NL1012584C1 - Detergent tablet. - Google Patents

Abstract

A multi-phase detergent 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 compressed body adhesively contained within said mould, and wherein the second phase comprises an enzyme. 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. 1

Background '20

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

Detergent tablets are most commonly prepared by premixing ingredients of a detergent composition z and forming a tablet z of the premixed detergent ingredients using a suitable equipment, preferably a tablet press. Tablets are usually formed by pressing the components of the detergent composition 35 so that the tablets produced are sufficiently robust to withstand processing and transport without permanent damage. In addition to the fact that tablets z 2 must be robust, they must also dissolve sufficiently quickly so that the detergent components are released into the wash water as soon as possible at the beginning of the washing 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 press 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 (where a tablet cross section of approximately 10 cm2 is assumed 101 2584 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 be I.

dissolve significantly within one cycle of the washing machine or dishwasher, i.e. within 15 to 120 minutes.

Summary of the invention

According to a first aspect of the invention, there is provided a multiphase detergent tablet for machine washing comprising: a) a first phase in the form of a pressed molded mass with at least one mold in its surface and "b) a second phase in the form of a pressed mass which is adhesively present in the mold, the second phase being formed by pressing a granular solid and additionally comprising an enzyme.

1012584 4

In preferred embodiments, the first phase is a pressed molded mass prepared at an applied pressurization of at least about 40 kg / cm2, 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 second phase granular solid (which terminology is meant to include the possibility of multiple 'second' phases sometimes referred to as Optional Subsequent Phases') into the mold at an applied pressing pressure lower than that applied to the first stage, and preferably at a pressing pressure less than about 3, 50 kg / cm2, preferably in the range of about 40 kg / cm2 to about 300 kg / cm2, and More preferably from about 70 to about 270 kg / cm2, with such tablets being preferred here as they provide optimal tablet integrity and strength (eg measured by the "Child Bite Strength" [CBS] -1 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 so. particularly greater than about 14 kg, with CBS being measured according to the "US 30 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 stand together.

The second stage is in the form of a pressed mass that adheres, for example, by physical or chemical 1012584 5

adhesion, is present 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 enzymes which are mainly concentrated in the second phase of the tablet, for example at least about 50% by weight, preferably at least about 60% by weight and in particular 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, thus providing, for example, tablet compositions capable of dissolving in the washing liquid, at least 50% by weight, preferably at least 60% wt% and more preferably at least 80 wt% of the cleaning active agent within 10, 5, 4 or even 3 l

is dispensed to the washing liquid 20 minutes from the start of the washing process.

According to another aspect of the invention, there is thus provided a multiphase detergent tablet for machine washing comprising: a) a first phase in the form of a pressed,

formed mass with at least one mold in the surface I.

thereof and b) a second phase in the form of a pressed mass which is adhesively present in the mold, the second phase being formed by pressing a granular solid and the tablet composition comprising an enzyme which mainly

is usually concentrated in the second phase. Z.

An additional advantage of the invention is the ability to "

equality of the phases at different times I

to dissolve that one phase of the tablet is substantially

1012584 I

6 will dissolve before another phase dissolves and can almost completely dissolve before the other phase has dissolved. This is especially valuable for the differential delivery of detergent actives.

! The enzyme active agents are particularly preferred for increasing the cleaning power I during the very first cool water stage of the washing or cleaning operation. For use herein, enzymes 10 and enzyme mixtures comprising one or more enzymes having: increased or optimal activity in the temperature range of 25 ° C to 55 ° C and at a pH value in the range of 8 to 10 (e.g. Natalase) have strong degree preferred.

Detailed description of the invention

It is an object of the present invention to provide a detergent tablet which is not only sufficiently robust to withstand processing 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 washing 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 washing machine

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

using at least six or a sufficient number 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 formed mass of a detergent composition comprising one or more detergent ingredients such as? described below. Preferred detergent ingredients include builders, bleaches, enzymes, and surfactants. The components of the detergent composition are mixed together by, for example, mixing dry ingredients or spraying liquid ingredients on them. The constituents are then formed into a first phase using appropriate equipment, but preferably by pressing,

for example in a tablet press. Otherwise, the first stage can be prepared by extrusion, casting, etc. The first I.

phase can take on various geometric shapes such as spheres, cubes, etc. but preferred embodiments I.

30 generally have an axially symmetrical shape with a generally round, square or rectangular cross section. ________.

The first phase is prepared such that it comprises at least one mold in the surface of the mass formed Γ 35. 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 can form a closed inner cavity or recess in the surface of the formed mass or they can extend between unconnected areas of the mass surface (for example axially opposite outer surfaces) so that one or more topological 'holes' in the formed mass become shaped; 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 squeezes the first phase of the multiphase detergent tablet. Preferably, the mold will have an inwardly facing concave or substantially concave surface so as 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 cavity extending axially between opposite 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, sprayable substances, 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 cleanser-5 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 which 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 application here, I

thought of known disintegrating or effervescent agents which I

suitable for use in laundry washing or dishwashing applications. Suitable disintegrants include! starches (such as natural, modified and pregelatinized starches, eg those derived from corn, rice and potato starches), starches; 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 ~) and Vivapur (trade name) both of which are available f from Rettenmaier, Nymcel (trade name) available from 2

Metsa-serla, Avicel (trade name), Lattice NT (trade name) “and Hanfloc (trade name), alginates, acetate trihydrate, burkeite, mono-hydrated carbonate of formula Na2CO3.H20, ~ 30 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, on contact with water, produce a gas L.

produce. Suitable effervescent agents may be agents = 35 which generate oxygen, nitrogen dioxide or carbon dioxide. ~

Preferred examples of effervescent agents can be selected from the group consisting of perborate, 1012584 percarbonate, carbonate, bicarbonate in combination with carboxylic 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 on them. 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 includes 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 can 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 so as 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 following 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. 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.

In 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. The first phase more preferably 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 about 0.1 g to about 3.5 g, preferably about 1 g to about 3.5 g, and most preferably about 1.3 g to about 2.5 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 ° comprises at least one binder selected from the =

group described above. The advantage of the L

The presence of a barrier layer is the prevention or = reduction of the migration of components from one phase to another phase, for example from the first phase to the second and / or possibly subsequent phases and vice versa. .........

The components of the second and optionally follow- = phases are preferably pressed at a very low = press pressure compared to the press pressure that is usually gewoonlijk

used to prepare tablets. An advantage of the I

The present invention is thus that because a low persg. .

35 is applied, detergent ingredients which z

sensitive to heat, power or chemicals in the Z.

detergent tablet can be included without the Z

101 2584 12 performance loss that usually occurs when such ingredients are incorporated into tablets. Alternatively, the second phase or phases can be pressed at the same j or higher pressing force than the first phase so that dissolution of the phases is accomplished 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 transportation. As described above, multiphase cleaners; detergent tablets 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 tablet 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, where one phase can be designed to preferably dissolve significantly earlier than another phase. In the present invention, 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, 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 that 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, the effect of which results in a lower susceptibility of the tablets of the present invention to break along the contact line. between the = phases. Ü 20

Werkwii them

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 so that the surface of the die die that comes into contact with the cleaning agent composition has a convex surface. ! " A first detergent composition is supplied to the mold 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 with the most preferably about 600 to about 1200 kg / cm2. The die punch is then raised to reveal the first 10 phase 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 cleaning 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.

30

Detergent ingredients

The first and second and / or optionally subsequent phases 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 comprise a variety of different detergent ingredients including builder compounds, surfactants, enzymes, bleaches, alkalinity sources, colorants, fragrances, lime soap dispersants, organic polymer compounds 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. Detergent ingredients from the second Ξ

highly preferred phases include builders, enzymes, crystal growth inhibitors and disrupting agents I.

and / or binders 1 20 Builder connection

The tablets of the present invention “preferably contain a builder compound 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 z cleaning active ingredients.

Water-soluble builder compound 3 0

Suitable water-soluble builder compounds include the water-soluble monomeric polycarboxylates or their acidic forms, homo- or copolymeric polycarboxylic acids or salts thereof, the polycarboxylic acid comprising at least two carboxylic acid groups having no more than two carbon atoms of separated from each other, 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 poly-5 carboxylates are generally preferred for their cost and performance.

Suitable carboxylates containing one carboxy group 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. Polycarboxylates containing three carboxy-15 groups include, in particular, 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 described in British Patent 1,389,732, and Aminosuccinates disclosed in Dutch application 7205873 and the oxypolycarboxylate materials such as 2-oxa-1,3,3-propane tricarboxylate described in British patent 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent 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 are described.

Alicyclic and heterocyclic polycarboxylates 35 include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentanedienepentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-101 2584 17 dicarboxylates, 2,2,5,5-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 having up to J

contain three carboxy groups per molecule and more particularly citrates.

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

Borate builders as well as buildefs "containing borate-forming materials which can produce borate upon storage of detergent 1 or under washing conditions may also be used but are not preferred at" 20 wash temperatures below 50 ° C and in particular lower r than 40 ° C. l

Examples of carbonate builders are the alkaline earth metal and alkali metal carbonates including sodium carbonate and sesqui carbonate and mixtures thereof ^ with ultrafine calcium carbonate as described in the Ξ

German patent application 2,321,001 which is on November 15, 1973 I

published. Γ

Highly preferred builder compounds for use in the present invention are water-soluble phosphate builders. Specific advance ^

images of water-soluble phosphate builders are the alkali Z

metal tripolyphosphates, sodium, potassium and ammonium pyrosophosphate, sodium and potassium orthophosphate, sodium polymer phosphate with a degree of polymerization ranging from 6 to 21, and salts of phytic acid.

1fl1? R84 i 18

Partially soluble or insoluble 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

NaMSixO2 + 1.yH2O15 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 are preferred. 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 of preparation; 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 above general formula has a value of 2, 3 or 4 and is preferably 2.

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

] 30 The crystalline layered sodium silicate material! 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 1 is selected from organic acids, salts of organic 1 n 1 ra 19 and inorganic acids, 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 [(A102) z (SiO2) y] .xH20 where 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 aluminosi- I

liceate exchange materials - they 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 describes colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles have a diameter greater than 1 μπι and no more than 5% of the particles have a diameter less than 0.05 μιη . Preferably, the aluminosilicate zeolite particles have an average particle diameter of between 0.01 30 μτη and 1 μιη, more preferably between 0.05 μπι and 0.9 μιιι z and most preferably between 0.1 μm and 0.6 μm . ~

Zeolite A has the formula I.

Nal2 [(AlO2) 12 (SiO2) 12] .xHaO ~

35 I

wherein x is from 20 to 30 and in particular 27. Zeolite X I.

has the formula Na86 [(A102) 86 (SiO2) 105]. 276H20. Zeolite MAP "101 2584: 20 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.

: 15 A surprising finding is that mixed aluminosilicate zeolite detergent compositions comprising colloidal Zeolite A and colloidal Zeolite Y provide an equal sequestering performance for calcium ions over an equal weight of commercially available Zeolite A. Another surprising finding is that J mixed aluminosilicate zeolite cleaning compositions, as described above, provide improved sequestering performance for magnesium ions over an equal weight of commercially available Zeolite A. 25

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 must have the property of producing little foam and foaming of the surfactant system; Thus, for use in dishwashing processes, it should be suppressed or, most preferably, should cause little foam 101 25 84 21 and usually have nonionic properties. Foaming caused by surfactant systems used in laundry washing processes need not be suppressed to the same degree as is necessary in washing. The surfactant is usually present at a concentration of 0.2 to 30% by weight, most preferably 0.5 to 10% by weight, and most preferably 1 to 5% by weight 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 15 suitable cationic surfactants becomes 1

in U.S. Patent No. 259,217, issued March 31, 1981 to Murphy. A list of I.

surfactants commonly included in detergent compositions for dishwashers are given, for example, in EP-A-0 414 549 and PCT applications WO 93/08876 and WO 93/08874.

Non-ionic surfactant 25 Almost any non-ionic surfactant that can be used for cleaning purposes can be cleaned.

detergent tablet to be included. Non-restrictive classes I.

Preferred useful nonionic surfactants are listed below.

30 .....

Non-ionic ethoxylated alcohol surfactant ^

The alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are S

3 5 suitable to be used here. The alkyl chain of the - aliphatic alcohol can be straight or branched, primary or

secondary and generally contains from 6 to 22 carbon Z.

1012584 22 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.

5

Alkvlalkoxvlak surfactant with an end group

A suitable alkylalkoxylate surfactant with an end group is the poly (oxyalkylated) alcohol 10 with an epoxy end group, represented by the formula:

RjO [ch2ch (ch3) 0] x [CH2CH2O] y [CH2CH (OH) R2] (I) wherein R is a linear or branched aliphatic hydrocarbon group of 4 to 18 carbon atoms, R2 is a linear or branched aliphatic hydrocarbon group with 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 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 WO 94/22800 issued by Olin Corporation on October 13, 1994 has been published.

1 Poly (oxyalkylated) alcohols with an ether end group

Preferred surfactants used herein include poly (oxyalkylated) alcohols having an ether end group having the formula: R * 0 [CH2CH (R3) O] x [CH2] kCH (OH) [CH2] ^ OR2 - 101 2584 23 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 5 is an integer with an average value of 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,

10 saturated or unsaturated, aliphatic or aromatic hydrocarbon groups of 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. R3 is with I.

most preferred H or a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms. Preferably x: 15 is an integer with an average value of 1 to 20 and more preferably 6 to 15. - I.

As described above, when in the preferred embodiments x is greater than 2, R3 may be the same or Γ

be different. That is, R3 at different I

20 may have alternating different alkyleneoxy units as 2 described above. For example, if x is 3, R3 may be selected to include ethyleneoxy (EO) or propyleneoxy (PO) and may have a different sequence such as (EO) (PO) (EO), (EO) ( EO) (PO), 2 25 (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). j

The integer three is, of course, chosen only as an example, and the variation may be much larger with a higher ~ integer value for x and may, for example, be a larger = number (EO) units and a much smaller number (PO) - _ 30 units contain.

Particularly preferred surfactants as described above include those which II

have 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 - 101 2584 24 to obtain judgments of excellent grease cleaning.

Most preferred poly (oxyalkylated) alcohol surfactants with an ether end group are those wherein kl is and j is 1, so that the surfactants have the formula: R30 [CH2CH (R3) O] xCH2CH (OH) CH2OR2 10 wherein R1, R2 and R3 are as defined above and x is an integer having an average value of 1 to 30, preferably 1 to 20, and even more preferably 6 to s 18. Surfactants in which R1 and R2 are in the range of 9 to 14, R3 is H to form an ethyleneoxy-15 unit, and x is in the range of 6 to 15 are most preferred. -

The poly (oxyalkylated) alcohol surfactants having 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 ether end group and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule, while the alkylene oxide group forms the hydrophilic, water-soluble portion 7 of the molecule.

These surfactants show significant improvements in stain-removing and film-forming properties and the removal of greasy stains when used in conjunction with high cloud point surfactants over conventional surfactants.

Generally speaking, the ether-terminated poly (oxyalkylene) 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 poly (oxyalkylated) alcohol surfactants having an ether end group are described below:

Preparation of C14 / 14-Alkyl Acid Vid Ether

A C12 / 14 fatty alcohol (100.00 g, 0.515 mol) and 10 tin (IV) chloride (0.58 g, 2.23 mmol available from Al drich) 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 15 (47.70 g, 0.515 mol, available from Aldrich) is added dropwise to keep 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 Γ

20 (61.80 g, 0.773 mol, 50%) while stirring mechanically. I

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

The filtrate is separated and the organic phase becomes 1

washed with water (100 ml), dried over MgSO 4, filtered

Troubled and concentrated. Distillation of the oil at 100-120 ° C (0.1 mm Hg) gave the glycidyl ether as an oil.

Preparation of an alcohol surfactant with a: C1V,., -Alkyl-C0 ,,, -ether end group 30

Neodol® 91-8 (20.60 g, 0.0393 mol) ethoxylated I.

alcohol (available from the Shell Chemical Co.) and tin! (IV) Chloride (0.58 g, 2.23 mmol) are combined in a 250 ml three-necked round bottom flask equipped with a condenser, 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, 101 2584: 26 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.

10

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 a degree of ethoxylation of 20 to 3, and most preferably these are the ethoxylated C12-C18 fatty alcohols with an ethoxylation degree of 3 to 40. Preferably the mixed ethoxylated / 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.

Non-ionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic phase formed by the condensation of propylene; oxides 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 connections from! This type includes some of the commercially available Pluronic ™ surfactants marketed by BASF.

101 2584 27

Non-ionic EO condensation products with naphthylene oxide ethylenediamine adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine 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 from 2500 to 3000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic ™ compounds marketed by BASF.

15 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 nonionic surfactant

with a low cloud point and at least one non-ionic I

surfactant with a high cloud point.

Cloud point, as used here, is a “

known property of non-ionic surfactants resulting from the less soluble Z.

of the surfactant 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. ~ 30 vol. 22, pp. 360-379). _

As used herein, a "low cloud point" nonionic surfactant is defined as a constituent of the system of non-Si ionic surfactants with a cloud point Z! Less than 30 ° C, preferably less than 20 ° C and most preferably less than 10 ° C. Typical non-ionic ™ surfactants with a low cloud point

101 2584 Z

28 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 (eg, Poly-Tergent® SLF18 series from the Olin Corporation), poly (oxyalkylated) alcohols with an epoxy end group (eg the Poly-Tergent® SLF18B of non-ionic surfactants from the Olin Corporation as described, for example, in WO 94/22800, published October 13, 1994 in the name of the 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 No. 4,223,163 issued September 16, 1980 in the name of 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 col, propylene glycol, glycerol, trimethylol propane and ethylene diamine as initiator reactive hydrogen compound. Some of the surfactant block polymer compounds, referred to as 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 low cloud point nonionic surfactants.

- 101 25 84 29

As used herein, a "high cloud point" nonionic surfactant is defined as a component of the system of nonionic surfactants having a cloud point above 40 ° C, preferably above 50 ° C and more preferably higher than 60 ° C. Preferably, the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkyl phenol with 8 to 20 carbon -10 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 15 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: 20 above) value. in the range of 9 to 15 and preferably: 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 preferred branched chain fatty alcohol or a Ξ secondary fatty alcohol of 6 to 20 carbon atoms (C6-C20-alcohol), including secondary alcohols and primary branched chain alcohols. Preferably, the _

high cloud point nonionic surfactants ethoxylates of a branched or secondary Z.

alcohol and more preferably mixed ethoxylates of z.

a C9 / 11 or C11 / 15 branched alcohol condensed with 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 ^ thus derived

101 2584 I

Nonionic surfactant has a narrow ethoxylate distribution from the average.

Anionic surfactant 5

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 ( especially saturated and unsaturated C6-C14 diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable such as natural resin, hydrogenated natural resin and resin acids and hydrogenated resin acids which are present in or derived from tallow oil.

5 25

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- (C1-C4-alkyl) -; and -N- (C 1 -Co-hydroxyalkyl) glucamine sulfates and sulfates of alkyl polysaccharides such as the sulfates of alkyl polygluco-side (wherein the nonionic unsulfated compounds are described here).

I 101 2584 31

Alkyl sulfate surfactants are added! preferably selected from the linear and branched C10-C18 primary alkyl sulfates and more preferably from the C11-C15 branched chain alkyl sulfates, and the C12-C14 straight chain alkyl sulfates.

Alkylethoxy sulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which are containing 0.5 to 20 moles of ethylene oxide per ml. molecule are ethoxylated. More preferably, the alkyl ethoxysulfate surfactant is one and most preferably Cu-C15 alkyl sulfate which is ethoxylated with 0.5 to 7, 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 ethoxy sulfate surfactants are used. Such mixtures are described in PCT application WO 93/18124.

20 Anionic sulfonate surfactant

Anionic sulfonate surfactants that i

suitable for use herein include the salts I.

of linear C5-C20 alkylbenzene sulfonates, alkyl ester sulfonates, primary or secondary C6-C22 alkane sulfonates, C6-C24 olefin sulfonates, polycarboxylic acids with sulfonate groups, "alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty glycol sulfonates, and mixtures thereof.

30 Anionic carboxylate surfactant -

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl poly-

ethoxypolycarboxylate surfactants and the soaps L.

("Alkyl carboxyls"), and in particular certain secondary soaps as described herein.

101 2584 32

Suitable alkyl ethoxycarboxylates include those of the formula RO (CH2CH2O) xCH2COO'M + wherein R is a C6 -C18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that the amount is by weight material, where x is 0, less than 20% and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those of the formula RO- (CHR1-CHR2-O) -R3 wherein R is a C6-C18 alkyl group, x1 to 25 and R2 and R2 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 of 1 to 8 carbon atoms and mixtures thereof.

Suitable soap surfactants include - the secondary soap surfactants containing a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants here 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.

25

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R1) CH2C00M, where R is a linear or branched C5-C17-

alkyl or alkenyl group, R 1 is a C 1 -C 20 alkyl group and M

an alkali metal ion. Preferred examples are the myristyl and oleoylmethylsarcosinates in the form of their sodium salts. 1 101 25 84 33

Amphoteric surfactant

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

Suitable aminoxides include those compounds of the formula R3 (OR4) ^ NO (Rs) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group, or mixtures thereof, with 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 I

up to 3 ethylene oxide groups. C10-C18-alkyl dimethylamine-:

Oxide and C10.18-acylamidoalkyldimethylamine oxide have the I.

preference. - -

A suitable example of an alkyl amphodicarboxylic acid is Miranol ™ C2M Conc. produced by Miranol, Ine., 5

Dayton, NJ.

20

Zwitterionic surfactant

Zwitterionic surfactants can also be included in their detergent compositions ”25. These surfactants can be broadly described as derivatives of secondary and z tertiary amines, derivatives of heterocyclic secondary z 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 * R2COO' where R is a C6 -C13 hydrocarbyl group ^ 3 5, each R 1 is normally C 1 -C 1 -alkyl and R 2 is a C 1 -C 1 -hydroxy 21 is carbyl group. Preferred betaines are C12-C13-dimethylammoniohexanoate and the C10-Cig-acylamidopropane-2-n-34 (or -ethane-) dimethyl- (or -diethyl-) betaines. Complex betaine surfactants are also suitable for use here.

5 Cationic surfactants

Preferred cationic ester surfactants used in this invention are water-dispersible compounds having surfactant properties comprising at least one ester (i.e. -C00-) 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 15 4228042, 4239660, and 4260529.

Suitable cationic surfactants 3 include the quaternary ammonium surfactants - selected from mono-C 1 -C 16, preferably C 6 -C 10, -N-alkyl or -alkenylammonium surfactants, preferably "20 wherein the remaining N positions are methyl, hydroxyethyl or hydroxypropyl groups are substituted.

Enzymes

fïS

Enzymes are detergent components of the first phase and more particularly of the second and / or optionally other preferred phases. When enzymes are present, they are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, | phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullalanases, tannases, pentosanases, malanases, / 3-glucanases, arabinosidases, hyaluronidase, chron-, droitinase, mixtures thereof.

Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase and / or cellulase 101 2584 35 together with one or more enzymes that degrade the plant cell wall.

The cellulases useful in the present invention 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 Unit). Suitable cellulases are described in US 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 be

writes 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

15 95/26398.

Examples of such cetases are cellulas

welds produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), in particular I

of the Humicola strain DSM 1800. Other suitable cellulases I

20 are cellulases from Humicola insolens Γ 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, which contains cellulase

shows activity; an endoglucanase constituent that the I.

Is preferred with its amino acid sequence in the PCT-1

application WO 91/17243. Also suitable cellulases I

are the EGIII cellulases from Trichoderma longibrachiatum

described in WO 94/21801, Genecor, published 29 I.

September 1994. Particularly suitable cellulases are the T

30 cellulases with color care benefits. ~

Examples of such cellulases are cellulases described in European patent application 91202879.2 filed November 6, 1991 (Novo). Carezyme = and Celluzyme (Novo Nordisk A / S) are particularly useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases for properties related to

1012584 I

Tissue care and / or cleaning 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, 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-propionic 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 of 0.0001 to 2% by weight of active enzyme based on the = 1 weight of the detergent composition.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases.

Suitable cleaning lipase enzymes include. 101 2584 37 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 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": 10. Other suitable commercially available lipases include Amano-CES, Chromobacter viscosum lipases, 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 M1:

Lipase ”and Lipomax” (Gist-Brocades) and Lipolase ”and Lipolase =

Ultra ”(Novo) which have been found to be very effective when used in conjunction with the compositions of the present invention. Also suitable enzymes are the lipolytic enzymes described in EP 258 068, WOr

92/05249 and WO 95/22615 in the name of Novo Nordisk and in WO Z.

94/03578, WO 95/35381 and WO 96/00292 in the name of Unilever.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special type of lipase, namely =

lipases that do not require interfacial activation. Add I

gene of cutinases to detergent compositions are described, for example, in WO-A-88/09367 (Genencor), WO ^

90/09446 (Plant Genetic System) and WO 94/14963 and WWI

30 94/14964 (Unilever). _

The lipases and / or cutinases are usually expressed in z

detergent composition included in concentrations of Z.

from 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 _

101PRR4 I

38 protease is obtained from a strain of Bacillus with a 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 (in particular, pages 17, 24 and 98) and herein referred to as "Protease B", and in European Patent Application No. 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 Bacillus in which lysine has replaced arginine at position 27, has replaced tyrosine valine at position 104, serine has replaced asparagine at position 123 J 274 has replaced alanine threonine. 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", is a carbonyl hydrolase variant with an amino acid sequence not found in nature and derived from | a precursor carbonyl hydrolase by replacing a number of amino acid residues at a position in the carbonyl hydrolase equivalent to position +76 with 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, 101 25 84 39 +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 5 Protease Enzymes" with US Serial No. 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 10 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 92/03529 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 ^

trypsin-like protease for detergents which is suitable here is described in WO 94/25583 in the name of I

Novo. Other suitable proteases are described in EP = 516,200 in the name of Unilever.

Other preferred protease enzymes -

include protease enzymes which are a carbonyl hydrolase variant 25 with an amino acid sequence that is not found in nature I

found, which is derived by replacing some amino acid residues of a precursor carbonyl hydrolase with other amino acids, the number of amino acid residues being replaced in the precursor enzyme corresponding to Γ 3 0 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, the numbered positions corresponding to naturally occurring subtilisin £ 35 from Bacillus amyloliguefaciens or equivalent amino acid residues in other carbonylhydrolases or subtilisins z (such as Bacillus lentus subtilisin). Enzymes of this type

1 o 1 9 ς a a I

Preferred 40 include those with changes at 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%, and more preferably 0.005 to 0.1 wt% pure enzyme based on the weight of the composition.

Amylases (a- and / or β-) can be included to remove carbohydrate-based stains. WO 94/02597, Novo Nordisk A / S, published February 3, 1994, discloses cleaning compositions comprising 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 α and β amylases. α-, Amylases are known in the art and include those

are 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 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 1 available from Novo Nordisk A / S Denmark. WO 95/26397 j describes other suitable amylases: α-amylases characterized by a specific activity which 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, measured with the Phadebas® α-amylase activity assay. Suitable are variants of the above enzymes, 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% by weight, preferably 0.00018 to 0.06% by weight, 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 include amylase enzymes, in particular those described in WO 95/26397 and the pending application? 20 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 (α-1 and / or β-) are described below. WO 94/02597 and WO_

95/10603, Novo Nordisk A / S, describe detergent E

compositions incorporating mutant amylases. I

Other amylases known to be in cleaning agents I

Partial compositions used include both α and β 3 ams. α-Amylases are known in the art and include those described in US patent z 5,003,257, EP 252,666, WO / 91/00353, FR 2,676,456, EP = 285,123, EP 525,610, EP 368,341, British Patent Specification% 1,296,839 (Novo). Other suitable amylases are stability-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

101 2584 E

42

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® 5 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 of 25 ° C to 55 ° C and at a pH-10 value in the range from 8 to 10 as measured by the Phadebas® a-amylase activity assay. Suitable variants of the z enzymes above 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-9573382. Preferred complementary amylases in the present invention are the amylases sold under the trade name Purafect Ox Am® described in WO 94/18314, WO 20 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 from 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 with the greatest! 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.).

101 2584 43

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 2% by weight of active enzyme based on the weight of the cleanser.

detergent composition. The enzymes can be separated as I

components (pills, granules, stabilized I.

15 liquids, etc. containing one enzyme) or as mixtures:

of two or more enzymes (e.g., pooled Z

granules).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in pending European patent application.

92870018.6, filed January 31, 1992. Examples of I

such enzyme oxidation scavengers are ethoxylated Z

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 Z

Novo and US 3,553,139, January 5, 1971, to McCarty et al. Enzymes are further described in US 4,101,457, 2 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 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents may be employed by various techniques.

are stabilized. Enzyme stabilization techniques are called Z

described and illustrated in US 3,600,319, August 17, 1012584 44 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. AC 13 providing proteases, xylanases and cellulases is described in WO 9401532 A in the name of Novo.

Bleach

Part of the composition of cleaning; Highly preferred 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 detergent ingredient compositions 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 in 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.

101 2584 45

Examples of inorganic perhydrate salts 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, the preferred embodiments of such granular compositions use a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate can be in the form of the monohydrate with the nominal formula NaB02H202 or the tetrahydrate =

Prevent NaB02H202.3H20.

Alkali metal percarbonates, in particular sodium percarbonate, are the preferred perhydra for inclusion in compositions of the invention. Sodium percarbonate is an addition compound of the formula corresponding to 2Na2CO3.3H2O2 and is commercially available as a crystalline solid.

Sodium Percarbonate, which is a hydrogen peroxide addition l.

bond, tends to dissolve hydrogen peroxide oplossen when dissolved

can be released fairly quickly, resulting in locally high bleaching I

concentrations can occur. The percarbonate is most preferably included in such composition

gene in a coated form that provides in-product stability.

A suitable coating material that provides an in-product stability includes a mixed salt of a water-soluble alkali metal sulfate and carbonate. _

Such coatings, along with the coating methods Ξ have previously been described in GB 1,466,799 issued to Ξ

Interox on March 9, 1977. The weight ratio of the -

mixed salt as coating material to the percarbonate L.

35 ranges from 1: 200 to 1: 4, more preferably h.

1:99 to 1: 9 and most preferably 1:49 to 1:19. At ^

preferably the mixed salt is a salt of sodium sulfate "I.

1012584 46 and sodium carbonate containing the general formula Na2 SO4. nNa 2 CO 3, wherein n is 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-5 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 and borate salts or boric acids or other inorganic compounds are also suitable.

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

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

2 0

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

30 ||

X-C-L

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

O

II

X-C-OOH

1012584 47.

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, 1147871, 2143231 and EP-A-0170386.

Departing groups

The leaving group, hereinafter referred to as L-group: 20, must be sufficiently reactive for the perhydrolyzer series reaction to occur within the optimal time span (e.g.

picture a wash cycle). However, if L is too reactive, I

this activator is difficult to stabilize in an I.

bleaching composition.

Preferred 25 L groups are selected 1 from the group consisting of: 101 2584 48 0 Λ ο

II, II

—Ν — C — R1 —Ν Ν —Ν — C — CH — R4

Ι5 Μ 'I, I

R R3 Υ Υ R3 Υ

I I

-0-CH = C-CH = CH2 -0-CH = C-CHrCH2 I * ο ν 0

II γ. II

ο ch2_c y — c. .

11 1 μ '\ | π4 -N> R.

-α-C-R1 5 1

o o

R3 O Y

1, and II I.

-O-C = CHR4 -N-S-CH-R4

I, II R3 O

and mixtures thereof, wherein R 1 is an alkyl, aryl or alkyl group of 1 to 14 carbon atoms, R 3 is an alkyl chain of 1 to 8 carbon atoms, R 4 is H or R 3, R 5 is an alkenyl chain of 1 to 8 carbon atoms and is YH or a solubility-enhancing group. R 1, R 3, and R 4 can be substituted by virtually any functional group, including, for example, alkyl, hydroxy, alkoxy, nalogenide, amine, nitrosyl, amide, and ammonium or alklammonium groups.

101 2584

4 S

The preferred solubility enhancing groups are -SO 3'M *, -CO / M *, -SO 4'M * (-N * (R3) 4X 'and 0 <-N (R3) 3 and most preferably - SO 3, M *, and -CO / NP wherein R 3 is an alkyl chain of 1 to 4 carbon atoms, M 5 is a cation that provides solubility to the bleach activator, and X is an anion that provides solubility to the bleach activator. M is an alkali metal, ammonium or substituted ammonium cation with sodium and potassium being most preferred, and 10 is a halide, hydroxide, methyl sulfate or acetate anion.

Perbenzoic acid pre-loner

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:

Also suitable are the benzoylation products of 20 sorbitol, glucose and all saccharides with benzoylating agents including for example: 101 2584 50 OAc j

AcO'T ^ -O

/ r \\ ^ 0Ac / OAc OBz = Ac = COCHj; Bz = benzoyl

Imide-type perbenzoic acid precursor compounds 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:

r ^ AvoJl ^

Oj o- o ^^ cooh

Phthalic anhydride is another perbenzoic acid precursor compound suitable here: 101 2584 51

O

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

II

o c-ch2-ch2 R6'-c_N "CH2- [CH1] n wherein n is 0 to 8 and preferably 0 to 2 and Re is a benzoyl group.

5 Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursors provide "substituted perbenzoic acids upon perhydrolysis. ï

Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic acid precursors described herein in which the benzoyl group is substituted by a non-positively charged (ie, 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 of the following general formulas: 101 25 84 52

R1 — C - N - R2 - c - L R1 — N —c —R2 - C - L.

!! I, II f L I! II:

OR5 O or R3 O O__I

wherein R1 is an aryl or alkaryl group of 1 to 14 carbon atoms, R2 is an arylene or 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 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 can be an aryl, substituted aryl or alkylaryl with branching, substitution, or both, and can be from synthetic 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, 15 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide substituted bleach activators of this type are described in EP-A-0170386.

Cat Ionic Peroxyacid Precursors 20 Cationic Peroxyacid Precursors; provide cationic peroxyacids on perhydrolysis.

Normally, 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 1 n 1 pro a 53 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; U.S. Patents 4,904,406, 4,751,015, 4,988,451,

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 one of the ammonium or alkyl ammonium substituted L

prior alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactams and monobenzoyl tetraacetyl glucose benzoyl peroxides.

A cationically substituted benzoyloxybenzene F

preferred sulfonate is the 4- (trimethylammonium) methyl derivative of benzoyloxybenzene sulfonate: 2

O

^ Or ^ s ° 3- v 1 / \

A preferred cationically substituted alkyloxybenzene sulfonate has the formula: o · ». so3 'x' - X .. A0 = 101 2584 54

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylene benzoyl caprolactams, especially trimethyl ammonium methylene benzoyl caprolacta:

? I

-V LQJ (..) Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammoniummethylenealkyl caprolactams: O 0

11 I

\ / N "^^ (CU2) n wherein n is 0 to 12 and especially 1 to 5.

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

Alkyl Carboxylic 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 I imide type include the Ν, Ν, Κτ, Ν1-tetraacetylated alkylene diamines in which the alkylene group contains 1 to c 6 carbon atoms and in particular those compounds of the alkylene group 1, 2 and 6 carbon atoms 101 2584 55. Tetraacetylethylenediamine (TAED) is particularly preferred.

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

Amide substituted Alkyl Peroxoic acid precursors

Amide substituted alkyl peroxyacid precursor-10 compounds are also suitable including those having the following general formulas:

R1 — c - N - R2 - C - L R1 — N - C R2 C L

II I li L II II

R5 O or R5 O0 wherein R 1 is an alkyl group of 1 to 14 carbon atoms, R 1 is an alkylene group of 1 to 14 carbon atoms and R 5 is H or 15 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. R 1 may be a linear or branched alkyl with branching, substitution or both and may be from synthetic sources or natural sources, including, for example, tallow fat. Analogous structural variations are possible for R 2. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is = 7 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-017 03 8 6.

Benzoxazine Organic Primoxic Acid Precursors

Also suitable are benzoxazine type precursor compounds as described, for example, in EP-A-332,294 and EP-A-482,807, in particular those of the formula.

: 06- - including the substituted benzoxazines of the S-type JtA.

4 γ N

R5 1 10 wherein R 1 is H, alkyl, alkaryl, aryl, arylalkyl and wherein R 1, R 3, R 4 and R 5 may be the same or different substituents selected from H, halogen, alkyl, 1: alkenyl, aryl, hydroxyl , alkoxyl, amino, alkvlamino, COOR ^ - (where R is K or an alkyl group) and carbonyl functions.

4 IS A particularly preferred precursor of the benzoxazine type is: 57

Preformed organic peroxic acid

The organic peroxyacid bleaching system can be in addition to or Γ

instead of an organic peroxyacid bleach precursor

per compound, a preformed organic peroxyacid: 5, normally 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 of I.

10 the following general formulas:

R1 C - N - R2 - C - OOH

! l 's J>

OR5 O

R1 N - C - R2 - C - OOH

I. II II

R3 O O

wherein R 1 is an alkyl, aryl or alkaryl group of 1 to 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group of 1 to 14 carbon atoms and R 5 is H or an alkyl 15 aryl or alkaryl group of 1 to 10 carbon atoms is atoms. R's

preferably contains 6 to 12 carbon atoms. R: contains at ZI

preferably 4 to 8 carbon atoms. R 1 may be a linear or Z 1 branched alkyl, substituted aryl or alkyl aryl with branching, substitution, or both, and may be from 101 2584 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. Rs is preferably H or methyl. R1 and Rs 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. Means for controlling the rate of release of the bleach may provide controlled release of peroxide species. provide 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 .j. Rate of Bleach Release may be coating 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 that the kinetics of dissolving the thick coating provide 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: 2 SiO 2: Na 2 O from 1.8: 1 to 3.0: 1 and preferably 1.8: 1 up to 2.4: 1 and / or sodium metasilicate which is preferably applied 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.

Any inorganic salt coating material can.

are combined with organic binder materials to make I.

composite coatings of an inorganic salt / organ- -

provide a binder. Suitable binders I

Comprising C10-C20 alcohol ethoxylates with 5-100 moles of ethylene oxide per mole of alcohol and more preferably the 1 primary C18-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 Z

polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10δ, 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 adjusting the solubility of the bleach compound by selecting the particle size of a granular component.

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

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 = 15 allows to achieve controlled release kinetics.

Metal-containing bleach catalyst

The compositions described herein, which contain bleaching agent as a detergent 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, and 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 catalytic activity, such as copper and s

iron cations and an auxiliary metal cation with a low or no I.

bleaching catalytic activity such as zinc or aluminum cations and a sequestrant with defined stability constants for the catalytic and auxiliary metal cations, in particular ethylenediamine tetraacetic acid, ethylenediamine tetra (methylene phosphonic acid) and water-soluble salts thereof. Such catalysts are described in U.S. Pat. No. 4,430,243.

101 2584 Ü 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 Mnrv2 (u-O) 3 (1,4,7-: 5 trimethyl-1,4,7-triazacyclononane) 2 (PFS) 2, Mnin2 (u-Oj ^ u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 4 (C10J2, MnIV4 (h-0) s (1,4,7-triazacyclononane) 4 (C104) 2, MnmMnIV4 (h-0) i (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (C104) 3 and mixtures thereof, others are described in Europe-10 patent application publication No. 549,272. suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triaza-cyclononane, 2-methyl-1,4,7-triazacyclononane, 1 , 2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

15 The bleaching catalysts used in the compositions

useful herein may also be selected for the present invention. For examples of suitable bleaching catalysts, see U.S. Patent 4,246,612 and U.S. Pat

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 discloses 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: i R2 R3 35 I] R * -N = CBC = NR '101 25 84 63 wherein R1, R2, R3 and R4 can each be selected from H, substituted alkyl and aryl groups such that each R3-N = C-R2 and R3-C = N-R4 form a 5- or 6-ring. 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 each may 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 10 may be optionally substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. The 2,2'-bispyridylamine ligand is particularly preferred. Preferred bleaching catalysts include Co-, "

Cu-, Mn-, Fe-bispyridylmethane- and -bispyridylamine-com- "

15 plexes. Highly Preferred Catalysts I.

include Co (2,2'-bispyridylamine) Cl77 di (isothiocyanate) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate, Co (2,2-bispyridylamine) 202C104, bis (2, 2'-bispyridylamine) copper (II) perchlorate, tris (di-2- "20 pyridylamine) iron (II) perchlorate and mixtures thereof. Γ

Preferred examples include binuclear Mn-I

complexes with N-tetrahedron and N-bidentate ligands with I.

including N4MnIIX (u-0) 2MnIVN4) * and [bipy2Mnxxx (u-O) 2Mnxvbipy2] - (C104) 3.

Although the structures of the bleach-catalysing I

manganese complexes according to the present invention

have been clarified, they can be expected to chelate or I

other hydrated coordination complexes include those resulting from the interaction of the carboxyl groups and ~ 30 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 Ξ (+ 11), (+ III), (+ IV) or (+ V) valency state. Because "

the ligand 6 possible connection points with the manganese II

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 101 2584 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-tooth ligand catalyst)

talysator), US 4,711,748 and European patent application publication no. 224,952 (catalyst consisting of absorbed manganese on aluminosilicate), US 4,601,845 (aluminosi: licate support with manganese and zinc or magnesium salt), US

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: i Co [(NH3) nM 'mB' bT 'tQqPp] Yy' 25 in which cobalt has the +3 oxidation state, n an integer from 0 to 5 (preferably 4 or 5 and most preferably 5), M 'represents a monodentate ligand, m is an integer from 0 to 5 (preferably 1 or 2 and most preferably 1), B' represents a bidentate ligand 1 30, b is an integer from 0 to 2, T 'represents a tridental ΐ ligand, t is 0 or 1, Q is a four-pronged ligand, jq is 0 or 1, P is a five-pronged ligand, p is 0 or 1 and n + m + 2b + 3t + 4q + 5p = 6, Y are one or more suitably chosen counter anions present in a number y where 35 y is an integer from 1 to 3 (preferably 2 to 3 and having 101 2584 65 is most preferred 2 when a Y is a -1 charged anion) to obtain 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) relative to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) relative to a conventional hydrogen electrode.

Preferred cobalt catalysts of this type have the formula: [Co (NH3) n (M ') ra] Yy where n is an integer from 3 to 5 (preferably 4 or 5 [and most preferably 5) is, M 'is an unstable coordinating moiety preferably selected from the group "

20 consisting of chlorine, bromine, hydroxide, water and (when m I

is greater than 1) combinations thereof, m is an integer from 1 to 3 (preferably 1 or 2 and most preferably)), m + n = 6 and Y is an appropriately chosen counter anion f present in a number y that is an integer of ^

1 to 3 (preferably 2 to 3 and most preferably 2 I.

when Y is a -1 charged anion) to obtain a salt with = charge equilibrium.

The cobalt catalysts of this type which provide the I

cobalt pen names are useful and useful here

30 chloride salts of the formula [Co (NH3) 5Cl] Yy and in II

particular [Co (NH3) 5Cl] Cl2.

More preferred are the compositions of the present invention which contain cobalt (III) bleach catalysts of the formula

101 2584 I

66 [Co (NH3) n (M) m (B) b] Ty, in which cobalt has the +3 oxidation state, n is 4 or 5 (preferably 5), M are one or more ligands! are coordinated with the cobalt in one place, m is 0, 1 or 5 2 (preferably 1), B is a ligand coordinated with the cobalt in two places, 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 counteranions present in the number y where y is an integer such that a salt with charge equilibrium (preferably y is 1 to 3 and most preferably 2 when T is a -1 charged anion) and further wherein the catalyst has a base hydrolysis rate constant - less than 0.23 M'1 s'1 (25 ° C).

T is preferably selected with the group consisting of chloride, iodide, I 3 ', 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 can be protonated if more than one anionic group is in T

is present, for example HP042 ', HCO3', H2PO4 ', etc. In addition, T may be selected from the group consisting of non-conventional inorganic anions such as anionic surfactants (eg linear alkylbenzenesulfonates (LAS ), alkyl sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or anionic polymers (e.g. 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 moiety or exist in its salt form). Optionally, M may be protonated if more than one anionic group occurs in M (e.g., 101 2584 67 HP042 ', HCO3 *, H2PO4', H0C (0) CH2C (0) 0-, etc.). Preferred M radicals are substituted and unsubstituted C3-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 -C 10 '(preferably C 1 -C 18 -alkyl), unsubstituted and substituted C 5 -C 30- (preferably C 6 -C 18-) aryl and unsubstituted and substituted C 3 -C 30- (preferably C5-10 C18-) heteroaryl in which substituents are selected from the j group consisting of -NR'3, -NR'4 *, -C0 (0) 0R ', -OR', -C (O) - NR'2, wherein R 'is selected from the group consisting of u hydrogen and C 2 -Cg radicals. Such a substituted R 1 therefore includes the radicals - (CH 2) nOH and ~ (CH 2) nNR '4+ wherein n 15 is an integer from 1 to 16, preferably 2 to 10, and most preferably 2 to 5 .

Most preferably M is a carboxylic acid of 1 of the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, linear or branched C 4 -C 12 alkyl and benzyl. Most preferably R is methyl. Preferred M-carboxylic acid residues include miere, benzoin, octane, nonane, decane, dodecane, malon, malein, amber, adipin, phthal, 2-ethylhexane, naphthene -, oil, palmitine, trifluora, “25”, tartar, stearin, butter, lemon, acrylic, asparagine, fumar, laurin, linole, milk, apple and = especially acetic acid.

The B radicals include carbonate, di and higher 1 carboxylates (eg oxalate, malonate, malate, “

Succinate, maleate), picolinic acid, and alpha and beta amino acids Z

ren (e.g. glycine, alanine, beta-alanine, phenylalaz

nine).

Cobalt bleach catalysts useful herein are known and are described, for example, at their base hydrolysis rates in M. L. Tobe, "Base Hydrolysis of Z101 2584 68

Transition-Metal Complexes ", Adv. Inorg. Bioinora. Mech., (1983), 2, biz. 1-94. For example, Table 1 on biz. 17 shows 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 "* M'1 s'1 (25 ° C)) formate (k0H = 5.8 x 10'4 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 as [Co (NH3) sOAc] (OAc) 2, [Co (NH3) 5OAc] (PF6) 2, [Co (NH3) 5OAc] (SO4), [Co (NH3) sOAc] (BF4) 2 and [Co (NH3) 50Ac] (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, Inorg. 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 synthetic routes described in US Patents 5,559,261, 5,581,005 and 5,597,936 to which reference is made herein.

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

Organic polymeric 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 incorporated into the detergent compositions of the invention at a concentration of from 0.05% to 30% by weight, preferably from 0.5 to 15% by weight, and most preferably from 1 to 15% by weight. = 10% by weight based on the weight of the compositions.

Examples of organic polymeric compounds;

include the water-soluble organic homo- or copolymer I.

polycarboxylic acids, modified polycarboxylates or their: salts wherein the polycarboxylic acid has at least two carboxylic acids

groups separated by no more than 2 carbon atoms I.

are separated. Polymers of the latter type are described in GB-A-1,596,756. Examples of such salts are polyacrylates with a molecular weight of 2,000 to 10,000 and their copolymers with some suitable other monomer units including modified acrylic, fumar, malein, itacon, aconitin, mesacon, citracon and methylene malonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinyl methyl ether, styrene and mixtures thereof. The copolymers of 1

acrylic acid and maleic anhydride with a molecular weight L.

from 20,000 to 100,000 are preferred.

Commercially available acrylic acid-containing polymers with a preferred molecular weight of less than 15,000 include those sold under 101 2584 70 tradename Sokalan PA30, PA20, PA15, ΡΑΙΟ and Sokalan CP10 by BASF GmbH and those sold under the tradename 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 to 80 wt% of a substituted acrylic monomer or its salts of the general formula - [ CR2-CRX (CO-O-Rj)] - wherein at least one of the substituents R1f Ra or R3, preferably R3 or R2, is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, R3 or R2 is a hydrogen atom can be and; r3 can be a hydrogen atom or an alkali metal salt. A 'substituted acrylic monomer in which Rx 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.

"· |

Dirt wasters i; Suitable polymeric soil removers 35 include those soil removers having: (a) one or 101 2584 71 more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization 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 where the 10 hydrophilic segments preferably 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 where, if the hydrophobic constituents I

also include oxyethylene terephthalate, the ratio of:

oxyethylene terephthalate: C3-oxyalkylene terephthalate units I.

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 polymerization Degree of at least 2 or (iv) C 1 -C 4 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

25 thereof, or a combination of (a) and (b). I

The polyoxyethylene segments of (a) (i) will be ^

normally a degree of polymerization from 200, although higher I.

values can be used, preferably from 3 to r

15 and more preferably from 6 to 100. Ge- II

30 suitable hydrophobic C 4 -C 6 oxyalkylene segments, but Z

are not limited to end groups of polymeric soil removers such as M03S (CH2) nOCH2CH2O- where M is sodium z and n is an integer from 4 to 6 as described in z

U.S. Patent 4,721,580, issued January 26, 1988 to Z

35 by Gosselink. a

Polymeric soil removers useful herein also include cellulose derivatives such as 101 2584 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 which can be used herein also include those selected from the group consisting of C 1 -C 4 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), eg, 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 together with 90 to 80 wt% polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol I 30 with an average molecular weight of 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 Nov. 6, 1, 9, P, 73, 1990, to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil removers include the terephthalate polyesters of U.S. Patent 4,711,730 issued December 8, 1987, to Gosselink et al., The oligomeric esters with anionic end groups of 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, in the name of:

Gosselink. Other polymeric soil removers 10 also include the soil removers of US

U.S. Patent 4,877,896 issued October 31, 1989, to Maldonado et al., which describes terephthalate esters with anionic, especially sulfoarolyl, end groups.

Another soil release agent is an oligomer having 15 repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethylene oxy1 and 1,2-oxypropylene oxy 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 comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, j

oxyethyleneoxy and 1,2-oxypropyleneoxy units in an I.

ratio of 1.7 to 1.8 and two end group units of i

sodium 2- (2-hydroxyethoxy) ethanesulfonate. T

25 Heavy metal ion sequestrant

The tablets according to the invention preferably contain, as an optional ingredient, a sequestrant for heavy metal ions. By heavy metal metal sequestrant is here 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.

101 2584 - 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 0.25 to 7.5 wt%, and most preferred 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 mole ratio of the counter cation to the heavy metal ion sequestrant is preferably at least 15 1: 1.

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

25 Other suitable sequestrants for heavy

metal ions that can be used here include H

Nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene diaminotetraacetic acid, ethylene triamine pentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or salts thereof.

Ethylenediamine-N, N'-disuccinic 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 thereof.

1ü12584 75

Crystal growth inhibitor component

The detergent 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. This definition therefore excludes the organo aminophosphonates which, however, can still be included in compositions of the invention as sequestrant components for heavy metal ions.

The organodiphosphonic acid is preferably a C 1 -C 3; Diphosphonic acid and more preferably a C2 diphosphonic acid:

such as ethylene diphosphonic acid or most preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP) and may be partially E

tally or completely ionized form and in particular when a salt or complex are present.

20 Water-soluble sulfate salt

The detergent tablet may contain an I.

water-soluble sulfate salt. If present, it is water

soluble sulfate salt present in a concentration of 0.1 to 40 wt%, more preferably 1 to 30 wt%, and most preferably 5 to 25 wt% 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 EE

Alkali and alkaline earth metals, in particular sodium sul-EE

fate.

101 25 84 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 in a concentration of at least 0.4% by weight, measured as SiO2. Sodium metasilicate z has a nominal SiO2: Na2O ratio of 1.0. sodium silicate relative 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. In a high pH composition, the colorant is thus preferably alkali stable 101 2584 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 monoazole dyes. Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING; 2 BLUE (trade name), TURQUOISE ACID BLUE ( trade name) and p SANDOLAN BRILLIANT GREEN (trade name), all available! from Clariant UK, HEXACOL QUINOLINE YELLOW (trade name) and f HEXACOL BRILLIANT BLUE (trade name), both available Ξ from Pointings, UK, ULTRA MARINE BLUE (trade name), 1

25 available at Holliday or LEVAFIX TURQUOISE BLUE EBA I

(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%, and most preferably 0.1 to 0 0.3% When present as a component of the second and / or optionally other phases, the colorant is generally present in a concentration of 0.001 to 0.1% by weight, more preferably 0.005 to 0, 05 wt% and most preferably 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 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 94/047 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 must 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 is present to treat the solid silver surfaces.

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

101 2584 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, c-glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid and / or fatty alcohol I

group of the fatty ester auxiliary material 1 to 24 carbon atoms

20 in the alkyl chain.

Preferred fatty esters here are ethyl-Z

glycol, glycerol and sorbitan esters in which the fatty acid portion of the ester usually comprises a species that I

is selected from behenic, stearic, oleic, palmitic, or myristic.

The glycerol esters also have a high I.

preference. These are the mono-, di- or triesters of glycerol Z.

and the fatty acids as defined above.

Specific examples of fatty alcohol esters that ~

Can be used here include: stearyl acetate, Z

palmityl dilactate, cocoyl isobutyrate, oleyl maleate, oleyl-Z

dimalate and talc alcohol propionate. Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan esters. ^

Suitable sorbitan esters include sorbitan monostearate, "7 sorbitan palmitate, sorbitan monolaurate, sorbitan monomyri- Ξ mi οςρΛ - 80 state, sorbitan monobehenate, sorbitan monooleate, sorbi-tandilaurate, sorbitan distearate, sorbitan dibenoalkylate, and sorbitan tallow diol.

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. a 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-methylamine oxide and | quaternary dialkyl ammonium 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 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 C25-C45- species with a ratio of cyclic 15 to non-cyclic hydrocarbons from 1:10 to 2: 1 and preferably 1: 5 to 1: 1. A paraffin option which has these properties, with a ratio of cyclic to non-cyclic hydrocarbons of. 32:68, being sold by ü

Wintershall, Salzbergen, Germany, under the tradename I.

2 0 WINOG 70. 1

Nitrogen-containing corrosion inhibitor compounds L.

Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as t-benzimidazole, 2-heptadecylimidazole and those imidazole derivatives which are disclosed in the Czech patent f

139,279 and British Patent GB-A-1,137,741, which also includes an F.

process for preparing imidazole compounds I

writes.

Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, in particular those in which the pyrazole at 1-,

3, 4 or 5 positions is substituted with substituents F.

R 1, R 3, R 4 and R 5 wherein R 1 H, CH 2 OH, CONH 3, or COCH 3, R 3 and R 5 z; C 1 -C 20 alkyl or hydroxy and R 4 is H, NH 2 or NO 2.

101 2584 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.

ίο Mn (II) corrosion inhibitor compounds

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% by weight, more preferably 0.01T to 1% by weight and most preferably 0.02 to 0.4% by weight. % based on the weight of the compositions. Preferably, the ^ Mn (II) compound is included 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. in a bleaching solution.

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 acids 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.

101 2584 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 C10-C20 fatty acids, or their salts, 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 the 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 an i

hydrocarbon oil, normally aliphatic hydrocarbons I.

20 with predominantly long chains and a number of carbon atoms in I.

* the range from 20 to 50; preferred hydrocarbons are saturated and / or branched; a preferred hydrocarbon oil is selected from a predominantly branched C25-C45 species in a ratio of cyclic to 25 non-cyclic hydrocarbons of 1:10 to 2: 1 and preferably 1: 5 to 1: 1. preferred hydrocarbon oil is paraffin. A paraffin oil having the above-described properties, with a ratio of cyclic "to non-cyclic hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the" trade name WINOG 70. = 101 2584 84

Water-soluble bismuth compound

The detergent tablets of the present invention which are suitable for use in dishwashing processes! can be used 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 on 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 bis-mut 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.

} i j 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 wt%, more preferably 1 to 20 wt%, and most preferably 2 to 10 wt% .% 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.

Foaming suppression system

The detergent tablets according to the following

The invention, when used in washing machine compositions, preferably includes a foam suppression system present in a concentration of 0.01 to 15 l

wt%, preferably 0.05 to 10 wt% and with the largest; preferably 0.1 to 5% by weight based on the weight of the composition.

Suitable suds suppression systems that can be used here can be practically any known anti-1

foam compound, including, for example, E

silicone antifoam compounds and 2-alkyl and -alkanol-20 antifoam compounds. Foaming suppression systems and ΐ

preferred antifoam compounds are I.

described in PCT application WO 93/08876 and EP-A-705 324.

Polymeric Colorant Transfer Inhibitors »

The detergent tablets can also be 0.01 I here

2 to 5 to 10 wt%, and preferably 0.05 to 0.5 wt%, of polymeric colorant transfer inhibitors. -

The polymeric colorant transfer inhibiting agents "are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole," polyvinylpyrrolidone polymers or combinations thereof. = 101? Σ «, ι 86

Optical rinse aid

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 having the structural formula: R2 'SO.-IM SO3M R, z wherein RL is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R2 is selected N-2 bis-hydroxye-10thyl, 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 R 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 R is anilino, R is: N-2-hydroxyethyl-N-2-methylamino and M is a cation; as sodium is, the brightener is 4,4'-bis [(4-amino-5-I-2 (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -! 2,2'stilbene disulfonic acid disodium salt. This specific 101 2584 87 glossant species is sold commercially under the trade name Tinopal-5BM-GX by Ciba Geigy Corporation.

When in the above formula R2 is anilino, R2 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 an I.

15 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. ï 20 Cationic fabric softeners ï

Cationic fabric softeners can also be used in; compositions of the present invention are included which are suitable for use in laundry washing processes. Appropriate Cationic Fabric Softening

25 ters include the water-insoluble tertiary amines or I.

two long 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% by weight. P

101 2584 88

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 5.5, 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 with a volume of 3 to 3 10 1, these typical product dosages and I being 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.

.. 101 25 RA

89

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 Wash ; of laundry.

According to a preferred use aspect, in the washing method, an application device is used. The dispenser is filled with the detergent product:

duet and is used to direct the product to the drum L.

from the washing machine before the washing cycle has started ï. Its volume capacity must be such that z 2 0 is able to absorb as much detergent product [

as commonly used in the washing process. Z.

As soon as the washing machine is filled with laundry, the I

dispenser containing the detergent product Z

placed in the drum. At the beginning of the wash cycle of r

The washing machine is supplied with water to the drum and I.

rotates the drum periodically. The administration device should be designed to allow -

makes the dry detergent product contain but I

then release this product during the wash cycle as Ξ 3 0 response to shaking as the drum rotates and 1; also as a result of its contact with the wash water.

To allow dispensing of the detergent product during washing, the device may include a number of 35 openings through which the product may pass. ~

Otherwise, the device may be composed of a Z

1 n 1 90 material that 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 quickly at the beginning of the wash cycle, thereby 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. Alternatively, it may be composed of a water-insoluble synthetic polymeric material which is provided with a corner seal or seal designed to break into 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 which is applied along one side of a pouch composed of a water-impermeable polymeric film such as polyethylene or polypropylene and seals it.

Examples 30 Abbreviations used in examples

In the detergent compositions, the 1 abbreviated ingredient identifiers have the following meanings: 101 2584 91 STPP: Sodium tripolyphosphate

Bicarbonate: Sodium hydrogen carbonate

Citric Acid: Anhydrous citric acid

Carbonate: Anhydrous sodium bicarbonate 5 Silicate: Amorphous sodium silicate (sioa: Na, 0 ratio = 2.0) SKS-6: Crystalline layered silicate with the formula δ-NajSijOj PBi: Anhydrous sodium perborate monohydrate

Non-ionically mixed ethoxylated / propoxylated C13-Cl5 fatty alcohol with an average ethoxylation degree of 3.8 and an average propoxylation degree 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 through .1

Wintershall

Protease: Proteolytic enzyme

Amylase: Amylolytic enzyme 15 BTA: Benzotriazole

Sulfate Anhydrous sodium sulfate _ PEG 3000: Polyethylene glycol with a molecular weight of about = 3000, available from Hoechst

PEG 6000: Polyethylene glycol with a molecular weight of about I.

6000, available from Hoechst pH Measured as a 1% solution in distilled water at ^

20 ° C

In the following examples, all concentrates I

tions indicated in parts by weight:

Examples I-IV ΐ

The following are examples of detergent T-L

tablets of the present invention which are suitable for use in a dishwasher are shown. -. -. - t 0 1 75 ft 4: 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 KEDP 0.18 0.18 0.18 0.2B 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, S7 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 -4 Sulfamic 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 2.0g 2.0g 2.0g 2.0g 2.0g 2. 0g

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 comprises 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 940 kg / cm2 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 2 101 2584 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.

1012584

Claims (14)

A multiphase detergent tablet for machine washing comprising: a) a first phase in the form of a pressed, J-shaped mass with at least one mold in its surface and b) a second phase in the form of a pressed mass, which present in the mold, the second phase being formed by pressing a granular solid and additionally comprising an enzyme. 1 AMENDED CONCLUSIONS A multi-phase detergent tablet according to claim 1 for use in a dishwasher, wherein the times in which the first and second phases dissolve in the dishwasher 15 are independent of each other. The multi-phase detergent tablet according to claim 1 or 2, wherein the first and second phases are in a weight ratio of at least 10: 1 to each other. A multi-phase 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 one of the preceding claims, wherein the formed mass is prepared at a pressure of at least 350 kg / cm2 and the second phase is pressed at a pressure of less than 350 kg / cm2. 6. Multiphase detergent tablet according to one: | of the preceding claims, wherein the pressures applied to the first and second phases are in a ratio of at least 2: 1 to each other. Multiphase detergent tablet according to any of the preceding claims, wherein at least 80% by weight of 1012584 of the enzyme is delivered to the washing liquid within the first five minutes of the washing process (Bosch dishwasher, 65 ° C wash program, 18 ° H, DIN 44990). A multi-phase detergent tablet according to any of the preceding claims, wherein the enzyme is selected from protease, amylase, lipase, peroxidases, cutinase and cellulase. A multi-phase detergent tablet according to any one of the preceding claims, wherein the second phase additionally comprises a disrupting agent selected from disintegrating agents and effervescent agents. The multi-phase detergent tablet according to any of the preceding claims, wherein the second phase "additionally comprises a binder selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers. A multi-phase detergent tablet for machine washing, comprising: a) a first phase in the form of a pressed, molded mass with at least one mold in its surface and b) a second phase in the form of a pressed mass which is adhesively present in the mold, the second phase being formed by pressing a granular solid and the tablet composition comprising an enzyme which is mainly concentrated in the second phase. A multi-phase detergent tablet according to any one of the preceding claims, further comprising a barrier phase between the first and second phases. The multi-phase detergent tablet according to claim 12, wherein the barrier layer comprises a binder applied in liquid form. 14. Multiphase detergent tablet according to con | Clusion 12, wherein the barrier layer comprises a binder selected from the group consisting of sugar and sugar derivatives, 1012584 starch and starch derivatives, inorganic and organic polymers. | 1012584