CZ20004657A3 - Tablet made by moulding particulate material and process for preparing thereof - 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

Technical field

The present invention relates to detergent tablets, especially those intended for washing.

BACKGROUND OF THE INVENTION

Although detergent compositions in the form of tablets have often been proposed, they have not gained (with the exception of soaps for personal washing), except for several successful products in the form of dispensing units, any substantial success. One reason may be that detergent tablets usually dissolve more slowly than the powder from which they are made, since the powder is strongly compressed in the tablets, and has relatively little chance for water to penetrate between its particles. This creates the problem that slow-dissolving tablets leave visible residues, for example, through the door of the washing machine during the washing cycle, or adhere to fabrics at the end of the washing cycle, or both.

EP-A-0 711 827, published May 5, 1996, discloses laundry detergent tablets containing a strongly water-soluble material which improves the disintegration of whole tablets and the dissolution of their soluble components.

However, especially in front-load washing machines, the problems of tablet remnants visible in the washing machine window are still topical.

SUMMARY OF THE INVENTION

It is an object of the present invention to prepare tablets formed by compressing a particulate material containing a surfactant. The tablets are suitable for storage, transport and handling without breaking up. Tablets dissolve easily and readily in the wash solution, releasing the active ingredients into the wash solution, and disintegrate and disperse in alkaline or surfactant-rich solutions such as wash liquors.

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To achieve the present invention, the above-mentioned kind of tablets are prepared, wherein the particulate material further comprises a highly soluble substance which exhibits a cohesive effect on the particulate material.

Another aspect of the invention is a proposed method of preparing an aqueous solution of laundry detergents for use in washing machines, the solution being formed in a water-soluble tablet prepared by compressing the particulate material. The tablet contains a surfactant and a highly soluble substance which has a cohesive effect on the particulate material.

The invention relates to a highly soluble substance with a cohesive effect on the particulate material.

Highly soluble compounds

The invention relates to a highly soluble compound. Such a substance can be prepared from a mixture or a single compound. According to the invention, a highly soluble substance is defined as follows: A solution containing deionized water and 20 g / l of a specific compound is prepared as follows:

1- 20 g of the specific compound is placed in a Sotax beaker. The beaker is immersed in a bath at a constant temperature of 10 ° C. Place the stirrer in the beaker so that its bottom is 5 mm from the bottom of the beaker. The mixer is set to 200 rpm. per min.

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

3- 10 seconds after the addition of water, the conductivity of the solution is measured with a conductivity meter.

4- Step 3 is repeated after 20 s, 30 s, 40 s, 50 s, 1 min, 2 min, 5 min, and 10 min. after step 2.

5- From measurements taken after 10 min, either a steady state or a maximum value is used.

A specific compound of the invention is defined as highly soluble when the conductivity of a solution reaches 80% of its maximum value in less than 10 seconds, from complete addition of deionized water to the compound. If the conductivity is monitored as described above, a steady-state value is reached after a certain time. This steady value is then considered the maximum value. This highly soluble compound is preferably used in the form of solid particles forming a meltable material at temperatures between 10 and 80 ° C for ease of handling. Other forms such as paste or liquid may also be used.

An example of a highly soluble compound is sodium diisoalkylbenzene sulfonate, or sodium toluene sulfonate.

Cohesive effect

For the purpose of the present invention, the cohesive effect on the particulate material is characterized by the force required to crush the tablet, which is made of the tested detergent matrix, compressed under controlled pressure conditions.

At a given pressure, the high tablet strength shows that the compressed granules have a strong adherence to each other, i.e. the cohesive effect is strong. Methods for determining tablet strength (also referring to diametral fracture stress) are described in Phaimaceutical dosage forms: tablets volume 1 Ed.H. A. Liebennan et al., Published in 1989.

The cohesive effect induced by the highly soluble compound is measured according to the invention by comparing the tablet strength of the original powdered material without the highly soluble compound to that of a tablet prepared from a powder mixture containing 97 parts of the original powder and 3 parts of the highly soluble compound. This compound is added to the matrix in substantially anhydrous form (water content below 10%, preferably below 5%). The temperature during the addition is between 10 and 80 ° C, more preferably between 10 and 40 ° C.

A highly soluble compound is defined as exhibiting a cohesive effect on the particulate material of the invention when, under a given compressive force of 3000 N, the tensile strength of a tablet having a detergent particulate weight of 50 g and a tablet diameter of 55 mm increases by 30%. preferably 60% and more preferably 100%) by adding 3% of such a highly soluble compound.

An example of a cohesive compound is sodium diisoalkylbenzenesulfonate.

It has been found that when the integrating highly soluble compound with a cohesive effect on the particulate material of the invention is added to a tablet made by compressing a surfactant-containing particulate material, dissolution of the tablet in aqueous solution is significantly accelerated. In a preferred embodiment, at least 1% by weight of the tablet is a highly soluble compound, more preferably at least 2%, even more preferably at least 3%, and most preferably 5% by weight of the tablet formed from a highly soluble compound with a cohesive effect on the particulate material. Such a composition comprising a highly soluble compound with a surfactant is described in EP-A-0 524 075. This composition is a liquid.

According to the present invention, it has been found that a highly soluble compound with a cohesive effect on the particulate material makes it possible to obtain a tablet having a higher tensile strength at a constant compression pressure or of the same tensile strength at a lower compression pressure as compared to traditional tablets. The tablet will typically have a tensile strength greater than 5 kPa, preferably greater than 10 kPa, more preferably, especially for washing machines, greater than 15 kPa,

0 · 000 00 000 000 000 000 000 000 000 000 000 000 000 000 000 000 000 000 000 000 000 000 0 0 0 ještě 0 0 ještě ještě ještě ještě ještě ještě ještě especially for use in dishwashing machines or car washes, but less than 300 kPa, preferably less than 200 kPa, more preferably less than 100 kPa, even more preferably less than 80 kPa and most preferably less than 60 kPa. For laundry applications, tablets should be less compressed than for car wash applications, since dissolution is then easier, and therefore, for laundry applications, the tensile strength is preferably less than 30 kPa.

This makes it possible to produce tablets with strength and mechanical resistance comparable to the strength and mechanical resistance of traditional tablets, but a tablet less compact is easier to dissolve. In addition, although the compound is highly soluble, dissolution of the tablet is further facilitated by a synergistic effect.

Production of tablets

The invention makes it possible, in comparison with traditional detergent tablets, to obtain a less compact and less dense tablet at a constant compression pressure.

The detergent tablets of the present invention can be prepared simply by mixing the solid ingredients and compressing the mixture in conventional tablet presses used, for example, in the pharmaceutical industry. The main components, in particular gel-like surfactants, are preferably used in particulate form. All liquid additives such as surfactants or suds suppressors are metered into the solid particulate additives in the usual manner. Additives such as filler and surfactants, especially in washing machine tablets, are dried in a conventional manner such as spraying and then compressed at a suitable pressure. The tablets of the invention are preferably compressed at a pressure of less than 100,000 N, more preferably less than 50,000 N, even more preferably less than 5,000 N, and most preferably less than 3,000 N. Car washing tablets are usually more compressed than washing machine tablets.

The particulate material for the manufacture of tablets according to the invention is produced by any suitable process or granulation. An example of such a process is spray drying (in a co-current or countercurrent drying tower), which typically provides a low bulk density of 600 g / l or less. The particulate material for making higher density tablets may be prepared by granulation and compacting in a batch mixer or high shear granulator, or by continuous granulation and compacting (eg using Lodige® CB and / or Lodige® KM mixers). Other suitable processes include fluidized bed technology, compaction processes (eg, rolling), extrusion, as well as any other chemical processes for producing particulate material such as flocculation, crystallization.

(crystallization sentering), etc. The individual particles may be any particle, e.g., granules, spherical particles, or grains.

The components of the particulate material can be mixed by any conventional means. The batch mixers are concrete mixer, Nauta mixer, ribbon mixer and others. Mixing can be carried out continuously, by weighing the individual components onto a moving belt and then mixing them in the drum (s) or in the mixer (s). The gel-forming filler can be sprayed into a mixture of some or all of the components of the particulate material. Other liquid additives may also be sprayed into a mixture of unmixed or premixed components. For example, perfumes and slurries of optical brighteners may be sprayed. The finely divided flow aid (spraying agent, such as zeolites, carbonates, silicates) may be added to the particulate material after the filler has been sprayed, preferably at the end of the process, so that the mixture is not sticky.

Tablets can be made by any compression method, such as tabletting, briquetting, or extrusion, preferably tableting. Suitable devices include standard shock or rotary bs (such as Courtoy®, Korch®, Manesty®, or Bonals®). The tablets prepared according to the invention have a diameter of between 20 mm and 60 mm, preferably of at least 35 to 55 mm, and a weight of between 25 and 100 g. The ratio of height to diameter (or width) of the tablets is preferably greater than 1: 3. more preferably greater than 1: 2. The compression pressure used to prepare these tablets should not exceed 100,000 kN / m ² , preferably 30,000 kN / m ² , more preferably 5,000 kN / m ² , even more preferably 3,000 kN / m ² , and most preferably not exceed 1000 N. Preferably, the tablet has a tablet weight of at least 0.9 g / cm ³ , more preferably at least 1.0 g / cm ³ , and preferably less than 2.0 g / cm ³ , more preferably less than 1.5 g / cm ³ , even more preferably less than 1.25 g / cm ^3, and most preferably less than 1.1 g / cm ³ .

Hydrotropic compound

In a preferred embodiment of the invention, the highly soluble cohesion effect compound is a hydrotrope. The test to determine whether a specific compound is hydrotropic is performed as follows (see S.E. Friberg and M.Chiu, J. Dispersion Science and Technology, 9 (5 &), pages 443 to 457, (1988-1989)):

1. A solution containing 25 wt. % specific substance and 75 wt. water.

2. Octanoic acid is then added to the solution in 1.6 times the weight of the specific compound in the solution, the temperature of the solution being 20 ° C. The solution is stirred in a Sotax beaker with a paddle stirrer, the stirrer is placed about 5 mm above the bottom of the beaker, stirring is set at a speed of 200 rpm.

5 mm above the bottom of the beaker, stirring is set at a speed of 200 rpm.

3. A specific compound is hydrotropic if the added octanoic acid is completely dissolved, ie if the solution contains only one phase and that phase is liquid.

The hydrotropic compound, according to a preferred embodiment of the invention, is a liquid substance composed of solid particles under operating conditions of between 15 ° C and 60 ° C.

Hydrotropic compounds include those listed below.

An overview of commercial hydrotropes can be found in Mc Cutcheon's Emulsifiers and Detergents, published by the Mc Cutcheon division of the Manufacturing Confectioners Company. Compounds of interest to the invention also include:

1. A nonionic hydrotrope having the general formula:

R-O- (CH ₂ CH ₂ O) _X (CH-CH ₂ O) y H

I CH ₃ wherein R is a C8-C10 alkyl chain, x has a value of 1 to 15, Y 3 to 10

2. Anionic hydrotropes such as alkali metal arylsulfonates. These include the alkali salts of benzoic, salicylic, benzenesulfonic and many derivatives thereof, naphthoic acid and various hydroaromatic acids. Examples thereof are the sodium, potassium and ammonium salts of benzenesulfonate derived from toluenesulfonic, xylenesulfonic, cumenesulfonic, tetralinsulfonic, naphthalenesulfonic, methylnaphthalenesulfonic, dimethylnaphthalenesulfonic, and trimethylnaphthalenesulfonic acids.

Other examples include dialkylbenzenesulfonic acid salts, such as diisopropylbenzenesulfonic acid, ethyl (methyl) benzenesulfonic acid and alkylbenzenesulfonic acid salts having an alkyl chain length of 3 to 10 (preferably 4-9), linear or branched alkyl sulfonate having an alkyl chain of 1 to 18 carbon atoms.

3. Hydrotropic solvents such as alkoxylated glycerines and alkoxylated glycerides, alkoxylated glycerine esters, alkoxylated fatty acids, glycerin esters, polyglycerol esters. Preferred alkoxylated glycerins have the following general formula:

R

AND

CH3-Oi-CHaCH-OJmH ¹ J

CHj-OGCHjČW-O-KW

R ·

CH 2 -O (-CH 3 CH-O 1, H wherein 1, m and n are numbers from 0 to 20, provided that 1 + m + n = about 2 to 60, preferably about 10 to 45 and represents H, CH ₃ or C ₂ H ₅ .

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Preferred alkoxylated glycerides have the following general formula:

H ^ -R,

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

4. Polymer hydrotropes as described in EP 636687:

R R,

- (CH _r fc) _x (CH 2 -O) _y ER ₂ wherein E is a hydrophilic functional group,

R is H or a C 1 -C 10 alkyl group, or a hydrophilic functional group;

R1 is H or a lower alkyl or aromatic group,

R 2 is H or a cyclic or aromatic group.

The polymer typically has a molecular weight of between about 1,000 and 1,000,000.

5. A hydrotrope of unusual structure such as 5-carboxy-4-hexyl-2-cyclohexen-1-yl octanoic acid (Diacid®).

The use of such compounds in the invention further increases the dissolution rate of the tablets, for example by making the hydrotropic compound facilitate the dissolution of surfactants. Such a substance may be a mixture, or it may be a simple compound.

Tablet coating

The compactness of the tablet according to the invention can be further improved by coating or coating uncoated tablets according to the invention, whereby the mechanical properties of the tablet are further improved while the solubility improvement remains.

In one embodiment of the invention, the tablets may be coated in such a way that the tablet does not absorb moisture or absorbs moisture very slowly. The coating is also so strong that the slight mechanical shocks experienced by the tablets during handling, ball and transport causes only slight breakage and abrasion. The coating is preferably brittle so that the tablet breaks when subjected to strong mechanical impact. Addition

it is preferred that the coating material is soluble in an alkaline medium or is easily emulsified with surfactants. This contributes to solving the problem of visible residues in the window of the front-loaded washing machine, during the washing cycle, as well as depositing undissolved particles or lumps of coating material in the load of the washing machine.

Water solubility is measured according to ASTM El 148-87 Standard Test Method for Aqueous Solubility.

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

The coating material preferably has a melting point of from 40 to 200 ° C.

This coating can be carried out in several ways. Two preferred methods are: a) coating with a molten material and b) coating with a solution of such a material.

In method a), the coating material is applied at a temperature above its melting point and solidifies on the tablet. In method b), the coating material is applied as a solution, then the solvent is evaporated from the coherent material by drying. The substantially insoluble material may be applied to the tablet by spraying or dipping. The molten material sprayed onto the tablet solidifies at night, quickly and forms a coherent coating. If the tablets are soaked in the molten material and then withdrawn from the melt, rapid cooling again causes the solidification of the coating material to solidify rapidly. Obviously, substantially insoluble materials, with a melting point below 40 ° C, are not sufficiently rigid at ambient temperatures, and materials found to have a melting point above about 200 ° C are not practical. Preferred materials melt in the range of 60 ° C to 160 ° C, more preferably from 70 ° C to 120 ° C.

By melting point is meant the temperature at which the material slowly changes into a liquid by heating, eg in a capillary tube.

Coating to any desired thickness may be performed according to the present invention. Typically, the coating comprises from 1% to 10%, preferably from 1.5% to 5% by weight of the tablet.

The tablet coatings of the present invention are very hard and impart extra strength to the tablet.

In a preferred embodiment of the present invention, the occurrence of coating fragments in the laundry can be reduced by adding disintegrants to the coatings. This disintegrator in contact with water swells and breaks the coating coating into small pieces. This will facilitate its dissolution in the wash solution.

The disintegrant is suspended in the melt of the coating up to a content of 30%, preferably between

% and 20%, most preferably between 5% and 10% by weight. Suitable disintegrants are described in the Handbook of Pharmaceutical Excipients (1986). Examples of suitable disintegrators include starches: natural, modified or pregelatinized, starch sodium gluconate; gums: agar gum, quar gum, locust bean gum, karay gum, pectin gum, tragacanth gum; sodium croscarmylose, crospovidone, cellulose, carboxymethylcellulose, alginic acid and its salts, including sodium alginate, silica, clay, polyvinylpyrrolidone, soy polysaccharides, ion exchange resins, and mixtures thereof.

Tensile strength

Depending on the composition of the starting material and the shape of the tablets, the compression pressure must be adjusted so as not to affect the tensile strength and the disintegration time in the washing machine. This process can be used to prepare homogeneous or layered tablets of all sizes or shapes.

For cylindrical tablets, the tensile strength corresponds to the diametrical fracture stress (DFS), which expresses the strength of the tablets and is determined by:

2F pDt where F is the maximum force (Newton) required for tensile failure (tear), as measured by a tester of the hardness of the VK 200 tablets supplied by Van Kell Industries, Inc. D is the diameter of the tablet and t is its thickness (Method Pharmaceutical Dosage Forms: Tablets Volume 2 to 217). A tablet with a diametrical fracture stress of less than 20 kPa is considered to be brittle, which is a probable cause of breaking of some tablets supplied to the consumer. A diametral fracture stress of at least 25 kPa is preferred.

Similarly, the definition of tensile strength applies to non-cylindrical tablets where the cross-section perpendicular to the height of the tablet is not circular and where the force acts perpendicular to the height and side of the tablet, the side of the tablet is perpendicular to the non-circular cross-section.

Dosage tablets

The dosage rate of the detergent tablet is determined as follows:

Two 50 g tablets are weighed and placed in the Baucknecht® WA9850 dispenser dispenser. The water for filling the washer is adjusted to 20 ° C and adjusted to a hardness of 3 mmoles / l (21 grains per gallon), the water is impregnated at a rate of 8 l / min. The amount of tablet residue remaining in the dispenser is controlled by starting the water and setting the wash cycle to program 4 (white / colored, short cycle). The percentage of residue is determined as follows:

% residue content = residue weight x 100 / original tablet weight

This procedure is repeated 10 times and the average residue is calculated from ten individual measurements. 40% of the remainder of the original tablet is considered acceptable in this test. A preferred residue is less than 30%, and more preferably less than 25%. Water hardness is measured in traditional grain per gallon units with 0.001 mol per liter = 7.0 grain per gallon, which represents the concentration of Ca ²⁺ ions in solution.

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Effervescent ingredient

In another preferred embodiment of the invention, the tablets further comprise an effervescent.

Noise as defined herein means the evolution of gas bubbles from a liquid, as a result of a chemical reaction between dissolved acid and an alkali carbonate, to produce carbon dioxide, eg C ₆ H ₈ O ₇ + 3 NaHCO ₃ -? + 3 CO ₂ f + 3 H ₂ O Additional examples of acid and carbonate, as a source of effervescence, and other effervescent systems can be found in (Pharmaceutical Dosage Forms: Tablets Volume 1 to 287).

The effervescent ingredient may be added to the tablet composition together with detergents. Addition of an effervescent component to detergent tablets improves tablet disintegration time. The amount of this component will preferably be between 5% and 20% and most preferably between 10% and 20% by weight of the tablet. Preferably, the effervescent component may be added as an agglomerate of different particles, or in compact form, but not as individual particles.

Due to the effervescent gas produced in the tablet, the tablets may have higher D.F.S. and the same disintegration time as a non-effervescent tablet. If D.F.S. the effervescent tablet is at the same level as the tablets without this ingredient, then the disintegration of the effervescent tablet will be faster.

Compounds such as sodium acetate or urea may be another means to facilitate tablet dissolution. An overview of such suitable formulations can be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, Second Edition, Edited by H. A. Lieberman et all, ISBN 0-8247-8044-2.

Cleaning surfactants

Surfactants are also included in the tablet of the invention. Dissolution of surfactants is improved by the addition of a highly soluble compound.

Nonlimiting examples of surfactants useful herein typically amounts of about 1% to about 55 wt.%, Include the conventional C _u -C ₈ alkyl benzene sulfonates (LAS) and primary, branched-chain and random C ₁₀ -C ₂₀ alkyl sulfates (AS), C ₀ -C ₈ secondary (2,3) alkyl sulfates of the formula _{CH3 (CH2) X} (C1IOS () -M ₃₎ CH ₃ and CDL3 (C? II _{2) y (CHOSO3} ^-M) CH ₂ CH ₃ where x and ( y + 1) are integers, 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 EO 1-7 ethoxy sulfates), C ₁₀ -C ₁₈ alkyl alkoxycarboxylates (especially EO 1-5 ethoxycarboxylates), C 10 -C ₁₈ glycerol ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12 -C 18 alpha-sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants, such as C ₁₂ -C ₁₈ alkyl ethoxylates (AE), including narrow peaked alkyl ethoxylates and C ₆ -C ₁₂ alkylphenolalkoxylates (particularly, may be included in the total blends) ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines (sultains), C ₁₀ -C ₁₈ amine oxides, and the like. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include the C ₁₂ -C ₁₈ N-methylglucamides. See WO 9 206 154. Other sugar-derived surfactants include N-alkoxypolyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamides. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can also be used to reduce foaming. Conventional soaps Ο ₁₀ -Ο ₂ ο can also be used. If high sudsing is desired, branched chain C10- _C16 soaps may be used. Particularly useful are mixtures of anionic and nonionic surfactants. Other conventionally useful surfactants are clearly arranged in standard texts. Preferably, the tablet comprises at least 5 wt. % surfactant, more preferably at least 15 wt.%, even more preferably at least 25 wt.%, and most preferably between 35% and 45%. of a surfactant.

Non-gel-forming binders

The non-gel-forming binder can be added to the particles from which the tablets are made for even easier dissolution.

Suitable types thereof include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers. The Pharmaceutical Excipients Manual, Second Edition, provides the following binder classification: acacia, alginic acid, carbomer, sodium carboxymethylcellulose, dextrin, ethylcellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethylcellulose, hydroxypropyl (methyl) cellulose , liquid glucose, magnesium aluminum silicate, maltodextrin, methyl cellulose, polymethacrylates, povidone, sodium alginate, starch and zein.

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The most preferred binders also have an active cleaning function in washing machines. They are cationic polymers, e.g., quaternary ethoxylated hexamethylenediamine, bis (hexamethylene) triamine, or others, such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers. Gel-forming binder materials are preferably sprayed onto the tablet and have a melting point below 90 ° C, preferably below 70 ° C, and even more preferably below 50 ° C, so that they do not damage or degrade other active ingredients in the matrix. Most preferred are non-aqueous liquid binders (i.e., not in aqueous solution) that can be sprayed in molten form. There are also solid binders which are dry-incorporated into the matrix and have bonding properties within the tablet. The non-gel forming materials are preferably used in an amount ranging from 0.1% to 15% of the composition, more preferably below 5% and, if it is not a scrubbing active material, below 2% by weight of the tablet.

It is preferred that non-gel-forming binders such as nonionic surfactants are not used in liquid or molten form. Nonionic surfactants and other non-gel forming binders are not excreted from the compositions, but it is preferable to add them to the tablets as components of particulate materials and some liquid.

Fillers

Detergent builders are optionally incorporated into the compositions of the invention as auxiliary agents for controlling mineral hardness. Both inorganic and organic fillers can be used. Typically, the fillers are used in laundry detergents to remove particular dirt.

The amount of filler may vary to a large extent depending on the end use of the composition.

Inorganic detergent builders or phosphorous builders include, but are not limited to, alkali, ammonium, and alkanolammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonate and carbonate carbonate) ), sulphates and aluminosilicates. However, phosphate-free fillers are required in some locations. Importantly, the compositions of the invention work surprisingly well even in the presence of so-called weak fillers (as compared to phosphates) such as citrates, or in the so-called underbuilt situation, which may occur with zeolites or for layered silicate fillers.

Examples of silicate fillers are alkali silicates, especially with a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1 and layer silicates such as the sodium layer silicates described in US Patent 4,664,839, issued May 12, 1987 by HPRieck. NaSKS-6 is a trademark of Hoechst Crystalline Layer Silicate (generally abbreviated herein as SKS-6).

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Unlike zeolite filler, SKS-6 does not contain aluminum. NaSKS-6 has a delta-Na ₂ SiO ₅ layer silicate morphology. It can be prepared by the methods described, eg in German DE-A 3 417 649 and DE-A-3 742 043. SKS-6 is a highly preferred layer silicate for use according to of the invention, but also other layer silicates, such as those with the general formula NaMSi _x O _{2x + 1} . . y H ₂ O, 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, may be used. A variety of other layer silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, alpha, beta and gamma forms. As mentioned above, deltaNa ₂ SiO ₅ (NaSKS-6 form) is most preferred for use according to the invention. Other silicates are also useful as, e.g., magnesium silicate, which may serve as a crispening agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component of antifoam systems.

Examples of carbonate fillers are alkaline or alkaline earth carbonates, as disclosed in German Patent Application No. 5,960,519. No. 2,321,001, issued November 15, 1973.

Aluminosilicate builders are useful in the present invention. These fillers are very important in the most commonly marketed granular detergent compositions requiring high throughput, and may also be a significant additive in liquid detergent formulations. Aluminosilicate fillers include compounds of the empirical formula:

[M _z (zAlO ₂ ) _y J x H ₂ O where z and y are integers of at least 6, the molar ratio of z and y is in the range of from 1.0 to about 0.5, x is an integer of from about 15 to 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may have a crystalline or amorphous structure, of natural or synthetic origin. A process for preparing aluminosilicate ion exchangers is described in U.S. Patent 3,985,669, Krummel, et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation 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 ) i ₂ ] xH ₂ O where x is from about 20 to 30, especially about 27. This material is known as Zeolite A.

Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicates have a particle size of about 0.1-10 microns in diameter.

00 0 4 0 00 * 00 0 00 0 0 0 00 0 0 0 0 « 0 0 0 0 9 0 0 0 0 0 0 0 0 0 0 * 0 00 000 00 00 00 •

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of different polycarboxylates. The term polycarboxylates as used herein means compounds having a plurality of carboxylate groups of at least 3 carboxylates. The polycarboxylate filler can generally be added to the mixture in acid form, but also in the form of neutral salts. When used in salt form, sodium, potassium, lithium or alkanoammonium salts are preferred.

Polycarboxylate fillers also include a variety of categories of useful materials. One important category of polycarboxylate fillers are ether polycarboxylates, including the oxydisuccinate reported by Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also TMS fillers. TDS, U.S. Patent 4,663,071, issued to Bush et al, issued May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds, such as described in U.S. Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874 and U.S. Pat. 4,102,903.

Other useful detergent builders include etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, various alkali, ammonium, and substituted ammonium salts of polyacetate acid, such as polyacetic acid acetate. and nitrilotriacetic acid as well as polycarboxylates such as mellithic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, i.e. citric acid and its soluble salts (especially sodium), are polycarboxylate builders of particular importance for sophisticated liquid detergent formulations due to their availability from renewable sources and their biodegradability. Citrates can also be used in granular compositions, particularly in combination with zeolites and / or layered silicate builders. In particular, oxydisuccinates are also useful in such mixtures and combinations.

Also suitable in the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in U.S. Patent 4,566,984, Bush, issued Jan. 28, 1986. Applicable fillers for succinic acid bases include C ₅ -C ₂₀ alkyl and alkenylsuccinic acid and salts thereof.

A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of amber fillers include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.

groups of preferred fillers, and are described in European Patent Application 86200690..5 / 0 200 263, published November 5, 1986.

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

Fatty acids, i.e., C ₁₂ -C ₁₈ monocarboxylic acids, can also be incorporated into the compositions alone or in combination with the aforementioned fillers, especially citrates and / or succinate fillers, to achieve further filler activity. Such use of fatty acids will generally result in a decrease in foaming which should be considered when designing the formulation.

In situations where phosphorus-based fillers can be used, and in particular in soap formulations used for hand washing, various alkaline phosphates, such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate, can be applied. Phosphate fillers such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, e.g., U.S. Patent 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Bleaching agents

The detergent compositions of the invention may optionally contain bleaching agents or bleaching compositions containing a bleaching agent with one or two bleach activators. The bleaching agents are used in an amount that typically ranges from about 1% to 30%, more typically from about 5% to 20%, for the detergent composition, especially for laundry washing. When bleach activators are used, their amount in the bleach composition containing the bleaching agent and bleach activator will typically be from about 0.1% to 60%, more typically from about 0.5% to 40%.

The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions intended for textile cleaning, hard surface cleaning, or other cleaning purposes that are known or will become known. These include oxygen bleaches and other bleaching agents. Perborate bleaches such as sodium perborate (mono- or tetrahydrate) may be used herein.

Another category of bleaching agents that can be used without limitation are percarboxylic acid agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, magnesium metachlorobenzoate, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. These bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued Nov. 20, 1984, U.S. Patent Application 740,446, Bums et al, filed June 3, 1985, European Patent Application Ser.

No. 133,354, Banks et al, published Feb. 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued Nov. 1, 1983. Highly preferred bleaching agents also include the 6-nonylamino-6-oxoperoxycaproic acid disclosed in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Bums et al.

Furthermore, peroxydic oxygen bleaching agents can be used. These include sodium carbonate peroxyhydrate, equivalent percarbonate bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleaches (e.g., OXONE, commercially available from DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles with an average size in the range of about 500 microns to 1000 microns, no more than 10% by weight. these particles are less than 200 microns and no more than about 10 wt. these particles are greater than 1250 microns. Optionally, the percarbonates may be coated with silicates, borates or water-soluble surfactants. Percarbonates are available from various commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be used.

Peroxygen bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators which form in situ in aqueous solution (i.e., during washing) the peroxyacid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Mao et al, issued April 10, 1990, and U.S. Patent 4,412,934. Typical activators that may also be used are nonanoyloxybenzenesulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) and mixtures thereof . See also US 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred bleach activators are of the following general formula:

R ¹ O (R ² O) R ² O (L) or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ¹ is an alkyl group containing from about 6 to 12 carbon atoms, R ² is an alkylene group containing from 1 up to 6 carbon atoms, R ⁵ is H and alkyl, aryl, or alkaryl containing from about 1 to 10 carbon atoms, and L is any leaving group. A leaving group is any group that is displaced from the bleach activator as a result of nucleophilic attack of the activator by a perhydrolysis anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula are (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyloxybenzenesulfonate), and mixtures thereof described in U.S. Patent 4,634,551, incorporated herein by reference.

• ·· · · · · · ·

Another class of bleach activators include the benzoxazine types of activators disclosed in U.S. Patent 4,966,723, Hodge et al, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazine type is:

Another class of preferred bleach activators include acyl lactam activators, particularly acyl caprolactams and acylvalerolactams of the general formula:

O

II

OC-CH ₂ —CH 2

R ⁶ —C — N / (CH2 ch ₂ —ch ₂ ⁾

R ⁶ —C—

O

II c — ch ₂ —ch ₂

NL I CH ₂ CH ₂ wherein R ⁶ is H or alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl, nonanoylkaprokaprolaktam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, Sanderson, issued October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed on sodium perborate. Bleaching agents other than oxygen bleaches are also well known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest is photoactivated bleaching agents such as sulfonated zinc and / or aluminum thalocyanines. See U.S. Patent 4,033,718, Holcombe et al, issued Jul. 5, 1977. When used, detergent compositions will typically contain from about 0.025% to 1.25% by weight. these bleaches, in particular sulfonated zinc phthalocyanine.

If desired, the bleaching components can be catalyzed by manganese compounds. Such compounds are well known in the art and include, for example, the manganese catalysts disclosed in US Patent 5,246,621; U.S. Patent 5,244,594; U.S. Patent 5,194

416; U.S. Patent 5,114,606; and in European patent application Pub. Nose. 549,271A1, 549,272A1, 544,440A2, and 544,490A1;

Preferred examples of these catalysts include Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-L 4,7-triazacyclononane) 2 (PF 6) 2, M ^and 2 (µ-O) ₁ (µ-OAc) ₂ (1). , 4,7-trimethyl-1,4,7-triazacyclononane) ₂

- (C1O _{4) 2,} Mn ^'V 4 (u-0) 6 (l, 4,7-triazacyclononane) 4 (C104) 4, Mn ^{ra MnIV4} (u O) ₁ (u-OAc) ₂ - (L 4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) 3, Mn ¹⁷ (1,4,7-trimethyl-1,4,7-triazacyclononane) - (OCH ₃ ) ₃ (PF ₆₎ ), and mixtures thereof. Other metal bleach catalysts are described in the US patent

430,243 and U.S. Patent 5,114,611. The use of manganese with various complex ligands to enhance the bleaching effect is also disclosed in the following U.S. Patents 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084.

Practically but without limitation, the compositions and processes of the invention can be adjusted such that the bleach catalyst content of the aqueous wash solution is of the order of at least one tenth millionth of the bleach catalyst active ingredient, which is preferably from about 0.1 ppm to 700 ppm, more preferably from about 1 to 500 ppm, catalyst additive in the wash solution.

Enzymes

Enzymes can be included in the formulations of the invention for a variety of uses in the textile washing industry, including stain removal, e.g., from proteins, hydrocarbons or triglycerides, and to prevent discoloration and to regenerate fabrics. Such enzymes include proteases, amylases, lipases, peroxidase cellulases, and mixtures thereof. Other types of enzymes of any suitable origin, such as plant, animal, bacterial, fungi and yeast, may also be used. However, their choice is governed by several factors such as pH and / or optimum stability, thermostability, stability with respect to active detergents, fillers, etc. In this regard, bacterial and fungal enzymes such as bacterial amylases and proteases, and fungal enzymes are preferred. cellulasy.

The enzymes are normally added in a sufficient amount, up to about 5 mg by weight, more typically about 0.01 mg up to 3 mg of active enzyme per gram of the composition. In other words, the compositions of the invention will typically contain from about 0.001% to 5%, preferably 0.01% to 1% by weight, based on the weight of the enzyme preparation. Protease enzymes are usually present in commercial preparations in an amount sufficient to achieve from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

Suitable examples of proteases are subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Other suitable proteases are obtained from a Bacillus strain having a maximum

pH 8-12 activity developed and marketed by Novo Industries A / S under the registered trademark ESPERASE. The preparation of this and analogous enzymes is described in British Patent 1,243,784 to Novo. Commercially available proteolytic enzymes suitable for removing protein stains include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A ^/ S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (Holland). Other proteases include Protease A (see European Patent Application 130 756, published January 9, 1987) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130 756, Bott et al, published January 9, 1985). Amylases include, eg. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

Cellulases useful in the present invention include both bacterial and viral cellulases. Preferably, they have a pH optimum between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase manufactured by Humicola insolens and Humicola strain DSM 1800 or a fungus producing cellulase 212 belonging to Aeromonas and cellulase extracted. from the marine shellfish hepatopancreas (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095..275 and DE-OS2.247.832. CAREZYME (Novo) is particularly useful.

Lipase enzymes suitable for detergent use include those which produce microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, disclosed in British Patent 1 372 034. See also lipases in Japanese Patent Application 53 20487, published February 24, 1978. This lipase available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P Amano, hereinafter referred to as Amano-P. Other commercial lipases include Amano-CES, ex Chromobacter viscose lipases, e.g. Chromobacter viscose var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and Chromobacter viscosum lipase from US Biochemical Corp., USA and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme, derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341 947), is a lipase preferred for use in the present invention.

Peroxidase enzymes are used in combination with sources of oxygen, e.g., percarbonates, perborates, persulfates, hydroperoxide, etc. They are used for solution bleaching, e.g., to prevent the transfer of dyes and pigments from washed substrates to other substrates in the wash solution. Peroxidases are well known in the art and include, for example, horseradish peroxidase, β-ligninase, and haloperoxidase, such as chloro-bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A / S.

A wide variety of enzyme-containing materials and methods for incorporating them into detergent compositions are also contemplated in U.S. Patent 3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al, and U.S. Pat. No. 4,507,219, Hughes, issued March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into these formulations are the subject of U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Various enzyme stabilization techniques are exemplified and exemplified in U.S. Pat. No. 3,600,319, issued August 17, 1971, to Gedge et al. 0 199 405, in application no. No. 86200586.5, published Oct. 29, 1986, Venegas. Enzyme stabilization systems are also described, e.g., in U.S. Patent 3,519,570.

Other components which are generally used in detergent compositions and which may be added to detergent tablets of the present invention include chelating agents, soil release agents, soil release agents, dispersants, brighteners, defoamers, fabric softeners, dye transfer inhibitors and perfumes.

Washing method

It is known to insert traditional laundry detergent tablets into the washing machine drum together with the laundry. In this method, however, unsightly tablet residues are visible in the washing machine window, especially with certain types of washing machines designed to operate with less water consumption.

In extreme cases, visible residues may remain on the laundry at the end of the wash cycle due to incomplete dissolution.

The present invention also relates to a method of washing which avoids this problem. The novel method is based on the preparation of an aqueous laundry detergent solution for use in washing machines, which solution consists of dissolving the tablet in water. The tablet made by compressing the particulate material comprises a surfactant and a highly soluble compound with a cohesive effect on the particulate material.

In a preferred embodiment of the present invention, the disclosed method relates to the execution of an aqueous laundry detergent solution for use in a front-loaded washing machine equipped with a dispensing drawer and a washing drum. In these scrubbers, an aqueous laundry detergent solution is formed by dissolving a detergent tablet in water, characterized in that it is placed in a dispenser drawer, and the flowing water dissolves the tablet to form an aqueous laundry detergent solution. The aqueous solution then flows into the scrubber.

DETAILED DESCRIPTION OF THE INVENTION

Basic mixture of particulate material:

Mixture A (% by weight) Anionic agglomerates 21.45 Anionic agglomerates 13.00 Cationic agglomerate 5.45 Layer silicate 10.8 Sodium percarbonate 14.19 Bleach activator agglomerates 5.49 Sodium carbonate 13.82 EDDS / sulfate particles 0.47 Ethyl sodium hydroxyethyl phosphonate 0.73 Dirt-releasing polymer 0.33 Fluorescer Encapsulated zinc-phthalocyanine sulfonate 0,025 Soap powder 1.40 Foam absorber 1.87 Citric acid 7.10 Proteasa 0.79 Lipasa 0.28 Cellulasa 0.22 Amylasa 1.08 Coating binder 1,325 TOTAL 100.00

Anionic agglomerates 1 contain 40% anionic surfactants, 27% zeolite and 33% carbonate.

·· · · · ·

Anionic agglomerates 2 contain 40% anionic surfactant, 28% zeolite and 32% carbonate.

Cationic agglomerates contain 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate contains 95% SKS 6 and 5% silicate.

The bleach activator agglomerates comprise 81% TAED, 17% acrylate maleate copolymer (acid form) and 2% water.

Sodium ethylenediamine-N, N-disuccinate / sulfate particles contain 58% sodium ethylenediamine-N, N-disuccinate, 23% sulfate and 19% water.

The encapsulated zinc phthalocyanine sulfonate has 10% activity.

The suds suppressor contains 11.5% silicone oil (ex Dow Corning); 59% zeolite a

29.5% water.

The binder coating contains 50% Lutensit K-HD 96 and 50% PEG (polyethylene glycol).

Example 1 (containing highly soluble compound with cohesive effect on particulate material)

i) The basic detergent powder of composition A (see table above) was prepared as follows: all particulate material of the basic composition A was mixed in a mixing drawer to form a homogeneous particulate composition. Binder was injected during mixing.

ii) 97 parts of base powder of mixture A was mixed in a mixing drawer with 3 parts of sodium diisoalkylbenzenesulfonate (highly soluble compound with cohesive effect on particulate material).

iii) The tablets were then made as follows: into a circular shape with a diameter

5.5 g of 50 g of the mixture were introduced, after compression a tablet having a tensile strength (or diametral fracture stress) of 15 kPa was obtained. The force required to produce a tablet having a tensile strength of 15 kPa was 2400 N. The tablet height was 1.94 cm.

iv) The amount of residue in the automatic washing machine dispenser was evaluated by the Tablet Dispensing Test. Two tablets were placed in a Baucknecht WA9850 dispenser, the water washer was adjusted to 20 ° C and the water hardness adjusted to 3 mmol / l, inlet 8 Emin. The amount of tablet residue remaining in the dispenser was controlled by switching on the wash cycle and setting it to program 4 (white / colored, short cycle). The percent residue at a given detergent dosage was evaluated as follows:

% residue = [(residue weight) x 100] / (original tablet weight)% residue is shown in the table% residue in the table

Example 2 (highly soluble compound)

i) The same mixture A was prepared by the same procedure as in Example 1.

ii) 97 parts of base powder of mixture A was mixed in a mixing drawer with 3 parts of sodium toluene sulfonate (highly soluble compound).

iii) The tablets were then made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 15 kPa was 3100 N. The tablet height was 1.88 cm.

iv) The amount of residue in the scrubber was evaluated in the same manner as Example 1. The% residue is shown in the table in the% residue column.

Example 3 (highly soluble compound)

i) The same mixture A was prepared by the same procedure as in Example 1.

ii) 97 parts of base powder of mixture A was mixed in a mixing drawer with 3 parts of Sorbitol (highly soluble compound).

iii) The tablets were then made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 15 kPa was 3500 N. The tablet height was 1.83 cm.

iv) The amount of residue in the scrubber was evaluated by the same procedure as in Example 1. The% residue is shown in Table 3.

Example 4 (compound with cohesive effect on particulate material)

i) The same mixture A was prepared by the same procedure as in Example 1.

ii) 97 parts of the base powder of mixture A was mixed in a mixing drawer with 3 parts of sodium dodecylbenzenesulfonate (a compound with a cohesive effect on particulate material).

iii) The tablets were then made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 15 kPa was 2600 N. The tablet height was 1.95 cm.

iv) The amount of residue in the scrubber was evaluated by the same procedure as in Example 1. The% residue is shown in Table 3.

• * «* * * * * * * * * * * * * * * * * * * * * * • * * ** · • * · · · · · · ···

Example 5 (basic mixture of particulate material)

i) The same mixture A was prepared by the same procedure as in Example 1.

ii) The tablets were then made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 15 kPa was 3200 N. The tablet height was 1.82 cm.

iii) The amount of residue in the scrubber was evaluated by the same procedure as in Example 1. The% residue is shown in Table 3.

Results

Table of tablet residues:

Example: 1 2 3 4 5 Pressing force (N) 2400 3100 3500 2600 3200 Tablet height (cm) 1.94 1.88 1.83 1.95 1.82 % residue 24.2 98.8 71.5 68.8 100 ALIGN!

Table of Conductivity of Compounds Added to Mixture A to Obtain the Tablets of Examples 1-4:

Examples of compounds: 1 2 3 4 Conductivity achieved in 10 seconds (%) 95 100 ALIGN! 100 ALIGN! 64

Other masterbatch of particulate material:

Mixture B (% by weight) Anionic agglomerates 21.45 Anionic agglomerates 13.00 Cationic agglomerate 5.45 Layer silicate 10.8 Sodium percarbonate 14.19 Bleach activator agglomerates 5.49 Sodium carbonate 12,645 EDDS / sulfate particles 0.47 Ethetriumhydroxyethyl phosphonate 0.73 Dirt-releasing polymer 0.33 Fluorescer 0.18

* ·

Encapsulated zinc-phthalocyanine sulfonate 0,025 Soap powder 1.40 Foam absorber 1.87 Citric acid 7.10 Proteasa 0.79 Lipasa 0.28 Cellulasa 0.22 Amylasa 1.08 Coating binder 2.5 TOTAL 100.00

Anionic agglomerates 1 contain 40% anionic surfactants, 27% zeolite and 33% carbonate.

Anionic agglomerates 2 contain 40% anionic surfactants, 28% zeolite and 32% carbonate.

Cationic agglomerates contain 20% cationic surfactants, 56% zeolite and 24% sulfate. The layered silicate contains 95% SKS 6 and 5% silicate.

The bleach activator agglomerates comprise 81% TAED, 17% acrylate / maleate (acid form) copolymers and 2% water.

Sodium ethylenediamine-N, N-disuccinate, sulfate particles contain 58% sodium ethylenediamine-N, N-disuccinate, 23% sulfate and 19% water.

The encapsulated zinc phthalocyanine sulfonate has 10% activity.

The suds suppressor contains 11.5% silicone oil (ex Dow Corning); 59% zeolite a

29.5% water.

The binder coating contains 50% Lutensit K-HD 96 and 50% PEG (polyethylene glycol).

Example 5 (mixture of base particulate material);

i) Mixture B was prepared by the same procedure as in Example 1.

ii) The tablets were then made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 10.9 kPa was 2000 N.

Example 7 (PEG)

i) Mixture B was prepared by the same procedure as in Example 1.

ii) iii) parts of base powder of mixture A were mixed in a mixing drawer with 3 parts of PEG (binder).

The tablets were made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 12.8 kPa was 2000 N.

Example 8 (Sodium diisoalkylbenzenesulfonate)

i) Mixture B was prepared by the same procedure as in Example 1.

ii) 97 parts of the base powder of mixture A were mixed in a mixing drawer with 3 parts of sodium diisoalkylbenzenesulfonate.

iii) The tablets were made in the same manner as described in Example 1. The force required to produce a tablet having a tensile strength of 17.8 kPa was 2000 N.

Example 9 tablets of the invention:

i) The detergent base powder of mixture C was prepared as follows: all of the particulate material of base mixture C was mixed in a mixing tray to form a homogeneous particulate mixture. Binder was injected during mixing. After this feed, sodium diisoalkylbenzenesulfonate (= DIBS) was added to the rest of the matrix.

ii) The tablets were made in the following way: 43 g of the mixture were introduced into a 5.5 cm diameter circular form, after compression a tablet having a tensile strength (or diametral fracture stress) of 15 kPa was obtained.

iii) The amount of the remainder of the 43 g tablet was less than 15%.

Mixture C (% by weight) Anionic agglomerates 9.1 Anionic agglomerates 22.5 Non-ionic agglomerates 9.1 Cationic agglomerates 4.6 Layer silicate 10.8 Sodium percarbonate 12.2 Bleach activator agglomerates 6.1 Sodium carbonate 7.27 EDDS / sulfate particles 0.5

«·

Tetranatriumhydroxyethylphosphonate 0.6 Dirt-releasing polymer 0.3 Fluorescer 0.2 Encapsulated zinc-phthalocyanine sulfonate 0.03 Soap powder 1,2 Foam absorber 2.8 Citric acid 5.5 Proteasa 1 Lipasa 0.35 Cellulasa 0.2 Amylasa 1.1 Coating binder 3.05 Spraying perfume 0.5 DH3S 2.1

Anionic agglomerates 1 contain 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerates 2 contain 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerate contains 26% nonionic surfactant, 6% Lutensite K-HD 96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite.

Cationic agglomerates contain 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate contains 95% SKS 6 and 5% silicate.

Bleach activator agglomerates contain 81% TAED, 17% acrylate / maleate copolymer (acid form) and 2% water.

Sodium ethylenediamine N, N-disuccinate / sulfate particles contain 58% sodium ethylenediamine N, N-disuccinate, 23% sulfate and 19% water.

The encapsulated zinc phthalocyanine sulfonate has 10% activity.

The suds suppressor contains 11.5% silicone oil (ex Dow Corning); 59% zeolite a

29.5% water.

The binder coating contains 0.5 parts of Lutensit K-HD 96 and 2.5 parts of PEG.

The following example was carried out in order to test the solubility of non-tablet, granular material with and without a highly soluble compound, i.e. using DBBS:

The detergent composition D was prepared as follows: all particulate materials except dried zeolite were mixed in a mixing drawer to form a homogeneous particulate composition. Binder was injected during mixing. After spraying, dry zeolite dusting was performed.

Table 1: Basic detergent powder composition

Mixture D (% by weight) Anionic agglomerates 32 Cationic agglomerates 5 Layer silicate 11.5 Sodium perulite 16.2 Bleach activator agglomerates 4.7 Sodium carbonate 3.76 Sodium bicarbonate 2,0 Sodium sulfate 2.4 EDDS / sulfate particles 0.5 Tetranatrium hydroxyethane diphosphonate 0.8 Dirt-releasing polymer 0.3 Fluorescer 0.1 Encapsulated zinc-phthalocyanine sulfonate 0.02 Foam absorber 2.1 Citric acid 2 Proteasa 0.7 Lipasa 0.2 Cellulasa 0.2 Amylasa 0.6 Encapsulated perfume 0.2 Polymer particles 3

0 * * · · · 0 · * ····· 00 · 0 0 0 · 0 · 0 ··· 0 · 0 ·

Spraying perfume 0.5 Non-ionic spray system 5.17 Zeolite 6.2

Anionic agglomerates 1 contain 40% anionic surfactant, 27% zeolite and 33% carbonate.

Cationic agglomerates contain 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate contains 95% SKS 6 and 5% silicate.

Bleach activator agglomerates contain 81% TAED, 17% acrylate / maleate copolymer (acid form) and 2% water.

Sodium ethylenediamine-N, N-disuccinate / sulfate particles contain 58% sodium ethylenediamine-N, N-disuccinate, 23% sulfate and 19% water.

The encapsulated zinc phthalocyanine sulfonate has 10% activity.

The suds suppressor contains 11.5% silicone oil (ex Dow Corning); 59% zeolite a

29.5% water.

The encapsulated perfume contains 50% perfume and 50% starch.

The polymer particle comprises 36%, 54% zeolite and 10% water.

The nonionic feed system contains 67% C12-C15 AE5 (alcohol with an average of 5 ethoxy groups per molecule), 24% glucose N-methylamide and 9% water.

150 g of this granular detergent composition D was placed in the Hotpoint dispenser of the machine. The filling of the water in the washing machine was set at a temperature of 20 ° C and a hardness of 21 grains to 4.51 of water, inflow of 2 L per min. After two minutes, 38 g of detergent composition D remained undissolved in the dispenser.

145 g of this granular detergent composition D was mixed with 5 g of DIBS. This granulated mixture was placed in the Hotpoint dispenser of the washing machine. The water feed to the washer was set at 20 ° C and the water hardness adjusted to 3 mmol / l, flow rate 21 per min. After 2 minutes, 30 g of detergent composition D remained undissolved in the dispenser.

In a further preferred embodiment, according to the examples below, it has been found that adding highly soluble compounds to the particulate material, wherein the highly soluble compound is preferably a hydrotrope, together with a mixture of at least two polymers, causes further improved dissolution. This synergistic effect is particularly useful with a blend of polymers such as PEG (polyethylene glycol), even more with PEG having a molecular weight of between 200 and

9000, a mixture of PEGs having a molecular weight of 1000 and 4000 was found to be satisfactory.

Such PEGs are described, for example, in EP-A-0 522 766. Other polymers include cationic polymers such as Lutensit KHD96. Molecular weight is considered herein as the average molecular weight for a given molecular weight distribution.

Example A (formulation used for modified National Wave 1)

i) The detergent base powder of mixture E (see below) was prepared as follows: all particulate materials of base mixture E were mixed in a mixing drawer to form a homogeneous particulate mixture. Binder was injected during mixing. After this feed, sodium diisoalkylbenzenesulfonate (sticky hydrotrope) was added to the rest of the matrix.

ii) The tablets were made in the following way: 43 g of the mixture were introduced into a 5.5 cm diameter circular form, after compression a tablet having a tensile strength (or diametral fracture stress) of 15 kPa was obtained.

iii) The tablets were immersed in a bath containing 80 parts of sebacic acid, mixed with 20 parts of Nymcel zsbló, at 140 ° C. The immersion time of the tablet in a heated bath was adjusted so that the described mixture acted on a 3 g tablet. The tablet was then cooled to room temperature of 25 ° C for 24 h.

iv) The amount of residue in the washer was measured by the stress tablet dispensing test: two tablets were placed in the Baucknecht WA9850. The machine was filled with water at a temperature of 20 ° C and the water hardness adjusted to 3 mmol / l, at a flow rate of 4 l / min. The amount of tablet residue remaining in the dispenser was monitored as the water flows through the dispenser for 78 s. The percentage of residues at a given detergent dosage in% was evaluated as follows:

% residue = [(weight of residue) x 100] / (original weight of tablet)

The amount of tablet residue in% is shown in the tables below.

Example B

The procedure for preparing the tablets of Example A was repeated for the powder of blend F. The polymer sprayed onto the matrix contained 0.67 parts PEG 4000 and 0.33 PEG 1000.

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

Basic detergent powder mixtures E and F

ExA (%) ExB (%) Anionic agglomerates 9.1 9.1 Anionic agglomerates 22.5 22.5 Non-ionic agglomerates 9.1 9.1 Cationic agglomerates 4.6 4.6 Layer 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 / sulfate particles 0.5 0.5 Sodium hydroxyethane diphosphonate 0.6 0.6 Dirt-releasing polymer 0.3 0.3 Fluorescer 0.2 0.2 Encapsulated zinc-phthalocyanine sulfonate 0.03 0.03 Soap powder 1,2 1,2 Foam absorber 2.8 2.8 Citric acid 5.5 5.5 Proteasa 1 1 Lipasa 0.35 0.35 Cellulasa 0.2 0.2 Amylasa 1.1 1.1 Binding spray system -PEG 4000 1 0.67 -PEG 1000 0.33 Spraying perfume 0.5 0.5 DIBS 3 3 Tablet dosage test% 14 6 The tensile strength of the tablets in kPa achieved application of pressing force 2000 N. 15.6 16.6

• ·

Anionic agglomerates 1 contain 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerates 2 contain 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerate contains 26% nonionic surfactant, 6% Lutensite K-HD 96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite.

Cationic agglomerates contain 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate contains 95% SKS 6 and 5% silicate.

Bleach activator agglomerates contain 81% TAED, 17% acrylate / maleate copolymer (acid form) and 2% water.

Sodium ethylenediamine N, N-disuccinate / sulfate particles contain 58% sodium ethylenediamine N, N-disuccinate, 23% sulfate and 19% water.

The encapsulated zinc phthalocyanine sulfonate has 10% activity.

The suds suppressor contains 11.5% silicone oil (ex Dow Corning); 59% zeolite a

29.5% water.

The binder coating contains 0.5 parts of Lutensit K-HD 96 and 2.5 parts of PEG.

Example C-D

The preparation of the tablets of Example A was repeated for the G-H powder. The strength of the tablet prior to coating with a mixture of sebacic acid and Nymcel was 12 kPa.

Use of a blend of three polymers for better dosing results than a blend of two polymers.

Basic detergent powder mixtures G and H

ExC (%) ExD (%) Anionic agglomerates 9.1 9.1 Anionic agglomerates 22.5 22.5 Non-ionic agglomerates 9.1 Cationic agglomerates 4.6 4.6 Layer silicate 9.7 9.7 Sodium percarbonate 12.2 12.2

• · fa fa · fafafa · «· · · · · fafa · fafafa

33 • fa • fa fa • · fa fa fa fafa fafa Bleach activator agglomerates 6.1 6.1 Sodium carbonate 8.32 8.32 EDDS / sulfate particles 0.5 0.5 Tetranatriumhydroxyethanediphosphonate 0.6 0.6 Dirt-releasing polymer 0.3 0.3 Fluorescer 0.2 0.2 Encapsulated zinc-phthalocyanine sulfonate 0.03 0.03 Soap powder 1,2 1,2 Foam absorber 2.8 2.8 Citric acid 5.5 5.5 Proteasa 1 1 Lipasa 0.35 0.35 Cellulasa 0.2 0.2 Amylasa 1.1 1.1 Binding spray system - Lutesite KHD 96 0.3 0.4 -PEG 4000 1.7 0.75 -PEG 1000 0.33 Spraying perfume 0.5 0.5 DIBS 2.1 2.1 Tablet dosage test% 53 9

Anionic agglomerates 1 contain 40% anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerates 2 contain 40% anionic surfactant, 28% zeolite and 32% carbonate.

The nonionic agglomerate contains 26% nonionic surfactant, 6% Lutensite K-HD 96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite.

Cationic agglomerates contain 20% cationic surfactant, 56% zeolite and 24% sulfate. The layered silicate contains 95% SKS 6 and 5% silicate.

The bleach activator agglomerates comprise 81% TAED, 17% acrylic / maleate copolymer (acid form) and 2% water.

* Φ φ * · · · · · · · · · · · · · ·

For triethylenediamine-N, N-disuccinate, the sulphate particles contained 58% sodium-ethylenediamine-N, N-disuccinate, 23% sulfate and 19% water.

The encapsulated zinc phthalocyanine sulfonate has 10% activity.

The suds suppressor contains 11.5% silicone oil (ex Dow Corning); 59% zeolite «

29.5% water.

The binder spray system contains 0.5 parts of Lutensit K-HD 96 and 2.5 parts of PEG.

9900 99 9 ^f f

Claims (11)

PATENT CLAIMS A tablet formed by compressing a particulate material, characterized in that the particulate material comprises a surfactant and a highly soluble compound, the highly soluble compound having a cohesive effect on the particulate material. Tablet according to claim 1, characterized in that at least 1% by weight, preferably at least 2% by weight. tablets are made of a highly soluble compound. 3. A tablet according to claim 1 wherein the highly soluble compound comprises sodium diisoalkylbenzenesulfonate. Tablet according to claim 1, characterized in that it has a tensile strength greater than 5 kPa, preferably less than 300 kPa. Tablet according to claim 1, characterized in that it is compressed with a force of less than 100,000 N. Tablet according to claim 1, characterized in that it contains at least 5 wt. of a surfactant. The tablet of claim 1, wherein the highly soluble compound is hydrotropic. A coated tablet, characterized in that the uncoated tablet corresponds to any one of the preceding claims. Tablet according to any one of the preceding claims, characterized in that the particulate material comprises a mixture of at least two polymers. A process for preparing an aqueous laundry detergent solution for use in a washing machine, wherein the aqueous laundry detergent solution is formed by dissolving a tablet in water, the tablet made by compressing particulate material comprising a surfactant and a highly soluble compound having a cohesive effect on the particulate material. Method according to claim 9, characterized in that the tablet has a density of at least 0.9 g / cm ³ , preferably less than 2 g / cm ³ .