DE69911623T2 - 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

Technical field

The present invention relates to Multiphase detergent tablets.

background

Detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form several advantages over detergent compositions in particle form, like a) simple) dosage, handling, Transport and Storage.

Detergent tablets are the most common by premixing components of a detergent composition and forming the premixed detergent components into a tablet using any suitable device, preferably a tablet press. Pills are typically by compressing the components of the detergent composition shaped so that the tablets produced are sufficiently stable to handle and survive the transport without sustained damage. tablets have to additionally to them are stable, also dissolve quickly enough so that the detergent components as soon as possible be released into the wash water at the start of the wash cycle.

However, there is a conflict than the rate of dissolution of the tablets slows down when the compression pressure is increased. The present invention therefore seeks to strike a balance between tablets stability and tablet dissolution to find.

solutions for this Problem, as according to the state The technique apparent included compressing the tablets at a low compression pressure. The manufactured in this way Tablets, however, tend to be quick relative dissolution rate exhibit, disintegrate, damaged and useless for to become the consumer. Other solutions included manufacturing tablets using a high relative compression pressure, the required degree of stability to achieve and including a dissolution aid, like an effervescent.

Multi-phase detergent tablets described in the prior art are made by compressing a first composition in a tablet press to form a substantially planar first layer. Another detergent composition is then applied to the top of the first layer in the tablet press. This second composition is then compressed to form another substantially planar second layer. In this way, the first layer is generally subjected to more than one compression, since it is also compressed during the compression of the second composition. Typically, the first and second compression pressures are of the same order of magnitude. The applicant has determined that, if applicable, the pressure used in both the first and second compression steps must range from about 4,000 to about 20,000 kg (assuming a tablet cross section of about 10 cm ² ) because the compression pressure is sufficient to connect the first and second compositions. One consequence of this is a slower tablet dissolution rate. Other multi-phase tablets that show different resolutions are made such that the second layer is compressed at a lower pressure than the first layer. However, although 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 handling and transportation.

EP-B-0,055,100 describes a toilet block, which by combining a slowly dissolving shaped one body is formed with a tablet. The toilet block is designed that he is placed in the water box of a toilet and over a Period of days, preferably weeks. As a means of slowing down the dissolution rate of the toilet block, the document teaches the addition of an or several 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 for washing laundry or automatic dishwashing have to essentially within one cycle of the washing machine or dishwasher dissolve, d. H. within 15 to 120 minutes.

Summary the invention

• a) eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung in dessen Oberfläche; und
• b) eine zweite Phase in Form eines komprimierten Körpers, welcher haftend innerhalb der Vertiefung enthalten ist, wobei die zweite Phase ein Enzym umfaßt, und die erste und zweite Phase in einem Gewichtsverhältnis von mindestens 6 : 1 zueinander vorliegen.

According to a first aspect of the invention there is provided a multi-phase detergent tablet for use in a laundry machine, the tablet comprising:

• a) a first phase in the form of a shaped body with at least one recess in the surface thereof; and
• b) a second phase in the form of a compressed body which is adhesively contained within the recess, the second phase comprising an enzyme, and the first and second phases being in a weight ratio of at least 6: 1 to one another.

In preferred embodiments, the first phase is a compressed molded body which, at an applied compression pressure of at least about 40 kg / cm ² , preferably at least about 250 kg / cm ² , more preferably at least about 350 kg / cm ² (3.43 kN / cm ² ), more preferably about 400 to about 2,000, and especially about 600 to about 1,200 kg / cm ² (the compression pressure herein is the pressure applied divided by the cross-sectional area of the tablet in a plane transverse to the pressure applied - in Reality is the transverse cross-sectional area of the press mold of the rotary press). It is also preferred that the second phase particulate solid (which terminology is intended to include the possibility of multiple "second phases", sometimes referred to herein as 'optional subsequent phases'), is compressed in the well at an applied compression pressure which is less than that applied to the first phase, and preferably at a compression pressure of less than 350 kg / cm ² , preferably in the range of 40 kg / cm ² to 300 kg / cm ² and more preferably 70 to 270 kg / cm ² Such tablets are preferred from the viewpoint of providing optimal tablet integrity and stability (as measured, for example, by the Child Bite Strength [CBS] test) and the product dissolution properties herein. The tablets according to the invention preferably have a CBS of at least 6 kg, preferably greater than 8 kg, more preferably greater than 10 kg, particularly greater than 12 kg and in particular greater than 14 kg, the CBS according to the US Consumer Product Safety Commission Test Specification is measured. The compression pressures applied to the first and second phases are also generally in a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1, to one another.

• (a) eine erste Phase in Form eines komprimierten geformen Korpers mit mindestens einer Vertiefung darin, wobei der geformte Körper bei einem Komprimierungsdruck von mindestens etwa 350 kg/cm² hergestellt ist;
• (b) eine zweite Phase in Form eines teilchenförmigen Feststoffes, welcher innerhalb der Vertiefung komprimiert ist, wobei die zweite Phase bei einem Druck von weniger als etwa 350 kg/cm² komprimiert ist.

Thus, in a preferred aspect of the invention, the tablet comprises:

• (a) a first phase in the form of a compressed molded body having at least one recess therein, the molded body being made at a compression pressure of at least about 350 kg / cm ² ;
• (b) a second phase in the form of a particulate solid which is compressed within the recess, the second phase being compressed at a pressure of less than about 350 kg / cm ² .

In another preferred embodiment the second phase is in the form of a compressed or shaped body in front; which is within the at least one recess of the first body is contained in an adhesive manner, for example by physical or chemical Adhesion. The first and second phases are in a relatively high weight ratio, at least 6: 1, preferably at least 10: 1, in front of each other, and also that the Tablet composition one or more detergent active ingredients (for example enzymes, bleaches, bleach activators, bleach catalysts, Contains surfactants, complexing agents etc.), which predominantly in the second phase concentrated, for example at least about 50%, preferably at least about 60%, especially about 80%, by weight of the active substance (based on the total weight of the active substance in the tablet), in the second phase of the tablet. Again there are Compositions optimal in terms of tablet strength, dissolution, cleaning and pH control properties, for example by tablet compositions are provided, which can dissolve in the wash liquor so that they at least 50% by weight, preferably at least 60% by weight and more preferably at least 80% by weight of the detergent active ingredient to the wash liquor within Dispense 10, 5, 4 or 3 minutes after the start of the washing process.

• (a) eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung darin; und
• (b) eine zweite Phase in Form eines teilchenförmigen Feststoffes, welcher innerhalb der Vertiefung komprimiert ist, und wobei die Tablette mindestens einen Detergenswirkstoff umfaßt und derart formuliert ist, daß mindestens 50 Gew.-%, vorzugsweise mindestens 60 Gew.-%, stärker bevorzugt mindestens 80 Gew.-%, des Detergenswirkstoffes an die Waschlösung innerhalb der ersten 10 Minuten, vorzugsweise innerhalb der ersten 5 Minuten und stärker bevorzugt innerhalb der ersten 3 Minuten des Waschverfahrens abgegeben werden.

According to the invention, the tablet thus comprises:

• (a) a first phase in the form of a shaped body with at least one recess therein; and
• (b) a second phase in the form of a particulate solid which is compressed within the well and wherein the tablet comprises at least one detergent active and is formulated such that at least 50% by weight, preferably at least 60% by weight, is more preferred at least 80% by weight of the detergent active to the wash solution within the first 10 minutes, preferably within the first 5 minutes and more preferably within the first 3 minutes of the washing process.

An additional advantage of the invention is the ability a different resolution to achieve the phases so that one phase of the tablet dissolves and dissolves significantly earlier than another phase even essentially complete dissolve can before the other phase has dissolved. This is special useful for the different release of detergent active ingredients.

• (a) eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung darin; und
• (b) eine zweite Phase in Form eines komprimierten Körpers, welcher haftend innerhalb der Vertiefung enthaltend ist, und wobei die Tablettenzusammensetuzung einen oder mehrere Detergenswirkstoffe umfasst, welche vorwiegend in der zweiten Phase konzentriert sind, und wobei die zweite Phase zusätzlich ein Disruptionsmittel umfasst.

Thus, according to another preferred aspect of the invention, the detergent tablet comprises:

• (a) a first phase in the form of a shaped body with at least one recess therein; and
• (b) a second phase in the form of a compressed body which adheres within the recess is sustained, and wherein the tablet composition comprises one or more detergent active ingredients which are predominantly concentrated in the second phase, and wherein the second phase additionally comprises a disrupting agent.

• (a) eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung darin; und
• (b) eine zweite Phase in Form eines komprimierten Körpers, welcher haftend innerhalb der Vertiefung enthalten ist, wobei die Tablettenzusammensetzung einen oder mehrere Detergenswirkstoffe umfaßt, die überwiegend in der zweiten Phase konzentriert sind und wobei die zweite Phase zusätzlich ein Bindemittel umfaßt.

According to another preferred aspect of the invention, the detergent tablet comprises:

• (a) a first phase in the form of a shaped body with at least one recess therein; and
• (b) a second phase in the form of a compressed body adhered within the cavity, the tablet composition comprising one or more detergent active ingredients that are predominantly concentrated in the second phase and the second phase additionally comprising a binder.

Suitably the one or several detergent ingredients selected from enzymes, bleaching agents, bleach activators, bleach catalysts, Surfactants, complexing agents, crystal growth inhibitors and mixtures of which, the enzyme actives to enhance cleaning performance while of the initial Stage of the washing or cleaning process with very cold water are particularly preferred.

Particularly preferred for use herein enzyme detergents and especially enzymes and enzyme mixtures, comprising one or more enzymes with an increased or optimal activity in the Temperature range from 25 ° C up to 55 ° C and at a pH in the range of 8 to 10 (e.g. Natalase).

• (a) eine erste Phase in Form eines geformten Körpers mit min estens einer Vertiefung darin; und
• (b) eine zweite Phase in Form eines komprimierten Körpers, welcher haftend innerhalb der Vertiefung enthalten ist, und wobei die zweite Phase zusätzlich ein Enzym umfaßt.

According to the invention, the detergent tablet comprises:

• (a) a first phase in the form of a shaped body with at least one recess therein; and
• (b) a second phase in the form of a compressed body which is adherently contained within the recess, and wherein the second phase additionally comprises an enzyme.

Detailed description of the invention

It is a task of the present Invention to provide a detergent tablet that is not only sufficient is stable in order to survive handling and transportation, but also has at least a substantial part, the in which wash water dissolves quickly, to provide a quick release of the active ingredient. It is preferred that itself at least one phase of the tablet in the wash water within the first 10 minutes, preferably 5 minutes, more preferred 4 minutes, the washing cycle of an automatic dishwasher or Laundromat dissolves. The washing machine is preferably either an automatic dishwasher or Laundromat. The periods within which the multi-phase tablet or a phase thereof or dissolves a detergent component, according to DIN 44990 using a dishwasher available from Bosch with the normal 65 ° C wash program with a water hardness at 18 ° H using at least 6 retries or one sufficient numbers to ensure reproducibility, certainly.

The multi-phase detergent tablet according to the invention comprises a first phase, a second and optionally a subsequent phase. The first phase is in the form of a shaped body of a detergent composition, comprising one or more detergent components as follows described before. Preferred detergent components include Builder, a bleach, enzymes and a surfactant. The components the detergent composition are mixed together, for example by mixing the dry components or spraying on liquid Components. The components are then made using any suitable device, but preferably by compression, for Example in a tablet press, shaped into a first phase. Alternatively, the first phase can be made by extrusion, molding, etc. become. The first phase can have a variety of geometric shapes like balls, cubes etc. assume, but preferred embodiments have an im general axially symmetrical shape with a generally round, square or rectangular cross section.

The first phase is made to have at least one recess in the surface of the molded body. The recess or recesses can also vary in size and shape and their position, orientation and topology in relation to the first phase. For example, the indentation or indentations may generally have a circular, square, or oval cross section; they may form an internal closed cavity or recess in the surface of the molded body, or they may extend between unconnected areas of the body surfaces (e.g. axially opposite surfaces) to form one or more topological 'openings' in the molded body form; and they can be axially or otherwise symmetrically inclined with respect to the first phase, or they can be asymmetrically inclined. In a preferred embodiment, the recess is created using a specially designed tablet press, the surface of the plunger which comes into contact with the detergent composition being shaped such that when it contacts and densifies the detergent composition, a recess is formed or several wells in the first phase of the multi-phase detergent tablet. Preferably, the recess has an inwardly concave surface, or generally a concave surface, to provide improved adhesion for the second phase. Alternatively, the recess can be created by compressing a preformed body of a detergent composition that is annularly distributed around a central die, thereby forming a shaped body with a recess in the form of a cavity that extends axially between opposing surfaces of the body.

The tablets of the invention also include one or more additional phases made from a composition or compositions comprising one or more detergent components as described below. At least one phase (referred to herein as a second phase) is preferably in the form of a particulate solid (the term including powders, granules, agglomerates and other particulate solids, including mixtures thereof with liquid binders, meltable solids, spray mixtures, etc.) in / within the one or more wells) of the first phase of the detergent tablet so that the second phase itself takes the form of a shaped body. Optional other phases include one or more compositions in the form of a separate layer or layers. Preferred detergent components include builders, colorants, binders, surfactants, disrupting agents. and enzymes, especially amylase and protease enzymes. According to the invention, the second and optionally subsequent phase comprises a disrupting agent, which can be selected from either a disintegrating agent or an effervescent agent. Suitable disintegrants include agents that swell upon contact with water or facilitate water inflow and / or outflow by forming channels in the detergent tablet. Any known disintegration or effervescent agent suitable for use in laundry or dishwashing applications is contemplated for use herein. Suitable disintegrants include starches (such as natural, modified and pre-gelled starches, e.g. those made from corn, rice and potato starch), starch derivatives such as U-Sperse (trade name), Primojel (trade name) and Explotab (trade name), celluloses, microcrystalline celluloses and cellulose derivatives such as Arbocel (trade name) and Vivapur (trade name), both available from Rettenmaier, Nymcel (trade name), available from Metsa-seria, Avicel (trade name), Lattice NT (trade name) and Hanfloc (trade name), alginates, Acetate trihydrate, Burkeite, the monohydrated carbonate formula Na ₂ CO ₃ . H ₂ O, hydrated STPP with a phase I content of at least about 40%, carboxymethyl cellulose (CMC), CMC-based polymers, sodium acetate and aluminum oxide. Suitable effervescent agents are those which produce a gas on contact with water. Suitable effervescent agents can be oxygen, nitrogen dioxide or species generating carbon dioxide. Examples of preferred effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate or bicarbonate, in combination with carboxylic acids or other acids such as citric, sulfamic, malic or maleic acid.

The components of the detergent composition by mixing dry components, for example and mixing or spraying of liquid Components manufactured. The components of the second and optional The following phase will then be deepened, which is the first Phase is provided, introduced and retained in it.

The tablet of the present invention comprises two phases; a first and a second phase. The first phase usually includes a deepening, and the second phase usually consists of a single detergent composition. However, it will considered that the the first phase can comprise more than one deepening and that the second Phase made from more than one detergent drug composition can be. Moreover it is also considered that the second phase is more than may comprise a detergent active composition which is within a recess is included. It is also considered that several Detergent compositions included in separate wells are. That way you can potentially chemically sensitive detergent components are separated, to avoid any loss of performance caused by components is caused, which react with each other and may be inactivated or be consumed.

According to a preferred aspect the present invention may be the first, second and / or optional following phase comprise a binder. If available, it is Binder chosen from the group consisting of organic polymers, for example Polyethylene and / or polypropylene glycols, especially those with a molecular weight of 4,000, 6,000 and 9,000, paraffins, polyvinylpyrolindone (PVP), especially PVP with a molecular weight of 90,000, polyacrylates, Sugars and sugar derivatives, starch and starch derivatives, for example hydroxypropylmethyl cellulose (HPMC) and carboxymethyl cellulose (CMC), and inorganic polymers, such as hexametaphosphate. The binder is for both the tablet integrity for promotion as well obtaining a different resolution of the first and second Phase as described below.

According to a preferred aspect of the present invention, the first phase weighs more than about 3 g, preferably more than about 4 g, more preferably more than about 5 g. More preferably, the first phase weighs about 10 g to about 30 g, more preferably about 15 g to about 25 g, and most preferably about 18 g to about 24 g. The second and optionally subsequent phase weighs less than about 4 g. More preferably the second and / or optionally subsequent phase weighs between about 0.1 g and about 3.5 g, preferably between about 1 g and about 3.5 g, most preferably about 1.3 g to about 2.5 g ,

In another embodiment according to the invention there is a barrier layer comprising a barrier layer composition, between the first and second and / or optionally following phase or indeed between the second and / or optional subsequent phase. The barrier composition comprises at least one binder selected from the group as described above. The advantage of being there a junction is the migration of components from a Phase into another phase, for example from the first phase in to prevent the second and / or optionally subsequent phase and vice versa or decrease.

The components of the second and optional following phase are preferably at a very low compression pressure compressed, based on the compression pressure which is normally used for Manufacture of tablets is used. An advantage of the present Invention is therefore that heat, pressure or chemically sensitive detergent components in the detergent tablet can be included since a low compression pressure is used without the one from it to get the following loss of performance that usually occurs when such components are introduced into tablets. Alternatively, the one or more second phases at the same or a higher compression pressure than the first phase can be compressed to a different resolution of the Achieve phases as described below.

Another advantage of the present Invention is the improved protection of the second phase from damage, which is caused, for example, by handling and transport becomes. As described above, multi-phase detergent tablets are made with the second layer at a lower compression pressure than the first layer is compressed. However, although the dissolution rate is improved, the second layer of these tablets becomes susceptible to damage, tends to crumble or crumble on contact. The slightly compressed phase (s) of the detergent tablets according to the invention are protected within the well, however, by the first phase the detergent tablet is provided.

Yet another advantage of the present Invention is the ability to produce a multi-phase detergent tablet, one phase can be designed so that it dissolves before another phase, preferably considerably earlier. According to the invention, it is preferred that itself dissolves the second and optionally following phase before the first phase. In line with the preferred weight ranges described above, it is preferred that itself the first phase within 5 to 20 minutes, more preferred within 10 to 15 minutes, dissolves, and the second and / or optionally following phase in less than 5 minutes, more preferred less than 4.5 minutes, most preferably less than 4 minutes, dissolves. Alternatively, the second phase can follow the first or one dissolve another phase, for example, if necessary, for cleaning or rinsing benefits towards the end of the washing or rinsing process transferred to. The periods within which the first, second and / or optionally following Phase dissolves, are independent of each other. On this way, according to the invention, becomes a different one resolution of phases achieved. A particular advantage of the ability to have a different resolution of the multi-phase detergent tablet is that one component which is chemically inactivated by the presence of another component can be separated in another phase. In this case the component that is inactivated is preferably in the second and optionally following phase.

Yet another advantage of the present Invention is the improved adhesion between the phases of the A multiphase tablet. It is believed that the improved adhesion through a reduction in exposure compared to the second phase to the multi-phase tablets known in the art is, the tablets of the invention be obtained for a break along the line of contact between the phases less susceptible are.

method

The multi-phase detergent tablets are made using any suitable tabletting device, z. B. a Courtoy 8253 device. Preferably the tablets are compressed in a tablet press which is capable of producing a tablet, which includes a recess. In a particularly preferred embodiment of the present Invention is the first phase using a specially developed Tablet press according to the below described method produced. The stamp (s) of this tablet press are modified so that the surface the stamp that comes into contact with the detergent composition, a concave surface having.

A first detergent composition is placed in the tablet press mold and the plunger is lowered to contact and then the detergent composition is compressed to form a first phase. The first detergent composition is made using a Be operating pressure of generally at least about 250 kg / cm ² , preferably between about 350 and about 2,000 kg / cm ² , more preferably about 500 to about 1,500 kg / cm ² , most preferably about 600 to about 1,200 kg / cm ² . The stamp is then raised, revealing the first phase that contains a recess. A second and optionally subsequent detergent composition is then introduced into the well. The specially designed tablet press ram is then lowered a second time to slightly compress the second and optionally subsequent detergent composition to form the second and optionally subsequent phase. In another embodiment of the present invention, wherein an optional subsequent phase is present, the optional subsequent phase is produced in an optional subsequent compression step that is substantially similar to the second compression step described above. The second and optionally subsequent detergent composition is compressed at a pressure of preferably less than about 350 kg / cm ² , more preferably about 40 to about 300 kg / cm ² , most preferably about 70 to about 270 kg / cm ² . After compression of the second detergent composition, the stamp is raised a second time and the multi-phase detergent tablet is ejected from the tablet press.

Detergent components

The first and second and / or optional following phase of the multi-phase detergent tablet described herein are made by compressing one or more compositions, comprising detergent active components. Suitably the compositions used in any of these phases Include a variety of different detergent components, including builder compounds, Surfactants, enzymes, bleaches, sources of alkalinity, colorants, Perfume, Lime soap dispersant, organic polymeric compounds, including polymers Dye transfer inhibitors, crystal growth inhibitors, Heavy metal ion sequestrants, metal ion salts, enzyme stabilizers, Corrosion inhibitors, foam suppressants, solvents, fabric softeners, optical brighteners and hydrotropes.

Particularly preferred detergent components close the first phase a builder compound, a surfactant, an enzyme and a bleach on. Particularly preferred detergent components of the second phase conclude Builders, enzymes, crystal growth inhibitors and disrupting agents and / or binders.

builder compound

The tablets according to the invention preferably contain a builder compound, which is typically present in a proportion of 1 to 80%, preferably 10 to 70%, most preferably 20 to 60%, based on the weight of the composition, of the active Detergent components are present.

Water soluble builder compound

Suitable water-soluble builder compounds conclude the water soluble monomeric polycarboxylates or their acid forms, homo- or copolymers polycarboxylic or their salts, wherein the polycarboxylic acid contains at least two carboxy groups comprises which are separated by no more than two carbon atoms are, carbonates, bicarbonates, borates, phosphates and mixtures of any of the above.

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

Suitable carboxylates with a carboxy group conclude the water soluble Salts of lactic acid, glycolic acid and Ether derivatives thereof. Polycarboxylates with two carboxy groups conclude the water soluble Salts of succinic acid, malonic, (Ethylenedioxy) diacetic acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. polycarboxylates close with three carboxy groups especially water soluble Citrates, aconitrates and citraconates as well as succinate derivatives, such as the carboxymethyloxysuccinates described in the British patent No. 1,379,241, the lactoxysuccinates described in British U.S. Patent No. 1,389,732, and the aminosuccinates described in U.S. Pat Dutch Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylate, described in British Patent No. 1,387,447.

Polycarboxylates with four carboxy groups conclude Oxydisuccinate, disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates with sulfo substituents conclude the sulfosuccinate derivatives disclosed in the British patents Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000, a.

Alicyclic and heterocyclic Close polycarboxylates Cyclopentancis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 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, a. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343 on.

Those preferred by the foregoing Polycarboxylates are the hydroxycarboxylates with up to 3 carboxy groups per molecule, stronger prefers citrate.

The parent acids of the monomeric or oligomeric Polycarboxylate complexing agents or mixtures thereof with their Salts, e.g. B. citric acid or citrate / citric acid mixtures, are considered useful Builder components also considered.

Boratbuilders as well as builders, which Contain borate-producing materials that contain borate under detergent storage and can generate washing conditions, can can also be used, but will be used in washing conditions of less than 50 ° C, especially less than 40 ° C, not preferred.

Examples of carbonate builders are Alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, as in US Pat German Patent Application No. 2,321,001, published November 15 1973.

Particularly preferred builder compounds for use according to the invention are water-soluble phosphate builders. Specific examples of water-soluble Phosphate builders are the alkali metal tripolyphosphates, sodium, Potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, Sodium and potassium orthophosphate, sodium polymetaphosphate, wherein the degree of polymerization is in the range of 6 to 21, and Salts of phytic acid.

Specific examples of water-soluble Phosphate builders are the alkali metal tripolyphosphates, sodium, Potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, Sodium and potassium orthophosphate, sodium polymetaphosphate, wherein the degree of polymerization is in the range of 6 to 21, and Salts of phytic acid.

Partially soluble or insoluble builder compound

The tablets according to the invention can contain a partially soluble or insoluble builder compound. Partially soluble or insoluble builder compounds are particularly suitable for use in tablets made for use in laundry cleaning processes. Examples of partially water-soluble builders include the crystalline layered silicates, as disclosed, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. The crystalline layered sodium silicates of the general formula are preferred NaMSi _X O _{2 + 1} .yH ₂ O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "sheet" structure, such as the so-called δ-layer structure, as described in EP-0-164514 and EP-0-293640. Methods for producing crystalline layered silicates of this type are disclosed in DE-A-3417649 and DE-A-3742043. For purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2.

The most preferred layered crystalline sodium silicate compound has the formula δ-Na ₂ Si ₂ O ₅ , known as NaSKS-6 (trade name), and is available from Hoechst AG.

The crystalline layered sodium silicate material is preferably granular Detergent compositions as a solid particle inside Mixing with a solid, water-soluble, ionizable material as described in PCT Patent Application No. WO 92/18594. The solid, water-soluble, ionizable material is chosen from organic acids, organic and inorganic hydrogen salts and mixtures thereof, being citric acid is preferred.

Examples of mostly water-insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na ₂ [(AlO ₂ ) ₂ (SiO ₂ ) _y ] .xH ₂ O, 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 hydrated form and is preferably crystalline, containing 10 to 28%, more preferably 18 to 22%, water in bound form.

The aluminosilicate zeolites can be naturally occurring Materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are among the designations zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS and available as mixtures thereof.

A preferred method of synthesis of aluminosilicate zeolites is that of Schoeman et al. (released in Zeolite 14 (2) (1994), 110-116) in which the author described a process for the preparation of describes colloidal aluminosilicate zeolites. The colloidal Aluminosilicate zeolite particles should preferably be such that not more than 5% of the particles are larger than 1 μm in Have diameters and no more than 5% of the particles have a size of less than 0.05 μm have in diameter. Preferably, the aluminosilicate zeolite particles an average particle size diameter between 0.01 μm and 1 μm, more preferred between 0.05 μm and 0.9 μm, particularly preferably between 0.1 μm and 0.6 μm, on.

Zeolite A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O where x is 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 276 H ₂ O. Zeolite MAP, as disclosed in EP-B-384,070, is a preferred zeolite builder herein.

Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. If as a component of a Detergent composition used, see colloidal aluminosilicate zeolites, especially colloidal zeolite A, an improved builder performance in With a view to providing improved stain removal in front. Improved builder performance is also being considered a reduced incrustation of tissue and improved white tone preservation of the tissue observed; what problems pose of which one assumes she are associated with inadequately composed detergent compositions.

A surprising finding is that detergent compositions with a mixed aluminosilicate zeolite comprising colloidal Zeolite A and colloidal zeolite Y, equivalent calcium ion sequestration performance compared to the equivalent weight of a commercially available one Provide zeolite A. Another surprising finding is that the A mixed detergent composition described above Aluminosilicate zeolite has improved magnesium ion sequestration performance compared to the equivalent weight of a commercially available one Provide zeolite A.

surfactant

Surfactants are preferred detergent active components of the compositions described herein. Suitable surfactants are chosen from anionic, cationic, nonionic, ampholytic and zwitterionic Surfactants and mixtures thereof. Products for automatic dishwashers should foam little, and consequently that Foam of the surfactant system for use in dishwashing processes are suppressed, or the surfactant system should be stronger preferably low foaming, typically non-ionic. The foam formation caused by those in laundry washing processes surfactant systems used does not have to be suppressed to the same extent, like washing it up is required. The surfactant is typically present in one proportion from 0.2 to 30% by weight, stronger preferably 0.5 to 10% by weight, most preferably 1 to 5% by weight, the composition of the active detergent components.

A typical list of anionic, nonionic, ampholytic and zwitterionic classes and Species of these surfactants is described in U.S. Patent 3,929,678 issued to Laughlin and Heuring on December 30, 1975. A list of suitable ones cationic surfactants is in U.S. Patent 4,259,217 issued to Murphy on March 31, 1981, specified. A list of surfactants typically found in detergent compositions for automatic dishwashing is included, for example, in EP-A-0-414 549 and PCT application numbers WO 93/08876 and WO 93/08874.

nonionic surfactant

In essence, any non-ionic Surfactants which for Cleaning purposes useful are included in the detergent tablet. preferred non-limiting classes more useful nonionic surfactants are listed below.

Nonionic ethoxylated alcohol surfactant

The alkyl ethoxylate condensation products aliphatic alcohols with 1 to 25 moles of ethylene oxide are used suitable herein. The alkyl chain of the aliphatic alcohol can either straight or branched, primary or secondary and contains generally 6 to 22 carbon atoms. Be particularly preferred containing the condensation products of alcohols having an alkyl group 8 to 20 carbon atoms, with 2 to 10 moles of ethylene oxide per mole Alcohol.

End-capped alkyl alkoxylate surfactant

A suitable end-capped alkylallcoxylate surfactant is the epoxy-capped, poly (oxyalkylated) alcohol of the formula: R ₁ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] y [CH ₂ CH (OH) R ₂ ] (I) wherein R _{1 is} a linear or branched, aliphatic hydrocarbon radical having 4 to 18 carbon atoms; R _{2 is} a linear or branched aliphatic hydrocarbon residue having 2 to 26 carbon atoms; x is an integer with an average value of 0.5 to 1.5, more preferably 1; and y is an integer with a value of at least 15, more preferably at least 20.

The surfactant of the formula I preferably has at least 10 carbon atoms in the terminal epoxy unit [CH ₂ CH (OH) R ₂ ]. Suitable surfactants of formula I of the invention are the nonionic POLY-TERGENT ^® SLF-18B surfactants described by Olin Corporation, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.

Ether-stale, popy (oxyalkylated) alcohols

Preferred surfactants for use herein include ether-capped poly (oxyalkylated) alcohols of the formula: R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² wherein R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms; R ^{3 is} H or a linear aliphatic hydrocarbon residue having 1 to 4 carbon atoms; x is an integer with an average of 1 to 30, where if x is 2 or greater, R ^{3 may be the} same or different, and k and j are integers with an average of 1 to 12, and more preferably 1 to 5 are.

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

As described above, when x is greater than 2, R ³ may be the same or different in the preferred embodiments. That is, R ³ can vary between any of the alkyleneoxy units as described above. For example, if x is 3, R ³ may be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and may be in the order of (EO) (PO) (EO); (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO) vary. Of course, the integer 3 is chosen only as an example, and the difference can be much larger, where x has a higher integer, and includes, for example, several (EO) units and a much smaller number of (PO) units.

Particularly preferred surfactants, such as described above, close those with a low cloud point of less than 20 ° C on. These surfactants with a low cloud point can then in combination with a surfactant with a high cloud point, as detailed below described for excellent grease cleaning benefits are used.

Particularly preferred ether-capped, poly (oxyalkylated) alcohol surfactants are those in which k is 1 and j is 1, so that the surfactants have the formula: R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² wherein R ¹ , R ² and R ^{3 are} as defined above, and x is an integer with an average value of 1 to 30, preferably 1 to 20 and even more preferably 6 to 18. Most preferred are surfactants wherein R ¹ and R ^{2 are} in the range 9 to 14, R ^{3 is} an ethyleneoxy forming H and x is in the range 6 to 15.

The ether-capped poly (oxyalkylated) alcohol surfactants include three general components, a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap. The alkyl ether end cap and alcohol serve as a hydrophobic oil-soluble Part of the molecule, while the alkylene oxide group forms the hydrophilic water-soluble part of the molecule.

These surfactants show significant improvements in terms of stain and film formation properties and Removal of greasy dirt when combined with surfactants with high cloud points compared to conventional surfactants.

In general, the ether-capped poly (oxyalkylated) alcohols useful in the present invention Wood surfactants are made by reacting an aliphatic alcohol with an epoxy to form an ether, which is then reacted with a base to form a second epoxy. The second epoxide is then reacted with an alkoxylated alcohol to form the new compounds of the invention. Examples of processes for making the ether-capped poly (oxyalkylated) alcohol surfactants are described below.

Preparation of C _12/14 alkyl glycidyl ether

AC _12/14 fatty alcohol (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol, available from Aldrich) are combined in a 500 ml three-necked round bottom flask which is fitted with a Capacitor, argon inlet, addition funnel, magnetic stirrer and an internal temperature probe. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise so that the temperature is kept between 60-65 ° C. After stirring for another hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) with mechanical stirring. After the addition has ended, the mixture is heated to 90 ° C. for 1.5 h, cooled and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO ₄ , filtered and concentrated. Distillation of the oil at 100-120 ° C [13.33 Pa (0.1 mm Hg)] gave the glycidyl ether as an oil.

Preparation of a C _12/14 alkyl-C _9/11 ether-blocked alcohol surfactant

Neodol ^® 91-8 (20.60 g, 0.0393 mol, an ethoxylated alcohol, available from Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) in a 250 ml three-necked round bottom flask, which is equipped with a condenser, argon inlet, addition funnel, magnetic stirrer and an internal temperature probe. The mixture is heated to 60 ° C, at which point the C _12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 minutes. After stirring at 60 ° C. for 18 hours, the mixture is cooled to room temperature and dissolved in an equal part of dichloromethane. The solution is passed through a 25.4 mm (1 inch) silica gel pad while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then evaporated in a Kugelrohr oven (100 ° C, 66.66 Pa (0.5 mm Hg)) to give the surfactant in the form of an oil.

Nonionic ethoxylated / uropoxated fatty alcohol

The ethoxylated C ₆ -C ₁₈ fatty alcohols and mixed ethoxylated / propoxylated C ₆ -C ₁₈ fatty alcohols are suitable surfactants for use herein, particularly where water soluble. The ethoxylated fatty alcohols are preferably the ethoxylated C ₁₀ -C ₁₈ fatty alcohols with a degree of ethoxylation of 3 to 50, particularly preferably these are the ethoxylated C ₁₂ -C ₁₈ fatty alcohols with a degree of ethoxylation of 3 to 40. Preferably, the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

Nonionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic part of these compounds preferably has a molecular weight of 1,500 to 1,800 and shows water insolubility. Examples of compounds of this type include certain of the commercially available Pluronic ^™ surfactants sold by BASF.

Nonionic EO condensation products with propylene 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 herein. The hydrophobic unit of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of 2,500 to 3,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ^™ compounds sold by BASF.

mixed nonionic surfactant system

In a preferred embodiment of the present invention, the detergent tablet comprises a A mixed nonionic surfactant system comprising at least one nonionic surfactant with a low cloud point and at least one nonionic surfactant with a high cloud point.

The "cloud point" as used herein is a well known property of nonionic surfactants which as a result of that Surfactant becomes less soluble with increasing temperature; the temperature, in which the occurrence of a second phase is observable referred to as the "cloud point" (cf. Kirk Othmer's Encyclopedia of Chemical Technology, 3rd edition, vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system component having a cloud point less than 30 ° C, preferably less than 20 ° C, and most preferably less than 10 ° C. Typical nonionic surfactants with a low cloud point i include nonionic alkoxylated surfactants, especially ethoxylates derived from a primary alcohol, and reverse polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) block polymers. Also include those nonionic surfactants having a low cloud point, for example, ethoxylated-propoxylated alcohols (eg. As Poly-Tergent ^® SLF18 from Olin Corporation), epoxy-capped poly (oxyalkylated) alcohols (eg. As the Poly-Tergent ^® SLF18B Series of nonionic surfactants from 0lin Corporation, such as described in WO 94/22800, published October 13, 1994 by Olin Corporation, and the ether-capped poly (oxyalkylated) allhol surfactants.

Nonionic surfactants can be optional Contain propylene oxide in an amount up to 15 wt .-%. Other preferred nonionic surfactants can by the in US patent 4,223,163, issued September 16, 1980, Builloty Processes are made.

Low cloud point nonionic surfactants additionally include a polyoxyethylene / polyoxypropylene block polymer compound. Polyoxyethylene / polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as a reactive hydrogen starter compound. Certain of the block polymer surfactant compounds designated PLURONIC ^®, REVERSED PLURONIC and TETRONIC ^{© ®, manufactured} by 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 typically useful as low cloud point nonionic surfactants herein.

As used herein is a nonionic surfactant with a "high Cloud point "defined as a nonionic surfactant system component with a cloud point of greater than 40 ° C, preferably larger than 50 ° C and stronger preferably greater than 60 ° C. Preferably comprises the nonionic surfactant system is an ethoxylated surfactant from the reaction of a monohydroxy alcohol or alkylphenol containing 8 up to 20 carbon atoms, with 6 to 15 moles of ethylene oxide per mole Alcohol or alkylphenol on an average basis. Such non-ionic Surfactants with a high cloud point conclude for example Tergitol 1559 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhone Poulenc) and Neodol 91-8 (sold through Shell).

For the purposes of the present invention are also preferred that the nonionic Surfactant with a high cloud point still a value for the hydrophillipophilic balance ("HLB", see. Kirk Othmer, above) within the range of 9 to 15, preferably 11 to 15, has. Such materials include Example Tergitol 1559 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhone Poulenc) and Neodol 91-8 (sold through Shell).

Another preferred high cloud point nonionic surfactant is derived from a straight or preferably branched chain or secondary fatty alcohol having 6 to 20 carbon atoms (C ₆ -C ₂₀ alcohol) including secondary alcohols and branched chain primary alcohols. Nonionic surfactants with a high cloud point are preferably branched or secondary alcohol ethoxylates, more preferably mixed C _9/11 or branched C _11/15 alcohol ethoxylates, which have an average of 6 to 15 moles, preferably 6 to 12 moles and particularly preferably 6 to 9 Moles of ethylene oxide are condensed per mole of alcohol. The ethoxylated nonionic surfactant derived in this way preferably has a narrow ethoxylate distribution in relation to the average.

anionic surfactant

Essentially any are anionic Suitable surfactants, which for Cleaning purposes are useful. these can Salts (including for example sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of the anionic sulfate, Include sulfonate, carboxylate and sarcosinate surfactants. 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 sulfosuccinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ - C ₁₄ diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids, which are present in or from sebum oil are directed.

anionic sulphate

Anionic sulfate surfactants suitable for use herein include the linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) - and -N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfates and sulfates of alkyl polysaccharides such as the sulfates of alkyl polyglucoside (the nonionic non-sulfated compounds described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched, primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably the branched chain C ₁₁ -C ₁₅ alkyl sulfates and the linear C ₁₂ -C ₁₄ alkyl sulfates.

Alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C ₁₀ -C ₁₈ alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. The alkylethoxysulfate surfactant is more preferably a C ₁₁ -C ₁₈ , particularly preferably a C ₁₁ -C ₁₅ alkyl sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred point of view of the invention uses mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such mixtures are in the PCT patent application No. WO 93/18124.

anionic sulfonate

Anionic sulfonate surfactants suitable for use herein include the salts of linear C ₅ -C ₂₀ alkylbenzenesulfonates, alkyl ester sulfonates, primary or secondary C ₆ -C ₂₂ alkanesulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acylglyceryl sulfate sulfonate mixtures, fatty acylglyceryl sulfonate mixtures, fatty acid mixtures of this one.

anionic carboxylate

Suitable anionic carboxylate surfactants conclude the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and soaps ('alkyl carboxyls'), especially certain secondary Soaps as described herein.

Suitable alkyl ethoxy carboxylates include those having the formula RO (CH ₂ CH ₂ O) _X CH ₂ COO ^- M ⁺ , wherein R is a C ₆ -C ₁₈ -alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that that, on a weight basis, the amount of material where x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula RO (CHR ₁ -CHR ₂ -O) -R ₃ , wherein R is a C ₆ to C ₁₈ alkyl group, x is 1 to 25, R ₁ and R ₂ are selected from the Group consisting of hydrogen, methyl acid residue, succinic acid residue, hydroxy succinic acid residue and mixtures thereof, and R _{3 is} selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon with between 1 and 8 carbon atoms and mixtures thereof.

Suitable soap surfactants include secondary Soap surfactants which contain a carboxy moiety which coexists with a secondary Carbon is linked. Preferred secondary soap surfactants for use therein are water soluble Representative, elected 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 as a foam suppressant be included.

Alkali

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOM, where R is a linear or branched C ₅ -C ₁₇ alkyl or alkenyl group, R ^{1 is} a C ₁ -C ₄ alkyl group , and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactant

Suitable amphoteric surfactants for use close in here the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include the compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ² , wherein R ^{3 is} selected from an alkyl, hydroxyallcyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing 8 to 26 carbon atoms; R ^{4 is} an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x is 0 to 5, preferably 0 to 3; and each R ^{5 is} an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide groups. C ₁₀ -C ₁₈ -Alkyldimethylamine oxide and C ₁₀ -C ₁₈ -acylamidoalkyldimethylamine oxide are preferred.

A suitable example of an alkyl amphodicarboxylic acid is Miranol (TM) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant

Zwitterionic surfactants can be found in detergent compositions may also be included herein. These surfactants can generally as derivatives of secondary and tertiary amines, Derivatives of heterocyclic secondary and tertiary amines or quaternary derivatives Ammonium, quaternary Phosphonium or tertiary Sulfonium compounds are described. Betaine and sulphate surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are the compounds of the formula R (R ¹ ) ₂ N ⁺ R ² COO ^- , wherein R is a C ₆ -C ₁₈ hydrocarbyl group, each R ^{1 is} typically a C ₁ -C ₃ alkyl, and R ^{2 is} one C ₁ -C ₅ hydrocarbyl group. Preferred betaines are C _12-18 dimethylammoniohexanoate and the C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants

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

Suitable cationic surfactants include the quaternary ammonium surfactants, which are selected from mono-C ₆ -C ₁₆ , preferably -C ₆ -C ₁₀ -N-alkyl- or -alkenylammonium surfactants, in which the remaining N positions are represented by methyl, hydroxyethyl or hydroxypropyl groups are substituted.

enzymes

Enzymes are preferred detergent components the first phase and more preferably the second and / or optional further phase. The enzymes are selected from the group consisting of from cellulases, hemicellulases, peroxidases, proteases, glucoamylases, Amylases, xylanases, lipases, phospholipases, esterases, cutinases, Pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, Ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, Arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures hereof.

Preferred enzymes include proteases, Amylases, lipases, peroxidases, cutinases and / or cellulases in Connection with one or more enzymes that break down plant cell walls.

The cellulases which can be used according to the invention both include bacterial as well as fungal cellulases. Preferably point they have a pH optimum between 5 and 12 and an activity above from 50 CEVU (cellulose viscosity unit) on. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., J-61078384 and WO 96/02653 which are fungal cellulases disclose which by Humicola insolens, Trichoderma, Thielavia or Sporotrichum are produced. EP-739 982 describes cellulases which were isolated from new Bacillus species. Suitable cellulases are also in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2.247.832; and WO 95/26398 discloses.

Examples of such cellulases are Cellulases produced by a strain of Humicola insolens (Humicola grisea, var. thermoidea), especially the Humicola strain DSM 1800, Other suitable cellulases are from Humicola insolent cellulases with a molecular weight of 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; and a 43 kD endoglucanase derived from Humicola insolens DSM 1800, which is a cellulase activity shows; a preferred endoglucanase component which is shown in FIG PCT Patent Application No. WO 91/17243 has the amino acid sequence disclosed. Also suitable cellulases are the EGIII cellulases from Trichoderma Iongibrachiatum, which is published in WO 94/21801, Genencor on September 29, 1994. Particularly suitable cellulases are the cellulases that have color care benefits. Examples such cellulases are cellulases which are filed in EP-A-495257 on November 6, 1991 (Novo). Carenzyme and Celluzyme (Novo Nordisk A / S) are particularly useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases for textile care and / or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

The cellulases are normal in the detergent composition in proportions of 0.0001 to 2% active Enzyme included based on the weight of the detergent composition.

Peroxidase enzymes are used in combination used with oxygen sources, e.g. B. percarbonate, perborate, persulfate, Hydrogen peroxide etc. They are used for "bleaching in solution", i.e. H. about the transfer of dyes or pigments made from substrates during the Washing procedures are removed on other substrates in the wash liquor to prevent. Peroxidase enzymes are known in the art and conclude for example horseradish peroxidase, ligninase and halogen peroxidase, such as chlorine and bromine peroxidase. Detergent compositions containing peroxidase are for example in the international PCT application WO 89/099813, and WO 89/09813 and in EP-A-540780, filed on November 6, 1991, and EP-A-WO 97/30143, filed February 20, 1996. The laccase enzyme is also suitable.

Preferred enhancers are substituted phenthiazine and phenoxasin-10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted Syringates (C3-CS substituted alkylsyringates) and phenols. Sodium percarbonate or perborate are preferred as sources of hydrogen peroxide.

The cellulases and / or peroxidases are normally in the detergent composition in proportions of 0.0001 to 2% active enzyme, based on the weight of the detergent composition, locked in.

Other preferred enzymes that can be included in the detergent compositions of the invention include lipases. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trademark Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. B. Chromobacter viscosum, Var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA, and Diosynth Co., Netherlands; and lipases from Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase ^® and Lipomax (Gist-Brocades) and Lipolase and Lipolase Ultra ^® (Novo), was used for the established that they are very effective when used in combination with the inventive compositions. The lipolytic enzymes which are described in EP-258 068; WO 92/05249 and WO 95/22615 by Novo Nordisk; and in WO 95/03578, WO 95/35381 and WO 96/00292 from Unilever.

Cutinases are also suitable [EC 3.1.1.50], which is regarded as a special type of lipase can be as lipases that do not require interfacial activation. The addition of cutinases to detergent compositions is e.g. B. in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System); and WO 94/14963 and WO 94/14964 (Unilever).

The lipases and / or cutinases are normally in the detergent composition in proportions of 0.0001 up to 2% active enzyme, based on the weight of the detergent composition, locked in.

Suitable proteases are the subtilisins which are obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, this was by Novo Industries A / S of Denmark, hereinafter "Novo", developed and sold as ESPERASE ^® , The preparation of this enzyme and analogous enzymes is described in GB-1,243,784 to 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 No. 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), referred to herein as "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protease enzyme, referred to herein as "Protease A". Also suitable is the protease referred to herein as "Protease C", which is a variant of an alkaline serine protease from Bacillus, wherein arginine in position 27 by lysine, valine in position 104 by tyrosine, asparagine in position 123 by serine and threonine in position 274 by Alanine has been replaced. Protease C is described in EP-A-251441, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, especially of protease C, are also included herein.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence which is derived from a precursor carbonyl hydrolase by substituting a plurality of amino acid residues with another amino acid in a position in this carbonyl hydrolase, that corresponds to position +76, preferably also in combination with egg nem or more amino acid residues corresponding to the positions selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, + 128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274, according to the numbering of Bacillus amyloliquefaciens subtilisin as described in WO 95/10591 and in the patent application by Ghosh C. et al., "Bleaching Compositions Comprising Protease Enzymes", with the application number 08 / 322,677, filed on October 13, 1994 (US 6,066,611).

Also suitable according to the invention are proteases, which are described in patent applications EP-251 446 and WO 91/06637, protease BLAP ^® , which is described in WO 91/02792, and their variants, which are described in WO 95/23221.

See also one at high pH values effective protease from Bacillus sp. NCIMB 40338, which is described in WO 93/18140 A is described on Novo. Enzymatic detergents, which a protease, one or more other enzymes and a reversible one Protease inhibitors are described in WO 92/03529 A to Novo. If necessary, a protease is available which has a reduced one Adsorption and an increased Has hydrolysis, as described in WO 95/07791 to Procter & Gamble is. A recombinant trypsin-like protease for cleaning agents, which is suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in Unilever EP 516 200.

Other preferred protease enzymes conclude Protease enzymes, which a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence -which are characterized by Replacing a variety of amino acid residues of a precursor carbonyl hydrolase through other amino acids is derived, the variety of amino acid residues found in the precursor enzyme the +210 position in combination with an or corresponds to several of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions of course Occurring subtilisin from Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those which exchange in positions +210, +76, +103, +104, +156 and +166.

The proteolytic enzymes are in the detergent compositions according to the invention in a proportion of 0.0001 to 2%, preferably 0.001 to 0.2%, stronger preferably 0.005 to 0.1% pure enzyme, based on the weight of the Composition included.

Amylases (α and / or β) can be used to remove carbohydrate stains be included. WO 94/02597, Novo Nordisk A / S on February 3, 1994, describes cleaning compositions which Include mutant amylases. See also WO 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases, which are for use in cleaning compositions are known to include both α- and β-amylases on. α-amylases are known in the art and include those described in U.S. Patent No. 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 No. 1,296,839 (Novo) are. Other suitable amylases are amylases with an improved one Stability, which is published in WO94 / 18314 on August 18, 1994 and WO 96/05295, Genencor on February 22, 1996, and amylase variants with an additional Modification in the immediate parent form, which are available by Novo Nordisk A / S, disclosed in WO 95/10603 in April 95. Also suitable are amylases, which are described in EP-277 216; WO 95/26397; and WO 96/23873 (all from Novo Nordisk) are.

Examples of commercial α-amylases products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^®, Duramyl ^® and Natalase, all of which are available from Novo Nordisk A / S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl ^® at a temperature range of 25 ° C to 55 ° C and a pH in the Range 8-10 is measured by the Phadebas ^® -α-amylase activity test. Variants of the above enzymes, which are described in WO 96/23873 (Novo Nordisk), are suitable. Other amylolytic enzymes with improved properties with regard to the degree of activity and the combination of heat stability and a higher degree of activity are described in WO 95/35382.

Preferred amylase enzymes include those which in WO 95/26397 and in the co-pending application WO 96/23873 by Novo Nordisk are described.

The amylolytic enzymes are in the detergent compositions according to the invention in a proportion of 0.0001 to 2%, preferably 0.00018 to 0.06%, stronger preferably 0.00024 to 0.048% pure enzyme by weight of the composition included.

In a particularly preferred embodiment the detergent tablets of the present invention include amylase enzymes, especially those which are described in WO 95/26397 and in the pending at the same time Application WO 96/23873 from Novo Nordisk, in combination with a complementary Amylase.

"Complementary" is the addition of one or more amylases, which are used for cleaning purposes are meant. Examples of complementary amylases (α and / or β) are described below. WO 94/02597 and WO 95/10603, Novo Nordisk A / S, describe cleaning compositions which include mutated amylases. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those described in U.S. Patent Nos. 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 No. 1,296,839 (Novo). Other suitable amylases are amylases with improved stability, which are described in WO 94/18314 and WO 96/05295, Genencor, and amylase variants with an additional modification in the immediate parent form, disclosed in WO 95/10603, which is available from Novo Nordisk A / S are available. Amylases which are described in EP-277 216 (Novo Nordisk) are also suitable. Examples of commercial α-amylases products are Purafect Ox Am from Genencor and Termamyl ^®, Ban, Fungamyl ^® and Duramyl ^®, all of which are available from Novo Nordisk A / S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl ^® at a temperature range of 25 ° C to 55 ° C and at a pH-value is in the range 8 to 10, measured by the Phadebas ^® -α-amylase activity test. Variants of the above enzymes, which are described in WO 96/23873 (Novo Nordisk), are suitable. Other amylolytic enzymes with improved properties with regard to the degree of activity and the combination of heat stability and a higher degree of activity are described in WO 95/35382. Preferred complementary amylases according to the invention are the amylases which are sold under the trade name Purafect Ox Am, described in WO 94/18314 and WO 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 general in the detergent compositions according to the invention in a proportion of 0.0001 to 2%, preferably 0.00018 to 0.06%, stronger preferably 0.00024 to 0.048% pure enzyme by weight of the composition included. The weight ratio is preferably based to the pure enzyme, the specific amylase to the complementary amylase between 9: 1 to 1: 9, stronger preferably between 4: 1 to 1: 4 and particularly preferably between 2 : 1 to 1: 2.

The above-mentioned enzymes can be any Be of origin, such as from plants, animals, bacteria, fungi and Yeast. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes can be used become. Mutants are also included by definition native enzymes. Mutants can z. B. by protein and / or genetic engineering changes, chemical and / or physical modifications of native enzymes can be obtained. Usual practice is also the expression of the enzyme with the help of host organisms, in which the genetic material used for the production of the enzyme responsible, has been cloned.

The enzymes are usually in of the detergent composition in proportions of 0.0001 to 2% active Enzyme included based on the weight of the detergent composition. The enzymes can as separate individual components (prills, granules, stabilized liquids etc., containing an enzyme) or as mixtures of two or more Enzymes (e.g. co-granules) can be added.

Other suitable detergent ingredients, that can be added are enzyme oxidation scavengers, which are described in EP-A-553607, filed January 31, 1992 are. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme materials and Funds for their admixture in synthetic detergent compositions also in WO 93/072263 A and WO 93/07260 A to Genencor International; WO 89/08694 A to Novo; and U.S. 3,553,139 issued January 5, 1971 to McCarty et al. Enzymes are further described in US 4,101,457, Place et al., July 18, 1978; and in U.S. 4,507,219, Hughes, March 26, 1985 disclosed. For liquid detergent formulations useful Enzyme materials and their admixture in such formulations are disclosed in U.S. 4,261,868, Hora et al., April 14, 1981. enzymes Can be used in detergents by various techniques be stabilized. Enzyme stabilization techniques are described in US 3,600,319, August 17, 1971, Gedge et al .; EP-199,405 and EP-200,586, October 29 1986, Venegas. Enzyme stabilization systems are also described, for example, in US 3,519,570. A useful bacillus, sp. AC13, which provides proteases, xylanases and cellulases in WO 94/01532 A to Novo.

bleach

A particularly preferred component The composition of detergent components is a bleach. Close suitable bleaches Chlorine and oxygen releasing bleach.

In a preferred aspect, the oxygen-releasing bleach contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor. The generation of the organi 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 aspect, a preformed organic peroxyacid is included directly in the composition. Compositions containing mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a preformed organic peroxyacid are also contemplated.

inorganic Perhydrate bleaches

The compositions of detergent components conclude preferably a source of hydrogen peroxide, such as an oxygen-releasing one Bleach, a. Suitable sources of hydrogen peroxide include inorganic perhydrate salts.

The inorganic perhydrate salts are usually in the form of the sodium salt in a proportion of 1 up to 40% by weight, stronger preferably 2 to 30% by weight and particularly preferably 5 to 25% by weight of the compositions included.

Examples of inorganic perhydrate salts conclude Perborate, percarbonate, perphosphate, persulfate and persilicate salts on. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be used as a crystalline solid without additional Protection. For however, certain perhydrate salts use the preferred designs such granular Compositions a coated form of the material, which a better shelf life for the Perhydrate salt in the granular Product.

Sodium perborate can be in the form of the monohydrate of the nominal formula NaBO ₂ H ₂ O ₂ or the tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O. Alkali metal percarbonates, especially sodium percarbonate, are preferred perhydrates for inclusion in the compositions of the invention. Sodium percarbonate is an addition compound according to the formula 2Na ₂ CO ₃ .3H ₂ O _2, and is available commercially as a crystalline solid. Sodium percarbonate, which is a hydrogen peroxide addition compound, tends to release the hydrogen peroxide very quickly on dissolution, which can increase the tendency for localized high bleach concentrations to occur. In such compositions, the percarbonate is particularly preferably closed in a coated form which provides stability in the product.

A suitable coating material which provides product stability comprises a mixed salt of a water-soluble alkali metal sulfate and carbonate. Such coatings along with coating processes have already been described in GB-1,466,799 issued to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to the percarbonate is in the range from 1: 200 to 1: 4, more preferably 1:99 to 1: 9 and particularly preferably 1:49 to 1:19. The mixed salt preferably consists of sodium sulfate and sodium carbonate and has the general formula Na ₂ SO ₄ .n. Na ₂ CO ₃ , wherein n is 0.1 to 3, n is preferably 0.3 to 1.0 and n most preferably the value 0.2 to 0.5 Has.

Another suitable coating material which provides product stability comprises sodium silicate with an SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 and / or Sodium metasilicate, preferably applied in a proportion of 2 to 10% (normally 3 to 5%) 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 species are also suitable.

Other coatings, which waxes, oils or Can contain fatty soaps can also be used advantageously according to the invention.

Potassium peroxymonopersulfate is a other inorganic perhydrate salt used in the compositions useful herein is.

Peroxyacid bleach precursor

worin L eine Abgangsgruppe ist und X im wesentlichen irgendeine Funktionalität ist, so daß bei der Perhydrolyse die Struktur der erzeugten Peroxysäure wie folgt istPeroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form a peroxyacid. In general, peroxyacid bleach precursors can be represented as

where L is a leaving group and X is essentially any functionality so that in perhydrolysis the structure of the peroxyacid produced is as follows

Peroxyacid bleach precursor compounds = are preferably in an amount of 0.5 to 20% by weight, more preferred 1 to 10% by weight, particularly preferably 1.5 to 5% by weight of the compositions locked in.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, being the precursor from a big one Range of classes chosen could be. Close appropriate classes Anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. suitable Esters are in GB-A-836988, 864798, 1147871 and 2143231, as well as in EP-A-0170386.

leaving groups

The leaving group, hereinafter the Group L, must be sufficient reactively be so that the perhydrolysis reaction within the optimal time Frame (e.g. a wash cycle). However, if L is too is reactive, it is difficult to use this activator in stabilize a bleaching composition.

und Mischungen hiervon, worin R¹ eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R³ eine Alkylkette mit 1 bis 8 Kohlenstoffatomen ist, R⁴ H oder R³ ist, R⁵ eine Alkenylkette mit 1 bis 8 Kohlenstoffatomen ist, und Y H oder eine solubilisierende Gruppe ist. Irgendeiner der Rest R¹, R³ und R⁴ kann durch im wesentlichen jede funktionelle Gruppe, einschließlich zum Beispiel Alkyl-, Hydroxy-, Alkoxy-, Halogen-, Amin-, Nitrosyl-, Amid- und Ammonium- oder Alkylammoniumgruppen, substituiert sein.Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R ^{1 is} an alkyl, aryl or alkaryl group with 1 to 14 carbon atoms, R ^{3 is} an alkyl chain with 1 to 8 carbon atoms, R ^{4 is} H or R ³ , R ^{5 is} an alkenyl chain with 1 to 8 carbon atoms and is YH or a solubilizing group. Any of R ¹ , R ^3, and R ⁴ may be substituted by essentially any functional group, including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkylammonium groups ,

The preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ₃ ) ₄ X ^- and O <- N (R ³ ) ₃ and most preferably -SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ , wherein R ^{3 is} an alkyl chain having 1 to 4 carbon atoms, M is a cation that provides solubility for the bleach activator, and X is an anion that provides solubility for provides the bleach activator. Preferably M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, Hy hydroxide, methyl sulfate or acetate anion.

Perbenzoic

Perbenzoic acid precursors see perbenzoic acid perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds conclude the substituted and unsubstituted benzoyloxybenzenesulfonates a, including for example benzoyloxybenzenesulfonate:

Ac = COCH3; Bz = Benzoyl Also suitable are the benzoylation products of sorbitol, glucose and all saccharides with benzoylation agents, including, for example:

Ac = COCH3; Bz = benzoyl

Perbenzoic acid precursor compounds of the imide type conclude N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl-substituted Urea. Suitable imidazole type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl groups Perbenzoic acid precursors include N-benzoylpyrrolidone, Dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include the benzoyldiacyl peroxides, the benzoyltetraacyl peroxides and the compound of the formula:

Phthalic anhydride is another perbenzoic acid precursor compound useful herein

worin n 0 bis 8, vorzugsweise 0 bis 2, ist und R⁶ eine Benzoylgruppe ist.Suitable N-acylated lactam perbenzoic acid precursors have the formula:

wherein n is 0 to 8, preferably 0 to 2, and R ^{6 is} a benzoyl group.

Perbenzoesäurederivatvorläufer

See perbenzoic acid derivative precursor substituted perbenzoic acids in perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic acid precursors disclosed here, wherein the benzoyl group is not positive by essentially any charged (i.e. non-cationic) functional group, including for Example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and Amide groups is substituted.

worin R¹ eine Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist und R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist, und L im wesentlichen irgendeine Abgangsgruppe sein kann. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann Aryl, substituiertes Aryl oder A1kylaryl, enthaltend eine Verzweigung, Substitution oder beides, darstellen und kann aus entweder synthetischen Quellen oder natürlichen Quellen, einschließlich zum Beispiel Talgfett, abgeleitet sein. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Aryl-, Halogen-, Stickstoff, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen einschließen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten nicht mehr als 18 Kohlenstoffatome insgesamt enthalten.A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulas:

wherein R ^{1 is} an aryl or alkaryl group with 1 to 14 carbon atoms, R ^{2 is} an arylene or alkarylene group with 1 to 14 carbon atoms and R ^{5 is} H or an alkyl, aryl or alkaryl group with 1 to 10 carbon atoms, and L can be essentially any leaving group. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ can be aryl, substituted aryl, or alkylaryl containing branching, substitution, or both, and can be derived from either synthetic sources or natural sources including, for example, tallow fat. Analogous structure variations are permitted for R ² . The substitution can include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total.

Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds generate cationic peroxyacids in perhydrolysis.

They are typically cationic Peroxyacid precursors Substitution of the peroxyacid portion suitable peroxyacid precursor compound by a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, educated. Cationic peroxyacid precursors lie typically in the compositions as a salt with an appropriate one Anion, such as a halide ion or a methyl sulfate ion, in front.

The cationically substituted in this way peroxyacid precursor compound can be a perbenzoic acid precursor, as described above, or a substituted derivative thereof his. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described below his.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; and 5,106,528; GB-1,382,594; EP-475,512, 458,396 and 284,292; and in JP-87-318,332.

Suitable cationic peroxyacid precursors include any the ammonium- or alkylammonium-substituted alkyl- or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyltetraacetylglucose benzoyl peroxides on.

A preferred cationically substituted one Benzoyloxybenzenesulfonate is the 4- (trimethylammonium) methyl derivative of benzoyloxybenzenesulfonate:

A preferred cationically substituted one Alkyloxybenzenesulfonate has the formula:

Preferred cationic peroxyacid precursors of Class of the N-acylated caprolactams include the trialkylammonium methylene benzoyl caprolactams, especially trimethylammonium methylene benzoyl caprolactam, a:

worin n 0 bis 12, besonders 1 bis 5, ist.Other preferred cationic peroxyacid precursors of the class N-acylated caprolactams include the trialkylammonium methylenate alkyl caprolactams:

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

Another preferred cationic Peroxyacid precursor 2- (N, N, N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate.

Alkyl bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in perhydrolysis. Preferred alkyl percarboxylic acid precursor compounds of the imide type include the N, N, N ¹ , N ¹ tetraacetylated alkylenediamines in which the alkylene group contains 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (MOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetyl glucose.

Amide substituted alkyl peroxyacid precursors

worin R¹ eine Alkylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen ist und R⁵ H oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen ist, und L im wesentlichen irgendeine Abgangsgruppe sein kann. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann ein geradkettiges oder verzweigtes Alkyl sein, welches eine Verzweigung, Substi tution oder beides enthält, und kann aus entweder synthetischen Quellen oder natürlichen Quellen, einschließlich zum Beispiel Talgfett, abgeleitet sein. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen einschließen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten nicht mehr als 18 Kohlenstoffatome insgesamt enthalten. Amidsubstituierte Bleichaktivatorverbindungen dieses Typs sind in EP-A-0170386 beschrieben.Amide substituted alkyl peroxyacid precursors are also suitable, including those of the following general formulas:

wherein R ^{1 is} an alkyl group of 1 to 14 carbon atoms, R ^{2 is} an alkylene group of 1 to 14 carbon atoms and R ^{5 is} H or an alkyl group of 1 to 10 carbon atoms, and L can be essentially any leaving group. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be straight chain or branched alkyl containing branching, substitution, or both, and may be derived from either synthetic sources or natural sources, including, for example, tallow fat. Analogous structure variations are permitted for R ² . The substitution can include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Organic benzoxazine peroxy acid precursors

einschließlich der substituierten Benzoxazine des Typs

worin R₁ H, Alkyl, Alkaryl, Aryl oder Arylalkyl bedeutet und worin R₂, R₃, R₄ und R₅ die gleichen oder verschiedene Substituenten sein können, gewählt aus H, Halogen, Alkyl, Alkenyl, Aryl, Hydroxyl, Alkoxyl, Amino, Alkylamino, COOR₆ (worin R₆ H oder eine Alkylgruppe ist) und Carbonylfunktionen.Also suitable are precursor compounds of the benzoxazine type, as disclosed, for example, in EP-A-332,294 and EP-A-482,807, especially those of the formula:

including the substituted benzoxazines of the type

in which R _{1 is} H, alkyl, alkaryl, aryl or arylalkyl and in which R ₂ , R ₃ , R ₄ and R _{5 can be} the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, Amino, alkylamino, COOR ₆ (wherein R _{6 is} H or an alkyl group) and carbonyl functions.

A particularly preferred precursor of the benzoxazine type is:

Preformed organic peroxy

The organic peroxyacid bleaching system can additionally or alternatively to an organic peroxyacid bleach precursor typically contain a preformed organic peroxyacid in a proportion of 0.5 to 25% by weight, more preferably 1 to 10% by weight, the composition.

worin R¹ eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Alkylen-, Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist und R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R1 kann ein geradkettiges oder verzweigtes Alkyl, substituiertes Aryl oder Alkylaryl sein, welches eine Verzweigung, Substitution oder beides enthält, und kann aus entweder synthetischen Quellen oder natürlichen Quellen, einschließlich zum Beispiel Talgfett, abgeleitet sein. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Aryl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen einschließen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten nicht mehr als 18 Kohlenstoffatome insgesamt enthalten. Amidsubstituierte organische Peroxysäureverbindungen dieses Typs sind in EP-A-0170386 beschrieben.A preferred class of organic peroxyacid compounds are the amide-substituted compounds of the following general formulas:

wherein R ^{1 is} an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ^{2 is} an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms and R ^{5 is} H or an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms Is 10 carbon atoms. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both, and may be derived from either synthetic sources or natural sources including, for example, tallow fat. Analogous structure variations are permitted for R ² . The substitution can include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ 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 diperoxydodecanedioic acid, diperoxytetradecanedioic acid and Diperoxyhexadecanedioc. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and diperazelaic acid, Mono- and diperbrassylic acid and N-phthaloylaminoperoxycaproic acid are also suitable herein.

Means to control the Freisetzungsgeschwindikeit

A means of controlling the Release rate of a bleach, especially an oxygen bleach, in the washing solution to be provided.

Release rate control agent of the bleach can intended for the controlled release of peroxide species into the wash solution become. Such means could for example controlling the release of any inorganic Perhydrate salt, which acts as a source of hydrogen peroxide is in the washing solution lock in.

Another control mechanism the rate of release of a bleaching agent can be coating of the bleach with a coating that is designed that she which provides for controlled release. The coating can therefore include, for example, a hardly water-soluble material or be a coating of sufficient thickness so that the kinetics the dissolution the controlled release rate of the thick coating provides.

The coating material can under Apply various methods. any Coating material is typically in a weight ratio of Coating material to the bleach from 1:99 to 1: 2, preferably 1:49 to 1: 9.

Suitable coating materials conclude Triglycerides (e.g. (partially) hydrogenated vegetable oil, soybean oil or cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures of these.

Other suitable coating materials can 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 bleach source, comprises sodium silicate with an SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied in a proportion of 2 to 10% (normally 3 to 5%) SiO ₂ , based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

Any inorganic salt coating materials can be combined with organic binder materials to provide composite inorganic salt / organic binder coatings. Suitable binders include the C ₁₀ -C ₂₀ alcohol ethoxylates containing 5-100 moles of ethylene oxide per mole of alcohol, and more preferably the primary C ₁₅ -C ₂₀ alcohol ethoxylates containing 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 × 10 ⁶ , preferably 1,000 to 400,000, particularly preferably 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 making up at least 20 mole percent of the polymer, are further examples of polymeric materials that are useful as binders. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the above-mentioned C ₁₀ -C ₂₀ alcohol ethoxylates containing 5-100 moles of ethylene oxide per mole of alcohol. Further examples of binders include the C ₁₀ -C ₂₀ mono- and diglycerol ethers and also the C ₁₀ -C ₂₀ fatty acids.

Cellulose derivatives such as methyl cellulose, Carboxymethyl cellulose and hydroxyethyl cellulose as well as homo- or copolymeric polycarboxylic acids or their salts are other examples of binders which are used are suitable herein.

A method of applying the Coating material closes the agglomeration. Preferred agglomeration methods include Use any of the organic described above Binder materials. Any conventional agglomerator / mixer can be used, including but not limited to on, pan, rotary drum and vertical mixer types. Melted coating compositions can also by casting on or spray on one moving layer of the bleach can be applied.

Other means of delivery the required controlled release includes mechanical means to change the physical properties of the bleach to solubility and control release rate. Appropriate protocols could compression, mechanical injection, manual injection and Adjust solubility the bleach compound by choosing any particle size particulate Include component.

Although the choice of particle size from both the composition of the particulate component as well from the desire to the desired Depending on the controlled release kinetics, it is desirable that the Particle size more than 500 μm, preferably with an average particle diameter of 800 to 1,200 μm, should be.

Other protocols to provide the controlled release agent include the appropriate one Choice of any other components of the detergent composition matrix so that when the composition is introduced into the wash solution, the ionic strength environment provided therein enables the required controlled release kinetics to be achieved.

Metallic bleaching catalyst

The compositions described herein which contain a bleach as a detergent component can be used as a preferred component in addition contain a metal-containing bleaching catalyst. Preferably the metal-containing bleaching catalyst contains a transition metal Bleaching catalyst, stronger preferably a bleach catalyst containing manganese or cobalt.

A suitable type of bleaching catalyst is a catalyst comprising a heavy metal cation with a defined bleaching catalytic activity, such as copper or iron ions, an additional metal cation with a low or no bleaching catalytic activity, such as zinc or aluminum cations, and a sequestrant with defined stability constants for the catalytic and additional Metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble Salts thereof. Such catalysts are in U.S. Patent 4,430,243 disclosed.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₁ (u-OAc) ₂ ( 1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ - (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2 , 4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

The bleach catalysts useful in the compositions herein can also be selected as appropriate in the present invention. For examples of suitable bleaching catalysts cf. U.S. Patent 4,246,612 and U.S. Patent 5,227,084. See also U.S. Patent 5,194,416 which shows mononuclear manganese (IV) complexes such as Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ).

Another type of bleach catalyst, as disclosed in U.S. Patent 5,114,606 is a water soluble complex of manganese (III) and / or (IV) with a ligand containing a non-carboxylate polyhydroxy compound is at least three consecutive C-OH groups. preferred Close ligands Sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof.

worin R¹, R², R³ und R⁴ jeweils gewählt sein können aus H, substituierten Alkyl- und Arylgruppen, so daß jedes R¹-N=C-R² und R³-C=N-R⁴ einen 5- oder 6-gliedrigen Ring bildet. Der Ring kann weiterhin substituiert sein. B ist eine Brückengruppe, gewählt aus O, S, CR⁵R⁶, NR⁷ und C=O, worin R⁵, R⁶ und R⁷ jeweils H, Alkyl- oder Arylgruppen, einschließlich substituierten oder unsubstituierten Gruppen, sein können. Bevorzugte Liganden schließen Pyridin-, Pyridazin-, Pyrimidin-, Pyrazin-, Imidazol-, Pyrazol- und Triazolringe ein. Wahlweise können die Ringe durch Substituenten wie Alkyl, Aryl, Alkoxy, Halogenid und Nitro substituiert sein. Besonders bevorzugt wird der Ligand 2,2'-Bispyridylamin. Bevorzugte Bleichkatalysatoren schließen Co-, Cu-, Mn-, Fe-Bispyridylmethan- und -Bispyridylamin-Komplexe ein. Besonders bevorzugte Katalysatoren schließen Co(2,2'-Bispyridylamin)Cl₂, Di(isothiocyanato)bispyridylaminkobalt(II), Trisdipyridylaminkobalt(II)-perchlorat, Co(2,2'-Bispyridylamin)₂O₂ClO₄, Bis-(2,2'-Bispyridylamin)kiipfer(II)-perchlorat, Tris(di-2-pyridylamin)-eisen(II)-perchlorat und Mischungen hiervon ein.U.S. Patent 5,114,611 shows a bleaching catalyst comprising a complex of transition metals including Mn, Co, Fe or Cu with a non- (macro) cyclic ligand. These ligands have the formula:

wherein R ¹ , R ² , R ³ and R ^{4 can} each be selected from H, substituted alkyl and aryl groups, so that each R ¹ -N = CR ² and R ³ -C = NR ^{4 has} a 5- or 6-membered group Ring forms. The ring can also be substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C = O, where R ⁵ , R ⁶ and R ^{7 can} each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. The rings can optionally be substituted by substituents such as alkyl, aryl, alkoxy, halide and nitro. The ligand 2,2'-bispyridylamine is particularly preferred. Preferred bleaching catalysts include Co, Cu, Mn, Fe bispyridylmethane and bispyridylamine complexes. Particularly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), tris dipyridylamine cobalt (II) perchlorate, Co (2,2'-bispyridylamine) ₂ O ₂ ClO ₄ , bis ( 2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

Preferred examples include dinuclear Mn complexes with tetra-N-like and bi-N-like ligands, including N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^III (uO) ₂ Mn ^IV bipy ₂ ] - (ClO ₄ ) ₃ , a.

Although the structures of the manganese complexes that catalyze the bleach have not been elucidated, it can be assumed that they include chelates or other hydrated coordination complexes that result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the oxidation level of the manganese cation during the catalytic process is not known with certainty and can be the (+ II) -, (+ III) -, (+ IV) - or (+ V) -value level. Since the ligand can attach to the manganese cation at six possible sites, it can reasonably be assumed that polynuclear species and / or "cage" structures can be present in the aqueous bleaching medium. Whatever form the active Mn ligand species is in, it is effective in an apparently catalytic manner to provide improved bleaching performance for stubborn stains such as tea, ketchup, coffee, wine, juice and the like.

Other bleach catalysts are for Example described in the European patent application with the Pub. 408,131 (cobalt complex catalysts); the European patent applications with the Publication Nos. 384.503 and 306.089 (metalloporphyrin catalysts); US 4,728,455 (Manganese / multidentate Ligand catalyst); US 4,711,748 and the European Patent application with publication no. 224.952 (manganese catalyst adsorbed on aluminosilicate); US 4,601,845 (aluminosilicate with manganese and zinc or magnesium salt); U.S. 4,626,373 (manganese / ligand catalyst); U.S. 4,119,557 (ferric complex catalyst); the German patent description 2,054,019 (cobalt chelate catalyst); Canadian Patent 866,191 (Transition metal containing salts); US 4,430,243 (chelators with manganese cations and non-catalytic metal cations); and U.S. 4,728,455 (manganese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts of the formula: Co [(NH ₃ ) _n M ' _m B' _b T _t Q _q P _p ] Y _y wherein cobalt is in the + 3 oxidation state, n is an integer from 0 to 5 (preferably 4 or 5, particularly preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, particularly preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q represents a tidentate ligand; q is 0 or 1; P represents a five-toothed ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more suitably selected counter anions which are present in the number y, where y is an integer from 1 to 3 (preferably 2 to 3; particularly preferably 2 if Y is a -1-charged anion) by one to obtain balanced salt in the charge, preferred Y being 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 which are bound to the cobalt is unstable under machine dishwashing conditions of use, and the remaining coordination sites stabilize the cobalt under machine dishwashing conditions so that the reduction potential from cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than 0.2 volts) than a normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula: [Co (NH ₃ ) _n (M ') _m ] Y _y wherein n is an integer from 3 to 5 (preferably 4 or 5, particularly preferably 5); M 'is an unstable coordination group, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (if m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, particularly preferably 1); m + n = 6; and Y is a suitably selected counter anion which is present in a number of y, where y is an integer from 1 to 3 (preferably 2 to 3; particularly preferably 2 if Y is a -1-charged anion) by one to get balanced salt in the cargo.

The preferred cobalt catalysts of this type useful herein are cobalt pentaamine chloride salts of the formula [Co (NH ₃ ) ₅ Cl] Y _y and especially [Co (NH ₃ ) ₅ Cl] Cl ₂ . The compositions according to the invention which use cobalt (III) bleaching catalysts having the formula: [Co (NH ₃ ) _n (M) _m (B) _b ] T _y wherein cobalt is in the + 3 oxidation state; n is 4 or 5 (preferably 5); M represents one or more ligands that are coordinated via a site on the cobalt; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to the cobalt through two sites; b is 0 or 1 (preferably 0) and if b = 0 then m + n = 6 and if b = 1 then m = 0 and n = 0; and T is one or more suitably selected counter anions which are present in a number of y, where y is an integer in order to obtain a salt which is balanced in the charge (preferably y is 1 to 3; particularly preferably 2 if T is a - 1-charged anion); and wherein the catalyst further has a base hydrolysis rate constant of less than 0.23 M ^-1 s ^-1 (25 ° C).

Preferred T are selected from the group consisting of chloride, iodide, I ₃ ^- , formate, nitrate, nitrite, sulfate, sulfate, citrate, acetate, carbonate, bromide, PF ₆ ^- , BF ₄ ^- , B (Ph) ₄ ^- , Phosphate, phosphite, silicate, tosylate, methanesulfonate and combinations thereof. Optionally, T can be protonated if there is more than one anionic group in T, e.g. B. HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- etc. Furthermore, T can be selected from the group consisting of from unusual inorganic anions, such as anionic surfactants (e.g. linear alkylbenzenesulfonates (LAS), alkylsulfates (AS), alkylethoxysulfonates (AES) etc.) and / or anionic polymers (e.g. polyacrylates, polymethacrylates etc.).

The M units include, but are not limited to, F ^- , SO ₄ ^-2 , NCS ^- , SCN ^- , S ₂ O ₃ ^-2 , NH ₃ , PO ₄ ^{3 -} and carboxylates (which are preferably monocarboxylates, but are more than one carboxylate can be present in the unit, as long as the binding to the cobalt occurs only via one carboxylate per unit, in which case the other carboxylate can be protonated in the M unit or be in its salt form). M can optionally be protonated if more than one anionic group is present in M (e.g. HPO ₄ ^2- , HCO ₃ ^- , HP ₂ O ₄ ^- , HOC (O) CH ₂ C (O) O- etc. ). Preferred M units are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids of the formula: RC (O) O- wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) alkyl, unsubstituted and substituted C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) aryl and unsubstituted and substituted C ₃ -C ₃₀ (preferably C ₅ -C ₁₈ ) heteroaryl, substituents being selected from the group consisting of -NR ' ₃ , -NR' ₄ ⁺ , -C (O) OR ', - OR 'or -C (O) NR' ₂ , wherein R 'is selected from the group consisting of hydrogen and C ₁ -C ₆ groups. Such substituted radicals R therefore include the groups - (CH ₂ ) _n OH and - (CH ₂ ) _n NR ' ₄ ⁺ , where n is an integer from 1 to 16, preferably 2 to 10 and particularly preferably 2 to 5.

The M units are particularly preferably carboxylic acids of the above formula, in which R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C ₄ -C ₁₂ alkyl and benzyl. R is particularly preferably methyl. Preferred carboxylic acid M units include ant, benzoic, octane, nonane, decane, dodecane, malone, maleic, amber, adipine, phthalic, 2-ethylhexane, naphthene, oleine , Palmitic, triflate, wine, stearic, butter, lemon, acrylic, asparagine, fumaric, lauric, linoleic, lactic, malic and especially acetic acid.

The B units include carbonate, Di and higher Carboxylates (e.g. oxalate, malonate, malic acid, succinate or maleate), picolinic and alpha and beta amino acids (e.g. glycine, alanine, beta-alanine and phenylalanine).

Cobalt bleach catalysts useful herein are known and are available, for example, along with their base hydrolysis rates at Tobe ML, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech. 2 (1983), pages 1-94. For example, Table 1 on page 17 gives the base hydrolysis rates (referred to therein as k _OH ) for cobalt pentaamine catalysts which are combined with oxalate (k _OH = 2.5 × 10 ^-4 M _-1 s ^-1 (25 ° C)), NCS ^- (k _OH = 5.0 x 10 ^-4 M ^-1 (25 ° C)), formate (k _OH = 5.8 x 10 ^-4 M ^-1 s ^-1 (25 ° C)) and acetate (k _OH = 9.6 × 10 ^-4 M ^-1 s ^-1 (25 ° C)) are complexed. The most preferred cobalt catalysts, useful herein, cobalt pentaamine acetate salts of the formula [Co (NH _{3) 5} OAc] T _y, wherein OAc represents an acetate group, and especially cobalt [Co (NH _{3) S} OAc] Cl _2; and [Co (NH ₃ ) ₅ OAc] (OAc) ₂ ; [Co (NH ₃ ) ₅ OAc] (PF ₆ ) ₂ ; [Co (NH ₃ ) ₅ OAc] (SO ₄ ); [Co (NH ₃ ) _S OAc] (BF ₄ ) ₂ ; and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (herein "PAC").

These cobalt catalysts can be used in can be easily produced by known methods, such as they are taught for example in the previous article by Tobe and those listed in it References ;, in U.S. Patent 4,810,410 to Diakun et al., Issued on 7th March 1989; J. Chem. Ed. 66: 12 (1043-1045); The Synthesis and Characterization of Inorganic Compounds, Jolly W.L. (Prentice-Hall; 1970), pp. 461-463; Inorg. Chem. 18: 1497-1502 (1979); Inorg. Chem. 21: 2881-2885 (1982); Inorg. Chem. 18: 2023-2025 (1979); Inorg. Synthesis (1960), 173-176; and Journal of Physical Chemistry 56 (1952), 22-25, and those below provided synthesis examples.

For admixing in the detergent tablets according to the invention suitable cobalt catalysts according to the synthetic routes which are disclosed in U.S. Patent Nos. 5,559,261; 5,581,005 and 5,597,936.

These catalysts can work together processed with additional materials, if necessary the color impairment because of the aesthetics to reduce the product or to enclose it in enzyme-containing particles, such as illustrated below, or the compositions may be so that they are manufactured Catalyst "spots" included.

organic polymeric compound

Organic polymeric compounds can be added as preferred components of the detergent tablets according to the invention. By organic polymeric compound is meant essentially any polymeric organic compound commonly found in detergent compositions that have dispersant, anti-redeposition, soil release, or other detergent properties has.

The organic polymeric compound is typically in the detergent compositions of the invention in a proportion of 0.1 to 30% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight of the compositions included.

Examples of organic polymeric compounds conclude the water soluble organic homo- or copolymeric polycarboxylic acids and modified polycarboxylates or their salts, in which the polycarboxylic acid contains at least two carboxyl radicals comprises which are separated by no more than two carbon atoms are a. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates with a molecular weight from 2,000-10,000 and their copolymers with any suitable other monomers Units, including modified acrylic, fumar, malein, itacon, aconite, mesacon, Citraconic and methylene malonic acid or their salts, maleic anhydride, Acrylamide, alkylene, vinyl methyl ether, styrene and any mixtures hereof. The copolymers of acrylic acid and maleic anhydride with a molecular weight of 20,000 to 100,000.

Preferred commercially available acrylic acid containing polymers with a molecular weight below 15,000 conclude those under the trade names Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH and under the trade name Acusol 45N, 480N and 460N by Rohm and Haas sold one.

Preferred copolymers containing acrylic acid include those which contain as monomeric units: a) 90 to 10% by weight, preferably 80 to 20% by weight, acrylic acid or its salts, and b) 10 to 90% by weight, preferably 20 to 80 wt .-%, a substituted acrylic monomer or its salts with the general formula - [CR ₂ -CR ₁ (CO-OR ₃ )] -, wherein at least one of the substituents R ₁ , R ₂ or R ₂ , preferably R ₁ or R _{2 is} a C _1-4 alkyl or hydroxyalkyl group, R ₁ or R ₂ may be hydrogen, and R _{3 may be} hydrogen or an alkali metal salt. A substituted acrylic acid monomer in which R _{1 is} methyl and R _{2 is} hydrogen (ie a methacrylic acid monomer) is particularly preferred. The most preferred copolymer of this type has a molecular weight of 3,500 and contains 60 to 80% by weight of acrylic acid and 40 to 20% by weight of methyl acrylic acid.

The polyamine and modified polyamine compounds are useful here including those derived from aspartic acid, such as those in EP-A-305282, EP-A-305283 and EP-A-351629.

Other optional polymers can be polyvinyl alcohols and acetates, both modified and unmodified, cellulose derivatives and modified cellulose derivatives, polyoxyethylenes, polyoxypropylenes and copolymers thereof, both modified and unmodified, Terephthalate ester of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.

Suitable examples are in the US patents Nos. 5,591,703, 5,597,789 and 4,490,271.

soil

Suitable polymeric soil release agents include such soil release agents comprising: (a) one or 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 degree of polymerization of 2 to 10, wherein the hydrophilic segment has no oxypropylene unit unless it is attached at each end to adjacent groups by ether linkages; or (iii) a mixture of oxyalkylene units comprising oxyethylene and 1 to 30 oxypropylene units, the hydrophilic segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components with 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising: (i) C ₃ oxyalkylene terephthalate segments, wherein if the hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is 2: 1 or less; (ii) C ₄ -C ₆ alkylene or oxy-C ₄ -C ₆ alkylene segments or mixtures thereof; (iii) poly (vinyl ester) segments, preferably poly (vinyl acetate), with a degree of polymerization of at least 2; or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents or mixtures thereof, the substituents being in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof; or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) have a degree of polymerization of 200, although higher degrees can be used, preferably from 3 to 150 and more preferably from 6 to 100. Suitable hydrophobic oxy-C ₄ -C ₆ alkylene segments include, but are not limited to, end caps of polymeric release agents such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, where M is sodium and n is an integer of 4 through 6 is as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful herein also include cellulose derivatives such as 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 close Hydroxyethers of cellulose such as METHOCEL (Dow). Cellulose soil release agents for use 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.

Soil repellants characterized by hydrophobic poly (vinyl ester) segments include graft copolymers of poly (vinyl ester), e.g. B. C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud et al.

Another dirt repellent is a copolymer with random blocks of Ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight this polymeric dirt repellent is in the range of 25,000 up 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 7, 1975.

Another suitable polymer Dirt repellent is a polyester with repeating units of ethylene terephthalate units, which is 10 to 15% by weight of ethylene terephthalate units together with 90 to 80 wt .-% polyoxyethylene terephthalate units contains derived from a polyoxyethylene glycol with an average Molecular weight from 300 to 5,000.

Another suitable polymer Soil repellent is a sulfonated product essentially linear ester oligomers consisting of an oligomeric ester backbone of recurring Terephthaloyl and oxyalkyleneoxy units and covalently bonded to the backbone End groups. These soil release agents are described in U.S. Patent 4,968,451, issued on November 6, 1990 to Scheibel J.J. and Gosselink E.P., described in detail. Other suitable polymeric soil release agents include Terephthalate polyester of U.S. Patent 4,711,730 issued December B. 1987 to Gosselink et al .; the anionically end-capped oligomers Esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomer compounds of U.S. Patent 4,702,857, issued to Gosselink on October 27, 1987. Other polymeric dirt repellants conclude also the soil release agents of U.S. Patent 4,877,896, issued on October 31, 1989 to Maldonado et al. one which is anionic, especially Sulfoarolyl end-capped terephthalate esters are disclosed.

Another dirt repellent is an oligomer with repeating units of terephthaloy units, Sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form the basic structure of the oligomer and are preferably terminated with modified isethionate end caps. A particularly preferred soil release agent of this type includes approximately one sulfoisophthaloyl unit, five Terephthaloy units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a relationship from 1.7 to 1.8 and two end cap units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

Heavy metal

The tablets of the invention contain as an optional component, preferably a heavy metal ion sequester. Heavy metal ion sequestrant means components here, which are effective in that they Sequestrate (complex) heavy metal ions. These components can too have calcium and magnesium chelation capacity, but they show preferably selectivity for the Binding of heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants lie generally in a proportion of 0.005 to 20% by weight, preferably 0.1 to 10 wt%, stronger preferably 0.25 to 7.5% by weight and particularly preferably 0.5 to 5% by weight of the compositions.

Heavy metal ion sequestrants, which are acidic in nature, for example phosphonic acid or Carboxylic acid functionalities, can either in their acid form or as a complex / salt with a suitable counter cation, such as an alkali or alkali metal ion, ammonium or substituted ammonium ion or any mixtures thereof. Are preferred any salts / complexes water soluble. The molar ratio of the counter cation to the heavy metal ion sequester is preferably at least 1: 1.

Heavy metal ion sequestrants suitable for use herein conclude organic phosphonates such as the aminoalkylene poly (alkylene phosphonates), Alkali metal ethane 1-hydroxydiphosphonates and nitrilotrimethylene phosphonates on. Preferred among the above species are diethylene triamine penta (methylene phosphonate), Ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for use herein nitrilotriacetic and polyaminocarboxylic acids, such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic, ethylenediamine, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts of this, a.

Particularly preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof. preferred EDDS compounds are the free acid form and the sodium or magnesium salt or a complex thereof.

Crystal growth inhibitor component

Contain the detergent tablets preferably a crystal growth inhibitor component, preferably an organodiphosphonic acid component, which is preferably in a proportion of 0.01 to 5% by weight, more preferably 0.1 to 2% by weight of the compositions included.

With organodiphosphonic acid herein an organodiphosphonic acid meant that no nitrogen as part of their chemical Contains structure. This definition closes therefore the organoaminophosphonates, which, however, in the compositions according to the invention included as heavy metal ion sequestrant components can.

The organodiphosphonic acid is preferably a C ₁ -C ₄ diphosphonic acid, more preferably a C ₂ diphosphonic acid such as ethylene diphosphonic acid or most preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP) and can be in a partially or fully ionized form, especially as a salt or complex.

water-soluble sulfate salt

The detergent tablet contains optional a water soluble Sulfate salt. If present, the water-soluble sulfate salt is in one Proportion of 0.1 to 40 wt .-%, stronger preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight, of the compositions.

The water-soluble sulfate salt can essentially be any salt of sulfate with any counter cation. preferred Salts are chosen from the sulfates of the alkali and earth metal, especially sodium sulfate.

Allcalimetallsilicat

An alkali metal silicate is a preferred component of the tablet of the invention. A preferred alkali metal silicate is sodium silicate with an SiO: Na ₂ O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, particularly preferably 2.0. Sodium silicate is preferably present in a proportion of less than 20%, preferably 1 to 15%, particularly preferably 3 to 12%, based on the weight of SiO ₂ . The alkali metal silicate can be in the form of either the anhydrous salt or a hydrated salt.

The alkali metal silicate can also as a component of an alkalinity system.

The alkalinity system also preferably contains sodium metasilicate, which is present in a proportion of at least 0.4% by weight of SiO ₂ . Sodium metasilicate has a nominal SiO ₂ : Na ₂ O ratio of 1.0. The weight ratio of sodium silicate to sodium metasilicate, measured as SiO ₂ , is preferably 50: 1 to 5: 4, more preferably 15: 1 to 2: 1, particularly preferably 10: 1 to 5: 2.

dye

The term "colorant" as used herein means any substance that has specific wavelengths of Absorbs light from the visible light spectrum. Such colorants have the effect when added to a detergent composition, the visible color and thus the appearance of the detergent composition to change. dye can for example, be either dyes or pigments. Preferably are the colorants stable in the composition into which they are introduced should. So is the colorant in a composition with a high pH, preferably alkali-resistant, and in a composition with a low pH is the colorant preferably acid-resistant.

The first and / or second and / or optionally another phase can be a colorant, a mixture of colorants, colored Contain particles or a mixture of colored particles, so that the different phases have a different visual appearance. Preferably includes either the first or the second phase a colorant. If the first and second and / or subsequent phase all containing a colorant is preferred that the dye have a different visual appearance.

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

The colorant can be by any suitable process can be introduced into the phases. suitable Close proceedings the mixing of all or selected detergent components with a colorant in a drum or spraying all or selected Detergent components with the colorant in a rotating drum.

If as a component of the first Phase is present, the colorant lies in a proportion of 0.001 to 1.5%, preferably 0.01 to 1.0%, particularly preferably 0.1 to 0.3%. If as a component the second and / or optional further phase is present the colorant generally in a proportion of 0.001 to 0.1%, more preferred 0.005 to 0.05%, particularly preferably 0.007 to 0.02%.

Hydrocarbon oils

Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain aliphatic hydrocarbon with a number of carbon atoms in the range of 20 to 50; preferred hydrocarbons are saturated and / or branched; the preferred hydrocarbon oil is selected from predominantly branched C _25-45 species with a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1, preferably 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin. A paraffin oil that fulfills the properties listed above, with a ratio of cyclic to noncyclic hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Enzyme stabilization system

Preferred enzyme-containing compositions in this can 0.001 to 10% by weight, preferably 0.005 to 8% by weight, particularly preferably 0.01 to 6% by weight of an enzyme stabilization system. The Enzyme stabilization system can be any stabilization system be compatible with the detergent enzyme. Such stabilization systems can Calcium ions, boric acid, Propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavenger and Mixtures thereof include. Such stabilization systems can also reversible enzyme inhibitors, such as reversible protease inhibitors, include.

lime soap dispersant compound

The tablets of the invention can Lime soap dispersant compound, which preferably in a proportion of 0.1 to 40% by weight, more preferably 1 to 20% by weight, most preferably 2 to 10% by weight of the compositions present.

A lime soap dispersant is a material that the precipitation of alkali metal, ammonium or amine salts of fatty acids Prevents calcium or magnesium ions. Preferred lime soap dispersant compounds are in the PCT application No. WO 93/08877.

Suds suppressing system

The detergent tablets according to the invention, if them for use in machine wash compositions are preferably comprised of a foam suppression system, which in a proportion of 0.01 to 15 wt .-%, preferably 0.05 up to 10% by weight, particularly preferably 0.1 to 5% by weight, of the composition is present.

Suitable foam suppression systems for use herein essentially comprise any known anti-foam compound including for example silicone antifoam compounds and 2-alkylalkanol antifoam compounds. Preferred foam suppression systems and anti-foam compounds are in PCT Application No. WO 93/08877 and disclosed in EP-A-705 324.

Polymeric dye transfer inhibitors

The detergent tablets herein can also 0.01 to 10 wt .-%, preferably 0.05 to 0.5 wt .-%, polymeric Dye transfer inhibitors include.

The polymeric dye transfer inhibitors are preferably chosen from polyamine-N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations hereof.

Optical brightener

For use in laundry processes, Suitable detergent tablets as described herein can also optionally 0.005 to 5% by weight of certain types of hydrophilic optical Brighteners included.

worin R₁ gewählt ist aus Anilino, N-2-Bis-hydroxyethyl und NH-2-Hydroxyethyl; R₂ gewählt ist aus N-2-Bis-hydroxyethyl, N-2-Hydroxyethyl-N-methylamino, Morphilino, Chlor und Amino; und M ein salzbildendes Kation ist, wie Natrium oder Kalium.Hydrophilic optical brighteners useful herein include those of the structural formula:

wherein R _{1 is} selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R _{2 is} selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chlorine and amino; and M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R _{1 is} anilino, R _{2 is} N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2 -bishydroxyethyl) -s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is marketed under the trade name Tinopal-UNPA-GX by Giba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

In the formula above, when R _{1 is} anilino, R _{2 is} N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis - [(4-anilino- 6- (N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is sold commercially by the Ciba-Geigy Corporation under the trade name Tinopal 5BM-GX.

In the formula above, when R _{1 is} anilino, R _{2 is} morphilino and M is a cation such as sodium, the brightener is 4,4'-bis - [(4-anilino-6-morphilino-s-triazine-2- yl) amino] -2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is sold commercially by the Ciba-Geigy Corporation under the trade name Tinopal AMS-GX.

Clay softening

For use in laundry processes suitable detergent tablets contain a clay softening system containing a clay mineral compound and optionally comprises a clay flocculant.

The clay mineral compound is preferred a smectite tone compound. Smectittone are disclosed in the U.S. patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. The European patents Nos. EP-A-299,575 and EP-A-313,146 on behalf of the Procter & Gamble Company describe suitable organic polymeric clay flocculants.

Cationic fabric softeners

Cationic fabric softeners can in the compositions according to the invention, which are for use in laundry processes are suitable to be included. Suitable cationic fabric softeners conclude the water-insoluble tertiary Amines or double long chain amide materials as in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softeners are typically more normal in total proportions of 0.5 to 15% by weight 1 to wt% included.

Other optional ingredients

Other optional ingredients which suitable for inclusion in the compositions according to the invention are close Fragrances and filler salts a, with sodium sulfate being a preferred filler salt.

pH of the compositions

The detergent tablets of the invention are preferably not formulated to have an excessively high pH, but preferably a pH, measured as a 1% solution in distilled water, from 8.0 to 12.5, more preferably 9.0 to 11 , 8, particularly preferably 9.5 to 11.5 point.

Laundry process

Machine washing processes herein typically involve treating dirty laundry with a aqueous washing solution, wherein an effective amount of a detergent tablet composition according to the invention solved for machine washing or dispensed in a washing machine. With an effective The amount of the detergent tablet composition is 40 g to 300 g Product, solved or dispersed in a wash solution with a volume of 5 to 65 liters, meant what typical product dosages and Wash solution volumes are that ordinary in conventional machine washing process can be used.

According to a preferred application aspect a dispensing device is used in the washing process. The dispensing device is filled with the detergent product and used to put the product directly into the drum of the washing machine before the start of the wash cycle. Your volume should be such that they can hold enough detergent product, as it normally does would be used in the washing process.

After loading the washing machine with laundry the dispensing device containing the detergent product, introduced into the drum. At the beginning of the washing cycle the washing machine will Water is introduced into the drum and the drum rotates periodically. The design of the dispensing device should be such that it the Inclusion of the allowed dry detergent product, but then the release of this Product while of the wash cycle in response to their movement when the drum turns, and also as a result of their contact with the wash water allows.

To release the detergent product while of washing, the device may have a series of openings through which the product can pass through. In another embodiment, the device be made of a material that is permeable to a liquid, but for the solid product impermeable is what the release of the solved Product allowed. Preferably the detergent product is initially of the wash cycle is released quickly, causing temporarily high local concentrations of the product in the drum of the washing machine at this stage of the Wash cycles are provided.

Preferred dispensing devices are reusable and are constructed in such a way that the Container integrity in both the dry state as well as during the wash cycle is maintained.

Alternatively, the dispensing device a flexible container to be like a bag or a bag. The pouch can be fibrous Construction that is coated with a waterproof protective material is to withhold the content as published in the European Patent Application No. 0018678 is disclosed. In another embodiment it can be made from a water-insoluble be formed synthetic polymeric material, which with a Edge sealing or a closure is provided, the / so is designed that she / he in an aqueous medium ruptures as published in European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A suitable one Form of a closure fragile in water includes a water-soluble one Adhesive placed along an edge of a pocket made from a waterproof polymer Film such as polyethylene or polypropylene is formed is distributed and seals it.

Claims (24)

Multi-phase laundry detergent tablet, full: a) with a first phase in the form of a shaped body at least one depression in its surface; and b) a second Phase in the form of a compressed body, which adheres within of the well, the second phase comprising an enzyme and the first and second phases in a weight ratio of at least 6: 1. A multi-phase detergent tablet according to claim 1, wherein the second phase is compressed at a pressure of less than 350 kg / cm ² . A multi-phase detergent tablet according to claim 1 or claim 2, wherein the first phase is a compressed molded body made at a compression pressure of at least 40 kg / cm ² , preferably at least 350 kg / cm ² . Multi-phase detergent tablet according to at least one preceding claim, wherein the second Phase dissolves faster than the first phase. Multi-phase detergent tablet after at least one of claims 1 to 3, the second phase dissolving after the first phase. Multi-phase detergent tablet after at least one preceding claim, wherein the first and / or second phase Include binders. Multi-phase detergent tablet according to claim 6, wherein the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers. Multi-phase detergent tablet after at least one The preceding claim, wherein the second phase is a disrupting agent includes, chosen from disintegrants, effervescent agents and mixtures thereof. Multi-phase detergent tablet after at least one preceding claim, additionally comprising a blocking phase between the first and the second phase. Multi-phase detergent tablet according to claim 9, the barrier layer being a liquid Form applied binder comprises. Multi-phase detergent tablet after at least a preceding claim, wherein the enzyme from protease, amylase, Lipase, peroxidase, cutinase and cellulase is chosen. Multi-phase detergent tablet after at least a preceding claim, wherein the recess is an inward directed concave surface has. Multi-phase detergent tablet after at least any preceding claim, wherein the first and second phases in a weight ratio of at least 10: 1. Multi-phase detergent tablet after at least any preceding claim, wherein the tablet is predominantly one concentrated enzyme in the second phase. Multi-phase detergent tablet after at least a preceding claim, wherein the to the first and the second Compression pressures applied in a ratio of are at least 2: 1. Multi-phase detergent tablet after at least any of the preceding claims, wherein the tablet is so designed is that when they are used, the resolution of the Phases occurs. Multi-phase detergent tablet after at least a preceding claim, wherein the times in which dissolve the first and second phases in the laundry machine from each other independently are. Method for washing laundry in a laundry washing machine, comprising loading a laundry machine with one or more multi-phase detergent tablets according to claim 1. The method of claim 18, wherein the multi-phase Detergent tablet itself in less than 15 minutes in the laundry machine dissolves or disintegrated. The method of claim 18 or claim 19, wherein the second phase dissolves faster than the first phase. Method according to at least one of claims 18 to 22, the second phase being inside the laundry machine 5 minutes dissolves. 22. The method of claim 18 or claim 21, wherein the second phase dissolves after the first phase. The method of claim 18 or claim 19, wherein at least 50 wt .-%, preferably at least at least 60% by weight, more preferably at least 80% by weight of the enzyme to the laundry within 10 minutes, preferably within 5 minutes, and more preferably within 3 minutes. Method according to at least one of claims 18 to 23, the tablets having any of the additional features as shown in FIGS claims 2, 3 and 6-14 called own.