NL1012583C1 - Detergent tablet. - Google Patents

Abstract

A multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a particulate solid compressed within said mould. The multi-phase tablets provide improved dissolution and cleaning characteristics together with excellent tablet integrity and strength.

Description

5 10

CLEANER TABLET

Technical area 15

The present invention relates to multiphase detergent tablets.

Background 20

Detergent compositions in the form of tablets are known in the art. It will be understood that detergent compositions in the form of tablets have a number of advantages over granular detergent compositions, such as ease of dosing, processing, transportation and storage.

Detergent tablets are most commonly prepared by premixing ingredients of a detergent composition and forming a tablet of the premixed detergent ingredients using suitable equipment, preferably a tablet press. Tablets are usually formed by pressing the components of the detergent composition so that the tablets produced are sufficiently robust to withstand processing and transportation without permanent damage. Except that tablets 101

1 I

2 must also be sufficiently rapid to dissolve so that the detergent components are released into the wash water as soon as possible at the start of the wash cycle.

However, there is a dichotomy because when the pressing force is increased, the dissolution rate of the tablets is slower. The present invention therefore seeks to strike a balance between tablet robustness and tablet dissolution.

Solutions to this problem as seen in the prior art include pressing the tablets at a low pressing pressure. Tablets made in this way, while having a high relative dissolution rate, tend to crumble, be damaged and become unacceptable to the consumer. Other solutions include preparing tablets using a high relative pressure to achieve the required level of robustness and using a dissolving aid such as an effervescent.

Multiphase detergent tablets described in the prior art are prepared by pressing a first composition into a tablet press to form a substantially flat first layer. Another detergent composition is then fed to the tablet press on top of the first layer. This second composition is then pressed to form another substantially flat second layer. Thus, the first layer is generally subjected to more than one pressing operation since it is also pressed during the pressing of the second composition. Usually, the first and second pressing forces are of the same order of magnitude. The applicant has found that when this is the case, since the pressing force must be sufficient to bind the first and second compositions together, the force applied in both the first and second pressing steps ranges from about 4000 to about 20,000 kg (a tablet cross-section of approximately 10 cm2 is assumed 101 2583 t 3). A consequence of this is a lower tablet dissolution rate. Other multiphase tablets that have differential dissolution behavior are prepared in that the second layer is pressed at a lower force than the first layer. However, while the dissolution rate of the second layer is improved, the second layer is soft compared to the first layer and is therefore susceptible to damage caused by processing and transportation.

EP-B-0.055.100 describes a toilet bowl block formed by joining a slowly dissolving molded mass and a tablet. The toilet bowl block is designed in such a way that it can be placed in the cistern of a toilet bowl and dissolves it in a period of days, preferably weeks. To decrease the dissolution rate of the toilet bowl block, the document proposes to mix one or more solubility control agents. Examples of such solubility control agents are paradichlorobenzene, waxes, long chain fatty acids and alcohols and esters thereof, and fatty alkyl amides. Detergent tablets 20 for use in automatic washing or dishwashing should dissolve to a significant degree within one cycle of the washing machine or dishwasher, that is, within 15 to 120 minutes.

Summary of the invention

According to a first aspect of the invention, a multiphase detergent tablet is provided for use in a washing machine, the tablet comprising: a) a first phase in the form of a formed mass with at least one mold therein and b) a second phase in the form of a granular solid pressed into the mold.

3 5

In preferred embodiments, the first phase is a pressed molded mass prepared at a press pressure of at least about 40 kg / cm2 applied, preferably at least about 250 kg / cm2, more preferably at least about 350 kg / cm2 (3.43 kN / cm2), even more preferably from about 400 to about 2000 and in particular from about 600 to about 1200 kg / cm2 (compression pressure here is the force applied divided by the cross-sectional area of the tablet in a plane transverse to the force applied - in fact, the cross-sectional area of the die of the rotary press). It is also preferred that the granular solid of the second phase (meaning terminology to include the possibility of multiple 'second' phases sometimes referred to herein as 'optional subsequent phases') is pressed into the mold at an applied press pressure less than 15 applied to the first stage, and preferably at a press pressure less than about 350 kg / cm2, preferably in the range of about 40 kg / cm2 to about 300 kg / cm2 and with greater preferred from about 70 to about 270 kg / cm2, with such tablets being preferred here as they provide optimal tablet integrity and strength (measured, for example, by the "Child Bite Strength" [CBS] test) and product solution properties. The tablets of the invention preferably have a CBS of about 6 kg, preferably greater than about 8 kg, more preferably greater than about 10 kg, especially greater than about 12 kg, and even more particularly greater than about 14 kg, with CBS measured according to the "US Consumer Product Safety Commission Test" specification. In addition, the pressures applied to the first and second phases will generally be in a ratio of at least about 1.2: 1, preferably at least about 2: 1, and more preferably at least about 4: 1 to each other stand.

According to another aspect of the invention, there is thus provided a multiphase detergent tablet for use in a washing machine, the tablet comprising: 1012583 a) a first phase in the form of a pressed molded mass having at least one mold therein, the molded mass is prepared at a press pressure of at least about 350 kg / cm2 and 5 b) a second phase in the form of a granular solid that has been pressed into the mold, the second phase at a pressure of less than about 350 kg / cm2 is pressed.

In other preferred embodiments, the second phase is in the form of a pressed or formed mass which is adherent, for example by physical or chemical bonding, in the at least one mold of the first mass. It is also preferred that the first and second phases are in a relatively high weight ratio to each other, for example at least about 6: 1, preferably at least about 10: 1. It is also preferred that the tablet composition contains one or more detergent actives (eg enzymes, bleaches, bleach activators, bleaching catalysts, surfactants, chelating agents, etc.) which are mainly concentrated in the second phase of the tablet, e.g. at least about 50% by weight, preferably at least about 60% by weight and especially about 80% by weight of the active agent (based on the total weight of the active agent in the tablet). Such compositions also have optimum tablet strength and optimum dissolution, cleaning and pH control properties, thereby providing, for example, tablet compositions capable of dissolving in the washing liquid at least 50% by weight, preferably at least 60% by weight. % and more preferably at least 80% by weight of the cleaning active agent is delivered to the washing liquid within 10, 5, 4 or even 3 minutes from the start of the washing process.

101? 583 6

According to another aspect of the invention, there is thus provided a multiphase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a formed mass with at least one mold therein and b) a second phase in the form of a granular solid pressed into the mold, the tablet comprising at least one cleaning agent and formulated such that at least 50% by weight, preferably at least 60% by weight and with greater preferably at least 80% by weight of the cleaning active agent is delivered to the washing liquid within the first 10 minutes, preferably within the first 5 minutes and more preferably within the first 3 minutes of the washing process.

An additional advantage of the invention is the possibility of allowing the phases to dissolve at different times such that one phase of the tablet will dissolve considerably before another phase dissolves and can even almost completely dissolve before the other phase is resolved. This is especially valuable for the differential release of cleaning agents.

The detergent actives are suitably selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof, with the enzyme active agents being particularly preferred for boosting the cleaning ability. during the very first cool water stage of the washing or cleaning operation. For use herein, enzyme cleaning agents and in particular enzymes and enzyme mixtures comprising one or more enzymes having an increased or optimal activity in the temperature range of from 25 ° C to 55 ° C and at a pH value in the range of 8 to 10 (eg Natalase) is highly preferred.

Detailed description of the invention

It is an object of the present invention to provide a detergent tablet which is not only robust enough to withstand handling and transportation but also at least a large portion of which dissolves quickly in the wash water thereby providing a rapid release of the detergent is going to be. It is preferred that at least one phase of the tablet dissolves in the wash water within the first 10 minutes, preferably 5 minutes, more preferably 4 minutes of the washing cycle of an automatic dishwashing or laundry washing machine. Preferably, the washing machine is an automatic dishwashing or laundry washing machine. The time during which the multiphase tablet or a phase thereof or a cleaning active ingredient dissolves is determined according to DIN 44990 using a dishwasher, available from Bosch, on the normal washing program at 65 ° C with a water hardness of 18 ° H at which a minimum of six or a sufficient number are used to ensure reproducibility.

The multiphase detergent tablet of the present invention comprises a first phase, a second and optionally subsequent phases. The first stage is in the form of a molded mass of a detergent composition comprising one or more detergent ingredients as described below. Preferred detergent ingredients include builders, bleaches, enzymes and surfactants. The components of the detergent composition are mixed together by, for example, adding dry ingredients or spraying liquid ingredients on them. A first phase is then formed from the components using suitable equipment, but preferably by pressing, for example in a tablet press. Otherwise, the first phase can be prepared by extrusion, casting, etc. The first phase can take various geometric shapes such as spheres, cubes, etc., but preferred embodiments generally have an axially symmetrical shape with a generally round, square or rectangular cross section.

The first phase is prepared to include at least one mold in the surface of the formed mass 10. The mold or molds may also have a different size and shape and position, orientation and topology from the first stage. For example, the mold or molds may generally have a circular, square or oval cross section; they may form a closed inner cavity or recess in the surface 15 of the formed mass, or they may extend between unconnected areas of the mass surface (e.g. axially opposite outer surfaces) so that one or more topological 'holes' in the formed mass 20 are being formed; and they can be placed axially or otherwise symmetrically with respect to the first phase or they can be placed asymmetrically. In a preferred embodiment, the mold is created using a specially designed tablet press in which the surface of the punch die that contacts the detergent composition is formed such that when it contacts and presses the detergent composition, it forms one mold or several molds in the first phase of the multiphase detergent tablet. Preferably, the mold will have an inwardly facing concave or substantially concave surface to provide improved adhesion to the second phase. Alternatively, the mold can be created by pressing a preformed mass of the detergent composition placed in a ring around a central mold thereby forming a molded mass with a mold in the form of a 1012583 9 cavity extending extends axially between opposing surfaces of the mass.

The tablets of the invention also contain one or more additional phases prepared from a composition or compositions comprising one or more of the detergent ingredients described below. At least one phase (referred to herein as a second phase) is preferably in the form of a granular solid (which term includes powders, granules, agglomerates and other granular solids including mixtures thereof with liquid binders, fusible solids, sprays, etc.) which are pressed into / within the one or more molds of the first phase of the detergent tablet such that the second phase itself takes the form of a formed mass. Any other phases include one or more compositions in the form of a separate layer or layers. Preferred detergent ingredients include builders, colorants, binders, surfactants, disruptants and enzymes, especially amylase and protease enzymes. According to another preferred aspect of the present invention, the second and optionally subsequent phases comprise a disrupting agent that can be selected from a disintegrant or an effervescent. Suitable disintegrants include agents which swell on contact with water or which facilitate water inflow and / or outflow through the formation of channels in the detergent tablet. For use here are thought of known disintegrating or effervescent agents which are suitable for use in laundry washing or washing applications. Suitable disintegrants include starches (such as natural, modified and pregelatinized starches, for example, those derived from corn, rice and potato starches), starch derivatives such as U-Sperse (trade name), Primojel (trade name) and Explotab (trade name) , celluloses, microcrystalline celluloses and cellulose derivatives such as Arbocel (trade name 101 2583 10 delsname) and Vivapur (trade name) both available from Rettenmaier, Nymcel (trade name) available from Metsa-serla, Avicel (trade name), Lattice NT (trade name) ) and Hanfloc (trade name), alginates, acetate trihydrate, burkeite, monohydrated carbonate of formula Na2CO3.H20, hydrated STPP with a phase I content of at least about 40%, carboxymethyl cellulose (CMC), CMC-based polymers, sodium acetate, aluminum oxide. Suitable effervescent agents are those which produce a gas 10 on contact with water. Suitable effervescent agents can be agents that generate oxygen, nitrogen dioxide or carbon dioxide. Preferred examples of effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with carbonic or other acids such as citric, sulfamic, malic or maleic acid.

The ingredients of the detergent composition are mixed together, for example by mixing the dry ingredients together and by mixing or spraying liquid ingredients. The components of the second and optionally subsequent phases are then fed to the mold provided by the first phase and held therein.

The preferred embodiment of the present invention comprises two phases; a first and a second phase. The first phase will usually comprise one mold and the second phase will usually consist of a single cleaning active composition. However, it can be envisioned that the first phase can contain more than one mold and the second phase can be prepared from more than one cleaning active composition. In addition, it can also be proposed that the second phase may comprise more than one cleaning active composition in one mold. It can also be proposed that a number of cleaning active compositions are contained in separate molds. In this way, potentially chemically sensitive detergent ingredients can be separated to avoid any performance loss caused by ingredients that react with each other and become potentially inactive or exhausted.

According to a preferred aspect of the present invention, the first, second and / or optionally subsequent phases may comprise a binder. In case the binder is present, it is selected from the group consisting of organic polymers, for example polyethylene and / or polypropylene glycols, in particular those with a molecular weight of 4000, 6000 and 9000, paraffins, polyvinylpyrrolidone (PVP), in the particular PVP with a molecular weight of 90,000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, for example hydroxypropylmethylcellulose (HPMC) and carboxymethylcellulose (CMC); and inorganic polymers such as hexametaphosphate-15. The binder is valuable both in terms of tablet integrity and in promoting dissolution of the first and second phases at different times as described below.

According to a preferred aspect of the present invention, the first phase weighs more than about 3 g, preferably more than about 4 g, and more preferably more than about 5 g. More preferably, the first phase weighs from about 10 g to about 30 g, even more preferably from about 15 g to about 25 g, and most preferably from about 18 g to about 24 g. The second and possibly subsequent phases weigh less than 4 g. The second and / or optionally subsequent phases more preferably weigh from about 0.1 g to about 3.5 g, preferably from about 1 g to about 3.5 g, and most preferably from about 1.3 g to about 3.5 g, 5 g.

In another embodiment of the present invention, a barrier layer comprising a barrier layer composition is placed between the first and second phases and / or optionally subsequent phases or even between the second and optionally subsequent phases. The barrier layer composition includes at least one binder selected from the group described above. The advantage of the presence of a barrier layer is to prevent or reduce the migration of components from one phase to another phase, for example from the first phase to the second and / or optionally subsequent phases and vice versa.

The components of the second and optionally subsequent phases are preferably pressed at a very low pressing pressure compared to the pressing pressure usually used to prepare tablets. An advantage of the present invention is thus that because a low pressing force is applied, detergent components that are sensitive to heat, strength or chemicals can be incorporated into the detergent tablet without the performance loss that usually occurs when such ingredients are incorporated into tablets. Alternatively, the second phase or phases can be pressed at the same or higher pressing force than the first phase so that the phases are dissolved at different times as described below.

Another advantage of the present invention is the improved protection of the second phase against damage caused, for example, by processing and transport. As described above, multiphase detergent tablets have been prepared in which the second layer is pressed at a lower pressing force than the first layer. Although the dissolution rate is increased, the second layer of these tablets becomes more susceptible to damage causing it to crumble or crumble upon contact. However, the lightly pressed phase (s) of the detergent tablets of the present invention are protected within the mold provided by the first phase of the detergent tablet.

Yet another advantage of the present invention is the ability to prepare a multiphase detergent tablet, wherein one phase can be designed to preferably dissolve significantly earlier than another phase. In the present invention 101? It is preferred that the second and optionally subsequent phase (s) dissolve earlier than the first phase. According to the preferred weight ranges described above, it is preferred that the first phase dissolves in 5 to 20 minutes, more preferably 10 to 15 minutes, and that the second and / or optionally subsequent phases dissolve in less than 5 minutes, more preferably less than 4.5 minutes and most preferably less than 4 minutes. Otherwise, the second phase may dissolve after the first or other phases 10, for example, in the event that it is desired to provide cleaning or rinsing effects towards the end of the wash operation. The time in which the first, second and / or possibly subsequent phases dissolve are independent of each other. According to a particularly preferred aspect of the present invention, a dissolution of the phases is thus achieved at different times. A particular advantage of dissolving the phases of the multiphase detergent tablet at different times is that a component which is chemically inactivated by the presence of another component can be kept separate in a different phase. In this case, the component which can be inactivated is preferably placed in the second and optionally subsequent phase (s).

Yet another advantage of the present invention is the improved inter-phase adhesion of the multiphase tablet. It is believed that the improved adhesion is achieved by a reduced exposure of the second phase compared to multiphase tablets known in the art, resulting in a lower susceptibility of the tablets of the present invention to break along the contact line between the phases.

Method 35

The multiphase detergent tablets are prepared using a suitable tabletting equipment, for example, a Courtoy R253. Preferably, the tablets are prepared by pressing in a tablet press capable of producing a tablet comprising a mold. In a particularly preferred embodiment of the present invention, the first phase is prepared using a specially designed tablet press following the procedure described below. The die punch (s) of this tablet press have been modified such that the surface of the die punch which contacts the cleaning media composition has a convex surface.

A first detergent composition is supplied to the die of the tablet press and the die punch is lowered so that it contacts the detergent composition, after which the detergent composition is pressed and a first phase is formed. The first detergent composition is pressed using an applied pressure of generally at least about 250 kg / cm2, preferably between about 350 and about 2000 kg / cm2, more preferably about 500 to about 1500 kg / cm2, and most preferably about 600 to about 1200 kg / cm2. The die punch is then raised to reveal the first stage containing a mold. A second and optionally subsequent detergent composition (s) is then fed to the mold. The specially designed tablet press die punch is then lowered a second time to lightly press the second and optionally subsequent detergent composition (s) to form the second and optionally subsequent phase (s). In another embodiment of the present invention in which an optional subsequent phase is present, the optional subsequent phase is prepared in an optional subsequent pressing step, which step is substantially the same as the second pressing step described above. The second and optionally subsequent detergent composition (s) is pressed at a pressure of preferably less than about 350 kg / cm2, more preferably about 40 to about 300 kg / cm2, and most preferably about 70 to about 270 kg / cm2. After pressing the second detergent composition, the die punch is raised a second time and the multiphase detergent tablet is released from the tablet press.

Detergent ingredients

The first and second and / or optionally subsequent phases 10 of the multiphase detergent tablet as described herein are prepared by pressing one or more compositions comprising detergent active ingredients. The compositions used in one or more of these phases may suitably include a variety of different detergent ingredients including builder compounds, surfactants, enzymes, bleaches, alkalinity sources, colorants, fragrances, lime soap dispersants, organic polymer compounds with including colorant transfer inhibiting polymers, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilizers, corrosion inhibitors, suds suppressants, solvents, fabric softeners, optical brighteners and hydrotropic agents.

Highly preferred first phase detergent ingredients include a builder compound, a surfactant, an enzyme and a bleaching agent. Highly preferred second phase detergent ingredients include builders, enzymes, crystal growth inhibitors and disruptors and / or binders

Builder compound 35 The tablets of the present invention preferably contain a builder compound which is usually present at a concentration of 1 to 80 wt%, preferably 10 to 70 wt% and most preferably 20 to 60 wt% on based on the weight of the composition of cleaning active ingredients.

5 Water-soluble builder compound

Suitable water-soluble builder compounds include the water-soluble monomeric polycarboxylates or their acidic forms, homo- or copolymeric polycarboxylic acids or salts thereof wherein the polycarboxylic acid comprises at least two carboxylic acid groups separated by no more than two carbon atoms, carbonates , bicarbonates, borates, phosphates and mixtures of one or more of the aforementioned.

The carboxylate or polycarboxylate builder can be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for their cost and performance.

Suitable carboxylates containing one carboxy group 20 include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salt of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartaric acid and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. In particular, polycarboxylates containing three carboxy groups include water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyl oxysuccinates disclosed in British Patent 1,379,241, lactoxy succinates disclosed in British Patent 1,389,732 and aminosuccines in Dutch application 7205873 and the oxypolycarboxylate materials such as 2-oxa-1,3,3-propane tricarboxylate which are described in British patent 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates described in British Patent 1 n125 83 17 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2, 3-propane tracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British patents 1,389,421 and 1,398,422 and in U.S. patent 3,936,448 and the sulfonated pyrolysed citrates disclosed in British patent 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentanedienidepentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicar 2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives described in British Patent 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule and more particularly citrates.

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

Borate builders as well as builders containing borate-forming materials that can produce borate when the detergent is stored or under washing conditions can also be used but are not preferred at washing temperatures below 50 ° C and in particular below 40 ° C.

Examples of carbonate builders are the alkaline earth 35 potassium and alkali metal carbonates including sodium carbonate and sesqui carbonate and mixtures thereof with ultrafine calcium carbonate as described in 101 2583 18

German Patent Application 2,321,001 published November 15, 1973.

Highly preferred builder compounds for use in the present invention are water-soluble phosphate builders. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymer phosphate where the degree of polymerization is in the range of 6 to 21, and salts of phytic acid.

Partially soluble or non-soluble builder compound

The tablets of the present invention may contain a partially soluble or insoluble builder compound. Partially soluble and insoluble builder compounds are particularly suitable for use in tablets prepared for use in laundry washing processes. Examples of partially water-soluble builders include the crystalline layered silicates as described, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. The crystalline layered sodium silicates of the general formula 2 NaMSixO 2 + 1.yH 2 O in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "sheet" structure, such as the so-called δ-layered structure, which is described in EP 0 164514 and EP 0 293640. Methods for the preparation of crystalline layered silicates of this type are described in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2.

10 2583 19

The most preferred crystalline layered sodium silicate compound has the formula 5-Na2Si2Os, known as NaSKS-6 (trade name) available from Hoechst AG.

The crystalline layered sodium silicate material 5 is preferably present in granular detergent compositions as a granular material intimately mixed with a solid, water-soluble ionizable material, as described in PCT application WO92 / 18594.

The solid, water-soluble ionizable material 10 is selected from organic acids, organic and inorganic acid salts, and mixtures thereof with citric acid being preferred.

Examples of highly water-insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites of the unit cell formula Naz [(AlO2) z (SiO2) y]. xH 2 O wherein z and y are at least 6, the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in the hydrated form and is preferably crystalline and contains from 10% to 28% and more preferably from 18% to 22% water in bonded form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably obtained synthetically. Synthetic crystalline aluminosilicate ion exchange materials are available under the trade names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.

A preferred method for synthesizing aluminosilicate zeolites is that described by Schoeman et al (published by Zeolite (1994) 14 (2), 110-116) in which the author describes a method for preparing colloidal aluminosilicate zeolites. Preferably, the colloidal aluminosilicate zeolite particles should be such that no more than 5% of the particles have a diameter greater than 1 μτα and no more than 5% of the particles have a diameter less than 1012583 20 than 0.05 μπι. Preferably, the aluminosilicate zeolite particles have an average particle diameter of between 0.01 μτα and 1 μπι, more preferably between 0.05 μτα and 0.9 μπι, and most preferably between 0.1 μπι and 0.6 μπι.

5 Zeolite A has the formula

Na12 [(AlO2) 12 (SiO2) 12]. Xh2 O where x is 20 to 30 and especially 27. Zeolite X 10 has the formula Na86 [(A102) 86 (SiO2) 106J. 276H20. Zeolite MAP as described in EP-B-384.070 is a preferred zeolite builder here.

Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When used as a constituent of a detergent composition, the colloidal aluminosilicate zeolites, especially the colloidal Zeolite A, provide increased builder performance in terms of providing improved stain removal. An increased builder performance is also seen in terms of reduced tissue build-up and improved preservation of the white color of tissues; problems believed to be associated with detergent compositions containing poor builders.

A surprising finding is that mixed aluminosilicate zeolite detergent compositions comprising colloidal Zeolite A and colloidal Zeolite Y provide an equally high sequestering performance for calcium ions over an equal weight of commercially available Zeolite A. Another surprising finding is that mixed aluminosilicate zeolite detergent compositions, as described above, provide improved sequestering performance for magnesium ions over an equal weight of commercially available Zeolite A. 35 1012583 21

Surfactant

Surfactants are preferred cleaning active ingredients of the compositions described herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic, and zwitterionic surfactants and mixtures thereof. Automatic dishwashing products should have the property of producing little foam and the foaming of the surfactant system for use in dishwashing processes should thus be suppressed or, most preferably, low foaming and usually have non-ionic properties. Foaming caused by surfactant systems used in laundry washing processes need not be to the same degree. suppressed as necessary when washing dishes. The surfactant is usually present at a concentration of 0.2 to 30 wt%, more preferably 0.5 to 10 wt%, and most preferably 1 to 5 wt% based on the weight of the composition of cleaning active ingredients.

A common list of anionic, nonionic, ampholytic and zwitterionic classes and species of these surfactants is given in U.S. Patent 3,929,678 issued December 30, 1975 to Laughlin and Heuring. A list of suitable cationic surfactants is given in U.S. Patent 4,259,217 issued March 31, 1981 to Murphy. A list of surfactants commonly included in dishwashing detergent compositions is given, for example, in EP-A-0 444 549 and PCT applications WO 93/08876 and WO 93/08874. 1 1012583 22

Non-ionic surfactant

Almost any nonionic surfactant useful for cleaning purposes can be included in the cleaning agent tablet. Preferred non-limiting classes of useful nonionic surfactants are listed below.

Non-ionic ethoxylated alcohol surfactant 10

The alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use here. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or 15 and generally contains 6 to 22 carbon atoms. The condensation products of alcohols with an alkyl group containing 8 to 20 carbon atoms, with 2 to 10 moles of ethylene oxide per mole of alcohol, are particularly preferred.

20

Alkylalkoxylate surfactant with an end group

A suitable alkylalkoxylate surfactant with an end group is the poly (oxyalkylated) alcohol with an epoxy end group, represented by the formula:

RiO [CH2CH (CHj) O] x [CHjCHjO] y [CH2CH (OH) R2] (I) wherein RL is a linear or branched aliphatic hydrocarbon group containing 4 to 18 carbon atoms, R2 is a linear or branched aliphatic hydrocarbon group having 2 to 26 carbon atoms, x is an integer with an average value of 0.5 to 1.5 and more preferably 1 and y is an integer with a value of at least 15 and more preferably at least 20 .

Preferably the surfactant of the formula I has at least 10 carbon atoms in the epoxide 101 23 end group [CH 2 CH (OH) R 2]. Suitable surfactants of the formula I of the present invention are the nonionic POLY-TERGENT® SLF-18B surfactants from Olin Corporation, as described, for example, in 5 WO 94/22800 published in the name of Olin Corporation on October 13, 1994 .

Polv (oxyalkylated) alcohols with an ether end group Preferred surfactants used here include poly (oxyalkylated) alcohols with an ether end group having the formula: R30 [CH2CH (R3) O] x [CH2] kCH (OH) [CH2] Jor2 15 wherein R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups of 1 to 30 carbon atoms, R 3 is H or a linear aliphatic hydrocarbon group of 1 to 4 carbon atoms, x 20 is an integer with an average is from 1 to 30, where when x is 2 or greater, R3 may be the same or different, and k and j are integers having an average value of 1 to 12 and more preferably 1 to 5.

R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups of 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. Most preferably R 3 is H or a linear aliphatic hydrocarbon group of 1 to 2 carbon atoms. Preferably x 30 is an integer with an average value of 1 to 20 and more preferably 6 to 15.

As described above, when in the preferred embodiments x is greater than 2, R3 may be the same or different. That is, R3 may have variously alternating different alkyleneoxy units as described above. For example, if x is 3, R3 can be chosen to include ethyleneoxy (EO) or 1012583 24 propyleneoxy (PO) and have different order such as (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). The integer three is, of course, chosen only as Example 5, and the variation may be much greater with a higher integer value for x and may include, for example, a larger number of (EO) units and a much smaller number of (PO) units.

Particularly preferred surfactants as described above include those having a low cloud point below 20 ° C. These low cloud point surfactants can then be used in conjunction with a high cloud point surfactant as described in detail below, so as to obtain judgments of excellent grease cleaning.

Most preferred poly (oxyalkylated) alcohol surfactants with an ether end group are those wherein k is 1 and j is 1, so that the surfactants have the formula: R30 [CH2CH (R3) O] xCH2CH (OH) CH 2 OR 2 wherein R 1, R 2 and R 3 are as defined above and 25 x is an integer with an average value of 1 to 30, preferably 1 to 20, and even more preferably 6 to 18. Surfactants in which R1 and R2 are in the range of 9 to 14, R3 is H to form an ethyleneoxy unit, and x is in the range of 6 to 15 are most preferred.

The poly (oxyalkylated) alcohol surfactants with an ether end group include three general ingredients, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end group. The alkyl-35 ether end group and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule, while the alkylene oxide group represents the hydrophilic, water-soluble portion of the molecule.

These surfactants show significant improvements in stain removal and film-forming properties and grease stain removal when used in conjunction with high cloud point surfactants over conventional surfactants.

Generally speaking, the ether-terminated poly (oxyalkylene-10) alcohol surfactants of the present invention can be prepared by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base so that a second epoxide is formed. The second epoxide is then reacted with an alkoxylated alcohol to form the new compounds of the present invention. Examples of methods for preparing the ether-terminated poly (oxyalkylated) alcohol surfactants are described below:

Preparation of C 1 -C 4 -alkyl glidyl ether

A C12 / 14 fatty alcohol (100.00 g, 0.515 mol) and 25 tin (IV) chloride (0.58 g, 2.23 mmol available from Aldrich) are combined in a 500 ml two-neck round bottom flask equipped with a cooler, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C. Epichlorohydrin 30 (47.70 g, 0.515 mol, available from Aldrich) is added dropwise to maintain the temperature between 60 and 65 ° C. After stirring an additional hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) while stirring mechanically.

After complete addition, the mixture is heated at 90 ° C for 1.5 hours, cooled and filtered with ethanol.

101 2583 26

The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO 4, filtered and concentrated. Distillation of the oil at 100-120 ° C (0.1 mm Hg) gave the glycidyl ether as an oil.

5

Preparation of an alcohol surfactant with a ClV2 -alkyl-Co / .alpha.1-ether end group

Neodol® 91-8 (20.60 g, 0.0393 mol) ethoxylated alcohol (available from the Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) are combined in a 250 ml three neck round bottom flask equipped with a cooler, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C at which point C12 / 14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 minutes. After stirring at 60 ° C for 18 hours, the mixture is cooled to room temperature and dissolved in an equal amount of dichloromethane. The solution is passed through a 1 inch (2.54 cm) silica gel pad eluting with dichloromethane. The filtrate is concentrated by film evaporation and then purified in a kugelrohr oven (100 ° C, 0.5 mm Hg) to obtain the surfactant as an oil.

25

Non-ionic ethoxylated / propoxylated fatty alcohol surfactant

The ethoxylated C6-C18 fatty alcohols and mixed ethoxylated / propoxylated C6-C18 fatty alcohols are suitable surfactants to use here, especially where they are water-soluble. Preferably, the ethoxylated fatty alcohols are the ethoxylated C10-C18 fatty alcohols with an ethoxylation degree of 3 to 50, most preferably these are the ethoxylated C12-C1B fatty alcohols with an ethoxylation degree of 3 to 40. Preferably the mixed ethoxylation The propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, an ethoxylation degree of 3 to 30 and a propoxylation degree of 1 to 10.

5 Non-ionic EO / PO condensates with propylene alcohol

The condensation products of ethylene oxide with a hydrophobic phase formed by the condensation of propylene oxide with propylene glycol are suitable for use here. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and is insoluble in water. Examples of compounds of this type include some of the commercially available Pluronic ™ surfactants marketed by BASF.

Non-ionic EO condensation products with propylene oxide ethylene diamine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine are suitable for use here. The hydrophobic residue of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic ™ compounds marketed by BASF.

30

Mixed system of non-ionic surfactants

In a preferred embodiment of the present invention, the detergent tablet comprises a mixed system of nonionic surfactants comprising at least one low cloud point nonionic surfactant 101 2583 28 and at least one high ionic nonionic surfactant cloud point.

"Cloud point", as used herein, is a known property of nonionic surfactants that results from the surfactant becoming less soluble with increasing temperature. The temperature at which a second phase appears noticeably is referred to as the "cloud point" (see Kirk Othmer's Encyclopedia of Chemical Technology, 3rd ed. 10 vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is defined as a component of the system of nonionic surfactants with a cloud point less than 30 ° C, preferably less than 20 ° C and with most preferably less than 10 ° C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from a primary alcohol and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Also, such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohols (e.g., Poly-Ter-gent® SLF18 series from the Olin Corporation), poly (oxyalkylated) alcohols with an epoxy end group (e.g. the Poly-Tergent® SLF18B of non-ionic surfactants from Olin Corporation as described, for example, in WO 94/22800, published October 13, 1994 in the name of Olin Corporation) and the poly (oxyalkylated) alcohol surfactants with an ether end group.

Non-ionic surfactants may optionally contain propylene oxide in an amount up to 15% by weight. Other preferred nonionic surfactants can be prepared by the methods described in U.S. Patent 1012583 29 4,223,163 issued September 16, 1980 to Builloty and referred to herein.

In addition, low cloud point nonionic surfactants include a polymeric compound containing polyoxyethylene, polyoxypropylene blocks. Polymeric compounds containing polyoxyethylene-polyoxypropylene blocks include those based on ethylene glycol, propylene glycol, glycerol, trimethylol propane, and ethylenediamine as initiator reactive hydrogen compound. Some of the surfactant block polymeric compounds designated PLURONIC®, REVERSED PLURONIC® and TETRONIC® from the BASF-Wyandotte Corp., Wyandotte, Michigan are suitable in ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactants are normally useful here as non-ionic low cloud point surfactants.

As used herein, a "high cloud point" nonionic surfactant is defined as a component of the system of nonionic surfactants with a cloud point greater than 40 ° C, preferably greater than 50 ° C, and more preferably higher than 60 ° C. Preferably, the system of non-ionic surfactants comprises an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkyl phenol with 8 to 20 carbon atoms, with an average of 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by Shell).

For the purposes of the present invention, it is also preferred that the high cloud point nonionic surfactants further have a "hydrophilic-lipophilic balance" ("HLB", see Kirk Othmer above) value in the range of 9 to 15 and preferably 101 to have 11 to 15. Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhoda-surf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another non-ionic high cloud point surfactant is derived from a linear or preferably branched chain fatty alcohol or a secondary fatty alcohol of 6 to 20 carbon atoms (C6-C20 alcohol), including secondary alcohols and primary 10 branched chain alcohols. Preferably, the high cloud point nonionic surfactants are ethoxylates of a branched or secondary alcohol and more preferably mixed ethoxylates of a C9 / 11 or C11 / ls branched alcohol condensed at an average of 6 to 15 moles , preferably 6 to 12 moles, and most preferably 6 to 9 moles, of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.

20

Anionic surfactant

Virtually any anionic surfactant useful for cleaning purposes is suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants fabrics. Anionic sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinate (in sulfosuccinate) especially saturated and unsaturated C6-C14 diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable such as rosin, hydrogenated rosin and resin acids and hydrogenated rosin acids present in or derived from tallow oil.

5

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, vetoleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17-acyl-N- (C ^ -C ^ - alkyl) and -N- (C 1 -C 2 -hydroxyalkyl) glucamine sulfates and sulfates of alkyl polysaccharides such as the sulfates of alkyl polygluco-15 side (the nonionic unsulfated compounds being described here).

Alkyl sulfate surfactants are preferably selected from the linear and branched C 1 -C 18 alkyl sulfates, and more preferably from the C 11 -C 15 -2 branched alkyl sulfates and the C 12 -C 14 linear chain alkyl sulfates.

Alkylethoxy sulfate surfactants are preferably selected from the group consisting of the C10-C1B alkyl sulfates ethoxylated with 0.5 to 20 moles of ethylene oxide per 25 molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cn-C18 and most preferably Cn-C18 alkyl sulfate which is ethoxylated with 0.5 to 7 and preferably 1 to 5 moles of ethylene oxide per molecule.

According to a particularly preferred aspect of the invention, mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants are used. Such mixtures are described in PCT application WO 93/18124.

35 1012583 32

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of linear C5-C20 alkylbenzene sulfonates, alkyl ester sulfonates, primary or secondary C5-C22 alkane sulfonates, C6-C24 olefin sulfonates, sulfonate polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, vetoleyl glycerol sulfonates and mixtures thereof.

10

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycolboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps ("alkyl carboxyls"), and in particular certain secondary soaps as described herein.

Suitable alkyl ethoxycarboxylates include those of the formula RO (CH 2 CH 2 O) x CH 2 COO M + wherein R is a C 6 -C 18 alkyl-2 O group, x ranges from 0 to 10 and the ethoxylate distribution is such that the amount of material is by weight where x is 0, less than 20% and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those of the formula RO- (CHRjl-CHRj-O) -R3 wherein R is a C6-C18 alkyl group, x is 1 to 25 and R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid group, succinic acid group, hydroxy succinic acid group and mixtures thereof and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants herein are water-soluble materials selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2 -propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressants.

5

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R1) CHlCOOM, where R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is a C 1 -C 2 alkyl group and M is an alkali metal ion is. Preferred examples are the myristyl and oleoylmethylsarcosinates in the form of their sodium salts.

15

Amphoteric surfactant

Suitable amphoteric surfactants used here include the aminoxide surfactants and the alkyl amphocarboxylic acids.

Suitable aminoxides include those compounds of the formula R3 (OR4) XN ° (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group, or mixtures thereof, having from 8 to 26 carbon atoms, R4 and alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof, x is 0 to 5 and preferably 0 to 3 and each R5 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide groups. C10-C1B-alkyl dimethylamine-3-oxide and C10.18-acylamidoalkyldimethylamine-oxide are preferred.

A suitable example of an alkyl amphodicarboxylic acid is Miranol ™ C2M Conc. produced by Miranol, Ine., Dayton, NJ.

35 .....

101 2583 34

Zwitterionic surfactant

Zwitterionic surfactants can also be included in their detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultain surfactants are examples of zwitterionic surfactants used here.

Suitable betaines are those compounds of the formula R (R ') 2N + R 2 COO' where R is a C 6 -C 18 hydrocarbyl group, each R 1 is normally C 1 -C 3 alkyl and R 2 is a C 1 -C 18 hydrocarbyl group. Preferred betaines are C12-C18 dimethylammoniohexanoate and the C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use here.

Cationic surfactants

Cationic ester surfactants used in this invention are preferably water-dispersible compounds with surfactant properties, comprising at least one ester (i.e. COO) bond and at least one cationically charged group. Other suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in U.S. Patents 4228042, 4239660, and 4260529.

Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono-C6-C16, preferably C6-C10, -N-alkyl or -alkenylammonium surfactants, preferably 1012583 wherein the remaining N positions are with methyl -, hydroxyethyl or hydroxypropyl groups are substituted.

Enzymes 5

Enzymes are detergent components of the first phase and more particularly of the second and / or optionally other preferred phases. When enzymes are present, these are selected from the group 10 consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullalanases, tannases, pentosanases, malana-15 senes, / S-glucanases, arabinosidases, hyaluronidase, chronroidinase, laccase or mixtures thereof.

Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase and / or cellulase together with one or more enzymes that degrade the plant cell wall.

The cellulases in. The present invention useful include both bacterial and fungal cellulose. Preferably they will have a pH optimum between 5 and 12 and an activity greater than 50 CEVU (Cellulose Viscosity 25 Unit). Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO 96/02653 which describe fungal cellulases produced from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. EP 739 982 discloses cellulases isolated from new Bacillus species. Suitable cellulases are also described in GB-A-2,075,028, GB-A-2,095,275, DE-OS-2,247,832 and WO 95/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. Thermoidea), in particular the Humicola strain DSM 1800. Other suitable cellulases are 1012583 36 cellulases from Humicola insolens with a molecular weight of 50 KDa, an isoelectric point of 5.5 and 415 amino acids, and a ~ 43 kD endoglucanase from Humicola insolens, DSM 1800, exhibiting cellulase-5 activity; a preferred endoglucanase component is described with its amino acid sequence in PCT application WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO 94/21801, Genecor, published September 10, 1994. Particularly suitable cellulases are the cellulases with color care benefits. Examples of such cellulases are cellulases described in European patent application 91202879.2 filed November 6, 1991 (Novo). Carezyme 15 and Celluzyme (Novo Nordisk A / S) are particularly useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases for tissue care and / or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

The cellulases are usually included in the detergent composition at concentrations of 0.0001 to 2% by weight of active enzyme based on the weight of the detergent composition.

Peroxidase enzymes are used together with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching the solution", ie preventing the transfer of dyes or pigments which, during washing operations of substrates are removed on other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chlorine and bromine peroxidase. Peroxidase-containing cleanser compositions are described, for example, in PCT International Applications WO 89/099813 and WO 89/09813 and in European Patent Application 91202882.6, 101 2583 37 filed November 6, 1991, and 96870013.8 filed February 20, 1996. The laccase enzyme is also suitable.

Preferred promoters are substituted phenanthiazine and phenoxasin, 10-phenothiazine-propion-5 acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP), and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (substituted C3 -C5 alkyl syringates) and phenols. Sodium percarbonate and / or perborate are preferred hydrogen peroxide sources.

The cellulases and / or peroxidases are usually included in the detergent composition at concentrations from 0.0001 to 2% by weight of active enzyme based on the weight of the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases. Suitable detergent lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, described in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody produced by the microorganism Pseudomonas fluorescent IAM 25 1057. This lipase is available from Amano

Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Amano-CES, lipases from Chromobacter viscosum, for example Chromobacter viscosum var. lipolytum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Diosynth Co., the Netherlands and lipases from Pseudomonas gladio li. Particularly suitable lipases are lipases such as M135 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR (Novo) which have proven to be very effective when combined with the compositions of the present invention.

thing to be used. Also suitable enzymes are the lipolytic enzymes described in EP 258 068, WO

92/05249 and WO 95/22615 in the name of Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 in the name of Unilever.

Also suitable are cutinases [EC 3.1.1.50] which are considered as

a special type of lipase can be considered, namely lipases that do not require interfacial activation. Addition of cutinases to detergent compositions are described, for example, in WO-A-88/09367 (Genencor), WO 10 90/09446 (Plant Genetic System) and WO 94/14963 and WO

94/14964 (Unilever).

The lipases and / or cutinases are usually included in the detergent composition at concentrations of 0.0001 to 2% by weight of active enzyme based on the weight of the detergent composition.

Suitable proteases are the subtilisins obtained from specific strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protease is obtained from a strain of Bacillus with maximum activity over the entire pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / s of Denmark, hereinafter referred to as "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 in the name of Novo. Other suitable proteases include KANNASE®, ALCALASE®, DURAZYM®, and SAVINASE®, from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM®, (protein-modified Maxacal) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in European Patent Application Serial No. 87 303761.8 filed April 28, 1987 (especially pages 17, 24 and 98) and herein referred to as "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme herein referred to as "Protease A". A suitable enzyme is what is here called "Protease C" and is a variant of an alkaline serine protease from Ί n1 9R R3 39

Bacillus in which position 27 replaced lysine nrginine, replaced tyrosine valine in position 104, replaced serine asparagine in position 123 and replaced alanine threonine in position 274. Protease C is described in EP 90915958.4 according to WO 91/06637 published May 16, 1991. Genetically modified variants, particularly those of Protease C, are also intended herein.

A preferred protease, designated "Protease D", 10 is a carbonyl hydrolase variant with an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by a number of amino acid residues at a position in the carbonyl hydrolase, equivalent to position + 76, to be replaced by another amino acid, preferably also together with one or more amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260 , +265 and / or +274 according to the numbering of Bacillus amyloliguefaciens subtilisin as described in WO 95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" with US serial number 08 / 322,677, filed October 13, 1994.

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO 91/02792 and the variants thereof described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A in the name of Novo. Enzymatic cleaners comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03 52 9 A in the name of Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available as described in WO 95/07791 in the name of Procter & Gamble. A recombinant detergent trypsin-like protease suitable herein 101 2583 40 is described in WO 94/25583 in the name of Novo. Other suitable proteases are described in EP 516 200 to Unilever.

Other preferred protease enzymes include protease enzymes which are a carbonyl hydrolase variant with an amino acid sequence not found in nature, which is derived by replacing some amino acid residues of a precursor carbonyl hydrolase with other amino acids, the number of amino acid residues replaced in the precursor enzyme corresponds to position +210 together with one or more of the following residues: + 33, +62, +67, +76, +100, +101, +103, +104, +107 , +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions correspond to naturally occurring subtilisin from Bacillus amvloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those with changes at 20 positions +210, +76, +103, +104, +156 and +166.

The proteolytic enzymes are included in the detergent compositions of the present invention at a concentration of 0.0001 to 2 wt%, preferably 0.001 to 0.2 wt%, more preferably 0.005 to 0.1 wt% pure enzyme based on the weight of the composition.

Amylases (a- and / or / 3-) can be included to remove carbohydrate-based stains. WO 94/02597, Novo Nordisk A / S, published February 3, 1994, discloses detergent compositions incorporating mutant amylases. See also WO 95/10603, Nordisk A / S, published April 20, 1995. Other amylases known to be used in detergent compositions include both ot and β-amylases. α-35 Amylases are known in the art and include those described in US 5,003,257, EP 252,666, WO 91/00353, FR 2,676,456, EP 285,123, EP 525,610, EP 368,341 and 1012583 41

British Patent Specification 1,296,839., (Novo). Other suitable amylases are stability-enhanced amylases described in WO 94/18314, published August 18, 1994, and WO 96/05295, Genencor, published February 22, 1996, and amylase variants with an additional modification in the immediate parent, available from Novo Nordisk A / S described in WO 95/10603 published April 1995. Also suitable are amylases described in EP 277 216, WO 95/26397 and WO 96/23873 (all in the name of Novo Nordisk).

Examples of commercially available α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, Natalase®, all available from Novo Nordisk A / S Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized by a specific activity that is at least 25% higher than the specific activity of Termamyl® in a temperature range from 25 ° C to 55 ° C and at a pH- value in the range of 8 to 10 as measured by the Phadebas® or amylase activity assay. Suitable variants of the above enzymes are described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO 95/35382.

Preferred amylase enzymes include those described in WO 95/26397 and in the pending application of Novo Nordisk PCT / DK96 / 00056.

The amylolytic enzymes are included in the detergent compositions of the present invention at a concentration of. 0.0001 to 2 wt%, preferably 0.00018 to 0.06 wt%, and more preferably 0.00024 to 0.048 wt% pure enzyme based on the weight of the composition.

In a particularly preferred embodiment, detergent tablets of the present invention comprise amylase enzymes, in particular those described in WO 95/26397 and pending application 101 2583 42 in the name of Novo Nordisk PCT / DK96 / 00056 in combination with a complementary amylase.

By "complementary" is meant the addition of one or more amylases suitable for cleaning purposes. Examples of complementary amylases (a-and / or β-) are described below. WO 94/02597 and WO 95/10603, Novo Nordisk A / S, describe detergent compositions incorporating mutant amylases. Other amylases known to be used in detergent compositions include both ar and β amylases. ar-Amylases are known in the art and include those described in US patent

5,003,257, EP 252,666, WO / 91/00353, FR 2,676,456, EP

285,123, EP 525,610, EP 368,341, UK Patent Specification 1,296,839 (Novo). Other suitable amylases are stable

titration enhanced amylases described in WO 94/18314 and WO 96/05295, Genencor, and amylase variants with an additional modification in the immediate parent, available from Nordisk A / S, described in WO 95/10603. Also suitable are amylases described in EP 277 216 (Novo Nordisk). Examples of commercially available ar-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl® all available from Novo Nordisk A / S Denmark. WO 95/26397 describes other suitable amylases: θ'-amylases characterized by a specific activity that is at least 25% higher than the specific activity of Termamyl® in a temperature range of 25 ° C to 55 ° C and at a pH value in the range of 8 to 10 as measured by the Phadebas® Q! amylase activity assay. Variants of the above enzymes described in WO 96/23873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO 95/35382. Preferred complementary amylases in the present invention are the amylases sold under the trade name Purafect Ox Am® described in WO 94/18314, WO

101 2583 43 96/05295 sold by Genencor, Termamyl®, Fungamyl®, Ban®, Natalase® and Duramyl®, all available from Novo Nordisk A / S, and Maxamyl® from Gist-Brocades.

The complementary amylase is generally included in the detergent compositions of the present invention at a concentration of 0.0001 to 2 wt%, preferably 0.00018 to 0.06 wt%, and more preferably 0.00024 to 0.048 wt% pure enzyme based on the weight of the composition. Preferably, the weight ratio of pure enzymes, from the specific amylase to the complementary amylase, is between 9: 1 to 1: 9, more preferably between 4: 1 and 1: 4, and most preferably between 2: 1 and 1: 2.

The above enzymes can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The lineage can furthermore be mesophilic or extremophilic (psychrophilic, psychrotropic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. By definition, mutants or native enzymes are also included. Mutants can be obtained, for example, by protein and / or genetic engineering and chemical and / or physical modifications of native enzymes. However, it is common to express the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.

The enzymes are usually included in the detergent composition at concentrations from 0.0001 to 30% by weight of active enzyme based on the weight of the detergent composition. The enzymes can be added as separate ingredients (pills, granules, stabilized liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (for example, combined granules).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in copending European Patent Application 92870018.6 filed January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A number of enzyme materials and methods of incorporating them into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A, in the name of Genencor International, WO 8908694 A in the name of Novo, and US 3,553,139, January 5, 1971, name of McCarty 10 et al. Enzymes are further described in US 4,101,457, Place et al, July 18, 1978 and in US 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent compositions and their incorporation into such compositions are described in US 15 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in US 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US 3,519,570. A useful Bacillus, sp. AC13 providing proteases, xylanases and cellulases is described in WO 9401532 A in the name of Novo.

25 Bleach

A highly preferred component of the composition of detergent ingredients is a bleaching agent. Suitable bleaching agents include chlorine and oxygen-releasing bleaching agents.

In a preferred aspect, the oxygen-releasing bleach contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs through an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In another preferred aspect, a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a preformed organic peroxyacid are also included.

Inorganic Perhydrate Bleaches The compositions of detergent ingredients preferably include a source of hydrogen peroxide as an oxygen-emitting bleach. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.

The inorganic perhydrate salts are usually included in the form of the sodium salt at a concentration of 1 to 40 wt%, more preferably 2 to 30 wt%, and most preferably 5 to 25 wt% based on the weight of the compositions.

Examples of inorganic perhydrate salts 20 include perborate, percarbonate, perphosphate, persulphate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, with respect to a number of perhydrate salts, in the preferred embodiments of such granular compositions, use is made of a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate may exist in the form of the monohydrate of the nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20.

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates for inclusion in compositions of the invention. Sodium percarbonate is an addition compound of the formula corresponding to 2Na2CO3.3H2O2 and is 101258346 commercially available as a crystalline solid. Sodium percarbonate, which is a hydrogen peroxide additive compound, tends to release the hydrogen peroxide rather quickly upon dissolution, which may result in locally high bleach concentrations. The percarbonate is most preferably incorporated into such compositions in a coated form that provides in-product stability.

A suitable coating material that provides in-product stability includes a mixed salt of a water-soluble alkali metal sulfate and carbonate. Such coatings, along with the coating processes described previously in GB 1,466,799, issued to Interox on March 9, 1977. The weight ratio of the mixed salt as coating material to the percarbonate is in the range of 1: 200 to 1: 4. more preferably 1:99 to 1: 9 and most preferably 1:49 to 1:19. Preferably, the mixed salt is a salt of sodium sulfate and sodium carbonate which has the general formula Na 2 SO 4 nNa 2 CO 3 20, wherein n 0.1 to 3, preferably 0.3 to 1.0, most preferably 0.2 to 0, 5.

Another suitable coating material that provides an in-product stability includes sodium silicate with an SiO 2: Na 2 O ratio of 1.8: 1 to 3.0: 1, and preferably 1.8: 1 to 2.4: 1 and / or sodium metasilicate which preferably in a concentration of 2 to 10 wt% (usually 3 to 5 wt%) SiO 2 based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings containing silicate-30 and borate salts or boric acids or other inorganic compounds are also suitable.

Other coatings containing waxes, oils, grease soaps can be used advantageously in the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt that can be used in the compositions here.

1012583 47

Peroxic acid bleach precursor __

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. In general, peroxyacid bleach precursors can be represented as

O

10 II

X-C-L

wherein L is a leaving group and X can be virtually any functionality, so that upon perhydrolysis the structure of the produced peroxyacid

O

II

X-C-OOH

20.

Peroxyacid agent precursor compounds are preferably included at a concentration of 0.5 to 20% by weight, more preferably 1 to 10% by weight, and most preferably 1.5 to 5% by weight based on the weight of the compositions.

Suitable peroxyacid bleach precursor compounds normally contain one or more N or O acyl groups which precursors can be selected from a wide class range. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 35 1147871, 2143231 and EP-A-0170386.

1012583 48

Departing groups

The leaving group, hereinafter referred to as L group, must be sufficiently reactive that the perhydrolysis series reaction occurs within the optimal time period (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of: 0 Λ o

II / ^ II

-N-C-R1 -N N-N-C-CH-R4 R5 'U' γ

Y.

R3 Y

I I

-o-ch = c-ch = ch2 —o-ch = c-ch = ch2

I I

O v o

II Y II

o ch2-c) - - - - c - R1 - J ^ NR4 -N '/ NR4

II II

o o

R3 and O Y

1 II I

-0 ~ C = CH R - N - S - CH - R4

L II R3 O

(01 2583 49 and mixtures thereof, wherein R 1 is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R 3 is an alkyl chain having 1 to 8 carbon atoms, R 4 is H or R 3, R 5 is an alkenyl chain with 1 to 8 carbon atoms and YH or is a solubility-enhancing group R1, R3 and R4 may be substituted by virtually any functional group, including, for example, alkyl, hydroxy, alkoxy, halide, amine, nitrosyl , amide and ammonium or alkyl ammonium groups.

Preferred solubility enhancing groups are -SO 3'M +, -CO 2'M +, -SO 4 "M *, -N * (R 3) 4X" and 0 <-N (R 3) 3, and most preferably -SO 3 "Pr, and -CO 2" M * where R 3 is an alkyl chain of 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. alkali metal, ammonium or substituted ammonium cation with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid upon perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyloxybenzene sulfonates including, for example, benzoyloxybenzene sulfonate:

O

101 2583 50

Also suitable are the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents including, for example: ^ OAc

AcO "T ^ _0) T ^ uOAc / O Ac OBz

Ac = COCHj; Bz = Benzoyl 5 Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoylethylene diamine and the N-benzoyl substituted urea compounds. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine, and benzoylpyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides and the compound of the formula: O o

(QJO 'O ^ COOH

Phthalic anhydride is another perbenzoic acid precursor compound suitable here: 101 2583 ®ί ο

Suitable N-acylated lactamper benzoic acid precursors have the formula: 0

II

o c-ch2-ch2 R 11 I I

R 5 -C-N 2, 1, CH 2 CH 2] n where n is 0 to 8 and preferably 0 to 2 and R 5 is a benzoyl group.

5 Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursors provide substituted perbenzoic acids upon perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include any of the perbenzo-10-acid acid precursors described herein in which the benzoyl group is substituted by a non-positively charged (i.e., non-cationic) functional group, including, for example, alkyl, hydroxy- , alkoxy, halide, amine, nitrosyl and amide groups.

A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds having the following general formulas:

r1_c_n_r2_c —L R1 — N —C —R2 —C —L

II | ! i L II II

0 R5 0 or RO 0 101 2583 52 wherein R1 is an aryl or alkaryl group having 1 to 14 carbon atoms, R2 is an arylene or alkarylene group having 1 to 14 carbon atoms and R5 is H or an alkyl, aryl or alkaryl group having Is 1 to 10 carbon atoms and L can be virtually any 5 leaving group. R1 preferably contains 6 to 12 carbon atoms. R2 preferably contains 4 to 8 carbon atoms. R1 may be an aryl, substituted aryl or alkylaryl with branching, substitution or both and may be from synthetic sources or natural sources, including, for example, tallow fat. Analogous structural variations are allowed for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 15 18 carbon atoms in total. Amide substituted bleach activators of this type are described in EP-A-0170386.

Cationic peroxyacid precursors

Cationic Peroxyacid Precursor Compounds 20 provide cationic peroxyacids upon perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid portion of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are normally present in the compositions as a salt with a suitable anion such as, for example, a halide ion or a methyl sulfate ion.

The peroxyacid precursor compound to be cationically substituted as such may be a perbenzoic acid or a substituted derivative thereof or a precursor compound as described above. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide-substituted alkyl peroxyacid precursor as described below.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406, 4,751,015, 4,988,451,

5 4.397.757, 5.269.962, 5.127.852, 5.093.022, 5.106.528, UK

1,382,594, EP 475,512, 458,396 and 284,292 and in JP 87-318,332.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactams and monobenzoyl tetraacetyl glucose benzoyl peroxides.

A preferred cationically substituted benzoyloxybenzene sulfonate is the 4- (trimethylammoni-15 µm) methyl derivative of benzoyloxybenzene sulfonate: O- <0) SO3- / + / \

A preferred cationically substituted alkyloxybenzene sulfonate has the formula: • ™ ^ _ioicrS01

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammoniummethylenebenzoylcaprolactams, especially trimethylammoniummethylenebenzoylcaprolactam: 1012583 54 O 0

. rJL

- '. jO ίο'

Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammoniummethylenealkyl caprolactams: 0 0

II U

wherein n is 0 to 12 and especially 1 to 5.

Another preferred cationic peroxyacid precursor is 2- (Ν, Ν, Ν-trimethylammonium) ethyl sodium 4-sulfophenyl carbonate chloride.

Alkyl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids upon perhydrolysis. Preferred precursors of this type provide peracetic acid upon perhydrolysis.

Preferred alkyl percarboxylic acid precursor compounds of the imide type include the N, N, N1, N1-15 tetraacetylated alkylenediamines in which the alkylene group contains 1 to 6 carbon atoms and in particular those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyl-101 2583 55 oxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS), and pentaacetyl glucose.

Amide Substituted Alkyl Peroxyacid Precursors Amide substituted alkyl peroxyacid precursors are also suitable including those having the following general formulas:

R1 — Q - n - R2 - C - L Rr — N - C - R2 - C - L

II L II L II II

0 Rb 0 o Rb 0 0 wherein R 1 is an alkyl group of 1 to 14 carbon atoms, R 2 10 is an alkylene group of 1 to 14 carbon atoms and R 5 is H or an alkyl group of 1 to 10 carbon atoms and L can be virtually any leaving group. R1 preferably contains 6 to 12 carbon atoms. R2 preferably contains 4 to 8 carbon atoms. R1 may be a linear or branched alkyl with branching, substitution or both and may be from synthetic or natural sources, including, for example, tallow fat. Analogous structural variations are possible for R2. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activators of this type are described in EP-A-0170386.

m1? R 83 56

Benzoxazine organic peroxic acid precursors

Also suitable are benzoxazine type precursor compounds as described, for example, in EP-A-332,294 and EP-A-482,807, especially those of the formula: including the substituted type benzoxazines

Ra rs wherein R3 is H, alkyl, alkaryl, aryl, arylalkyl and wherein R2, R3, R4 and Rs may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino , alkylamino, COOR6 (where R5 is H or an alkyl group) and carbonyl functions.

A particularly preferred precursor of the benzoxazine type is: 1012583 57

O

Pre-formed organic neroxic acid

The organic peroxyacid bleaching system may contain, in addition to or instead of an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid 5, typically in a concentration of 0.5 to 25 wt%, and more preferably 1 to 10 wt% based on the weight of the composition. '

A preferred class of organic peroxyacid compounds are the amide substituted compounds having the following general formulas:

R1 - C - N - R2 - C - OOH

II 15 II

0 Rb O

R1-N - Q - r2-c - OOH

I. II II

R5 O O

wherein R1 is an alkyl, aryl or alkaryl group of 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group of 1 to 14 carbon atoms and R5 is H or an alkyl, aryl or alkaryl group of 1 to 10 carbon atoms. R1 preferably contains 6 to 12 carbon atoms. R2 preferably contains 4 to 8 carbon atoms. R1 may be a linear or branched alkyl, substituted aryl or alkylaryl with branching, substitution or both and may be from 1012581 58 from synthetic sources or natural sources, including, for example, tallow fat. Analogous structural variations are possible for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxy dodecanoic acid, diperoxy tetradecanoic acid and diperoxy hexadecanoic acid. Dibenzoyl peroxide is a preferred organic peroxyacid here. Mono- and diperazelaic acid, mono- and diper-15 brassylic acid and N-phthoylaminoperoxycaproic acid are also suitable here.

Controlled release rate - means

An agent can be provided to control the rate of release of the bleach, especially the oxygen bleach, to the wash solution.

Bleaching rate control means can provide controlled delivery of peroxide species to the wash solution. Such an agent could, for example, control the delivery of an inorganic perhydrate salt acting as a source of hydrogen peroxide to the wash solution.

Another mechanism for controlling the rate of release of bleach may be to coat the bleach with a coating designed to provide controlled release. Thus, the coating may, for example, comprise a poorly water soluble material or a coating of sufficient thickness such that the kinetics of dissolving the thick coating provides the controlled rate of release.

The coating material can be applied by various methods. Each coating material is normally present in a coating material to bleach weight ratio of 1:99 to 1: 2, and preferably 1:49 to 1: 9.

Suitable coating materials include triglycerides, (eg, partially) hydrogenated vegetable oil, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and mixtures thereof.

Other suitable coating materials may include the alkali and alkaline earth metal sulfates, silicates and carbonates, including calcium carbonate and silicas.

A preferred coating material, especially for an inorganic perhydrate salt bleaching source, comprises sodium silicate in a ratio of 20 SiO 2: Na 2 O from 1.8: 1 to 3.0: 1, and preferably 1.8: 1 to 2 , 4: 1 and / or sodium metasilicate, which is preferably applied in a concentration of 2 to 10% by weight (usually 3 to 5% by weight) of SiO 2 based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

Any inorganic salt coating material can be combined with organic binder materials to provide composite coatings of an inorganic salt / organic binder. Suitable binders include C10-C20 alcohol ethoxylates with 5-100 moles of ethylene oxide per mole of alcohol and more preferably the primary C15-C20 alcohol ethoxylates with 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 106, preferably from 1000 to 400,000 and most preferably from 1,000 to 10,000 are examples of such polymeric materials .

Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride being at least 20 mol% of the polymer, are other examples of polymeric materials useful as binders. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the above C10-C20 alcohol ethoxylates with 5-100 moles of ethylene oxide per mole. Other examples of binders include the C10-C20 mono- and diglycerol ethers and also the C10-C20 fatty acids.

Cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose and homo- or copolymeric polycarboxylic acids or their salts are other examples of binders suitable for use here.

One method of applying the coating material relates to agglomeration. Preferred agglomeration processes include the use of any of the organic binder materials described above. A conventional agglomerator / mixer 25 can be used, including but not limited to a pan, rotary drum and vertical mixer types. Molten coating compositions can also be applied, either by pouring or spraying them over a moving bed of the bleach.

Another means of providing the required controlled release includes a mechanical agent for modifying the physical properties of the bleach to control its solubility and rate of release. Suitable protocols may also include pressing, mechanical injection, manual injection, and adjustment of the solubility of the bleaching compound by selection of the particle size of a granular component.

Although the choice of particle size will depend on both the composition of the granular constituent and the desire to meet the desired controlled release kinetics, it is desirable that the particle size be greater than 500 μτη with the average particle diameter preferably 800 to 1200 μιη.

Additional protocols for providing the controlled release agent include the appropriate selection of one or more other components of the detergent composition matrix so that, when the composition is added to the wash solution, the ionic strength environment provided therein is the required one. kinetics of controlled release.

Metal-containing bleach catalyst

The compositions described herein which contain bleaching agent as a cleaning agent ingredient may additionally contain as a preferred ingredient a metal-containing bleaching catalyst. Preferably, the metal-containing bleaching catalyst is a transition metal-containing bleaching catalyst, more preferably a manganese or cobalt-containing bleaching catalyst.

A suitable type of bleaching catalyst is a catalyst comprising a heavy metal cation with a defined bleaching activity, such as copper and iron cations, and an auxiliary metal cation with a low or no bleaching activity, such as zinc or aluminum cations, and a sequestrant with defined stability constants for the catalytic and auxiliary metal cations, in particular ethylene diamine tetraacetic acid, ethylene diamine tetra (methylene phosphonic acid) and water-soluble salts thereof. Such catalysts are described in US patent 4,430,243.

1012583 62

Preferred bleaching catalyst types include the manganese-based complexes described in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of these catalysts include MnIV2 (u-0) 3 (1,4,7-5 trimethyl-1,4,7-triazacyclononane) 2 (PF6) 2 / MnIJI2 (u-0) 3 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 4 (ClO 4) 2,1MnIV4 (h-0) 6 (1,4,7-triazacyclononane) 4 (C104) 2, MnITIMnIV4 (u- 0) j, (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (C104) 3 and mixtures thereof. Others are described in Europe-10se patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

The bleaching catalysts useful in the compositions herein may also be suitably selected for the present invention. For examples of suitable bleaching catalysts, see U.S. Patent 4,246,612 and U.S. Patent 5,227,084. See also US Patent 5,194,416 which describes mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH3) 3 (PF6).

Yet another type of bleaching catalyst, as described in US Patent 5,114,606, is a water-soluble complex of manganese (III), and / or (IV), with a ligand containing a non-carboxylate polyhydroxy compound with at least 3 consecutive C- OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meserythritol, meso-inositol, lactose and mixtures thereof.

US patent 5,114,611 describes a bleaching catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a non- (macro) cyclic ligand. The ligands have the formula: R2 R3 35 I | R * -IT = CBC = M-R4 1012583 63 wherein R 1, R 2, R 3 and R 4 can each be selected from H, substituted alkyl and aryl groups such that each R 1 -N = C-R2 and R 3 -C = N-R 4 5- or 6-ring shapes. The ring may be further substituted. B is a bridging group selected from 0, S, CR5R6, NR7 and C = 0, wherein R5, R6 and R7 can each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. The rings may be optionally substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. The 2,2'-bispyridylamine ligand is particularly preferred. Preferred bleach catalysts include Co, Cu, Mn, Fe bispyridylmethane and bispyridylamine complexes.

Highly preferred catalysts include ten Co (2,2'-bispyridylamine) Cl2, di (isothiocyanate) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate, Co (2,2 bis-pyridylamine) 202C104, bis (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron-20 (II) perchlorate and mixtures thereof.

Preferred examples include binuclear Mn complexes with N-tetrahedron and N-bidentate ligands including N4Mnirr (u-0) 2MnIVN4) + and [bipy2MnIIJ (u-O ^ Mn ^ bipyJ - (C104)).

Although the structures of the bleach-catalyzing manganese complexes of the present invention have not been elucidated, they can be expected to include chelates or other hydrated coordination complexes resulting from the interaction of the carboxyl groups and nitrogen atoms of the ligand with the manganese cation. The oxidation state of the manganese cation during the catalytic process is also not known with certainty and may be the (+ 11), (+ III), (+ IV) or (+ V) valency state. Since the ligand has 6 potential junctions to the manganese-35 cation, it can be reasonably expected that multi-nuclear species and / or "cage" structures may be present in the aqueous bleach environments. Whatever the form of the 1012583 64 active Mn ligand species that actually exists, it functions in a seemingly catalytic manner to provide improved bleaching performance with regard to stubborn stains such as tea, ketchup, coffee, wine, juice and the like.

Other bleaching catalysts are described, for example, in European Patent Application Publication No.

408,131 (cobalt complex catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (metalloporphyrin-10 catalysts), US 4,728,455 (manganese / multi-toothed ligand catalyst), US 4,711,748 and European patent application publication no. 224,952 (catalyst consisting of absorbed manganese on aluminosilicate), US 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), US 15 4,626,373 (manganese / ligand catalyst), US. 4,119,557 (iron (II) complex catalyst), German patent specification

2,054,019 (cobalt chelating catalyst), Canadian Application 866,191 (transition metal-containing salts), US

4,430,243 (chelating compounds with manganese cations and 20 non-catalytic metal cations) and US 4,728,455 (manganese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts of the formula:

Co [(NH3) nM 'mB' bT 'tQqPp] Yy 25 in which cobalt has the +3 oxidation state, n is an integer from 0 to 5 (preferably 4 or 5 and most preferably 5), M' is one-toothed ligand, m is an integer from 0 to 5 (preferably 1 or 2 and most preferably 1), B 'represents a bidentate ligand-30, b is an integer from 0 to 2, T' represents a tridentate ligand, t is 0 or 1, Q is a four-pronged ligand, q is 0 or 1, P is a five-pronged ligand, p is 0 or 1 and n + m + 2b + 3t + 4q + 5p = 6, Y is one or more suitably chosen counter anions are present in a number y where 35 y is an integer from 1 to 3 (preferably 2 to 3 and 101 2583 65 most preferably 2 when a Y is a -1 charged anion) so that a charge-balanced salt, Y is preferably selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof, and wherein further at least one of the coordination sites, bound to the cobalt, is labile under automatic dishwashing conditions and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (III) over cobalt (II) under alkaline conditions is less than 0, 4 volts (preferably less than 0.2 volts) relative to a regular hydrogen electrode.

Preferred cobalt catalysts of this type have the formula: [Co (NHj) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5 and most preferably 5) , M 'is a labile coordinating moiety preferably selected from the group 20 consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof, m an integer from 1 to 3 (preferably 1 or 2 and most preferably 1), m + n = 6 and Y is an appropriately selected counter anion present in a number y which is an integer from 25 to 3 (preferably 2 to 3 and most preferred 2 when Y is a -1 charged anion) to obtain a charge balanced salt.

The preferred cobalt catalysts of this type which are useful herein are cobalt pentamein chloride salts of the formula [Co (NH3) 5Cl] Yy and in particular [Co (NH3) 5Cl] Cl2.

More preferred are the compositions of the present invention which contain cobalt (III) bleach catalysts of the formula 1012583 66 [Co (NH3) n (M) m (B) b] Ty, wherein cobalt has the +3 oxidation state, n is 4 or 5 (preferably 5), M is one or more ligands coordinated with the cobalt in one place, m is 0, 1 or 5 2 (preferably 1), B is a ligand that is aligned with the cobalt two places is coordinated, B is 0 or 1 (preferably 0), and when b = 0 then m + n = 6 and when b = 1 then m = 0enn = 4, and T are one or more suitably chosen counter anions present in the number y where y is an integer to give a charge-balanced salt (preferably y is 1 to 3 and most preferably 2 when T is a -1 charged anion) and wherein the catalyst further comprises a base hydrolysis rate constant of less than 0.23 M'1 s'1 (25 ° C).

T is preferably selected from the group consisting of chloride, iodide, I3 ', formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6', BF4 ', B (Ph) 4 ", phosphate, phosphite, silicate, tosylate, methanesulfonate and combinations thereof Optionally, T 20 may be protonated if more than one anionic group is present in T, for example HP042 ~, HC03 ', H2PO4', etc. In addition, T can be selected from the group consisting of non-conventional inorganic anions such as anionic surfactants (eg linear alkylbenzene-sulfonates (LAS), alkyl sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or anionic polymers (eg polyacrylates, polymethacrylates, etc. .).

The M radicals include, but are not limited to, for example, F ', S042 ", NCS', SCN ', S2032', NH3, P043" and 30 carboxylates (which are preferably monocarboxylates but more than one carboxylate may be in the moiety be present as long as the bond with the cobalt occurs with only one carboxylate per residue, in which case the other carboxylate may be protonated in the M residue or in its salt form). Optionally, M may be protonated if more than one anionic group is present in M (e.g., 101 2583 67 HP042 · HCO 3 ', Ρ2ΡO4 ·, H0C (0) CH2C (0) 0-, etc.). Preferred M radicals are substituted and unsubstituted C1-C30 carboxylic acids of the formula: RC (0) 0-5 wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C1 -C30- (preferably C3-C18-) alkyl, unsubstituted and substituted C6-C30- (preferably C6-C18-) aryl and unsubstituted and substituted C3-C30- (preferably C5-10 C18-) heteroaryl in which substituents are selected from the group consisting of -NR'3, -NR'4 +, -C0 (0) 0R ', -0R', -C (O) - NR'2, wherein R 'is selected from the group consisting of hydrogen and C 1 -C 8 radicals. Thus, such substituted R includes the residues - (CH2) nOH and - (CH2) nNR'4 + wherein n 15 is an integer from 1 to 16, preferably 2 to 10, most preferably 2 to 5.

Most preferably M is a carboxylic acid of the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, linear or branched C4 -C12 alkyl and benzyl. Most preferably R is methyl. Preferred M-carboxylic acid residues include miere, benzoin, octane, nonane, decane, dodecane, malon, maleine, amber, adipine, phthalic, 2-ethylhexane, naphthene, oil -, palmitine, trifluora-25, tartar, stearin, butter, lemon, acrylic, asparagine, fumar, lauric, linole, milk, apple and in particular acetic acid.

The B radicals include carbonate, di- and higher carboxylates (eg oxalate, malonate, malate, succinate, maleate), picolinic acid and alpha and beta amino acids (eg glycine, alanine, beta-alanine, phenylalanine) .

Cobalt bleach catalysts useful herein are known and are described, for example, at their base hydrolysis rates in M. L. Tobe, "Base Hydrolysis of Im 583 68

Transition-Metal Complexes ", Adv. Inorg. Bioinorg. Mech .. (1983), 2, biz. 1-94. Table 1 on biz. 17 shows, for example, the base hydrolysis rates (referred to there as k0H) for cobalt pentamine catalysts, complexed with 5 oxalate (k0H = 2.5 x ΙΟ'4 M'1 s'1 (25 ° C)), NCS '(k0H = 5.0 x 10'4 M'1 s'1 (25 ° C)) , formate (k0H = 5.8 x ΙΟ'4 M'1 s'1 (25 ° C)) and acetate (k0H = 9.6 x 10 "4 M'1 s'1 (25 ° C)). The most preferred and useful cobalt catalyst are cobalt pentamine acetate salts of the formula [Co (NH3) 5OAc] Ty, in which OAc represents an acetate residue, and in particular cobalt pentamine acetate chloride [Co (NH3) 5OAc] Cl2, as well [Co (NH3) sOAc] (OAc) 2, [Co (NH3) 5OAc] (PF6) 2, [Co (NH3) 5OAc] (SO4), [Co (NH3) sOAc] (BF4) 2 and [Co ( NH3) 5OAc] (NO3) 2 (here "PAC").

These cobalt catalysts are readily prepared by known procedures as described, for example, in the Tobe article above and the references cited therein, in US Patent 4,810,410, to Diakun et al., Issued March 7, 1989, J. Chem. Ed. (1989), 66. (12), 20 1043-45, The Synthesis and Characterization of Inorganic

Compounds, W.L. Jolly (Prentice-Hall, 1970), biz. 461-3, Inorq. Chem. 18., 1497-1502, (1979), Inorg. Chem. . 21.

2881-2885 (1982), Inorg. Chem. 18, 2023-2025 (1979),

Inorg. Synthesis, 173-176 (1960), and Journal of Physical Chemistry. 56, 22-25 (1952) as well as the synthesis examples given below.

Cobalt catalysts suitable for inclusion in the detergent tablets of the present invention can be prepared according to the disclosures referred to herein in accordance with the synthetic routes described in US patents 5,559,261, 5,581,005 and 5,597,936.

These catalysts can be processed together with auxiliary materials so that the color impact is reduced, if desired because of the appearance of the product, or can be incorporated into enzyme-containing particles, examples of which are given below, or the compositions. can be prepared to contain catalyst "speckles".

Organic polymer fiber compound

Organic polymeric compounds can be added as preferred components of the detergent tablets of the invention. By organic polymeric compound is meant virtually any polymeric organic compound commonly found in detergent compositions and having dispersant, anti-redeposition, soil release or other cleaning properties.

The organic polymeric compound is usually included in the detergent compositions of the invention at a concentration of 0.1 to 30% by weight, preferably 0.5 to 15% by weight, and most preferably 1 to 10% by weight based of the weight of the compositions.

Examples of organic polymeric compounds include the water-soluble organic homo- or copolymeric polycarboxylic acids, modified polycarboxylates or their salts wherein the polycarboxylic acid comprises at least two carboxyl groups separated by no more than 2 carbon atoms. Polymers of the latter type are described in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight from 2000 to 10,000 and their copolymers with any suitable other monomer units including modified acrylic, fumar, maleine, itacone, aconitin, mesacon, citracon and methylene malonic acid. or their salts, maleic anhydride, acrylamide, alkylene, vinyl methyl 30 ether, styrene and mixtures thereof. The copolymers of acrylic acid and maleic anhydride with a molecular weight of 20,000 to 100,000 are preferred.

Preferred commercially available acrylic acid-containing polymers with a molecular weight of less than 15,000 include those sold under 101 2583 70 trade name Sokalan PA30, PA20, PA15, ΡΑΙΟ and Sokalan CP10 by BASF GmbH and those sold under the trade name Acusol 45N, 480N, 460N by Rohm and Haas.

Preferred acrylic acid-containing copolymers include those containing as monomer units: a) 90 to 10 wt% and preferably 80 to 20 wt% acrylic acid or its salts and b) 10 to 90 wt% and preferably 20 up to 80% by weight of a substituted acrylic monomer or its salts of the general formula - [CR2-CR1 (CO-O-R3)] - wherein at least one of the substituents is r3, R2 or R3, preferably R3 or R2; an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, Rx or R2 may be a hydrogen atom and R3 may be a hydrogen atom or an alkali metal salt. A substituted acrylic monomer in which R3 is methyl and R2 is a hydrogen atom (ie a methacrylic acid monomer) is most preferred. The most preferred copolymer of this type has a molecular weight of 3500 and contains 60 to 80 wt% acrylic acid and 40 to 20 wt% methacrylic acid.

The polyamine and modified polyamine compounds useful herein include those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Other optional polymers may include polyvinyl alcohols and acetates, both modified and unmodified, cellulose compounds and modified cellulose compounds, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, both modified and unmodified, terephthalate esters of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.

Suitable examples are described in U.S. Patent Nos. 5,591,703, 5,597,789 and 4,490,271.

Soil wasters

Suitable polymeric soil removers 35 include those soil removers having: (a) one or 1012583 71 more non-ionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a polymerization degree of at least 2 or (ii) oxypropylene or polyoxypropylene segments with a polymerization degree of from 2 to 10 wherein the hydrophilic segment does not comprise an oxypropylene unit unless it is attached to adjacent residues at each end by ether linkages or (iii) a mixture of oxyalkylene units comprising oxyethylene and 1 to 30 oxypropylene units wherein the 10 hydrophilic segments preferably comprise at least 25% oxyethylene units and more preferably, especially for those components having 20 to 30 oxypropylene units, comprise at least 50% oxyethylene units or (b) one or more hydrophobic components comprising (i) C3-oxyalkylene teref- 15 talate segments wherein, if the hydrophobic constituents are also oxyethylene erephthalate, the ratio of oxyethylene terephthalate: C3-oxyalkylene terephthalate units is 2: 1 or less, (ii) C4-C6 alkylene or C4-C6 oxyalkylene segments or mixtures thereof, (iii) poly (vinyl ester) segments , preferably polyvinyl acetate, with a degree of polymerization of at least 2 or (iv) C 1 -C 2 -alkyl ether or C 4 -hydroxyalkyl ether substituents or mixtures thereof wherein the substituents are in the form of C 3 -C 4 alkyl ether or C 4 -hydroxyalkyl ether cellulose derivatives or mixtures thereof, or a combination of (a) and (b).

The polyoxyethylene segments of (a) (i) will normally have a degree of polymerization from 200, although higher values can be used, preferably from 3 to 150 and more preferably from 6 to 10. Suitable hydrophobic C4 -C6 oxyalkylene segments include, but are not limited to, end groups of polymeric soil removers such as M03S (CH2) nOCH2CH2O- wherein M is sodium and n is an integer from 4 to 6 as described in US U.S. Patent 4,721,580, issued January 26, 1988, to 35 of Gosselink.

Polymeric soil removers useful herein also include cellulose derivatives such as 1019ZQ3 72 hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate and the like. Such agents are commercially available and include cellulose hydroxy ethers such as METHOCEL (Dow). Cellulose soil removers that can be used herein also include those selected from the group consisting of C 1 -C 2 alkyl and C 4 -hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Dirt removers characterized by hydrophobic poly (vinyl ester) segments include graft copolymers of poly (vinyl ester), for example, C 1 -C 6 vinyl esters, preferably poly (vinyl acetate) grafted on polyalkylene oxide backbones such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 in the name of Kud, et al.

Another suitable soil release agent is a copolymer with random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, and U.S. Patent 3,893,929 to Basadur, issued July 8, 1975.

Another suitable polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units containing 10 to 15 wt% ethylene terephthalate units along with 90 to 80 wt% polyoxyethylene terephthalate units from a polyoxyethylene glycol having a average molecular weight from 300 to 5000.

Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer consisting of an oligomer ester backbone of repeating terephthaloyl and oxyalkyleneoxy units and terminal moieties covalently attached to the backbone. These soil removers are fully described in U.S. Patent 4,968,451 issued November 6, 101 2583 73 1990, to J.J. Scheibel and E_.P. Gosselink. Other suitable polymeric soil removers include the terephthalate polyesters from U.S. Patent 4,711,730 issued December 8, 1987, to Gosselink et al., The oligomeric esters having anionic end groups from U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the oligomeric block polyester compounds of U.S. Patent 4,702,857, issued October 27, 1987, to Gosselink. Other polymeric soil removers also include the soil removers of U.S. Patent 4,877,896 issued October 31, 1989, to Maldonado et al., Which describes terephthalate esters having anionic, especially sulfoarolyl, end groups.

Another soil release agent is an oligomer having 15 repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and 1,2-oxypropyleneoxy units. The repeating units form the backbone of the oligomer and preferably have modified isethionate groups as end groups. An especially preferred soil release agent of this type includes one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and 1,2-oxypropyleneoxy units in a ratio of 1.7 to 1.8 and two end group units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

25 Heavy metal ion sequestrant

The tablets according to the invention preferably contain as optional ingredient a heavy metal ion sequestrant. By heavy metal ion sequestrant herein is meant components which sequester (chelate) heavy metal ions. These components can also chelate with calcium and magnesium, but preferably they show selectivity over the bond with heavy metal ions such as iron, manganese and copper.

1012 583 74

Heavy metal ion sequestrants are generally present at a concentration of 0.005 to 20 wt%, preferably 0.1 to 10 wt%, more preferably 0.2 to 7.5 wt%, and most preferably 0.5 to 5 wt% based on the weight of the compositions.

Naturally acidic heavy metal ion sequestrants having, for example, phosphonic or carboxylic acid functionalities may be present in their acid form or as a complex / salt with a suitable counter-cation such as an alkali or alkaline earth metal ion, ammonium or substituted ammonium ion or mixtures thereof. Preferably the salts / complexes are water soluble. The molar ratio of the counter cation to the heavy metal ion sequestrant is preferably at least 15 1: 1.

Suitable heavy metal ion sequestrants that can be used here include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxy diphosphonates, and nitrilotrim-thylene phosphonates. Of the above species, diethylene triamine penta (methylene phosphonate), ethylenediaminetri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate are preferred.

Other suitable heavy metal ion sequestrants that can be used herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene diaminotetraacetic acid, ethylene triamine pentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine digluvaric acid, 2-hydroxypropylene diamine disuccinic acid or salts thereof.

Ethylenediamine-Ν, Ν'-succinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof are particularly preferred. Preferred EDDS compounds are the free acid form and its sodium or magnesium salt or complex.

101 75

Crystal growth inhibitor component

The detergent tablets preferably contain a crystal growth inhibitor component, preferably an organo-diphosphonic acid component which is preferably included at a concentration of 0.01 to 5% by weight and more preferably 0.1 to 2% by weight based on the weight of the compositions.

By organodiphosphonic acid is here meant an organodiphosphonic acid that does not contain nitrogen as part of its chemical structure. Therefore, this definition excludes the organo aminophosphonates which can nevertheless be included in compositions of the invention as sequestrant components for heavy metal ions.

The organodiphosphonic acid is preferably a C 1 -C 15-15 diphosphonic acid, more preferably a C 2 -diphosphonic acid such as ethylene diphosphonic acid or most preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP) and may be in partial or completely ionized form and especially when a salt or complex are present.

20 Water-soluble sulfate salt

The detergent tablet optionally contains a water-soluble sulfate salt. When present, the water-soluble sulfate salt is present in a concentration of 0.1 to 40% by weight, more preferably 1 to 30% by weight, and most preferably 5 to 25% by weight based on the weight of the compositions.

The water-soluble sulfate salt can be virtually any sulfate salt with any counter cation. The preferred salts are selected from the sulfates of the alkali and alkaline earth metals, especially sodium sulfate.

mi 76

Alkali metal silicate

An alkali metal silicate is a preferred component of the tablet of the present invention. A preferred alkali metal silicate is 5 sodium silicate with an SiO 2: Na 2 O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, and most preferably 2.0. Sodium silicate is preferably present in a concentration of less than 20% by weight, preferably 1 to 15% by weight and most preferably 3 to 12% by weight, measured as SiO 2. The alkali metal silicate may be in the form of the anhydrous salt or a hydrated salt.

Alkali metal silicate can also be present as a component of an alkalinity system.

The alkalinity system preferably also contains sodium metasilicate, present at a concentration of at least 0.4% by weight, measured as SiO2. Sodium metasilicate has a nominal SiO2: Na2O ratio of 1.0. The weight ratio of the sodium silicate to the sodium metasilicate, measured as SiO 2, is preferably 50: 1 to 5: 4, more preferably 15: 1 to 2: 1 and most preferably 10: 1 to 5: 2.

Colorant

The term "colorant" as used herein means any substance that absorbs specific light wave lengths from the visible light spectrum. Such colorants, when added to a detergent composition, have the effect of changing the visible color and thus the appearance of the detergent composition. Colorants can, for example, be dyes or pigments. Preferably, the colorants are stable in the composition in which they are to be incorporated. The colorant in a high pH composition is thus preferably alkali stable 1012583 77 and in a low pH composition, the colorant is preferably thus acid stable.

The first and / or second and / or optionally other phases may contain a colorant, a mixture of colorants, colored particles or a mixture of colored particles so that the different phases appear visually different. Preferably, one of the first or second phases comprises a colorant. In case the first and second and / or subsequent phases comprise a colorant 10, it is preferred that the colorants look visually different.

Examples of suitable dyes include reactive dyes, direct dyes and azo dyes. Preferred dyes include phthalocyanine, anthraquinone, quinoline, monoazo, disazo and polyazo dyes. More preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING 20 BLUE (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name), all available from Clariant UK, HEXACOL QUINOLINE YELLOW (trade name) and HEXACOL BRILLIANT BLUE (trade name), both available from Pointings, UK, ULTRA MARINE BLUE (trade name), available from Holliday or LEVAFIX TURQUOISE BLUE EBA (trade name), available from Bayer, USA.

The colorant can be incorporated into the phases by any suitable method. Suitable methods include mixing all or selected detergent ingredients with a colorant in a drum or spraying all or selected detergent ingredients with the colorant in a rotary drum.

The colorant, when present as a component of the first phase, is present in a concentration of 0.001 to 1.5%, preferably 0.01 to 1.0%, most preferably 0.1 to 0.3%. When present as a component of the second and / or optionally other phases, the m 1 ος 78 colorant is generally present at a concentration of 0.001 to 0.1 wt%, more preferably 0.005 to 0.05 wt%, and most preferred 0.007 to 0.02 wt%.

5 Corrosion inhibitor connection

The tablets of the present invention suitable for use in dishwashing processes may contain corrosion inhibitors, which are preferably selected from organic silver coatings, especially paraffin, nitrogen-containing corrosion inhibitor compounds and Mn (II) compounds and especially Mn (II) salts of organic ligands.

Organic silver coatings are described in PCT publication WO 94/16047 and pending European application EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are described in the pending European application EP-A-634,478. Mn (II) compounds for use in corrosion inhibition are described in the pending European application EP-A-672749.

Organic silver coatings can be included in a concentration of 0.05 to 10% by weight, and preferably 0.01 to 5% by weight, based on the weight of the total composition.

The functional role of the silver coating agent 25 is to "form" a protective coating layer on silverware laundry wax components for which the compositions of the invention are used. The silver coating agent should therefore have a high affinity for bonding to solid silver surfaces, especially if it is contained in a component of an aqueous wash and bleach solution with which the solid silver surfaces are treated.

Suitable organic silver coating agents here include fatty esters of mono- or polyhydric alcohols having 1 to 40 carbon atoms in the hydrocarbon chain.

A A a Of 00 79

The fatty acid portion of the fatty ester can be obtained from mono- or polycarboxylic acids with 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic, stearic, oleic, palmitic, myristic, lauric, acetic, propionic, butyric, isobutyric, valeric, lactic, glycolic and β, β'-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butyl malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

The fatty alcohol group in the fat ester can be represented by mono- or polyhydric alcohols with 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include: behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid and / or fatty alcohol group of the fatty ester adjuvant has 1 to 24 carbon atoms in the alkyl chain.

Preferred fatty esters here are ethylene glycol, glycerol and sorbitan esters in which the fatty acid portion of the ester usually comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

The glycerol esters are also highly preferred. These are the mono-, di- or triesters of glycerol and the fatty acids as defined above.

Specific examples of fatty alcohol esters that can be used here include: stearyl acetate, palmityl dilactate, cocoyl isobutyrate, oleyl maleate, oleyl dimeate, and tallow alcohol propionate. Fatty acid esters useful here include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol mono-stearate, ethylene glycol monostearate and sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyrin 1 or o 80 state, sorbitan monobehenate, sorbitan monooleate, sorbitan silaurate, sorbitan distearate, sorbitan dibehenate, sorbitan diolate and mixed tallow mono

Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are preferred glycerol esters here.

Suitable organic silver coating agents include triglycerides, mono- or diglycerides and fully or partially hydrogenated derivatives thereof and mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grape seed oil, palm oil and corn oil.

Waxes, including microcrystalline waxes, are suitable organic silver coatings here. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise 12 to 70 carbon atoms. Paraffinic microcrystalline type petroleum waxes composed of long chain saturated hydrocarbon compounds are preferred.

Alginates and gelatin are suitable organic silver coatings here.

Dialkylamine oxides such as C12-C20 methyl amine oxide and quaternary dialkylammonium compounds and salts such as the C12-C20 methyl ammonium halides are also suitable.

Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methyl cellulose, carboxy-

* a λ r Λ O

Methyl cellulose and hydroxyethyl cellulose are examples of such polymeric materials.

Certain fragrance materials, particularly those that show a higher substantivity to metallic surfaces, are also useful here as the organic silver coatings.

Polymeric soil removers can also be used as an organic silver coating agent.

A preferred organic silver coating agent is a paraffin oil, usually a predominantly branched aliphatic hydrocarbon with a number of carbon atoms in the range of 20 to 50. A preferred paraffin oil is selected from predominantly branched C2S-C45 species at a ratio of cyclic 15 to non-cyclic hydrocarbons from 1:10 to 2: 1 and preferably 1: 5 to 1: 1. A paraffin oil having these properties, with a cyclic to non-cyclic hydrocarbon ratio of 32:68, is sold by Wintershall, Salzbergen, Germany, under the tradename 20 WINOG 70.

Nitrogen-containing corrosion inhibitor compounds

Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecylimidazole and those imidazole derivatives described in Czech Patent 139,279 and British Patent GB-A-1,137,741, which also includes a process for the preparation of imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, especially those in which the pyrazole is substituted in the 1, 3, 4 or 5 positions with substituents

Ra, R3, R4, and R5 wherein R3 are H, CH2 OH, CONH3, or CO2 CH3, R3, and R5 are C1-C20 elkyl or hydroxy and R4 is H, NH2, or NO2.

101 2583 82

Other suitable nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.

Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrogen citrate are also suitable.

10 Mn (II) corrosion inhibitor compound

The detergent tablets may contain an Mn (II) corrosion inhibitor compound. The Mn (II) compound is preferably included at a concentration of 0.005 to 5 wt%, more preferably 0.01 to 1 wt%, and most preferably 0.02 to 0.4 wt% at based on the weight of the compositions. Preferably, the Mn (II) compound is incorporated at a concentration of from 0.1 to 250 ppm, more preferably 0.5 to 50 ppm, and most preferably 1 to 20 ppm by weight of Mn (II) ions 20 in a bleaching solution is provided.

The Mn (II) compound can be an inorganic salt in anhydrous or hydrated forms. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The 25 Mn (II) compound can be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.

The Mn (II) compound can be a salt or complex of an organic ligand. In one preferred aspect, the organic ligand is a heavy metal ion sequestrant. In another preferred aspect, the organic ligand is a crystal growth inhibitor.

• "* '83 83

Other corrosion inhibitor compounds

Other suitable additional corrosion inhibitor compounds include mercaptans and diols, especially mercaptans of 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionaphthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated C 10 -C 20 fatty acids, or the salts thereof, in particular aluminum tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphated octadecane 10 and other antioxidants such as beta hydroxytoluene (BHT) are also suitable.

Copolymers of butadiene and maleic acid, especially those supplied under trade reference no. 07787 by Polysciences Ine, has been found to be particularly useful as corrosion inhibitor compounds.

Hydrocarbon oils

Another preferred detergent ingredient for use in the present invention is a hydrocarbon oil, normally aliphatic hydrocarbons having predominantly long chains and a number of carbon atoms in the range of 20 to 50; preferred hydrocarbons are saturated and / or branched; a preferred hydrocarbon oil is selected from a predominantly branched C25-C45 species with a ratio of cyclic to 25 non-cyclic hydrocarbons of 1:10 to 2: 1 and preferably 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin. A paraffin oil having the above-described properties, with a cyclic to non-cyclic hydrocarbon ratio of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

101 2583 84

Water-soluble bismuth compound

The detergent tablets of the present invention suitable for use in dishwashing processes may contain a water-soluble bismuth compound 5, preferably present in a concentration of 0.005 to 20% by weight, more preferably 0.01 to 5% by weight and most preferably 0.1 to 1% by weight based on the weight of the compositions.

The water-soluble bismuth compound can be virtually any salt or complex of bismuth with virtually any inorganic or organic counteranion. Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with an organic counter anion.

Enzyme stabilization system

Preferred enzyme-containing compositions herein may comprise 0.001 to 10 wt%, preferably 0.005 to 8 wt%, and most preferably 0.01 to 6 wt%, of an enzyme stabilization system. The enzyme stabilization system can be a stabilization system compatible with the cleaning enzyme. Such stabilizing systems can include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acid, chlorine bleach scavengers and mixtures thereof.

Such stabilization systems can also include reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap dispersant compound

The tablets of the present invention may contain a lime soap dispersant compound, preferably present in a concentration of 0.1 to 40% by weight, more preferably 1 to 20% by weight, and most preferably 2 to 10% by weight. % based on the weight of the compositions.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine 5 salts of fatty acids by calcium or magnesium ions. Preferred lime soap dispersant compounds are described in PCT application WO 93/08877.

S c hu imvo rm i ngonde pressure system

The detergent tablets of the present invention, when used in washing machine compositions, preferably comprise a foaming suppression system present in a concentration of 0.01 to 15 wt%, preferably 0.05 to 10 wt%, and most preferably 0.1 to 5 wt% based on the weight of the composition.

Suitable suds suppression systems that can be used here may include virtually any known anti-foam compound, including, for example, silicone anti-foam compounds and 2-alkyl and -alkanol-20 anti-foam compounds. Preferred foaming suppression systems and anti-foam compounds are described in PCT application WO 93/08876 and EP-A-705 324.

Polvmere colorant transfer inhibitors

The detergent tablets here may also include 0.01 to 10 wt%, and preferably 0.05 to 0.5 wt%, of polymeric colorant transfer inhibitors.

The polymeric colorant transfer inhibitors are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

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Optical Qlance

The detergent tablets suitable for use in laundry washing processes as described herein optionally also contain 0.005 to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those of the structural formula: r / so3m SO3m R wherein Rr is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R2 is selected from N-2-bis-hydroxye -10 thyl, N-2-hydroxyethyl-N-methylamino, morphilino, chlorine and amino and M is a salt-forming cation such as sodium or potassium.

When in the above formula Rx is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium 15, the brightener is 4,4'-bis [(4-anilino-6- (N-2-bis) -hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid disodium salt. This particular brightener species is sold commercially under the trade name Tinopal-UNPA-GX by Ciba Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the cleaning compositions herein.

When in the above formula Rx is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6-2 5 ( N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] - 2,2'-stilbene disulfonic acid disodium salt. This particular 1012583 9 87 glossant species is sold commercially under the trade name Tinopal-5BM-GX by Ciba Geigy Corporation.

When in the above formula R 1 is anilino, R 2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6-morphilino-s-triazin-2-yl) amino] 2,2'-stilbene disulfonic acid sodium salt. This particular brightener species is sold commercially under the trade name Tinopal AMS-GX by Giga Geigy Corporation.

Clay Softener System The detergent tablets suitable for use in laundry washing processes may contain a clay softener system comprising an inorganic clay compound and optionally a clay flocculant.

The inorganic clay compound is preferably a smectite clay compound. Smectite clays are described in U.S. Patents 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patents EP-A-299,575 and EP-A-313,146, in the name of the Procter and Gamble Company, disclose suitable organic polymeric clay flake forming agents.

20 Cationic fabric softeners

Cationic fabric softeners can also be included in compositions of the present invention suitable for use in laundry washing processes. Suitable cationic fabric softeners include the water-insoluble tertiary amines or two-chain amide materials as described in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softeners are normally included in total concentrations of 0.5 to 15 wt% and usually 1 to 5 wt%.

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Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include fragrances and filler salts with sodium sulfate being a preferred filler salt.

pH of the compositions

The detergent tablets of the present invention are preferably not formulated to have an extremely high pH, preferably having a pH, measured as a 1% solution in distilled water, of 8.0 to 12.5 , more preferably 9.0 to 11.8 and most preferably 9.5 to 11.5.

Machine washing method 15 Some suitable methods for machine washing or cleaning dirty tableware are considered.

A preferred machine washing method comprises treating contaminated articles selected from pottery, glassware, silverware, metal objects, cutlery and mixtures thereof, with an aqueous liquid containing or dispersing an effective amount of a detergent tablet according to the invention. By an effective amount of the detergent tablet is meant 8 to 60 g of product, dissolved or dispersed in a washing solution of 3 to 10 l volume, these being typical product dosages and wash solution volumes commonly used in conventional machine washing processes. Preferably, the detergent tablets have a weight of 15 to 20 g, and more preferably 20 to 35 g.

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Laundry washing work

Laundry washing methods here typically include treating soiled laundry with an aqueous washing solution in a washing machine in which an effective amount of a detergent tablet composition of the invention for machine washing of laundry is dissolved or dispersed. By an effective amount of the detergent tablet composition is meant 40 to 300 g of product which is dissolved or dispersed in a wash solution of 5 to 10 65 L volume, these being typical product dosages and wash solution volumes commonly used in conventional machine washing methods washing of laundry can be used.

According to a preferred use aspect, an administration device is used in the washing process. The dispenser is filled with the detergent product and is used to supply the product directly to the washing machine drum before the washing cycle has started. Its volume capacity should be such that it is able to contain as much detergent product as is normally used in the washing process.

Once the washing machine has been filled with laundry, the dispenser containing the detergent product is placed in the drum. At the beginning of the washing cycle of the washing machine, water is supplied to the drum and the drum rotates periodically. The design of the dispenser should be such that it allows to contain the dry detergent product but then release this product during the wash cycle in response to shaking as the drum rotates and also as a result of its contact with the wash water , may I make.

To enable dispensing of the detergent product during washing, the device may include a number of openings through which the product can pass.

Alternatively, the device may be composed of a material which is permeable to liquid but impermeable to the solid product, which will allow release of a dissolved product. Preferably, the detergent product will be released rapidly at the beginning of the wash cycle, providing temporary high local product concentrations in the washing machine drum at this stage of the wash cycle.

Preferred delivery devices are reusable and are designed in such a way that the container integrity is maintained both in the dry state and during the wash cycle.

Alternatively, the delivery device may be a flexible container, such as a bag or pouch. The bag may be a fibrous construction coated with a water-impermeable protective material to retain the contents, as described in published European patent application 0018678. Otherwise, it may be composed of a water-insoluble synthetic polymer material. Eel provided with a corner seal or seal designed to break in aqueous media as described in published European patent applications 0011500, 0011501, 0011502 and 0011968. A suitable form of a water-breakable seal comprises a water-soluble adhesive. agent, which is applied along one side of a bag composed of a water-impermeable polymeric film such as polyethylene or polypropylene and closes it.

Examples 30 Abbreviations used in examples

In the detergent compositions, the abbreviated ingredient identifiers have the following meanings: 1Π1 83 * 91 stpp: Sodium tripolyphosphate

Bicarbonate: Sodium hydrogen carbonate

Citric Acid: Anhydrous citric acid

Carbonate: Anhydrous sodium carbonate 5 Silicate: Amorphous sodium silicate (Si02: Na20 ratio = 2.0) SKS-6: Crystalline layered silicate of the formula 6-Na2Si2Os PBl: Anhydrous sodium perborate monohydrate

Non-ionic: mixed ethoxylated / propoxylated C 1 -C 15 fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trade name Plurafac by BASF TAED: Tetraacetylethylenediamine 10 HEDP: Ethane 1-hydroxy-1,1-diphosphonic acid PAAC: Pentaamine acetate cobalt (III) salt

Paraffin: Paraffin oil sold under the trade name Winog 70

Wintershall

Protease: Proteolytic enzyme

Amylase: Amylolytic enzyme 15 BTA: Benzotriazole

Sulfate: Anhydrous sodium sulfate PEG 3 0 00 Polyethylene glycol with a molecular weight of about 3000, available from Hoechst PEG 6000: Polyethylene glycol with a molecular weight of about 6000, available from Hoechst pH: Measured as a 1% solution in distilled water at

20 ° C

In the following examples, all concentrations are expressed in parts by weight:

Examples I-IV

Shown below are examples of detergent tablets according to the present invention suitable for use in a dishwasher.

1012583

"P

92

Phase 1 I II III IV V VI

STPP 9.62 9.62 10.45 9.57 9.57 11.47

Silicate 0.50 0.67 1.60 1.00 1.00 2.40 SKS-6 1.5 1.50 2.30 2.25 5 Carbonate 2.33 2.74 3.5 3.59 4. 10 5.25 HEDP 0.18 0.18 0.18 0.28 0.28 0.28 PB1 2.45 2.45 2.45 3.68 3.68 3.68 PAAC 0.002 0.002 0.002 0.003 0.004 0.004

Amylase 0.148 0.110 0.110 0.252 0.163 0.163 10 Protease 0.06 0.06 0.06 0.09 0.09 0.09

Non-ionic 0.40 0.80 0.80 1.20 1.20 1.20 PEG 6000 0.4 0.26 0.26 0.38 0.39 0.39 BTA 0.04 0.04 0. 04 0.06 0.06

Paraffin 0.10 0.10 0.10 0.15 0.15 0.15 15 Fragrance 0.02 0.02 0.02 0.013 0.013 0.013

Sulphate 0.502 0.05 2.843

Total 17.75 g 18.55 g 19.57 g 23.0 g 23.0 g 23.0 g

Phase 2

Amylase 0.30 0.35 0.25 0.30 0.35 0.25 Protease 0.25 0.22 0.30 0.25 0.22 0.30

Citric acid 0.3 0.30 0.3 0.30

Sulphamic acid 0.3 0.3

Bicarbonate 1.09 0.45 0.45 1.09 0.45 0.45

Carbonate 0.55 0.55 25 Silicate 0.64 0.64

CaCl2 0.07 0.07 PEG 3000 0.06 0.06 0.06 0.06 0.06 0.06

Total 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g

The multiphase tablet compositions are prepared as follows. The stage 1 cleaning active composition is prepared by mixing the granular and liquid ingredients and is then transferred to the mold of a conventional rotary press. The press includes a die punch which has an appropriate shape for forming the mold. The cross section of the mold is approximately 30 x 38 mm. The composition is then subjected to a pressing force of 94 kg / cm 2 and the die punch is then raised to reveal the first phase of the tablet containing the mold in its top surface. The cleaning active composition of 1012583 f 93 phase 2 is prepared in a similar manner and transferred to the mold. The granular active composition is then subjected to a pressing force of 170 kg / cm 2 and then the punching die is raised and the multiphase tablet is released from the tablet press. The resulting tablets dissolve or disintegrate in a washing machine as described above within 12 minutes. Phase 2 ”of the tablets dissolves within 5 minutes. The tablets provide excellent dissolving and cleaning properties along with good tablet integrity and strength.

101? 5 83

Claims (14)

94 'AMENDED CONCLUSIONS A multiphase detergent tablet for use in a washing machine, the tablet comprising: 5 a) a first phase in the form of a formed mass with at least one mold therein and b) a second phase in the form of a granular solid which pressed into the mold. A multi-phase detergent tablet according to claim 1, wherein the second phase is pressed at a pressure less than about 350 kg / cm2. 3. Multiphase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a pressed molded mass with at least one mold therein, the molded mass being prepared at a pressure of at least about 350 kg / cm2 and b) a second phase in the form of a granular solid that has been pressed into the mold, the second phase being pressed at a pressure of less than about 350 kg / cm2. Multiphase detergent tablet according to any of the preceding claims, wherein the second phase dissolves faster than the first phase. Multiphase detergent tablet according to any of the preceding claims, wherein the second phase dissolves in a dishwasher within 5 minutes. 6. Multiphase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a formed mass with at least one mold therein and 1012583 95: b) a second phase in the form of a mass; granular solid that has been pressed into the mold and the tablet comprises at least one cleaning active agent and is formulated such that at least 50% by weight, preferably at least 60% by weight and more preferably at least 80% by weight of the cleaning agent within 10 minutes, preferably within 5 minutes and more preferably; is delivered to the washing liquid within 3 minutes. A multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a formed mass with at least one mold therein and; B) a second phase in the form of a granular solid that has been pressed into the mold and wherein the tablet composition is one or more; detergents, selected from enzymes, bleaches, bleach activators, bleaching catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof, which are mainly concentrated in the second phase. A multi-phase detergent tablet according to any one of the preceding claims, wherein the second phase additionally comprises a disrupting agent. The multi-phase detergent tablet according to any one of the preceding claims, wherein the second phase comprises an enzyme. 10. Multiphase detergent tablet for use in a washing machine ^ 30, the tablet comprising:? a) a first phase in the form of a formed mass 1 with at least one mold therein and b) a second phase in the form of a granular solid which has been pressed into the mold, wherein the second phase comprises an enzyme. : T012583 Multiphase detergent tablet according to any of the preceding claims, wherein the first and / or second phases comprise a binder. The multi-phase detergent tablet according to claim 11, wherein the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers. A multi-phase detergent tablet according to any of the preceding claims, further comprising a barrier phase between the first and second phases. The multi-phase detergent tablet according to claim 13, wherein the barrier layer comprises a binder applied in liquid form. 1012583