Application DE-A-2 321 001, published November 15, 1973.

Aluminosilicate builders are suitable for use herein. Aluminosilicate builders are of importance in most heavy duty granular detergent compositions currently sold and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the following empirical formula:

M _z (zAlO ₂ ) _y ]·xH ₂ O

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

Suitable aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring aluminosilicates or synthetic. A method for the production of aluminosilicate ion exchange materials is disclosed in US 3 985 669 (Krummel et al. issued October 12, 1976). Synthetic crystalline aluminosilicate ion exchange materials preferred for use in the present invention are commercially available under the designations Zeolite A, Zeolite P(B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

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

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

Organic detergency builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" means a compound having a plurality of carboxylate groups, preferably at least three carboxylate groups. Polycarboxylate builders can generally be incorporated into the compositions in acid form, but can also be incorporated in neutralized salt form. When used in salt form, alkali metal salts such as sodium, potassium and lithium salts or alkanolammonium salts are preferred.

Included in the polycarboxylate-type builders are all suitable materials. An important class of polycarboxylate builders includes ether polycarboxylates, including oxydisuccinates such as US3 128287 (issued to Berg on April 7, 1964) and US3 635 830 (issued to 18 to Lamberti et al). See also the "TMS/TDS" builders of US 4 663 071 (Bush et al., issued May 5, 1987). Suitable ether polycarboxylates also include cyclic compounds, especially cycloaliphatic compounds, such as those described in US Pat.

Other suitable builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; and polycarboxylic acids such as mellitic acid, succinic acid, oxygen Disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and their soluble salts.

Citrate builders such as citric acid and its soluble salts (especially the sodium salt) are important polycarboxylate builders for heavy duty liquid detergents due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly suitable for use in this composition and combination.

Also suitable for use in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US 4 566 984 (Bush 28 January 1986) . Suitable succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. 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-pentadecanyl succinate alkenyl succinate, etc. Lauryl succinate is a preferred builder of this group and is described in European Patent Application 86200690.5/0 200 263 (published November 5, 1986).

Other suitable polycarboxylates are disclosed in US 4 144 226 (Crutchfield et al., March 13, 1979) and US 3 308 067 (Diehl, March 7, 1967). See also US 3 723 322 (Diehl).

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

Where phosphorus-based builders can be used, particularly in soap bar formulations for hand laundry operations, the various alkali metal phosphates such as the well known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see e.g. US 3 159 581; 3 213 030; 3 422 021; 3 400148 and 3 422 137).

bleach

The detergent compositions of the present invention may optionally comprise a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. Bleaching agents, when present, are typically used at levels of from about 1 to about 30%, more typically from about 5 to about 20%, of the detergent compositions, especially for laundering fabrics. Bleach activators, if present, are typically present in amounts of from about 0.1 to about 60%, more typically from about 0.5 to about 40%, of the bleaching composition comprising said bleach plus bleach activator.

The bleaching agent used in the present invention can be any bleaching agent which is or will be known to be suitable for use in fabric cleaning, hard surface cleaning or other cleaning detergent compositions. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches such as sodium perborate (eg, mono or tetrahydrate) are useful herein.

Another class of bleaches which may be used without limitation includes percarboxylic acid bleaches and their salts. Examples of suitable bleaching agents of this type include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of mesochloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecane di acid. Such bleaches are disclosed in US4 483 781 (issued to Hartman on November 20, 1984), USSN 740446 (applied on June 3, 1985 by Burns et al), EP-A-0 133 354 (Banks et al, issued on February 20, 1985) Publication) and US4 412 934 (issued to Chung et al. on November 1, 1983). Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US 4634 551 (Burns et al., issued January 6, 1987).

Peroxygen bleach can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleaches (eg, OXONE, commercially available from DuPont) may also be used.

Preferred percarbonate bleaches include dry particles having an average particle size in the range of about 500 microns to about 1000 microns, with no more than about 10% by weight of said particles smaller than about 200 microns and no more than about 10% by weight greater than about 1250 microns. Optionally, the percarbonate may be coated with a silicate, borate or water soluble surfactant. Percarbonate is commercially available from many sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaches can also be used.

Peroxygen bleaches (perborates, percarbonates, etc.) are preferably combined with a bleach activator, which results in the generation in situ (ie during the wash) of an aqueous peroxyacid solution corresponding to said bleach activator. Various non-limiting examples of activators are disclosed in US 4 915 854 (Mao et al., issued April 10, 1990) and US 4 412 934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. See also US 4 634 551 for other typical bleaches and activators suitable for use in the present invention.

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

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

wherein ^R is an alkyl group containing about 6 to about ¹² carbon atoms, R is an alkylene group containing 1 to about 6 carbon atoms, and R is H or ^an alkyl group containing about 1 to about 10 carbon atoms , aryl, or alkaryl, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator by nucleophilic attack of the perhydrolyzed anion on the bleach activator. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include (6-octanoylamino-caproyl)oxybenzenesulfonate, (6-nonanoylamino-caproyl)oxybenzenesulfonate, (6-decanoylamino- -hexanoyl)oxybenzenesulfonate, and mixtures thereof, as described in US 4 634 551, which is incorporated herein by reference.

Another class of bleach activators includes the benzoxazine-type activators disclosed in Hodge et al., US 4,966,723 (October 30, 1990), incorporated herein by reference. Highly preferred benzoxazine-type activators are:

Another preferred class of bleach activators includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula: wherein R is H or ^{an alkyl} , aryl, alkoxyaryl, or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecyl caprolactam, benzoyl valerolactam , capryl valerolactam, decanoyl valerolactam, undecyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also US 4 545 784, issued 8 October 1985 to Sanderson, incorporated herein by reference, which discloses that acyl caprolactams adsorbed to sodium perborate include benzoyl caprolactam.

Bleaching agents other than oxygen bleaching agents are also known in the art and find use in the present invention. One class of non-oxygen bleaches of particular interest includes photosensitive bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718 (issued July 5, 1977 to Holcombe et al.). Detergent compositions, if used, will typically contain from about 0.025 to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanine.

The bleaching compounds can be catalyzed with manganese compounds if desired. Such compounds are well known in the art and include, for example, manganese-based catalysts as disclosed in US 5 246 621 ; US 5 244 594 ; US 5 194 416 ; US 5 114 606 ; Preferred examples of these catalysts include: Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ 、Mn ^Ⅳ ₄ (uO) ₆ (1,4 ,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^Ⅲ Mn ^Ⅳ ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^Ⅳ (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ), and its mixture. Other metal based bleach catalysts include those disclosed in US4430243 and US5114611. The use of manganese with various ligands to enhance bleaching is also reported in the following US patents: 4 728 455; 5 284 944; 5 246 612; 5 256 779; 5 280 117; 5 227 084.

Indeed and without limitation, the compositions and methods of the present invention can be adjusted to have about at least 0.1 ppm of said active bleach catalyst in the aqueous wash liquor, preferably about 0.1 to about 700 ppm, more preferably about 1 to about 500 ppm in the laundry liquor the catalyst.

enzyme

Enzymes may be included in the formulations of the present invention for a variety of fabric laundering uses including, for example, the removal of protein-based, carbohydrate-based, or triglyceride-based stains and for the prevention of refugee dye transfer and for fabric restoration. Enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice depends on several factors such as pH-activity and/or stability optima, thermostability, stability relative to active detergents, builders, etc. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, fungal cellulases.

Enzymes are generally incorporated in amounts sufficient to provide up to about 5 mg, more preferably about 0.01 to about 3 mg, of active enzyme per gram of composition. In other words, the compositions of the present invention typically comprise from about 0.001 to about 5%, preferably from 0.01 to 1%, by weight of an industrial enzyme preparation. The protease is usually present in such commercial formulations in an amount sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

Examples of suitable proteases are subtilisins, from specific strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is derived from a strain of Bacillus, having maximum activity in the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trademark ESPERASE. The preparation of this and similar enzymes is described in GB1 243784 (Novo). Commercially available proteases suitable for the removal of protein-based stains include those sold under the trademarks ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Biosynthesis Ltd (Netherlands). Other proteases include Protease A (see EP130 756, published January 9, 1985) and Protease B (see EPSN 87303761.8, filed April 28, 1987 and EP130 756, published January 9, 1985).

Amylases include, for example, alpha-amylases described in GB1 296 839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

Cellulases suitable for use in the present invention include bacterial or fungal cellulases. Preferably, they have an optimum pH between 5 and 9.5. Suitable cellulases are disclosed in US 4 435 307 (issued to Barbesgoard et al. on March 6, 1984) which discloses fungal cellulases produced by Humicolainsolens and Humicola strain DSM1800 or belonging to the genus Aeromonas Cellulase 212 produced by fungi, and cellulase extracted from the hepatopancreas of marine molluscs (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-2247 832. CAREZYME (Novo) is particularly suitable.

Lipases suitable for use in detergents include those produced by microorganisms of the Pseudomonas class, such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB1 372 034. See also lipases in JP-A-53-20487, published February 24, 1978. The lipase was purchased from Amano Pharmaceutical Co., Ltd., Nagoya, Japan under the trade name Lipase P "Amano" (hereinafter referred to as "Amano-P"). Other commercially available lipases include: Amano-CES available from Toyo Jozo Co., Tagata, Japan, lipases from Chromobacter viscosum, such as lipolyticum NRRLB3673 mutated by Chromobacter viscosum; and from American Biochemical Corporation, USA and Disoynth, Netherlands Other Chromobacterium viscosus lipase, and lipase from Pseudomonas gladioli. The LIPOLASE enzyme from Novo (see EPO 341 947) derived from Humicola lanuginosa is a preferred lipase for use in the present invention.

Peroxidases are used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", ie preventing the transfer of dyes or pigments removed from a substrate during washing operations to other substrates in the wash liquor. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidases. Detergent compositions comprising peroxidases are disclosed, for example, in WO 89/099813 (published October 19, 1989, O. Kirk, assigned to Novo Industries A/S).

A number of enzymes and their incorporation into synthetic detergent compositions are also disclosed in US 3 553 139 (issued to McCarty et al. on January 5, 1971). Enzymes are also disclosed in US 4 101 457 (July 18, 1978 to Place et al) and US 4 507 219 (March 26, 1985 to Hughes). Enzymes suitable for use in liquid detergent formulations and methods of their incorporation are disclosed in US4 261 868 (issued to Hora et al. on April 14, 1981). Enzymes for use in detergents can be stabilized by a number of techniques. Enzyme stabilization techniques are disclosed, for example, in US3 600 319 (issued to Gedge et al. on August 17, 1971) and EP-A-199 405 (application number 86200586.5, published on October 29, 1986, Venegas). Enzyme stabilization systems are also described, for example, in US 3 519 570. middle.

Other ingredients commonly used in detergent compositions and which may be incorporated into the tablets of the present invention include sequestrants, soil release agents, soil antiredeposition agents, dispersants, brighteners, suds suppressors, fabric softeners , Dye Transfer Inhibitors and Fragrance.

cleaning method

Conventional laundry detergent tablets are known to be placed in the drum with the laundry. However, this method tends to make unsightly residue visible in the window, especially in some washing machines designed to operate with low water consumption. In extreme cases, visible residue may remain on the laundry at the end of the wash cycle due to incomplete dissolution.

The invention also relates to a washing method which significantly avoids this problem. The new method involves the preparation of an aqueous laundry detergent solution for use in washing machines, wherein the aqueous laundry detergent solution is formed by dissolving in water a tablet formed of compressed granular material, the tablet comprising a surfactant and a highly soluble Compound, said highly soluble compound has a binding effect on said particulate material.

In a preferred embodiment of the present invention, the method relates more particularly to the preparation of an aqueous laundry detergent solution for a front-loading washing machine having a feed drawer and a washing tub, wherein the laundry detergent An aqueous solution of detergent is formed by dissolving a tablet in water, characterized in that the tablet is placed in the feed drawer and water is passed through the feed drawer so that the tablet becomes laundry detergent Feed in the form of an aqueous solution, which is then passed into the tub.

Example

The composition of the basic granular material: Composition A (%wt) Anionic Agglomerates 1 21.45 Anionic Agglomerates 2 13.00 cationic agglomerates 5.45 layered silicate 10.8 sodium percarbonate 14.19 Bleach Activator Agglomerates 5.49 Sodium carbonate 13.82 EDDS/Sulphate Granules 0.47 Tetrasodium salt of hydroxyethanediphosphonic acid 0.73 dirt release polymer 0.33 fluorescent agent 0.18 Zinc Phthalocyanine Sulfonate Capsules 0.025 soap powder 1.40 Foam suppressor 1.87 citric acid 7.10 protease 0.79 Lipase 0.28 cellulase 0.22 Amylase 1.08 adhesive spray system 1.325 total 100.00

Anionic agglomerate 1 consisted of 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerate 2 consisted of 40% anionic surfactant, 28% zeolite and 32% carbonate.

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

Phyllosilicate is composed of 95% SKS 6 and 5% silicate.

Bleach activator agglomerates consisted of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

Ethylenediamine N,N-disuccinate sodium salt/sulfate granules consisted of 58% ethylenediamine N,N-disuccinate sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor consisted of 11.5% silicone oil (from Dow Corning), 59% zeolite and 29.5% water.

The adhesive spray system consisted of 50% Lutensit K-HD96 and 50% PEG (polyvinyl alcohol).

Example 1 (comprising a highly soluble compound that has a binding effect on the particulate material)

i) A detergent base powder of Composition A (see table above) was prepared by mixing all the particulate materials of Base Composition A together in a mixing drum to form a homogeneous particulate mixture. The spraying takes place during this mixing.

ii) 97 parts of composition A base powder were mixed with 3 parts sodium diisoalkylbenzene sulfonate (a highly soluble compound that binds the particulate material) in a mixing bowl.

iii) Tablets were made in the following manner: 50 g of the mixture was added into a circular mold with a diameter of 5.5 cm, and compressed into a tablet with a tensile strength (or radial breaking stress) of 15 kPa. The force required to obtain a tablet with a tensile strength of 15 kPa is 2400N. The height of the tablet is 1.94 cm.

iv) Assess residue in washing machine hopper by "tablet dosing test": Two laundry tablets are placed in a Baucknecht WA9850 hopper. The water supply to the washing machine was set at a temperature of 20°C and a hardness of 21 grains per gallon. The feeder water inlet flow was set at 8 l/min. Turn on the washing machine and set the wash cycle to wash program 4 (white/coloured, short cycle) and check for the amount of tablet residue left in the hopper. The residual percentage of the feedstock was determined as follows:

% Feeding = [(residue weight)×100]/(original tablet weight)

The % feedstock is shown in the table "Feedstock Residue".

Embodiment 2 (highly soluble compound)

i) The same composition A was prepared in the same manner as in Example 1.

ii) Mix 97 parts of base powder of composition A with 3 parts of sodium toluenesulfonate (highly soluble compound) in a mixing bowl.

iii) Tablets were then prepared in the same manner as in Example 1. The force required to obtain a tablet with a tensile strength of 15 kPa is 3100N. The height of the tablet is 1.88 cm.

iv) The residual amount in the hopper of the washing machine was evaluated in the same manner as in Example 1. The % feedstock is shown in the table "Feedstock Residue".

Embodiment 3 (highly soluble compound)

i) The same composition A was prepared in the same manner as in Example 1.

ii) 97 parts composition A base powder was mixed with 3 parts sorbitol (highly soluble compound) in a mixing bowl.

iii) Tablets were then prepared in the same manner as in Example 1. The force required to obtain a tablet with a tensile strength of 15 kPa is 3500N. The height of the tablet is 1.83 cm.

iv) The residual amount in the hopper of the washing machine was evaluated in the same manner as in Example 1. The % feed is shown in Table 3.

Example 4 (compounds that have a binding effect on the particulate material)

i) The same composition A was prepared in the same manner as in Example 1.

ii) 97 parts of base powder of Composition A were mixed with 3 parts of sodium dodecylbenzene sulfonate (the compound that has a binding effect on the particulate material) in a mixing bowl.

iii) Tablets were then prepared in the same manner as in Example 1. The force required to obtain a tablet with a tensile strength of 15 kPa is 2600N. The height of the tablet is 1.95 cm.

iv) The residual amount in the hopper of the washing machine was evaluated in the same manner as in Example 1. The % feed is shown in Table 3.

Embodiment 5 (basic particulate material composition)

i) The same composition A was prepared in the same manner as in Example 1.

ii) Tablets were then formed in the same manner as in Example 1. The force required to obtain a tablet with a tensile strength of 15 kPa is 3200N. The height of the tablet is 1.82 cm.

iii) The residual amount in the hopper of the washing machine was evaluated in the same manner as in Example 1. The % feed is shown in Table 3.

result:

Feed residual table: Example 1 2 3 4 5 pressure (N) 2400 3100 3500 2600 3200 Tablet height (cm) 1.94 1.88 1.83 1.95 1.82 Feeding residue (%) 24.2 98.8 71.5 68.8 100

Table of conductivity of compounds added to composition A to obtain tablets of examples 1 to 4: Examples of compounds 1 2 3 4 Conductivity achieved within 10 seconds (%) 95 100 100 64

Composition of other basic granular materials: Composition B (%wt) Anionic Agglomerates 1 21.45 Anionic Agglomerates 2 13.00 cationic agglomerates 5.45 layered silicate 10.8 sodium percarbonate 14.19 Bleach Activator Agglomerates 5.49 Sodium carbonate 12.645 EDDS/Sulphate Granules 0.47 Tetrasodium salt of hydroxyethanediphosphonic acid 0.73 soil release polymer 0.33 fluorescent agent 0.18 Zinc Phthalocyanine Sulfonate Capsules 0.025 soap powder 1.40 Foam suppressor 1.87 citric acid 7.10 protease 0.79 Lipase 0.28 cellulase 0.22 Amylase 1.08 adhesive spray system 2.5 total 100.00

Anionic agglomerate 1 consisted of 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerate 2 consisted of 40% anionic surfactant, 28% zeolite and 32% carbonate.

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

Phyllosilicate is composed of 95% SKS 6 and 5% silicate.

Bleach activator agglomerates consisted of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

Ethylenediamine N,N-disuccinate sodium salt/sulfate granules consisted of 58% ethylenediamine N,N-disuccinate sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor consisted of 11.5% silicone oil (from Dow Corning), 59% zeolite and 29.5% water.

The adhesive spray system consists of 50% Lutensit K-HD 96 and 50% PEG (polyethylene glycol).

Embodiment 6 (basic granular material composition)

i) Composition B was prepared in the same manner as in Example 1.

ii) Tablets were then formed in the same manner as in Example 1. The applied force is 2000N. The tensile strength of the tablet was 10.9 kPa.

Example 7 (PEG)

i) The same composition B was prepared in the same manner as in Example 1.

ii) Mix 97 parts composition B base powder with 3 parts PEG (binding compound) in a mixing bowl.

iii) Tablets were then prepared in the same manner as in Example 1. The applied force is 2000N. The tensile strength of the tablet was 12.8 kPa.

Embodiment 8 (sodium diisoalkylbenzenesulfonate)

i) The same composition B was prepared in the same manner as in Example 1.

ii) Mix 97 parts of composition B base powder with 3 parts sodium diisoalkylbenzene sulfonate in a mixing bowl.

iii) Tablets were then prepared in the same manner as in Example 1. The applied force is 2000N. The tensile strength of the tablet was 17.8 kPa.

Embodiment 9 (tablet of the present invention)

i) A detergent base powder of Composition C is prepared by mixing all the particulate materials of Base Composition C together in a mixing bowl to form a homogeneous particulate mixture. The spraying takes place during this mixing. After spraying, sodium diisoalkylbenzenesulfonate (=DIBS) was added to the rest of the matrix.

ii) Tablets were then made in the following manner: 43 g of the mixture was added to a circular die with a diameter of 5.5 cm and compressed into a tablet with a tensile strength (or radial breaking stress) of 15 kPa.

iii) The 43 g tablet has a dosing residual percentage of less than 15%. Composition C (%) Anionic Agglomerates 1 9.1 Anionic Agglomerates 2 22.5 nonionic agglomerates 9.1 cationic agglomerates 4.6 layered silicate 9.7 sodium percarbonate 12.2 Bleach Activator Agglomerates 6.1 Sodium carbonate 7.27 EDDS/Sulphate Granules 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 soil release polymer 0.3 fluorescent agent 0.2 Zinc Phthalocyanine Sulfonate Capsules 0.03 soap powder 1.2 Foam suppressor 2.8 citric acid 5.5 protease 1 Lipase 0.35 cellulase 0.2 Amylase 1.1 adhesive spray system 3.05 spice spray 0.5 DIBS 2.1

Anionic agglomerate 1 consisted of 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerate 2 consisted of 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerates consisted of 26% nonionic surfactant, 6% Lutensit K-HD 96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite.

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

Phyllosilicate is composed of 95% SKS 6 and 5% silicate.

Bleach activator agglomerates consisted of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

Ethylenediamine N,N-disuccinate sodium salt/sulfate granules consisted of 58% ethylenediamine N,N-disuccinate sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor consisted of 11.5% silicone oil (from Dow Corning), 59% zeolite and 29.5% water.

The binder spray system consisted of 0.5 parts of Lutensit K-HD96 and 2.5 parts of PEGs.

The following tests were also performed to test the solubility of the uncompressed granular material with and without the highly soluble compound i.e. DIBS:

A detergent of composition D was prepared by mixing together in a mixing drum all particulate materials except the dry zeolite to form a homogeneous particulate mixture. The spraying takes place during this mixing. After spraying, the dry zeolite is used for dusting.

Table 1: Detergent Base Powder Composition Composition D (%) Anionic Agglomerates 1 32 cationic agglomerates 5 layered silicate 11.5 sodium percarbonate 16.2 Bleach Activator Agglomerates 4.7 Sodium carbonate 3.76 sodium bicarbonate 2.0 sodium sulfate 2.4 EDDS/Sulphate Granules 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.8 soil release polymer 0.3 fluorescent agent 0.1 Zinc Phthalocyanine Sulfonate Capsules 0.02 Foam suppressor 2.1 citric acid 2 protease 0.7 Lipase 0.2 cellulase 0.2 Amylase 0.6 Spice Capsules 0.2 polymer particles 3 spice spray 0.35 non-ionic spray system 5.17 Zeolite 6.2

Anionic agglomerate 1 consisted of 40% anionic surfactant, 27% zeolite and 33% carbonate.

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

Phyllosilicate is composed of 95% SKS 6 and 5% silicate.

Bleach activator agglomerates consisted of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

Ethylenediamine N,N-disuccinate sodium salt/sulfate granules consisted of 58% ethylenediamine N,N-disuccinate sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The foam suppressor consisted of 11.5% silicone oil (ex Dow Corning), 59% zeolite and 29.5% water.

Spice capsules contain 50% flavor and 50% starch.

The polymer particles consisted of 36% polymer, 54% zeolite and 10% water.

The non-ionic spray system consists of 67% C12-C15 AE5 (alcohol with an average of 5 ethoxy groups per molecule), 24% N-methylglucamide and 9% water.

150 g of this granular detergent of composition D are added to the feed drawer of a "Hotpoint" washing machine. The water supply of the washing machine is set at a temperature of 20°C, a hardness of 21 grains/gallon., and a flow rate of 2 l/min. After 2 minutes, 38 g of Detergent Composition D remained undissolved in the dispenser drawer.

145g of this composition D granular detergent was mixed with 5g of DIBS. Add this granulated mixture to the feed drawer of your "Hotpoint" washing machine. The water supply of the washing machine is set to a temperature of 20° C., a hardness of 21 grains per gallon, and a flow rate of 2 liters per minute. After 2 minutes, 30 g of detergent composition D remained undissolved in the feeder drawer.

In a more preferred embodiment according to the following practice, it has been found that the addition of a highly soluble compound, preferably a hydrotrope compound, and a mixture of at least two polymers to the particulate material further facilitates dissolution, in particular This synergistic effect is favored when using polymers such as PEG (polyethylene glycol), especially mixtures of PEG's with molecular weights between 200 and 9000, preferably PEG's with molecular weights between 1000 and 4000. Such PEG's are described e.g. in EP-A-0 522 766. Other polymers include cationic polymers such as Lutensit KHD96. The stated molecular weights are average molecular weights for a given molecular weight distribution.

Embodiment A (formulation that is used for National Wave 1 modification)

i) A detergent base powder of composition E (see table below) was prepared by mixing all the particulate materials of base composition E together in a mixing drum to form a homogeneous mixture of granules. The spraying takes place during this mixing. After spraying, sodium diisoalkylbenzene sulfonate (a viscous hydrotrope) was added to the rest of the matrix.

ii) Tablets were then made in the following manner: 43 g of the mixture was added to a circular die with a diameter of 5.5 cm and compressed into a tablet with a tensile strength (or radial breaking stress) of 15 kPa.

iii) The tablets are then immersed in a bath containing 80 parts of sebacic acid and 20 parts of Nymcelzsb16 at 140°C. The immersion time of the tablets in the hot bath was adjusted so that they were coated with 3 g of the mixture. The tablets were then cooled for 24 hours at room temperature of 25°C.

iv) Assess residue in washing machine hopper by "stress tablet dosing test": Two laundry tablets are placed in a Baucknecht WA9850 hopper. The water supply to the washing machine was set at a temperature of 8°C and a hardness of 21 grains per gallon. The feeder water inlet flow was set at 4 l/min. Run water through the hopper for 78 seconds and check for tablet residue left in the hopper. The residual percentage of the feedstock was determined as follows:

% Feeding Residue = [(Residue Weight)×100]/(Original Tablet Weight)

The % feed is shown in the table below.

Example B

The tableting procedure of Example A was repeated for the powder of Composition F. The polymer sprayed on the substrate contained 0.67 parts PEG4000 and 0.33 parts PEG1000.

Using a mixture of two PEG polymers resulted in better formulation results than using one PEG.

Detergent base powder compositions E and F Example A (%) Example B (%) Anionic Agglomerates 1 9.1 9.1 Anionic Agglomerates 2 22.5 22.5 nonionic agglomerates 9.1 9.1 cationic agglomerates 4.6 4.6 layered silicate 9.7 9.7 sodium percarbonate 12.2 12.2 Bleach Activator Agglomerates 6.1 6.1 Sodium carbonate 8.42 8.42 EDDS/Sulphate Granules 0.5 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 0.6 soil release polymer 0.3 0.3 fluorescent agent 0.2 0.2 Zinc Phthalocyanine Sulfonate Capsules 0.03 0.03 soap powder 1.2 1.2 Foam suppressor 2.8 2.8 citric acid 5.5 5.5 protease 1 1 Lipase 0.35 0.35 cellulase 0.2 0.2 Amylase 1.1 1.1 adhesive spray system PEG4000 1 0.67 PEG1000 0.33 spice spray 0.5 0.5 DIBS 3 3 Tablet Stress Feed (%) 14 6 Tablet tensile strength obtained by applying a pressure of 2000N (kPa) 15.6 16.6

Anionic agglomerate 1 consisted of 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerate 2 consisted of 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerates consisted of 26% nonionic surfactant, 6% Lutensit K-HD96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite.

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

Phyllosilicate is composed of 95% SKS 6 and 5% silicate.

Bleach activator agglomerates consisted of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

Ethylenediamine N,N-disuccinate sodium salt/sulfate granules consisted of 58% ethylenediamine N,N-disuccinate sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor consisted of 11.5% silicone oil (from Dow Corning), 59% zeolite and 29.5% water.

The binder spray system consisted of 0.5 parts of Lutensit K-HD96 and 2.5 parts of PEGs.

Examples C-D

The tableting procedure of Example A was repeated for powders of compositions G-H. The tensile strength of the tablet before coating the sebacic acid and Nymcel mixture was 12 kPa.

Using a mixture of three polymers resulted in better compounding results than using two polymers.

Detergent base powder compositions G and H Example C (%) Example D (%) Anionic Agglomerates 1 9.1 9.1 Anionic Agglomerates 2 22.5 22.5 nonionic agglomerates 9.1 9.1 cationic agglomerates 4.6 4.6 layered silicate 9.7 9.7 sodium percarbonate 12.2 12.2 Bleach Activator Agglomerates 6.1 6.1 Sodium carbonate 8.32 8.32 EDDS/Sulphate Granules 0.5 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 0.6 soil release polymer 0.3 0.3 fluorescent agent 0.2 0.2 Zinc Phthalocyanine Sulfonate Capsules 0.03 0.03 soap powder 1.2 1.2 Foam suppressor 2.8 2.8 citric acid 5.5 5.5 protease 1 1 Lipase 0.35 0.35 cellulase 0.2 0.2 Amylase 1.1 1.1 adhesive spray system Lutensit KHD 96 0.3 0.4 PEG4000 1.7 0.75 PEG1000 0.85 spice spray 0.5 0.5 DIBS 2.1 2.1 Tablet Stress Feed (%) 53 9

Anionic agglomerate 1 consisted of 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerate 2 consisted of 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerates consisted of 26% nonionic surfactant, 6% Lutensit K-HD96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite.

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

Phyllosilicate is composed of 95% SKS 6 and 5% silicate.

Bleach activator agglomerates consisted of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.

Ethylenediamine N,N-disuccinate sodium salt/sulfate granules consisted of 58% ethylenediamine N,N-disuccinate sodium salt, 23% sulfate and 19% water.

Zinc phthalocyanine sulfonate capsules are 10% active.

The suds suppressor consisted of 11.5% silicone oil (from Dow Corning), 59% zeolite and 29.5% water.

The binder spray system consisted of 0.5 parts of Lutensit K-HD96 and 2.5 parts of PEGs.

Claims (11)

1. A tablet formed by compressing a particulate material, the particulate material comprising a surfactant and a highly soluble compound, the highly soluble compound having a binding effect on the particulate material.

2. A tablet according to claim 1, wherein at least 1% by weight of the tablet is formed from the highly soluble compound, preferably at least 2% by weight.

3. The tablet of claim 1, wherein the highly soluble compound comprises sodium diisoalkylbenzene sulfonate.

4. The tablet according to claim 1, wherein the tensile strength of the tablet is greater than 5kPa, and preferably less than 300 kPa.

5. The tablet according to claim 1, wherein the tablet is compressed with a force of less than 100000N.

6. The tablet of claim 1, wherein the tablet comprises at least 5% by weight of a surfactant.

7. The tablet of claim 1, wherein the highly soluble compound is a hydrotrope compound.

8. A coated tablet, wherein the non-coated tablet is a tablet according to any one of the preceding claims.

9. A tablet according to any one of the preceding claims wherein the particulate material comprises a mixture of at least two polymers.

10. A process for the preparation of an aqueous laundry detergent solution for use in a washing machine, wherein the aqueous laundry detergent solution is formed by dissolving in water tablets formed by compressing a particulate material, the tablets comprising a surfactant and a highly soluble compound, the highly soluble compound having a binding effect on the particulate material.

11. The process of claim 10, wherein the tablet has a density of at least 0.9g/cc, preferably less than 2 g/cc.