DE69836835T2 - detergent tablet - Google Patents

Abstract

The present invention provides a detergent tablet comprising: a) a compressed portion comprising active detergent components; b) a non compressed, non-encapsulating portion comprising active detergent components. Detergent components which are sensitive to compression can be incorporated into tablets and greater control of washing processes can be achieved.

Description

TECHNICAL TERRITORY

 The The present invention provides a detergent tablet comprising a compressed part and a non-compressed, non-encapsulating one Part.

BACKGROUND

 detergent compositions in tablet form correspond to the prior art. It goes without saying itself, that detergent compositions in tablet form in Comparison to detergent compositions in particulate form several Advantages, such as easy handling, transporting and storage.

detergent tablets become the most common by premixing components of a detergent composition and forming the premixed detergent components into a tablet made using a tablet press. Be tablets usually by compression of the components of the detergent composition shaped into a tablet. However, the applicant has stated that some components of a detergent composition by the Compression applied to form the tablets be adversely affected. These components have been so far not included in a detergent tablet composition without losing any of their performance. In some cases, the Components even unstable or inactive due to compression have become.

Further The components of the detergent composition, if they are compressed, in close proximity brought to each other. A result of the close proximity of the components may be that certain of the components react with each other, causing them unstable, inactive or exhausted become. A solution of this Problems, as seen in the prior art, lay in the separation of components of the detergent composition that may be react with each other when the detergent composition in a Tablet shape is pressed. The separation of the components was achieved, for example, by producing multilayer tablets, being the components that possibly react with each other, contained in different layers of the tablet are. Multilayer tablets are conventionally used by means of several Compression steps made. Tablet layers that more than undergo a compression step become cumulative and potentially greater total compression pressure subjected. An increase The compression pressure of the tablet press is known to lower the dissolution rate the tablet with the effect of having such a multiple layer may not work satisfactorily dissolves.

It Other methods have been described which allow the separation of Detergent components is achieved. For example, describes EP A 0,224,135 a dishwashing detergent in a form comprising a melt soluble in warm water, in one soluble in cold water Tablet is pressed. The document teaches a detergent composition, which consists of two parts, with the first part in the Vorspülflotte dissolves and the second part dissolves in the main washflask of the dishwasher.

EP B 0,055,100 describes a toilet block, which by combining a with slowly dissolving molding with a tablet is formed. The toilet block is destined to be in the cistern is given to a toilet and over a period of days, preferably dissolves weeks. As a means of controlling the resolution of the toilet block, the document teaches mixing one or more Löslichkeitssteuerungsmittel. examples for such solubility control agents are paradichlorobenzene, waxes, long chain fatty acids and Alcohols and esters thereof and fatty alkylamides.

detergent tablets for use in laundry washing or automatic dishwashing need essentially dissolve within one cycle of the washing machine or dishwashing machine, d. H. within 30 to 120 minutes.

Of the Applicant has found that by providing a detergent tablet, which is a compressed part and a non-encapsulating, not Compressed part includes, detergent components, previously considered not acceptable for Detergent tablets were considered, in a detergent tablet can be included. About that can out potentially reactive components of the detergent composition are effective be separated.

One Another advantage of using a detergent tablet, as here described, are the performance advantages that can be achieved can, that it is possible is to make the detergent tablet so that if necessary the compressed part and the non-compressed part different dissolution rates exhibit. Such performance benefits are achieved by adding detergent actives selectively dispensed into the wash solution at different times become.

SUMMARY THE INVENTION

• (a) einen komprimierten Teil, der einen Waschmittelwirkstoff umfasst; und
• (b) einen nicht komprimierten, nicht einkapselnden Teil, der einen Waschmittelwirkstoff umfasst; und
• (c) eine Überzugsschicht auf dem nicht komprimierten, nicht einkapselnden Teil, wodurch der nicht komprimierte, nicht einkapselnde Teil am komprimierten Teil angebracht oder befestigt ist.

According to the invention, there is provided a detergent tablet for use in a washing machine or dishwashing machine, the tablet comprising an enzyme and comprising:

• (a) a compressed part comprising a detergent active; and
• (b) a non-compressed, non-encapsulating member comprising a detergent active; and
• (c) a coating layer on the uncompressed, non-encapsulating member, whereby the non-compressed, non-encapsulating member is attached or attached to the compressed member.

Further Also, there is a process for making the laundry detergent tablets described herein provided.

DETAILED DESCRIPTION OF THE INVENTION

 Consequently has been found according to the invention, that detergent ingredients of a detergent tablet, the previously through the compression pressure applied to form the tablets were adversely affected, now included in a detergent tablet can be. examples for close these components Bleaching agents and enzymes. Furthermore, it has been found according to the invention that detergent ingredients of a detergent tablet from each other can be separated by placing one or more compatible components in a compressed one Part and one or more compatible components in one not compressed part of the tablet are included. Examples of components, that can interact and therefore possibly have to be disconnected include bleaches, bleach activators or catalysts, and enzymes; Bleaching agents and bleach catalysts or activators; Bleaching agents and surfactants; Alkalinity sources and enzymes.

Furthermore It may be advantageous to compress and uncompressed Part to provide so that they are different in the wash liquor dissolution rate dissolve. By controlling the dissolution rate the individual parts relative to each other and by selecting the detergent ingredients in the respective parts, the order of their release controlled in the wash liquor and the cleaning performance of the detergent tablet be improved. For example, it is often preferred that enzymes before the bleach and / or bleach activator in the wash liquor be delivered. It may also be preferred that a source of alkalinity is liberated faster into the wash liquor than other components the detergent tablet. It is also considered that it may be advantageous to produce a laundry detergent tablet according to the invention, in which the release of certain components of the tablet relative to delayed other components is.

It It is also considered that the tablet a variety of may include compressed or uncompressed parts. For example A variety of compressed parts can be arranged in layers can be, and / or a variety of non-compressed parts as individual sections of the tablet by a compressed Part are separated, be present. Thus, a first and a second and optional subsequent compressed and / or uncompressed Parts are present, each comprising a detergent active and wherein at least the first and second parts are different Detergent agents or -wirkstoffmischungen may include. A such a variety of compressed or uncompressed parts may be advantageous as it allows the production of a tablet, for example, a first and a second and optional subsequent parts so that they have different resolution speeds exhibit. Such performance benefits are achieved by adding detergent actives selectively dispensed into the wash liquor at different times become.

The detergent tablets described herein preferably have a weight between 15 g and 100 g, more preferably between 18 g and 80 g, even more preferably between 20 g and 60 g. The detergent tablets described herein, which are suitable for use in automatic dishwashing processes, most preferably have a weight between 20 g and 40 g. Detergent tablets suitable for use in fabric laundering processes most preferably have a weight of between 40 g and 100 g, more preferably between 40 g and 80 g, most preferably between 40 g and 65 g. The Weight ratio between the compressed part and the uncompressed part is generally greater than 0.5: 1, preferably greater than 1: 1, more preferably greater than 2: 1, even more preferably greater than 3: 1 or even 4: 1, most preferably at least 5: 1.

The Detergent tablets described herein have a childrens bite resistance (Child Bite Strength, CBS), which is generally larger than 10 kg, preferably greater than 12 kg, most preferably greater than 14 kg. The CBS will be according to the test specification measured by the US Consumer Product Safety Commission.

Child Bite Strength Test Method According to this Method is to place the tablet horizontally between two metal strips / plates placed. The upper and lower plates fold on one side attached so that the plates resemble a human jaw. On the top plate becomes an increasing downward Power exercised, which the closing movement of the jaw until the tablet breaks. The CBS of the tablet is a measure of the force in kilograms required to break the tablet.

The detergent tablets described herein generally have a dissolution rate of more than 0.33 g / min, preferably more than 0.5 g / min, more preferably greater than 1.00 g / min, more preferably greater than 2.00 g / m, most preferably more than 2.73 g / min. The dissolution rate is determined by means of the SOTAX resolution test method measured. For the purposes of the present invention, the resolution of Detergent Tablets Using a SOTAX (Trade Mark) Device, Model Number AT7, available from SOTAX.

SOTAX dissolution test method: The SOTAX device consists of a temperature controlled water bath with lid. 7 Pots are hung in the water bath. Hang from the bottom of the lid 7 electric stirring rods in positions the the positions of the pots in a water bath. The lid of the water bath also serves as Cover for the pots.

The SOTAX water bath is filled with water and the temperature measuring device is set to 50 ° C. Everyone Pot is then filled with 1 liter of deionized water, and the stirrer is set to rotate at 26.2 rad / s (250 rpm). The lid of the water bath is closed, so the temperature of the deionized water in the pots for 1 hour with the Equilibrate water in a water bath can.

The Tablets are weighed and one tablet is placed in each pot, subsequently the lid is closed. The tablet is visually monitored until it is complete disbanded Has. The time after which the tablet has completely dissolved is noted. The dissolution rate the tablet is expressed as the average weight (g) of dissolved tablet calculated in deionized water per minute.

compressed part

 Of the compressed part of the detergent tablet comprises at least one Detergent active, but may be a mixture of several detergent ingredients include, which are compressed. Any detergent tablet component, the conventionally Used in known detergent tablets is for inclusion in the compressed portion of the detergent tablets of this invention suitable. Suitable detergent actives are described below. Preferred Detergents include Builder Compound, Surfactant, Bleach, bleach activator, bleach catalyst, enzyme and a Alkalinity source.

One Detergent active or detergent active ingredients in the compressed Layer can exist optionally in combination with a carrier and / or a binder, for example, water, polymer (eg PEG), liquid silicate become. The detergent ingredients are preferably in particulate form (i.e., powder or granule form) and can be prepared by Any known method, for example conventional spray drying, Granulation or agglomeration, are produced. Then be the particulate Detergent active or the particulate detergent active ingredients using compressed to any suitable device for molding of compressed tablets, blocks, Bricks or briquettes is suitable, as described in more detail below described.

Not compressed, not encapsulating part

The uncompressed, non-encapsulating member (hereinafter the non-compressed member) comprises at least one detergent agent, but may comprise a mixture of several detergent ingredients sen. Detergent actives that are suitable for inclusion in the uncompressed portion include components that interact with one or more detergent components present in the compressed portion. Preferred components of the uncompressed part are, in particular, those which are adversely affected by the compression pressure of, for example, a compression tablet press. Examples of such detergent actives include, but are not limited to, surfactant, bleach, bleach activator, bleach catalyst, enzyme, corrosion inhibitor, perfume and an alkalinity source. These components are described in more detail below. The detergent active may be in any form, for example, in particulate form (ie, powder or granule form), gel form, or liquid form. The uncompressed part may also optionally comprise a carrier component in addition to a detergent active. The detergent active may be present prior to combination with a carrier component in the form of a solid, gel or liquid.

Of the uncompressed part of the detergent tablet may be in solid, gel or more fluid Form present.

The Detergent tablet of the present invention requires that the uncompressed part is fed to the compressed part so that the compressed part and the non-compressed part are each other touch. The uncompressed part may be in solid or flowable form fed to the compressed part become. If the uncompressed part is in solid form, it is prepared in advance, optionally shaped and then the compressed Part fed. Subsequently The uncompressed part is compressed to a preformed one Part attached, for example by adhesion or by introducing the uncompressed part on or in a cooperating surface of the compressed part. Preferably, the compressed part comprises a pre-made depression or mold into which the non-compressed Part is introduced.

Of the uncompressed part is preferable to the compressed part in flowable form fed. Subsequently, will the non-compressed part is attached to the compressed part, by putting a cover over the uncompressed layer is formed to this at the compressed Part to attach.

Preferably The compressed part comprises a pre-made depression or shape (hereinafter referred to as 'shape'), in which the non-compressed part is introduced. In an alternative embodiment includes the surface of the compressed part more than one shape into which the non-compressed part can be introduced. The shape or shapes preferably take at least partially one or more non-compressed parts on. The non-compressed part or non-compressed parts are then placed in the mold and attached to the compressed part, as described above.

Of the uncompressed part may comprise particles. The particles can pass through Any known method, for example conventional Spray drying, Granulation, encapsulation or agglomeration. Particles are formed by forming a coating layer over the uncompressed part attached to the compressed part.

If the detergent tablet more than one non-compressed part includes, can the first and the second and optional subsequent non-compressed Parts include particles that are essentially a different average Have particle size. By substantially different average particle size is meant that the difference between the average particle size of the first and the second and / or subsequent compositions are larger than 5%, preferably greater than 10%, more preferably greater than 15% or even 20% of the smaller average particle size.

The average particle size of here used particulate Detergent ingredients are made by means of a series of Tyler sieves calculated. The series consists of a number of sieves, each with a different opening size. rehearse a composition of detergent active ingredients are characterized by the Sieve row (usually 5 sieves) sieved. The weight of one in the Sieve held back Composition sample is graphed against the opening size of the screen. The average particle size of the composition is defined as the opening size, would pass through the 50% by weight of the composition sample.

In another embodiment, the first and second and optional subsequent detergent agent compositions have a substantially different density so that the difference between the density of the first and second and / or subsequent compositions is greater than 5%, preferably greater than 10%. more preferably greater than 15% or even 20% of the lower density is. The density of the particulate detergent ingredients composition can be measured by any known method suitable for measuring the density of particulate matter.

Preferably is the density of the composition of detergent ingredients based a simple funnel / cup device measured, consisting from a conical funnel, which is stiffly formed on a base and equipped with a flap valve at its lower end, to enable that the contents of the funnel into an axially aligned cylindrical Cup is emptied, which is located under the funnel. Of the Funnel is 130 mm high and has an inside diameter of 130 mm or 40 mm at its upper or lower end. He will be like that attached so that the lower end 140 mm above the upper surface of Base is located. The cup has a total height of 90 mm, an interior height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

A Density measurement is done by hand by adding the composition is poured into the funnel. Once the funnel is full, will the flap valve opened, and powder is run through the funnel, overfilling the beaker. The stuffed Cup is taken out of the frame, and excess powder is made by passing a Tool with straight edge, z. B. a knife, over his upper edge removed. Subsequently will the filled Cup weighed, and the value obtained for the weight of the powder is doubled to give a bulk density in grams / liter. repeated Measurements are made as required.

tablets, where one or more of the non-compressed parts are particles and the average particle size and / or density of the first and the second and optionally subsequent uncompressed Parts are essentially different, are preferred when the first and the second and optionally subsequent uncompressed Share different resolution speeds must have.

If the non-compressed part comprises a solidified melt The melt is made by adding a composition containing a Detergent active and an optional carrier component or optional carrier components includes until over heats up its melting point is going to be a flowable melt to build. Subsequently becomes the flowable melt poured into a mold and allowed to cool calmly. While the melt cools, it becomes firm and takes the shape of the mold at ambient temperature at. If the composition contains one or more carrier components includes, can the carrier component or the carrier components to about to be heated to their melting point, and subsequently a detergent active may be added. Carrier components, which are suitable for producing a solidified melt, are usually non-active components that are heated above the melting point can, to a liquid to form, and cooled can be to form an intermolecular matrix, the detergent actives effectively include can. A preferred non-active carrier component is an organic Polymer that is solid at ambient temperature. Preferably the non-active detergent component polyethylene glycol (PEG). The compressed part of the detergent tablet preferably delivers a mold to absorb the melt.

Of the flowable, not compressed part may be in a form that has a dissolved or comprises suspended detergent active. The flowable, not Compressed part can harden over time to go through one of the above described a solid, semi-solid or high-viscosity, liquid to form uncompressed part. In particular, the flowable, not cure compressed part by evaporation of a solvent. Solvent, to the relevant Use are suitable any known solvent lock in, in which a binder is soluble is. Preferred solvents can be polar or can be non-polar Water, alcohol (for example ethanol, acetone) and alcohol derivatives lock in. In an alternative embodiment can be more than a solvent be used.

The flowable, uncompressed part may comprise one or more binders. Any binder which causes the composition to become solid, semi-solid or highly viscous over time is contemplated for use herein. Without wishing to be bound by theory, it is believed that mechanisms by which the binder causes a non-solid composition to become solid, semi-solid, or highly viscous include: chemical reaction (such as chemical cross-linking) or interaction between two or more components flowable compositions; mixing or physical interaction of the binder with a component of the composition. Preferred binders include a sugar / gelatin combination, starch, glycerol and organic polymers. The sugar can be any monosaccharide (eg, glucose), disaccharide (eg, sucrose or Maltose) or polysaccharide. The most preferred sugar is the commonly available sucrose. For the purposes of the present invention, Type A or Type B gelatin can be used, available for example from Sigma. Type A gelatin is preferred because it is more stable compared to Type B under alkaline conditions. Preferred gelatin also has a bloom strength between 65 and 300, most preferably between 75 and 100. Preferred organic polymers include polyethylene glycol (PEG) having a molecular weight of from 500 to 10,000, preferably from 750 to 8,000, most preferably from 1,000 to 6,000, available from Hoechst.

If the non-compressed part is an extrudate becomes the extrudate by premixing the detergent ingredients with optional carrier components prepared to form a viscous paste. The viscous paste is then removed by means of a suitable, generally available extrusion device, for example, a single or twin screw extruder, available for Example of APV Baker, Peterborough, United Kingdom extruded. Subsequently is the extrudate either after delivery to the compressed part or before dispensing to the compressed part of the detergent tablet tailored. Preferably, the compressed part comprises the tablet a mold into which the extruded non-compressed part is inserted can be.

Of the uncompressed part is coated with a coating layer. The coating is used to compress an uncompressed part Part to install.

The coating layer preferably comprises a material which after contact with the compressed and / or the non-compressed parts within preferably less before than 15 minutes, more preferably less than 10 minutes, more preferably less than 5 minutes, most preferably less than 60 seconds is fixed. Preferably, the coating layer is water-soluble. Preferred coating layers include materials that are selected are from the group consisting of fatty acids, alcohols, diols, esters and Ethers, adipic acid, Carboxylic acid, dicarboxylic acid, Polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA), Polyethylene glycol (PEG) and mixtures thereof. Preferred carbon or dicarboxylic acids preferably comprise an even number of carbon atoms. Preferably, carboxylic or dicarboxylic acids comprise at least 4, more preferably at least 6, more preferably at least 8 carbon atoms, most preferably between 8 and 13 carbon atoms. preferred Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and Mixtures thereof. Preferred fatty acids are those with a Carbon chain length from C12 to C22, most preferably from C18 to C22. The coating layer may also preferably include a disruptor. The coating layer is generally in a proportion of at least 0.05%, preferably at least 0.1%, more preferably at least 1%, most preferably at least 2% or even at least 5% of the detergent tablet is present.

When alternative embodiment can the coating layer encapsulate the detergent tablet. In this embodiment is the coating layer in a proportion of at least 4%, more preferably at least 5%, most preferably at least 10% of the detergent tablet is present.

In a preferred embodiment include the compressed and / or uncompressed parts and / or the coating layer additionally a disruptor. The disruptor may be a decomposing agent or a foaming be. Suitable disintegrating agents include agents that upon contact swell with water or that the water inflow and / or outflow by forming channels in the compressed and / or uncompressed parts. Any known disintegrating agents or foaming agents, for use in laundry washing or dishwashing applications are suitable, are considered for the relevant use drawn. Suitable disintegrating agents include starch, starch derivatives, Alginates, carboxymethylcellulose (CMC), CMC-based polymers, Sodium acetate, alumina. Suitable foaming agents are those which generate a gas on contact with water. Suitable foaming agents can oxygen, Be nitrogen dioxide or carbon dioxide evolving species. Examples for preferred foaming can selected be from the group consisting of perborate, percarbonate, carbonate, Bicarbonate and carboxylic acids, like citric acid or maleic acid.

One Advantage of including a disruptor in the detergent tablet The present invention is in the transport, storage and Handling advantages that can be achieved by the hardness of the Detergent tablet increased without adversely affecting the cleaning performance.

method

• (a) Komprimieren eines Waschmittelwirkstoffs zum Bilden eines komprimierten Teils;
• (b) Zuführen eines nicht komprimierten, nicht einkapselnden Teils, der einen Waschmittelwirkstoff umfasst, zu dem komprimierten Teil; und anschließend
• (c) Beschichten von zumindest einem Teil des nicht komprimierten Teils mit einer Überzugsschicht, um den nicht komprimierten Teil am komprimierten Teil anzubringen oder zu befestigen.

According to the invention, a method for producing a detergent tablet for Ge used in a washing machine or dishwashing machine, the tablet comprising an enzyme, the method comprising the steps of:

• (a) compressing a detergent active to form a compressed part;
• (b) supplying an uncompressed, non-encapsulating member comprising a detergent active to the compressed member; and subsequently
• (c) coating at least a portion of the uncompressed portion with a coating layer to attach or secure the uncompressed portion to the compressed portion.

As described above, the detergent tablets described herein are by separately preparing the composition of detergent actives, which respectively the compressed part and the uncompressed one Make up part, and subsequent Respectively or adhering the composition of the uncompressed part made to or on the compressed part.

The compressed part is made by obtaining at least one detergent active and optionally pre-mixed with carrier components. Any premixing is carried out in a suitable mixer, for example a tray mixer, a rotary drum, a vertical mixer or a high shear mixer. Preferably, dry particulate components are mixed in a mixer as described above, and liquid components are applied to the dry particulate components, for example, by directly spraying the liquid components onto the dry particulate components. The resulting composition is then formed into a compressed part in a compression step by any known suitable device. Preferably, the composition is formed into a compressed part by means of a tablet press, wherein the tablet is made by compressing the composition between an upper and a lower punch. In a preferred embodiment of the present invention, the composition is placed in a die cavity of a tablet press and compressed to form a compressed part, with a pressure of preferably more than 6.3 KN / cm ² , more preferably more than 9 KN / cm ² , most preferably more than 14.4 KN / cm ^{2 is} applied.

Around to form a preferred tablet of the invention, wherein the compressed Part provides a mold for receiving the uncompressed part, the compressed part is made using a modified tablet press, the modified upper and / or lower stamps made. The upper and lower punches of the modified tablet press will be modified so that the compressed part one or more wells provides that form a shape or forms in which the non-compressed Part is introduced.

Of the non-compressed part comprises at least one detergent active. When the uncompressed part is more than one detergent active includes, the components are known by any known premixed suitable mixing device. Additionally, the uncompressed Part of a carrier include, with which the detergent ingredients are combined. Of the uncompressed part can be made in solid or flowable form. Once made, the composition is compressed Part fed. The non-compressed part can by manual dispensing or by means of a dosing nozzle or an extruder supplied to the compressed part. If the compressed part has a shape, it becomes uncompressed Part preferably using a precise dispensing device, for example, a metering nozzle, such as a differential scale dosing screw, available from Optima, Germany, or an extruder, introduced into the mold.

If the flowable, not Compressed part is in particulate form, includes the method the feeding a flowable, not compressed part to the compressed part in a dispensing step and subsequently coating at least a portion of the uncompressed portion with a coating layer, so that the coating layer causes the non-compressed part substantially at the compressed part sticks.

It is also considered that the compressed part with a Variety of shapes can be produced. The variety of shapes is then filled with an uncompressed part. It will also be considered pulled that each shape with another non-compressed part filled can be, or alternatively, any shape with a variety of various non-compressed parts are filled.

detergent ingredients

The compressed portion of the laundry detergent tablets described herein is made by compression of a composition of detergent actives. A suitable composition can be a variety including various detergent ingredients, including builders, surfactants, enzymes, bleaches, alkalinity sources, colorants, perfume, lime soap dispersants, organic polymeric compounds, including polymeric dye transfer inhibitors, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilizers, corrosion inhibitors, suds suppressors, solvents, fabric softeners, optical brighteners and hydrotropes.

Especially preferred detergent actives include a builder compound, a surfactant, an enzyme and a bleach.

Builder Connection

The Detergent tablets of the present invention preferably contain a builder compound, typically in a proportion of From 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition of detergent ingredients is present.

Water-soluble builder compound

suitable water-soluble Builder compounds include the water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals which are not more than two carbon atoms are separated from one another, carbonates, bicarbonates, Bristles, phosphates and mixtures of any of the foregoing.

The Carboxylate or polycarboxylate builders can be monomeric or oligomeric Type, although monomeric polycarboxylates for cost and performance reasons in Are generally preferred.

suitable Carboxylates with a carboxy group include the water-soluble ones Salts of lactic acid, glycolic acid and Ether derivatives thereof. Polycarboxylates with two carboxy groups include 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 with three carboxy groups include in particular water-soluble citrates, Aconitrates and citraconates as well as succinate derivatives such as carboxymethyloxysuccinates, described in British Patent No. 1,379,241, lactoxysuccinates, described in British Patent No. 1,389,732, and aminosuccinates, described in the Dutch Application 7205873, and the oxypolycarboxylate materials, such as 2-oxa-1,1,3-propanetricarboxylates, described in British Patent No. 1,387,447.

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

alicyclic and heterocyclic polycarboxylates include cyclopentancis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofurant tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives, which are disclosed in British Patent No. 1,425,343.

The preferred polycarboxylates of the above are hydroxycarboxylates with up to three carboxy groups per molecule, especially citrates.

The parent acids the monomeric or oligomeric polycarboxylate chelating agent or Mixtures thereof with their salts, eg. As citric acid or Citrate / citric acid mixtures, are also considered useful Builder components are considered.

Borate builders and builders that contain borate-forming materials, which are disclosed in U.S. Pat Detergent storage or washing conditions can produce borate, too are used, but under washing conditions below 50 ° C, in particular below 40 ° C not preferred.

Examples for carbonate builder are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultrafine calcium carbonate, as disclosed in German Patent Application No. 2,321,001 on November 15, 1973, disclosed.

Especially preferred builder compounds for use in the present invention Invention are water-soluble Phosphate builder. 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, Natriumpolymeta / phosphate, in which the degree of polymerization in the range from 6 to 21, and salts of phytic acid.

specific examples for 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 polymeta / phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.

Partially soluble or insoluble Builder Connection

The detergent tablets of the present invention may contain a partially soluble or insoluble builder compound. Partially soluble and insoluble builder compounds are particularly suitable for use in tablets made for use in laundry washing 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 sodium layer silicates of the general formula are preferred NaMSi _x O _{2 + 1} · yH ₂ O wherein 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 'plate' structure, such as the so-called δ-layer structure, as in EP 0 164514 and EP 0 293640 described.

method for the preparation of crystalline sheet silicates of this type in DE A 3417649 and DE A 3742043. For the purpose of the present The invention has x in the above general formula Value of 2, 3 or 4 and is preferably 2.

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

The Crystalline layered sodium silicate material is in granular detergent compositions preferably as a particulate Fabric in intimate mixture with a solid, water-soluble, ionizable material, as in PCT Patent Application No. WO92 / 18594 described. The solid, water-soluble, ionizable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.

Examples of substantially water-insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na _z [(AlO ₂ ) _z (SiO ₂ ) y] .xH ₂ O wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0 , 5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is in hydrogenated form and is preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in bound form.

The Aluminosilicate zeolites can Naturally occurring materials, but are preferably synthetic derived. Synthetic crystalline aluminosilicate ion exchange materials are under the designations zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS and mixtures thereof.

One preferred method of synthesis of aluminosilicate zeolites is that of Schoeman et al. described (published in Zeolite (1994) 14 (2), 110-116), wherein the author describes a method for producing colloidal aluminosilicate zeolites describes. The colloidal aluminosilicate zeolite particles should preferably be such that not more than 5% of the particles one Size of more than 1 μm in diameter and not more than 5% of the particles a size of less than 0.05 μm in diameter. Preferably, the aluminosilicate zeolite particles have an average particle size diameter between 0.01 μm and 1 μm, more preferably between 0.05 μm and 0.9 μm, most preferably between 0.1 μm and 0.6 μm.

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

preferred Aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When used as a component of a detergent composition colloidal aluminosilicate zeolites, especially colloidal zeolite A, an increased Builder performance in terms of better stain removal. A increased Builder Performance will also be in terms of decreased fabric encrustation and a better preservation of the whiteness of the substance, problems that are believed to be they are related to poorly built detergent compositions.

A surprising The finding is that mixed aluminosilicate zeolite detergent compositions, comprising colloidal zeolite A and colloidal zeolite Y, compared to commercially -available Zeolite A same weight the same performance in masking of calcium ions. Another surprising finding is that the above described mixed aluminosilicate zeolite detergent compositions across from commercially available Zeolite A same weight better masking performance of magnesium ions.

surfactant

surfactants are preferred detergent actives of the compositions described herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof. Because products for automatic dishwashers low-foaming type should be foaming of the surfactant system for use in dishwashing processes are suppressed or more preferably less foaming, usually be nonionic type. One through surfactant systems used in purification processes for washing clothes foaming does not have to be used in the same way Dimensions are suppressed, as is for wash the dishes is required. The surfactant is typically in one portion from 0.2 wt% to 30 wt%, more preferably from 0.5 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the composition of detergent ingredients available.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes and species of these surfactants is disclosed in U.S. Patent 3,929,678, issued to Laughlin and Heuring on December 30, 1975. A listing of suitable cationic surfactants is disclosed in U.S. Patent 4,259,217, issued to Murphy on March 31, 1981. A list of surfactants, which are usually used in dishwashing detergent compositions is disclosed, for example, in EP A 0414 549 and in the PCT applications No. WO 93/08876 and WO 93/08874.

nonionic surfactant

 in the Essentially can any nonionic surfactants useful for cleaning purposes, be included in the detergent tablet. Preferred, non-limiting classes suitable nonionic surfactants are listed below.

nonionic ethoxylated alcohol surfactant

 The Alkylethoxylate condensation products of aliphatic alcohols with From 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondarily be and contain generally 6 to 22 carbon atoms. Particularly preferred the condensation products of alcohols with an alkyl group 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole Alcohol.

endcapped alkyl alkoxylate

A suitable end-capped alkyl alkoxylate surfactant is the epoxy-capped poly (oxyalkylated) alcohols represented by 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 radical having 2 to 26 carbon atoms; x is an integer having an average value of 0.5 to 1.5, more preferably 1; and y an integer with one Value of at least 15, more preferably at least 20.

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

Ether-capped poly (oxyalkylated) alcohols

Preferred surfactants for use herein include ether-capped poly (oxyalkylated) alcohols having 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 radical having 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30, and when x is 2 or more, R ^{3 may be the} same or different, and k and j are integers having an average value of 1 to 12, and more preferably 1 to 5 ,

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. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms are most preferred for R ³ . Preferably, x is an integer having an average value of 1 to 20, more preferably 6 to 15.

As described above, in the preferred embodiments, R ^{3 may be the} same or different when x is greater than two. That is, R ³ may vary between any of the alkyleneoxy units as described above. Thus, R ³ may be, for example, selected to form ethyleneoxy (EO) or propyleneoxy (PO), when x is 3, and may be in the order between (EO) (PO) (EO), (EO) (EO) (PO ), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO), and (PO) (PO) (PO). Of course, the integer number three is chosen only as an example, and the variation may be much larger with a higher integer value for x and include, for example, numerous (EO) units and a much smaller number of (PO) units.

Especially preferred surfactants as described above include those with a low cloud point less than 20 ° C one. These low cloud point surfactants can then used in conjunction with a high cloud point surfactant, as detailed below described to achieve excellent grease cleaning benefits.

The most preferred ether-capped poly (oxyalkylated) alcohol surfactants are those wherein k is 1 and j is 1 such that the surfactants have the following 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 having an average value of 1 to 30, preferably 1 to 20 and more preferably 6 to 18. Most preferred are surfactants wherein R ¹ and R ^{2 are} in the range of 9 to 14, R ^{3 is} H to form ethyleneoxy, and x is in the range of 6 to 15.

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

These Surfactants have significant compared to conventional surfactants Improvements in their stain removal and film forming properties and the removal of grease spills when in contact with surfactants with a high cloud point be used.

Generally expressed can the ether-capped poly (oxyalkylated) alcohol surfactants of the present invention Be prepared by adding an aliphatic alcohol with an epoxide is reacted to form an ether, which then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol, to form the novel compounds of the present invention. examples for Process for preparing the ether-capped, poly (oxyalkylated) Alcohol surfactants are described below:

Preparation of C _12/14 alkyl glycidyl ether

A C _12/14 fatty alcohol (100.00 g, 0.515 mol) and stannic chloride (0.58 g, 2.23 mmol, available from Aldrich) are dissolved in a 500 ml three-necked round bottom flask equipped with a Cooler, an argon inlet, an addition funnel, a magnetic stirrer and an internal temperature probe is combined. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise to keep the temperature between 60-65 ° C. After stirring at 60 ° C for an additional hour, the mixture is cooled to room temperature. The mixture is treated with a 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) while being mechanically stirred. After the addition is complete, the mixture is heated to 90 ° C for 1.5 hours, cooled and filtered with 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 (13.3 Pa (0.1 mm Hg)) provides the glycidyl ether as an oil.

Preparation of C _12/14 4-alkyl-C _9/11 ether capped alcohol surfactant

Neodol ^® 91-8 (20.60 g, 0.0393 mol 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 equipped with condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C, at which point C _12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 minutes. After being stirred at 60 ° C for 18 hours, the mixture is cooled to room temperature and dissolved in an equal portion of dichloromethane. The solution is passed through a 2.54 cm (1 inch) pad of silica gel while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then stripped in a Kugelrohr oven (100 ° C, 66.7 Pa (0.5 mm Hg)) to give the surfactant as an oil.

Nonionic ethoxylated / propoxylated fatty alcohol

The ethoxylated C ₆ -C ₁₈ fatty alcohols and the mixed ethoxylated / propoxylated C ₆ -C ₁₈ fatty alcohols are suitable surfactants for use herein, especially when they are water-soluble. Preferably, the ethoxylated fatty alcohols are the ethoxylated C ₁₀ -C ₁₈ fatty alcohols having a degree of ethoxylation of from 3 to 50, most preferably these are the ethoxylated C ₁₂ -C ₁₈ fatty alcohols having a degree of ethoxylation of from 3 to 40. The mixed ethoxylated / propoxylated fatty alcohols preferably 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 1500 to 1800 and is water-insoluble. Examples of compounds of this type include certain of the commercially available Pluronic ^™ surfactants marketed by BASF.

Nonionic EO condensation products with propylene oxide / ethylenediamine adducts

The condensation products of ethylene oxide with the product of the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ^™ compounds marketed by BASF.

mixed nonionic surfactant system

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

"Cloud point" as used herein is a well known property of nonionic surfactants that results from the surfactant becoming less soluble with increasing temperature, the temperature the appearance of a second phase is known as the "cloud point" (see Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is defined as an ingredient of a nonionic surfactant system having a cloud point of less than 30 ° C, preferably less than 20 ° C, and most preferably less than 10 ° C Low cloud point surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and reverse polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) block polymers., These low cloud point nonionic surfactants also include, for example, ethoxylated-propoxylated alcohol (z. B. poly-Tergent SLF18 ^® Olin Corporation), epoxy-capped poly (oxyalkylated) alcohols (eg. as the poly-Tergent ^® SLF18B series of non-ionic compounds of the Olin Corporation, as described for example in WO 94/22800, published on October 13, 1994, by Olin Corporation) and the ether-capped poly (oxyalkylated en) alcohol surfactants.

nonionic Surfactants can optionally contain propylene oxide in an amount of up to 15 wt .-%. Other preferred nonionic surfactants can be prepared by the methods in U.S. Patent 4,223,163, issued September 16, 1980 at Builloty.

nonionic Surfactants with low cloud point include in addition a polyoxyethylene / polyoxypropylene block polymer compound.

Polyoxyethylene / polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. Certain of the block polymer surfactant compounds designated PLURONIC ^®, REVERSED PLURONIC ^® and Tetronic ^® by the BASF-Wyandotte Corp., Wyandotte, Michigan, in ADD compositions of the invention are suitable. Preferred examples include REVERSED PLURONIC ^® 25R2 and TETRONIC ^® 702. Such surfactants are also suitable nonionic surfactants with low cloud point herein generally.

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

For the purpose It is also preferred in the present invention that the high cloud point nonionic surfactant has a value for the hydrophilic-lipophilic balance ("HLB", see Kirk Othmer above) in the range of 9 to 15, preferably 11 to 15. Such materials include, for example, Tergitol 15S9 (available from Union Carbide), Rhodasurf TMD 8.5 (available from Rhone-Poulenc) and Neodol 91-8 (available from Shell).

Another preferred high cloud point nonionic surfactant is derived from a straight or preferably branched or secondary fatty alcohol having from 6 to 20 carbon atoms (C ₆ -C ₂₀ alcohol), including secondary alcohols and branched chain primary alcohols. Preferably, high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed branched C9 / 11 or C11 / 15 alcohol ethoxylates having an average of 6 to 15 moles, preferably 6 to 12 moles and most preferably 6 to 9 moles of ethylene oxide per Mol of alcohol are condensed. Preferably, the thus-derived ethoxylated nonionic surfactant has a narrow ethoxylate distribution relative to the average.

In a preferred embodiment includes the detergent tablet containing such a mixed surfactant system Also includes an amount of water-soluble salt for conductivity in deionized water, measured at 25 ° C, of more than 3 millisiemens / cm, preferably more than 4 millisiemens / cm, most preferably more to provide 4.5 millisiemens / cm.

In another preferred embodiment, the mixed surfactant system dissolves in water having a hardness of 1.246 mmol / L in any suitable cold feed automatic dishwasher to produce a Solution with a surface tension of less than 0.4 Pa (4 dynes / cm ² ) at less than 45 ° C, preferably less than 40 ° C, most preferably less than 35 ° C.

In another preferred embodiment become the surfactants with a high cloud point and the low cloud point surfactants the mixed surfactant system so that either the surfactant with high cloud point or the low cloud point surfactant is present in a first matrix and the other in a second Matrix is present. For the purposes of the present invention For example, the first matrix may be a first particulate matter and the second Matrix a second particulate Be fabric. A surfactant may be by any suitable known Process on a particulate Preferably, the surfactant is applied to the particulate matter sprayed. In a preferred aspect, the first matrix is the compressed one Part and the second matrix of the non-compressed part of the detergent tablet of the present invention. Preferably, the surfactant is low cloud point in the compressed part and the high cloud point surfactant in the uncompressed portion of the detergent tablet of the present invention Invention available.

anionic surfactant

 in the Essentially, any are for Suitable cleaning anionic surfactants suitable. These can be salts (including For example, sodium, potassium, ammonium salts and substituted Ammonium salts, such as mono-, di- and triethanolamine salts) of the anionic Sulfate, sulfonate, carboxylate and sarcosinate surfactants. anionic Sulfate surfactants are preferred.

Other anionic surfactants include the isethionic acids, such as the acyl isethionic acids, 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), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

anionic sulphate

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

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

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ₁₀ -C ₁₈ alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ₁₁ -C _{18 -,} most preferably a C ₁₁ -C ₁₅ alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.

In In a particularly preferred aspect of the invention are mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such mixtures are disclosed in PCT Patent Application No. WO 93/18124 disclosed.

anionic sulfonate

Suitable anionic sulfonate surfactants for use herein include the salts of linear C ₅ -C ₂₀ alkyl benzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any of these Mixtures thereof.

anionic carboxylate

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

Suitable alkyl ethoxy carboxylates include those of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ wherein R is a C ₆ to C ₁₈ alkyl group, x is in the range of 0 to 10, and the ethoxylate distribution is the amount of material by weight is less than 20% when x is 0 and M is a cation. Suitable alkylpolyethoxypolycarboxylate 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 from 1 to 25, R ₁ and R _{2 are} selected are selected from the group consisting of hydrogen, a methyl acid residue, a succinic acid residue, a hydroxysuccinic acid residue and mixtures thereof, and R _{3 is} selected from the group consisting of hydrogen or unsubstituted hydrocarbyl having from 1 to 8 carbon atoms and mixtures thereof.

suitable Soap surfactants include the secondary soap surfactants which have a Carboxyl unit bound to a secondary carbon. Preferred secondary Soap surfactants for use herein are water-soluble Elements selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain Soaps can also as suds suppressor be included.

Alkali-Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOM, wherein 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 Oleylmethylsarcosinate in the form of their sodium salts.

amphoteric surfactant

suitable amphoteric surfactants for this purpose Use include 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, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof having from 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 of 1 to 3 or a polyethylene oxide group of 1 to 3 ethylene oxide groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxide, and C _10-18 -Acylamidoalkyldimethylaminoxid.

A suitable example of an alkylaphodicarboxylic acid is Miranol ^™ C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

zwitterionic Surfactants can also included in the present detergent compositions become. These surfactants can generally as derivatives of secondary and tertiary amines, Derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary Ammonium, quaternary Phosphonium or tertiary Sulfonium compounds are described. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for this purpose Use.

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

cationic surfactants

 In Cationic ester surfactants used in this invention are preferred water-dispersible compounds having surfactant properties, comprising at least one ester (i.e., -COO-) bond and at least one cationic loaded group. Other suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat. Nos. 4,282,842, 4,239,660 and 4260529 discloses.

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

enzymes

 In In the present invention, an enzyme is an essential feature the detergent tablet. The enzymes are selected from the group consisting 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 from that.

preferred Enzymes include protease, amylase, lipase, peroxidases, cutinase and / or cellulase in association with one or more plant cell wall degrading agents Enzymes.

The cellulases usable in the present invention include cellulase from bacteria or fungi. Preferably, they have a PH optimum between 5 and 12 and an activity of over 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., J61078384 and WO96 / 02653 which disclose cellulases from fungi formed from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. EP 739 982 describes cellulases isolated from a novel Bacillus species. Suitable cellulases are also disclosed in GB A 2,075,028, GB A 2,095,275, DE OS 2,247,832 and WO95 / 26398.

Examples of such cellulases are cellulases which are formed from a strain of Humicola insolens (Humicola grisea var. Thermoidea), in particular the Humicola strain DSM 1800. Other suitable cellulases are Humicola insolens-derived cellulases which have a molecular weight of 0.08 ag (50 kDa) and an isoelectric point of 5.5 and contain 415 amino acids and an endoglucanase of 0.07 ag ( ^~ 43 kD). derived from Humicola insolens DSM 1800 showing cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases of Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published September 29, 1994. Particularly suitable cellulases are the cellulases which have color care benefits. Carezyme and Celluzyme (Novo Nordisk A / S) are particularly useful. See also WO91 / 17244 and WO91 / 21801. Other suitable cellulases for fabric care and / or having cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

The Cellulases are normally in the detergent composition in concentrations of 0.0001% to 2% active enzyme, based on the weight of the detergent composition.

Peroxidase enzymes are used in combination with oxygen sources, e.g. Percarbonate, perborate, persulfate, hydrogen peroxide. They are used for "solution bleaching," ie, to prevent dyes or pigments removed from substrates during washing from being transferred to other substrates in the wash solution. Peroxidase enzymes are well known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase Peroxidase-containing detergent compositions are described, for example, in PCT International Applications WO 89/099813, WO89 / 09813 and in the European patent application EP 540,784 disclosed. Also suitable is the laccase enzyme.

preferred amplifier are substituted phenthiazine and phenoxasine-10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-Phenoxazinopropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted Syringates (C3-C5 substituted alkylsyringates) and phenols. sodium or perborate are preferred sources of hydrogen peroxide.

The Cellulases and / or peroxidases are in the detergent composition normally in concentrations from 0.0001% to 2% active enzyme, based on the weight of the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases. Include suitable lipase enzymes for use in laundry detergents those formed 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 which show a positive immunological cross-reaction with the antibody of the lipase formed by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase Lipomax ^® and ^® (Gist-Brocades) and Lipolase ^® and Lipolase Ultra ^® (Novo) which have proved to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes which are in EP 258,068 , WO 92/05249 and WO 95/22615 to Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 to Unilever.

Also suitable are cutinases [EC 3.1.1.50], which as a special kind can be viewed by lipase, as lipases that do not require interfacial activation. The addition of cutinases to detergent compositions is e.g. 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 in the detergent composition normally in concentrations from 0.0001% to 2% active enzyme, based on the weight of the detergent composition.

Suitable proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protease with a maximum efficacy in the pH range of 8 to 12 is obtained from a Bacillus strain. developed and sold as ESPERASE ^® by Novo Industries A / S, Denmark, hereafter referred to as "Novo." The production of this enzyme and analogous enzymes is described in GB 1,243,784 described at Novo. Other suitable proteases include ALCALASE ^®, DURAZYM ^® and SAVINASE ^® from Novo and MAXATASE MAXACAL ^{® ®,} PROPERASE® ^® and MAXAPEM ^® (protein engineered Maxacal after) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application EP-A-251,446, herein called "Protease B", and those in European Patent Application 199,404, Venegas, published October 29, 1986, which contains a modified bacterial proteolytic serine enzyme, referred to herein as "protease A." Suitable herein is the so-called "protease C", which is a variant of an alkaline serine protease from Bacillus in which arginine at position 27 has been replaced by lysine, at position 104 valine has been replaced by tyrosine, at position 123 asparagine has been replaced by serine and at position 274 threonine has been replaced by alanine Protease C is in EP 451,244 , corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, especially protease C, are also included herein.

A preferred protease, termed "protease D", is a carbonyl hydrolase variant having a non-naturally occurring amino acid sequence derived from a precursor carbonyl hydrolase by substitution of several amino acid residues by another amino acid at a position in the carbonyl hydrolase, the position +76, preferably also in combination with one or more amino acid residue positions corresponding to those 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 subtilisin from Bacillus amyloliquefaciens, as in WO95 / 10591 and in the patent application of C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes", US 5,677,272 , described.

Also suitable for the present invention are proteases disclosed in the patent applications EP 251 446 and WO 91/06637, protease BLAP ^® described in WO91 / 02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant detergent-type protease-like protease useful herein is described in WO 94/25583 to Novo. Other suitable proteases are in EP 516 200 described by Unilever ben.

Other preferred protease enzymes include protease enzymes which a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence which is derived by substitution of multiple amino acid residues a precursor carbonyl hydrolase through other amino acids, the several being in the precursor enzyme substituted amino acid residues Position +210 in combination with one or more of the following Remains correspond to: +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, with the numbered positions of course occurring subtilisin from Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as subtilisin from Bacillus lentus). Preferred enzymes of this type include those one, the changes at the positions +210, +76, +103, +104, +156 and +166.

The proteolytic enzymes are in the detergent compositions of the present invention in a concentration of 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme, by weight of the composition, contain.

Amylases (α and / or β) can be included to remove carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S, published February 3, 1994, describes cleaning compositions containing amylase mutants. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β-amylases. Alpha-amylases are well known in the art and include those described in US Pat. No. 5,003,257, US Pat. EP 252,666 , WO / 91/00353, FR 2,676,456 . EP 285,123 . EP 525,610 . EP 368,341 and in British Patent No. 1,296,839 (Novo). Other suitable amylases are improved stability amylases described in WO94 / 18314, published August 18, 1994, and WO96 / 05295, Genencor, published February 22, 1996, and amylase variants with additional modification in the immediate starting material, available from Novo Nordisk A / S, disclosed in WO 95/10603, published in April 95. Also suitable are amylases which are disclosed in U.S. Pat EP 277 216 WO95 / 26397 and WO96 / 23873 (all to Novo Nordisk).

Examples of commercial α-amylases products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, all available from Novo Nordisk A / S, Denmark. WO95 / 26397 describes other suitable amylases: α-amylases, characterized in that they have a specific activity in a temperature range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10, which is at least 25 is% higher than the specific activity of Termamyl ^®, measured by the Phadebas ^® assay for α-amylase activity. Suitable variants of the abovementioned enzymes are those described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes having improved properties in terms of activity level and the combination of thermal stability and a higher level of activity are described in WO95 / 35382.

preferred Close amylase enzymes those described in WO95 / 26397.

The amylolytic enzymes are in the detergent compositions of present invention in a concentration of 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme, by weight of the composition, contain.

In a particularly preferred embodiment Detergent tablets of the present invention include amylase enzymes, in particular those described in WO95 / 26397, in Combination with a complementary Amylase.

By "complementary" is meant the addition of one or more amylases suitable for washing Examples of complementary amylases (α and / or β) are described below: WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S, describe cleaning compositions containing amylase mutants Other amylases known for use in cleaning compositions include both α- and β-amylases, α-amylases are well 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 in British Patent No. 1,296,839 (Novo). Other suitable amylases are improved stability amylases described in WO94 / 18314 and WO96 / 05295, Genencor, and amylase variants with additional modification in the immediate starting material, available from Novo Nordisk A / S, disclosed in WO 95/10603. Also suitable are amylases which are in EP 277 216 (Novo Nordisk) are. Examples of commercial α-amylases products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, all available from Novo Nordisk A / S, Denmark. WO95 / 26397 describes other suitable amylases: α-amylases, characterized in that they have a specific activity in a temperature range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10, which is at least 25 is% higher than the specific activity of Termamyl ^®, measured by the Phadebas ^® assay for α-amylase activity. Suitable variants of the abovementioned enzymes are those described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes having improved properties in terms of activity level and the combination of thermal stability and a higher level of activity are described in WO95 / 35382. Preferred complementary amylases for the present invention are the amylases sold under the tradename Purafect Ox Am ^®, described in WO 94/18314, WO96 / 05295 sold by Genencor; Termamyl ^®, Fungamyl.RTM ^®, Ban ^® and Duramyl ^®, all available from Novo Nordisk A / S, and Maxamyl ^® by Gist-Brocades.

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

The mentioned above Enzymes can have any suitable origin, such as plants, animals, Bacteria, fungi and yeasts. The origin may also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic). It can purified or non-purified forms of these enzymes are used become. Included by definition are also mutants of native enzymes. Mutants can z. B. by protein and / or Gene engineering, chemical and / or physical modifications native enzymes are obtained. usual Practice is also the expression of the enzyme via host organisms in which that for cloned the formation of the enzyme responsible genetic material has been.

The Enzymes are normally in concentrations in the detergent composition from 0.0001% to 2% of active enzyme, by weight of the detergent composition, contain. The enzymes can as separate individual components (granules produced by prilling, Granules, stabilized liquids, containing a single enzyme) or as mixtures of two or more enzymes (eg cogranulates) are added.

Other suitable detergent components that can be added are enzyme oxidation scavengers described in co-pending European Patent Application EP 553,607 are described. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A number of enzyme materials and means for their inclusion in synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo and US 3,553,139 , January 5, 1971 to McCarty et al. Enzymes are also in US 4,101,457 , Place et al., July 18, 1978, and in US 4,507,219 , Hughes, March 26, 1985. Enzyme materials useful in liquid detergent formulations and their inclusion in such formulations are disclosed in U.S. Pat US 4,261,868 , Hora et al., Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various methods. Enzyme stabilization methods are in US 3,600,319 , August 17, 1971, Gedge et al., EP 199,405 and EP 200,586 , October 29, 1986, Venegas, discloses and illustrates. For example, enzyme stabilization systems are also available in US 3,519,570 described. A useful Bacillus, sp. AC13, which provides proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

bleach

 A particularly preferred component of the composition of detergent active ingredients is a bleach. Suitable bleaching agents include chlorine and oxygen-releasing bleaches.

In a preferred aspect, the oxygen-releasing bleach contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid is carried out by an in situ reaction of the precursor with a hydrogen peroxide source. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred aspect, a precursor-formed organic peroxyacid is included directly in the composition. Compositions comprising mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a precursor-formed organic peroxyacid are also contemplated.

inorganic perhydrate

 The Detergent agent compositions preferably comprise a hydrogen peroxide source as an oxygen-releasing bleaching agent. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.

The inorganic perhydrate salts are usually in the form of the sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% and most preferably 5% by weight to 25% by weight of the compositions.

Examples for inorganic Perhydrate salts include perborate, percarbonate, perphosphate, persulphate and persilicate salts. The inorganic perhydrate salts are normal the alkali metal salts. The inorganic perhydrate salt may be crystalline Solid without additional Protection included. For certain Perhydrate salts, however, in the preferred embodiments of such granular compositions a coated form of the material used for a better Storage stability of the perhydrate salt in the granular product provides.

Sodium perborate may be in the form of the monohydrate of nominal formula NaBO ₂ H ₂ O ₂ or of the tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O.

Alkali metal percarbonates, especially sodium percarbonate, are preferred perhydrates for inclusion in compositions of the invention. Sodium percarbonate is ₂ CO ₃ .3H ₂ O ₂ corresponds to an addition compound having a formula corresponding to 2Na, and is available commercially as a crystalline solid obtained. Sodium percarbonate, a hydrogen peroxide addition compound, tends to release the hydrogen peroxide quite rapidly upon dissolution, which may increase the tendency for localized high levels of bleach to form. The percarbonate is most preferably included in such compositions in a coated form which provides stability within the product.

A suitable coating material which provides stability within the product comprises the mixed salt of a water-soluble alkali metal sulfate and carbonate. Such coatings were previously used together with coating methods in GB 1,466,799 granted to Interox on March 9, 1977. The weight ratio of mixed salt to percarbonate coating material ranges from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate and has the general formula Na ₂ SO ₄ .n. Na ₂ CO ₃ , where n is from 0.1 to 3, preferably n is from 0.3 to 1.0, and Most preferably, n is from 0.2 to 0.5.

Another suitable coating material which provides stability within the product comprises sodium silicate having a 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, which is preferably applied in a proportion of 2% to 10% (normally from 3% to 5%) of SiO ₂ , based on the weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating. Coatings containing silicate and borate salts or boric acids or other inorganic substances are also suitable.

Other coatings that Waxes, oils, Fat soaps can contain can also be used advantageously in the present invention.

Potassium is another inorganic perhydrate salt used in the present compositions is useful.

Peroxyacid bleach precursor

worin L eine Abgangsgruppe ist und X im Wesentlichen eine beliebige Funktionalität ist, so dass die bei Perhydrolyse gebildete Peroxysäure die folgende Struktur besitzt:

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form a peroxyacid. Peroxyacid bleach precursors can generally be represented as

wherein L is a leaving group and X is essentially any functionality such that the peroxyacid formed on perhydrolysis has the following structure:

Peroxyacid bleach precursor compounds are preferably in a concentration of 0.5% by weight to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.

suitable Peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, their precursor from a big one Diversity of classes selected could be. Suitable classes include 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 described in GB A 836988, 864798, 1147871, 2143231 and EPA 0170386.

leaving groups

 The Leaving group, hereinafter called L group, must be sufficiently reactive so that the perhydrolysis reaction can be within the optimal time frame (eg within a wash cycle). If L, however too reactive, this activator is difficult to use in a bleaching composition to stabilize.

und Mischungen davon, 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 R ³ ist, R⁵ eine Alkenylkette mit 1 bis 8 Kohlenstoffatomen ist und Y H oder eine lösungsvermittelnde Gruppe ist. R¹, R³ und R⁴ können jeweils durch im Wesentlichen eine beliebige funktionelle Gruppe substituiert werden, einschließlich beispielsweise Alkyl-, Hydroxy-, Alkoxy-, Halogen-, Amin-, Nitrosyl-, Amid- und Ammonium- oder Alkylammoniumgruppen.Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R ^{1 is} an alkyl, aryl or alkaryl group of 1 to 14 carbon atoms, R ^{3 is} an alkyl chain of 1 to 8 carbon atoms, R ^{4 is} H or R ³ , R ^{5 is} an alkenyl chain of 1 to 8 carbon atoms is and is YH or a solubilizing group. Each of R ¹ , R ³ and R ⁴ may be substituted by substantially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium 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 of 1 to 4 carbon atoms, M is a cation which imparts solubility to the bleach activator and X is an anion which imparts solubility to 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, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid at perhydrolysis.

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

Ac = COCH3; Bz = BenzoylAlso useful are the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, including, for example:

Ac = COCH3; Bz = benzoyl

Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl-substituted ureas. Suitable perbenzoic acid precursors of Imidazole type include N-benzoylimidazole and N-benzoylbenzimidazole, and other suitable N-acyl group-containing perbenzoic acid precursors N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:

Phthalic anhydride is another perbenzoic acid precursor compound useful herein:

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

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

Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursor provide in perhydrolysis substituted perbenzoic acids.

Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic acid precursors disclosed herein in which the benzoyl group is not positively unsaturated by essentially any one charged (ie non-cationic) functional group, including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.

worin R¹ eine Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist, R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist und L im Wesentlichen eine beliebige Abgangsgruppe sein kann. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann Aryl, substituiertes Aryl oder Alkylaryl mit Verzweigungen, Substitutionen oder beidem sein und kann synthetischer Herkunft oder natürlicher Herkunft sein, einschließlich beispielsweise Talgfett. 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 insgesamt nicht mehr als 18 Kohlenstoffatome enthalten. Amidsubstituierte Bleichaktivator-Verbindungen dieses Typs sind in EP A 0170386 beschrieben.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 having 1 to 14 carbon atoms, R ^{2 is} an arylene or alkarylene group having 1 to 14 carbon atoms, R ^{5 is} H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms and L im Essentially any leaving group can be. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be aryl, substituted aryl, or alkylaryl with branches, substitutions, or both, and may be of synthetic or natural origin, including, for example, tallow fat. Analogous structure variations are allowed for R ² . The substitution may 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 contain no more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP A 0170386.

cationic Peroxyacid precursor

cationic Peroxyacid precursor compounds form perhydrolysis cationic peroxyacids.

In Typically, cationic peroxyacid precursors are formed by the peroxyacid moiety a suitable peroxyacid precursor compound by a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, is substituted. Cationic peroxyacid precursors are typically as a salt with a suitable anion, such as a halide ion or a methylsulfate ion present in the compositions.

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

Cationic peroxyacid precursors are disclosed 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; 5,106,528; UK 1,382,594 ; EP 475,512 , 458,396 and 284,292; and in JP 87 318,332 described.

suitable cationic peroxyacid precursors any of the ammonium or alkylammonium-substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyl tetraacetyl glucose benzoyl peroxides.

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

A preferred cationically substituted alkyloxybenzenesulfonate has the formula:

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

worin n von 0 bis 12, insbesondere von 1 bis 5 ist.Other preferred cationic peroxyacid precursors of the class of N-acylated caprolactams include the trialkylammoniummethylene-alkylcaprolactams:

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

One Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) ethylsodium-4-sulfophenyl carbonate chloride.

Alkyl bleach precursor

Alkyl percarboxylic acid bleach precursor form in perhydrolysis percarboxylic acids. Preferred precursors of this type deep in perhydrolysis peracetic acid.

Preferred imidype alkyl percarboxylic acid precursor compounds include the N, N, N ¹ N ¹ tetraacetylated alkylenediamines wherein the alkylene group contains from 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include Sodium 3,5,5-trimethyl (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

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 eine beliebige Abgangsgruppe sein kann. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann ein geradkettiges oder verzweigtes Alkyl mit Verzweigungen, Substitutionen oder beidem sein und kann synthetischer Herkunft oder natürlicher Herkunft sein, einschließlich beispielsweise Talgfett. 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 insgesamt nicht mehr als 18 Kohlenstoffatome enthalten. Amidsubstituierte Bleichaktivator-Verbindungen dieses Typs sind in EP A 0170386 beschrieben.Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those having the following general formulas:

wherein R ^{1 is} an alkyl group having 1 to 14 carbon atoms, R ^{2 is} an alkylene group having 1 to 14 carbon atoms, and R ^{5 is} H or an alkyl group having 1 to 10 carbon atoms and L may be substantially 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 a straight chain or branched alkyl with branches, substitutions or both, and may be of synthetic or natural origin including, for example, tallow fat. Analogous structure variations are allowed for R ² . The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is before preferably H or methyl. R ¹ and R ⁵ should contain no more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP A 0170386.

Organic benzoxazine peroxyacid precursors

einschließlich der substituierten Benzoxazine des Typs

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

including the substituted benzoxazines of the type

wherein R _{1 is} H, alkyl, alkaryl, aryl, arylalkyl and wherein R ₂ , R ₃ , R ₄ and R _{5 may be} the same or different substituents selected from H, halo, 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:

Formed as a precursor organic peroxyacid

The organic peroxyacid bleach system can additionally or as an alternative to an organic peroxyacid bleach precursor compound contain an organic peroxyacid formed as a precursor, typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of 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 mit Verzweigungen, Substitutionen oder beidem sein und kann synthetischer Herkunft oder natürlicher Herkunft sein, einschließlich beispielsweise Talgfett. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Aryl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen umfassen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten insgesamt nicht mehr als 18 Kohlenstoffatome enthalten. Amidsubstituierte organische Peroxysäure-Verbindungen 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 with 1 to 10 carbon atoms. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be a straight chain or branched alkyl, substituted aryl or alkylaryl with branches, substitutions or both, and may be of synthetic or natural origin including, for example, tallow fat. Analogous structure variations are allowed for R ² . The substitution may 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 contain no 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-phthaloylaminoperoxicaproic acid also suitable herein.

Means for a controlled release rate

 It may be a means of controlling the rate of release a bleaching agent, in particular an oxygen bleaching agent, in the washing solution to be provided.

The Means for controlling the release rate of the bleaching agent can for provide controlled release of peroxide species into the wash solution. Such means could for example controlling the release of any inorganic Perhydrate salt, which serves as a source of hydrogen peroxide, in the wash solution lock in.

suitable Controlled release agents may be limited by the Bleach on either the compressed or the uncompressed Include part. If there is more than one uncompressed part, this can Bleach at first and / or second and / or optional be limited subsequent non-compressed parts.

One different mechanism for controlling the rate of release bleaching agent may be the coating of the bleaching agent with a coating, which is meant for to provide the controlled release. The coating can therefore be, for example a poorly water-soluble Cover material or a cover sufficient thickness, so that the dissolution kinetics of the thick coating for the controlled release rate ensures.

The coating material can be applied by various methods. Any cover material is typically in a weight ratio of coating material to bleaching agent from 1:99 to 1: 2, preferably from 1:49 to 1: 9.

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

Other suitable coating materials can the alkali and alkaline earth metal sulphates, silicates and carbonates, including Calcium carbonate and silicas.

A preferred coating material, especially for an inorganic perhydrate salt bleach source, comprises sodium silicate having a 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, which is preferably applied in a proportion of from 2% to 10% (normally from 3% to 5%) SiO ₂ , based on the weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating.

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

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones having an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) having a Average molecular weight of 600 to 5 × 10 ⁶ , preferably 1,000 to 400,000, most preferably 1,000 to 10,000 are examples of such polymer materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein the maleic anhydride constitutes at least 20 mole percent of the polymer, are further examples of polymeric materials useful as binders. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above C ₁₀ -C ₂₀ alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole. 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 methylcellulose, carboxymethylcellulose and hydroxyethylcellulose and homo- or copolymeric polycarboxylic acids or their salts further examples of Binders for the purpose Use are suitable.

One Method for applying the coating material includes agglomeration. Preferred agglomeration methods include Use of any of the organic described above Binder materials. Any conventional agglomerator / mixer can be used, including, but not limited to, Trough, rotary drum and vertical mixer types. Melted coating compositions can also be applied by placing on a moving bleach bed either poured or applied by spray atomization.

Other Means to go for To provide the required controlled release include mechanical Means to change the physical properties of bleach for control his solubility and release rate. Suitable protocols could include compaction, mechanical injection, manual injection and adjustment the solubility bleach compound by selecting the particle size of any one particulate Component include.

Even though the choice of particle size both from the composition of the particulate component as well of the desire to target the targeted release kinetics reach, depending is, it is desirable that the particle size is more than 500 microns, preferably with an average particle diameter of 800 to 1200 microns.

additional Protocols for providing the controlled release means include the proper selection of any other components of the detergent composition matrix, so that when introducing the composition into the washing solution the ionic strength environment provided therein achieving the required controlled release kinetics allows.

of metal bleach catalyst

The Compositions described herein containing bleaches as a detergent active can contain additionally a metal-containing bleach catalyst as a preferred component contain. Preferably, the metal-containing bleach catalyst a bleach catalyst which is a transition metal contains more preferably a manganese or cobalt-containing bleach catalyst.

One suitable type of bleach catalyst is a catalyst containing a Heavy metal cation with a defined catalytic bleaching activity, such as copper, Iron cations, an auxiliary metal cation with little or no catalytic Bleaching activity, such as zinc or aluminum cations, and a masking agent with defined stability constants for the catalytic metal cations and the Hilfsmetallkationen, in particular ethylenediaminetetraacetic acid, Ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts of which includes. Such catalysts are disclosed in U.S. Patent 4,430,243.

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 ) ₂ , 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 present compositions may also be selected as appropriate to the present invention. Examples of suitable bleach catalysts are found in U.S. Patent 4,246,612 and U.S. Patent 5,227,084. See also U.S. Patent 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ - (PF ₆ ).

Yet another type of bleach catalyst, as in U.S. Patent 5,114,606 discloses is a water-soluble Complex of manganese (III) and / or - (IV) with a ligand containing a Non-carboxylate polyhydroxy compound having at least three consecutive following C-OH groups. Preferred ligands include sorbitol, Iditol, dulcitol, mannitol, xylitol, arabitol, adonite, meso-erythritol, meso-inositol, lactose and Mixtures thereof.

worin R¹, R², R³ und R⁴ jeweils aus H, substituierten Alkyl- und Arylgruppen ausgewählt sein können, so dass jedes R¹-N=C-R² und R³-C=N-R⁴ einen fünf- oder sechsgliedrigen Ring bildet. Der Ring kann weiter substituiert sein. B ist eine brückenbildende Gruppe, ausgewählt aus O, S, CR⁵R⁶, NR⁷ und C=O, worin R⁵, R⁶ und R⁷ jeweils H, eine Alkyl- oder Arylgruppe, einschließlich substituierter oder nichtsubstituierter Gruppen, sein können. Bevorzugte Liganden umfassen Pyridin-, Pyridazin-, Pyrimidin-, Pyrazin-, Imidazol-, Pyrazol- und Triazolringe. Wahlweise können die Ringe durch Substituenten wie Alkyl, Aryl, Alkoxy, Halogenid und Nitro substituiert sein. Besonders bevorzugt ist der Ligand 2,2'-Bispyridylamin. Bevorzugte Bleichkatalysatoren umfassen Co-, Cu-, Mn-, Fe-Bispyridylmethan- und -Bispyridylaminkomplexe. Besonders bevorzugte Katalysatoren umfassen Co(2,2'-Bispyridylamin)Cl₂, Di(isothiocyanato)bispyridylamin-kobalt(II), Trisdipyridylamin-kobalt(II)-perchlorat, Co(2,2-Bispyridylamin)₂O₂ClO₄, Bis(2,2'-Bispyridylamin)-kupfer(II)-perchlorat, Tris(di-2-pyridylamin)-eisen(II)-perchlorat und Mischungen davon.U.S. Patent 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a non- (macrocyclic) ligand. The ligands have the formula:

wherein R ¹ , R ² , R ³ and R ^{4 may} each be selected from H, substituted alkyl and aryl groups such that each R ¹ -N = CR ² and R ³ -C = NR ⁴ forms a five- or six-membered ring , The ring may be further substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C = O, wherein R ⁵ , R ⁶ and R ^{7 may} each be H, an alkyl or aryl group, including substituted or unsubstituted groups , Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, the rings may be substituted by substituents such as alkyl, aryl, alkoxy, halide and nitro. More preferably, the ligand is 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe bispyridylmethane and bis-pyridylamine complexes. Particularly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), trisdipyridylamine 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 binuclear Mn complexes with tetra-N-dentate and Bi-N-dentate ligands, including N ₄ Mn ^III (μO) 2Mn ^IV N ₄ ) ⁺ and [bipy ₂ Mn ^III (μO) ₂ Mn ^IV bipy ₂ ] - (ClO ₄ ) ₃

Even though the structures of the bleach - catalyzed manganese complexes of The present invention has not been elucidated, it can be speculated Be they chelates or other hydrated coordination complexes include, from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation arise. Likewise, the oxidation number of the manganese cation in the catalytic process is not certain known and can be the valence state (+ II), (+ III), (+ IV) or (+ V) be. Because of the six possible Make the ligands for a bond to the manganese cation can reasonably be speculated that polynuclear species and / or "cage" structures are present in the aqueous bleaching medium can. Independently from the form in which the effective Mn ligand species are actually present, they work in an obviously catalytic way with stubborn Stains like tea, ketchup, coffee, wine, juice for better bleaching performance to care.

Other bleach catalysts are described, for example, in European Patent Application Publication No. 408,131 (cobalt complex catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (metal porphyrin catalysts), US 4,728,455 (Manganese / multidentate ligand catalyst), US 4,711,748 and European Patent Application Publication No. 224,952 (adsorbed manganese on aluminosilicate catalyst), US 4,601,845 (Aluminosilicate carrier with manganese and zinc or magnesium salt), US 4,626,373 (Manganese / ligand catalyst), US 4,119,557 (Iron (III) complex catalyst), German Patent 2,054,019 (cobalt chelant catalyst), CA 866,191 (Transition metal-containing salts), US 4,430,243 (Chelant with manganese cations and non-catalytic metal cations) and US 4,728,455 (Manganese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts having the formula: Co [(NH ₃ ) _n M ' _m B' _b T ' _t Q _q P _p ] Y _y wherein cobalt is in the oxidation number +3; n is an integer of 0 to 5 (preferably 4 or 5, most preferably 5); M 'represents a monodentate ligand; m is an integer of 0 to 5 (preferably 1 or 2, most preferably 1); B 'represents a bidentate ligand; b is an integer of 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y on or more suitably selected counter anions present in a number y, where y is an integer of 1 to 3 (preferably 2 to 3, most preferably 2 if Y is an anion of charge -1) to obtain a balanced charge salt, preferred Ys are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and further wherein at least one of the coordination sites attached to the cobalt is inconsistent under automatic dishwashing application conditions and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (III) to cobalt (II) is below alkaline conditions to a normal hydrogen electrode is less than 0.4 volts (preferably less than 0.2 volts).

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

The preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co (NH ₃ ) ₅ Cl] Y _y and especially [Co (NH ₃ ) ₅ Cl] Cl ₂ .

More preferred are the compositions of the present invention wherein cobalt (III) bleach catalysts having the following formula are used: [Co (NH ₃ ) _n (M) _m (B) _b ] T _y wherein cobalt is in the oxidation number +3; n is 4 or 5 (preferably 5); M represents one or more ligands coordinated to the cobalt through a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by 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 = 4; and T is one or more suitably selected counter anions present in a number y, where y is an integer, to obtain a balanced charge salt (preferably, y is 1 to 3, most preferably 2, when T is one) Anion with the charge is -1); and wherein the rate of basic hydrolysis rate of the catalyst is further 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, sulfite, citrate, acetate, carbonate, bromide, PF ₆ ^- , BF ₄ ^- , B (Ph) ₄ ^- , Phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T may be protonated if more than one anionic group is present in T, e.g. B. HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- . Further, T may be selected from the group consisting of non-conventional inorganic anions, such as anionic surfactants (eg, linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl ethoxyl sulfonates (AES)), and / or anionic polymers (eg, polyacrylates , Polymethacrylates).

The M moieties include, but are not limited to, for example, F ^-, SO ₄ ^2-, NCS ^-, SCN ^-, S ₂ O ₃ ^-2, NH _3, PO ₄ ^3-, and carboxylates (which preferably are mono-carboxylates, however, more than one carboxylate may be present in the unit as long as the attachment to the cobalt is by only one carboxylate per unit, in which case the other carboxylate in the M unit may be protonated or in its salt form). Alternatively, M may be protonated if more than one anionic group is present in M (eg, HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- , HOC (O) CH ₂ C (O) O-). Preferred M moieties are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids having the formulas: 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, wherein substituents are selected from the group consisting of -NR ' ₃ , -NR' ₄ ⁺ , -C (O) OR ', -OR ', -C (O) NR' ₂ , wherein R 'is selected from the group consisting of hydrogen and C ₁ -C ₆ units. Such substituted Rs therefore include the moieties - (CH ₂ ) _n OH and - (CH ₂ ) _n NR ' ₄ ⁺ wherein n is an integer from 1 to 16, preferably from 2 to 10 and most preferably from 2 to 5 ,

Most preferred M are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C ₄ -C ₁₂ alkyl and benzyl. The most preferred R is methyl. Preferred carboxylic acid M units include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenic, oleic, palmitic, triflate, tar Stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic acids.

The B units include carbonate, di- and higher carboxylates (eg, oxalate, Malonate, malate, succinate, maleate), picolinic acid and alpha and beta amino acids (e.g. Glycine, alanine, beta-alanine, phenylalanine).

Cobalt bleach catalysts useful herein are known and are described, for example, together with their base hydrolysis rates in ML Tobe, "Base Hydrolysis of Transition Metal Complexes", Adv. Inorg., Bioinorg., Mech., (1983) 2, pp. 1-94 Table 1 on page 17 gives the base hydrolysis rates (referred to therein as k _OH ) for cobalt pentaamine catalysts reacted with oxalate (k _OH = 2.5 x 10 ^-4 M ^-1 s ^-1 (25 ° C)), NCS ^- (k _OH = 5.0 x 10 ^-4 M ^-1 s ^-1 (25 ° C)), formate (k _OH = 5.8 x 10 ^-4 M ^-1 s ^-1 (25 ° C)) and acetate (k _OH = 9.6 x 10 ^-4 M ^-1 s ^-1 (25 ° C)) are complexed. the most preferred suitable herein are cobalt pentaamine acetate cobalt catalyst having the formula [Co (NH _{3) 5} OAc] T _y, wherein OAc a Acetate, and in particular cobalt pentaamine acetate chloride, [Co (NH ₃ ) ₅ 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 ) ₅ OAc] ( BF ₄ ) ₂ and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (herein "PAC").

These Cobalt catalysts can easily prepared by known methods, such as in the above article by Tobe and the references cited therein, in U.S. Patent 4,810,410 to Diakun et al., issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960), and in Journal of Physical Chemistry, 56, 22-25 (1952), and taught in the synthesis examples provided below become.

Cobalt catalysts for inclusion in the detergent tablets of the present invention Invention are suitable be prepared in the synthetic ways described in the US patents No. 5,559,261, 5,581,005 and 5,597,936.

These Catalysts can along with additional Materials are processed to reduce the color effect, if for the aesthetics of the product desired, or to be included in enzyme-containing particles as follows exemplified, or the compositions can be prepared so that they have catalyst "speckles".

organic polymer compound

organic Polymer compounds can be added as preferred components of the laundry detergent tablets according to the invention. With organic polymer compound is essentially any polymeric organic compound commonly used in detergent compositions and the dispersants, anti-redeposition agents, Dirt-repellent or other cleaning-effective properties having.

The organic polymer compound is in the detergent compositions of the invention typically in a proportion of 0.1% by weight to 30 wt%, preferably from 0.5 wt% to 15 wt%, most preferably from 1% to 10% by weight of the compositions.

Examples for organic Polymer compounds include the water-soluble, organic, homo- or copolymeric polycarboxylic acids, modified polycarboxylates or their salts in which the polycarboxylic acid is at least comprises two carboxyl radicals, represented by not more than two carbon atoms are separated from each other. Polymers of the latter type are in the UK A 1,596,756. Examples of such salts are polyacrylates having a molecular weight of 2,000 to 10,000 and their copolymers with any other suitable monomer units, including modified ones Acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic or their salts, maleic anhydride, Acrylamide, alkylene, vinyl methyl ether, styrene and any mixtures from that. The copolymers of acrylic acid and maleic anhydride are preferred with a molecular weight of 20,000 to 100,000.

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

Preferred acrylic acid-containing copolymers include those comprising as monomer units: a) from 90% to 10%, preferably from 80% to 20%, by weight of acrylic acid or its salts, and b) from 10% by weight. from% to 90% by weight, preferably from 20% to 80% by weight, of a substituted acrylic monomer or its salts having the general formula - [CR ₂ -CR ₁ (COO-R ₃ )] - wherein at least one of the substituents R ₁ , R ₂ or R ₃ , preferably R ₁ or R ₂ , is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, R ₁ or R _{2 may be} a hydrogen and R _{3 may be} a hydrogen or an alkali metal salt , Most preferred is a substituted acrylic monomer wherein R _{1 is} methyl, R _{2 is} hydrogen (ie, a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500 and contains from 60% to 80% by weight of acrylic acid and from 40% to 20% by weight of methacrylic acid.

The Polyamine compounds and modified polyamine compounds are suitable herein including those of aspartic acid are derived, such as those described in EP A 305282, EP A 305283 and EP A 351629 are disclosed.

Other optional polymers can Polyvinyl alcohols and acetates, both modified and unmodified, cellulosic and modified cellulosic compounds, 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 U.S. Patent Nos. 5,591,703, 5,597,789 and 4,490,271 disclosed.

soil

Suitable polymeric soil release agents include soil release agents comprising: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of 2 to 10, wherein the hydrophilic segment does not comprise an oxypropylene moiety unless it is attached to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene moieties comprising oxyethylene and 1 to 30 oxypropylene moieties, wherein the hydrophilic segments are preferably at least 25% oxyethylene units, and more preferably, especially those components having 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 when the hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate to C ₃ oxyalkylene terephthalate units is 2: 1 or lower, (ii ) C ₄ -C ₆ -alkylene or oxy-C ₄ -C ₆ -alkylene segments or mixtures thereof, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having 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, wherein the substituents in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives, or mixtures thereof are present, or a combination of ( a) and (b).

The polyoxyethylene segments of (a) (i) typically have a degree of polymerization of 200, although higher levels may be used, preferably from 3 to 150, 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 soil release agents such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, where M is sodium and n is an integer from 4 to 6, as in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Suitable polymeric soil release agents herein also include cellulosic derivatives such as cellulosic hydroxyether polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic 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 release agents characterized by hydrophobic poly (vinyl ester) segments include graft copolymers of poly (vinyl ester), e.g. 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 suitable soil release agent is a copolymer having random blocks of ethylene lenterephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, and U.S. Patent 3,893,929 to Basadur, issued July 8, 1975.

One another suitable polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units, the 10-15 Wt% ethylene terephthalate units together with 90-80 wt% Contains polyoxyethylene terephthalate units derived from a polyoxyethylene glycol with an average molecular weight of 300-5,000.

One another suitable polymeric soil release agent is a sulfonated Product of a substantially linear ester oligomer consisting from an oligomeric ester backbone of recurring terephthaloyl and oxyalkyleneoxy units and terminal units that are covalent to the skeleton are bound. These soil release agents are described in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink, Completely described. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730 issued 8 December 1987 to Gosselink et al., The anionic, end-capped, oligomeric esters of U.S. Patent 4,721,580, issued January 26 1988 to Gosselink, and the oligomeric block polyester compounds from U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink. Other polymeric soil release agents also include the soil release agents U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which end-capped anionic terephthalate esters, especially Sulfoarolyl terephthalate ester disclosed.

am Another soil release agent is an oligomer with recurring Units of terephthaloyl units, sulfoisoterephthaloyl units, Oxyethyleneoxy and oxy-1,2-propylene units. The recurring Units form the backbone of the oligomer and are preferably modified with isethionic acid end caps completed. A particularly preferred soil release agent of this Type comprises a sulfoisophthaloyl unit, 5 terephthaloyl units, Oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8 and two end-cap units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

Heavy metal ion sequestrant

 The Detergent tablets of the invention preferably contain as optional Component a heavy metal ion sequestrant. With heavy metal ion sequestrant Here are meant components that act to release heavy metal ions be masked (chelated). These components can too the ability to the formation of calcium and magnesium chelates possess show but preferably selectivity across from the binding of heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrant are generally in a proportion of 0.005 wt .-% to 20 wt .-%, preferably from 0.1% to 10% by weight, more preferably from 0.25 Wt% to 7.5 wt% and most preferably from 0.5 wt% to 5% by weight of the compositions are present.

Heavy metal ion sequestrant are acidic in nature, for example, have phosphonic acid or carboxylic acid functionalities, can either in their acid form or as a complex / salt with a suitable counter cation, such as a Alkali or alkali metal ion, ammonium or substituted ammonium ion or any mixtures thereof are present. Preferably, any Salts / complexes soluble in water. The molar ratio from counter cation to heavy metal ion sequestrant is preferably at least 1: 1.

suitable Heavy metal ion sequestrants for use herein include organic ones Phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxydisphosphonates and nitrilotrimethylene phosphonates. Preferred among the above mentioned species are diethylene triamine penta (methylene phosphonate), Ethylenediaminetri (methylenephosphonate), hexamethylenediamine tetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for this purpose Use include nitrilotriacetic acid and polyaminocarboxylic, such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic, Ethylenediamine disuccinic acid, ethylenediamine-diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, one.

Particularly preferred are 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 the sodium or magnesium complex thereof.

Crystal growth inhibitor component

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

With organo By this is meant an organodiphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore concludes the organoaminophosphonates, which, however, in compositions of the invention as heavy metal ion sequestrant components could be.

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

water-soluble sulfate salt

 The Detergent tablet contains optionally a water-soluble Sulfate salt. If present, the water-soluble sulfate salt is in one Content of 0.1% by weight to 40% by weight, more preferably 1% by weight to 30% by weight, most preferably from 5% to 25% by weight of the Contain compositions.

The water-soluble Sulfate salt can essentially be any salt of sulfate be any countercation. Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, in particular sodium sulfate.

Alkali metal silicate

According to one embodiment of the present invention, an alkali metal silicate is an essential component of the detergent tablet. In other embodiments of the present invention, the presence of an alkali metal silicate is optional. A preferred alkali metal silicate is sodium silicate having a SiO ₂ : Na ₂ O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0. Sodium silicate is preferably present at a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight SiO ₂ . The alkali metal silicate may be in the form of the anhydrous salt or a hydrated salt.

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

The alkalinity system preferably also 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 between the sodium silicate and the sodium metasilicate, measured as SiO ₂ , is preferably from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, most preferably from 10: 1 to 5: 2.

colorants

 Of the Expression 'colorant', As used herein, any substance means light specific wavelengths absorbed from the visible light spectrum. Such colorants act when added to a detergent composition such that they have the visible color and thus the appearance of the detergent composition change. Colorants can for example, either dyes or pigments. Preferably are the colorants in the composition in which they are enclosed to be stable. In a high pH composition Therefore, the colorant is preferably base stable, and in a composition At low pH, the colorant is preferably acid resistant.

The compressed part and / or the uncompressed part may contain a colorant, a mixture of colorants, colored particles or a mixture of colored particles so that the compressed part and the non-compressed part have different visual appearances. Preferably around either the compressed part or the non-compressed part holds a colorant.

If the non-compressed part has two or more compositions of Detersive active ingredients, preferably comprises at least one of either the first and the second and / or subsequent Compositions a colorant. If both the first as well the second and / or subsequent compositions are a colorant Preferably, the colorants preferably have a different visual Appearance on.

The coating layer preferably comprises a colorant. If the compressed part and the coating layer include a colorant, the colorants preferably provide for a different visual effect.

Examples for suitable Close dyes reactive dyes, direct dyes, azo dyes. preferred Close dyes Phthalocyanine dyes, anthraquinone dyes, quinoline dyes, Monoazo, disazo and polyazo dyes. More preferred dyes shut down 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 UK, HEXACOL QUINOLINE YELLOW (trade name) and HEXACOL BRILLIANT BLUE (trade name), both available from Pointings, United Kingdom, ULTRA MARINE BLUE (trade name), available from Holliday, or LEVAFIX TURQUISE BLUE EBA (trade name), available from Bayer, USA.

The Colorant may be incorporated into the composition by any suitable method compressed and / or the uncompressed part included become. Suitable methods include mixing all or selected Detergents with a colorant in a drum or the spraying all or selected Detergent agents with the colorant in a rotary drum.

If Colorant is present as a component of the compressed part, it is in a proportion of 0.001% to 1.5%, preferably of 0.01% to 1.0%, most preferably from 0.1% to 0.3%. If it is present as a component of the uncompressed part Colorants generally in a proportion of 0.001% to 0.1%, more preferably from 0.005% to 0.05%, most preferably from 0.007% to 0.02% present. If it is present as a component of the overcoat layer, is colorant in a proportion of 0.01% to 0.5%, more preferred from 0.02% to 0.1%, most preferably from 0.03% to 0.06%.

Corrosion inhibitor compound

The Detergent tablets of the present invention for use in dishwashing process are suitable Contain corrosion inhibitors, preferably selected from organic silver coating compositions, in particular paraffin, nitrogen-containing corrosion inhibitor compounds and Mn (II) compounds, especially Mn (II) salts, organic Ligands.

organic Silver coating agents are in the PCT publication No. WO 94/16047 and in the co-pending European application No. EP A 690122. Nitrogen-containing corrosion inhibitor compounds are in the co-pending European Application No. EP A 634,478. Mn (II) compounds for use in corrosion inhibition are described in the co-pending European application No. EP A 672 749.

organic Silver coating agents can in a proportion of 0.05% by weight to 10% by weight, preferably of 0.1 wt% to 5 wt% of the total composition included be.

The Function of the silver coating agent lies in, 'in use' one protective coating layer any silver components of the dishwashing charge to which the compositions of the invention are used. The silver coating agent should therefore have a high affinity have for attachment to solid silver surfaces, in particular when present as a component of an aqueous rinse or bleach solution is with which the solid silver surfaces are treated.

suitable organic silver coating agents to conclude here fatty acid ester of mono- or polyhydric alcohols having 1 to 40 carbon atoms in the hydrocarbon chain.

Of the fatty acid moiety of the fatty acid ester may be mono- or polycarboxylic acids having 1 to 40 carbon atoms in the hydrocarbon chain become. Suitable examples of Monocarboxylic fatty acids include behenic, stearic, oleic, palmitic, myristic, lauric, acetic, propionic, butyric, isobutyric, valeric, lactic, glycolic and β, β'-dihydroxyisobutyric acids. examples for suitable polycarboxylic acids include: n-butylmalonic acid, isocitric, citric acid, Maleic acid, malic acid and Succinic acid.

Of the Fatty alcohol residue in the fatty acid ester can be replaced by mono- or polyhydric alcohols having 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable Fatty alcohols include: behenyl, arachidyl, cocoyl, oleyl and Lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, Diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or Sorbitan.

The Fatty acid- and / or fatty alcohol group of the fatty acid ester additive material preferably 1 to 24 carbon atoms in the alkyl chain.

preferred fatty acid ester herein are ethylene glycol, glycerol and sorbitan esters, wherein the fatty acid moiety of the ester normally comprises one species selected made of behenic acid, Stearic acid, oleic acid, palmitic acid or Myristic.

The Glycerol esters are also particularly preferred. These are the Mono-, di- or Tri-esters of glycerol and the fatty acids specified above.

specific examples for Fatty alcohol esters for this purpose Uses include: stearyl acetate, palmityl dlactate, cocoyl isobutyrate, Oleyl maleate, oleyl dimaleate and tallow propionate. Suitable here fatty acid ester include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, Glycerol monostearate, ethylene glycol monostearate, sorbitan esters. suitable Sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, Sorbitan monomyristate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, Sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and as well mixed tallow alkyl sorbitan mono- and diesters.

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

suitable organic silver coating agents shut down Triglycerides, mono- or diglycerides and fully or partially hydrogenated Derivatives thereof and any mixtures thereof. Suitable sources for fatty acid esters shut down Vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.

waxes, including microcrystalline waxes, are suitable organic silver coating agents here in. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C on and generally comprise from 12 to 70 carbon atoms. Prefers are petroleum waxes of paraffin type and of microcrystalline type consisting of long-chain saturated Hydrocarbon compounds are composed.

alginates and gelatin are suitable organic silver coating agents herein.

Dialkylamine oxides, such as C ₁₂ -C ₂₀ -methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C ₁₂ -C ₂₀ -methylammonium halides, are also suitable.

Other suitable organic silver coating agents shut down certain polymeric materials. Polyvinylpyrrolidone with a average molecular weight from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, Polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole and cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose are examples of such polymeric materials.

Certain Fragrance materials, especially those which show high substantivity for metal surfaces, are also suitable as the organic silver coating agents herein.

polymers Dirt-repellent agents can also as organic silver coating agents be used.

A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of 20 to 50; preferred paraffin _oil is selected from predominantly branched C _25-24 species having a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A paraffinic oil meeting these properties with a 32:68 ratio of cyclic to noncyclic hydrocarbons is sold by Wintershall, Salzbergen, Germany, under the trade designation WINOG 70.

nitrogenous Corrosion inhibitor compounds

 suitable Nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof, such as benzimidazole, 2-heptadecylimidazole and those Imidazole derivatives disclosed in Czech Patent No. 139,279 and U.S. Pat in British Patent GB A 1,137,741 which also discloses a process for the preparation of imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, especially those in which the pyrazole is substituted at the 1, 3, 4 or 5 position by substituents R ₁ , R ₃ , R ₄ and R ₅ , wherein R _{1 is} H, CH ₂ OH, CONH ₃ or COCH ₃ , R ₃ and R _{5 are} C ₁ -C ₂₀ -alkyl or -hydroxyl and R _{4 is} H, NH ₂ or NO ₂ .

Other suitable nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalid, Morpholine, melamine, distearylamine, stearoylstearamide, cyanuric acid, aminotriazole, Aminotetrazole and indazole.

nitrogenous Compounds such as amines, especially distearylamine, and ammonium compounds such as Ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrogen citrate, are also suitable.

Mn (II) compounds -Korrosionsinhibitor

The Detergent tablets can contain an Mn (II) corrosion inhibitor compound. The Mn (II) compound is preferably in a proportion of 0.005 wt .-% to 5 wt .-%, more preferably from 0.01% to 1% by weight, most preferably from 0.02% to 0.4% by weight of the compositions. Preferably, the Mn (II) compound is included in a proportion, in any bleach solution 0.1 wt ppm to 250 wt ppm, more preferably 0.5 wt ppm to 50 Ppm by weight, most preferably 1 ppm by weight to 20 ppm by weight of Mn (II) ions provide.

The Mn (II) compound may be an inorganic salt in an anhydrous one or any hydrated form. Suitable salts shut down Manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and man gan chloride. The Mn (II) compound may be a salt or a complex of an organic fatty acid, such as manganese acetate or Manganese stearate, be.

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

Other corrosion inhibitor compounds

Other suitable additional corrosion inhibitor compounds include mercaptans and diols, especially mercaptans having from 4 to 20 carbon atoms, including laurylmercaptan, thiophenol, thionaphthol, thionalid and thioanthranol. Also suitable are saturated or unsaturated C ₁₀ -C ₂₀ fatty acids or their salts, especially aluminum tristearate. The C ₁₂ -C ₂₀ hydroxy fatty acids or their salts are also suitable. Phosphonated octadecane and other antioxidants such as beta-hydroxytoluene (BHT) are also suitable.

copolymers from butadiene and maleic acid, in particular those listed under trading reference No. 07787 supplied by Polysciences Inc. have proven to be special useful Corrosion inhibitor compounds proved.

Hydrocarbon oils

Another preferred detergent active for use in the present invention is a hydrocarbon oil, typically predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from 20 to 50; preferred hydrocarbons are saturated and / or branched; Preferred hydrocarbon _oil is selected from predominantly branched C _25-24 species having a ratio of cyclic to _non- cyclic hydrocarbons of from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin. A paraffin oil satisfying the abovementioned characteristics with a ratio of cyclic to noncyclic hydrocarbons of 32:68 is marketed by Wintershall, Salzbergen, Germany, under the trade designation WINOG 70.

Water-soluble bismuth compound

The Detergent tablets of the present invention for use suitable in dishwashing process are, can a water-soluble Bismuth compound, preferably in a proportion of 0.005 Wt% to 20 wt%, more preferably from 0.01 wt% to 5 wt%, most preferably from 0.1% to 1% by weight of the compositions is available.

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

Enzyme stabilization system

 preferred Enzyme-containing compositions herein can range from 0.001% to 10% Wt .-%, preferably from 0.005 wt .-% to 8 wt .-%, most preferably from 0.01% to 6% by weight of an enzyme stabilization system. The enzyme stabilization system can be any stabilization system which is compatible with the cleaning enzyme. Such stabilization systems can Calcium ions, boric acid, Propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers, and mixtures include. Such stabilization systems may also include reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap dispersant compound

The Detergent agent compositions can include a lime soap dispersant compound contained, preferably in a proportion of 0.1 wt .-% to 40 Wt%, more preferably from 1 wt% to 20 wt%, most preferably from 2% to 10% by weight of the compositions.

One Lime soap dispersant is a material which prevents the precipitation of Alkali metal, ammonium or amine salts of fatty acids Calcium or magnesium ions prevented. Preferred lime soap dispersant compounds are in PCT Application No. WO93 / 08877.

Suds suppressing system

 If the detergent tablets of the present invention for use in compositions for machine wash are formulated, they preferably comprise a foam suppression system, in a proportion of 0.01% by weight to 15% by weight, preferably from 0.05% to 10%, most preferably 0.1% by weight to 5 wt .-% of the composition is present.

suitable Foam suppression systems for this purpose Can use essentially any known antifoam compounds include, including For example, silicone antifoam compounds, 2-alkyl and Alcanol antifoam compounds. Preferred foam suppression systems and antifoam compounds are disclosed in PCT Application No. WO93 / 08876 and EP A 705,324.

Polymeric dye transfer inhibitor

The detergent tablets herein may also be from 0.01% to 10% by weight, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibitor are preferably selected of polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations from that.

Optical brightener

The Detergent tablets for use in laundry processes, as here optionally described, also contain 0.005% by weight. to 5% by weight of certain types of hydrophilic optical brighteners.

worin R₁ ausgewählt ist aus Anilino, N-2-Bis-hydroxyethyl und NH-2-Hydroxyethyl; R₂ ausgewählt ist aus N-2-Bis-hydroxyethyl, N-2-Hydroxyethyl-N-methylamino, Morphilino, Chlor und Amino; und M ein salzbildendes Kation wie Natrium oder Kalium ist.Suitable hydrophilic optical brighteners herein include those having 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, chloro 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 -bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the present detergent compositions.

In the above formula, 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 marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

In the above formula, 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-triazin-2-yl) amino] 2,2'-stilbene disulfonic acid sodium salt. This particular brightener species is marketed under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Clay softening

 The Detergent tablets suitable for use in cleaning processes for laundry washing may include Clay softening system containing a clay mineral compound and optionally comprising a clay flocculating agent.

The Clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in U.S. Patent Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. In European Patent Nos. EP A 299,575 and EP A 313,146 are in the name of the Procter and Gamble Company suitable organic polymeric clay flocculating agents are described.

cationic fabric softener

cationic Fabric softeners can also in compositions according to the invention, for use in laundry processes are suitable to be included. Suitable cationic fabric softeners include the water-insoluble ones tertiary Amine or amide materials with two long chains, as in GB A 1 514,276 and EP B 0 011 340.

Cationic fabric softeners are typically in total proportions of 0.5% to 15% Wt .-%, usually from 1 wt .-% to 5 wt .-% included.

Other optional ingredients

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

pH of the compositions

 The Detergent tablets of the present invention are preferably not formulated to have an excessively high pH, preferably such that it has a pH, measured as a 1% solution in distilled water, from 8.0 to 12.5, more preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.

In In another aspect of the present invention, the compressed and the uncompressed parts are formulated so that they provide different pH levels.

Machine dishwashing

any suitable methods for mechanical rinsing or cleaning of soiled Dishes are considered.

One preferred machine dishwashing method includes the treatment of soiled items selected from Tableware, glassware, silverware, metal objects, cutlery and blends of it, with an aqueous one Liquid, in which an effective amount of a detergent tablet according to the invention dissolved or is dispersed. With an effective amount of detergent tablet 8 g to 60 g of product are meant to be used in a washing solution a volume of 3 to 10 liters are dissolved or dispersed, which the typical product dosages and wash solution volumes are those commonly used in conventional automatic dishwashing process be used. Preferably, the detergent tablets have a weight of 15 g to 40 g, more preferably from 20 g to 35 g.

Laundry process

Machine laundry methods These usually include the treatment of soiled laundry with an aqueous wash solution in a washing machine comprising an effective amount of a detergent tablet composition of the invention for machine wash or dissolved is dispersed. With an effective amount of the detergent tablet composition 40 g to 300 g of product are meant to be used in a washing solution are dissolved or dispersed in a volume of 5 to 65 liters, which typical product dosages and wash solution volumes are those commonly used in conventional machine laundry method be used.

In A preferred utility aspect is in the washing process a dispenser used. The dispenser is with filled the detergent product and is used to direct the product before beginning the wash cycle into the drum of the washing machine. Your volume capacity should be Be such that they have adequate detergent product as it normally would used in the washing process may contain.

As soon as the washing machine with the laundry is loaded, the dispenser, which is the detergent product contains placed in the drum. At the beginning of the washing cycle of the washing machine Water is introduced into the drum and the drum rotates periodically. The dispenser should be designed so that however, it may contain the dry detergent product allows that this product during the wash cycle due to its reciprocation during the rotation of the drum and also released as a result of his contact with the wash liquor becomes.

Around to allow the release of the detergent product during washing, the device must several openings through which the product can pass. As alternative The device may be made of a material suitable for liquid permeable, for the solid product, however, impermeable is what allows the release of dissolved product. Preferably, the detergent product is at the beginning of the wash cycle quickly released, causing temporary, at this stage of the wash cycle, localized high product concentrations in the drum of the washing machine to be provided.

preferred Dispensers are reusable and designed so that the container integrity both in the dry state as well as during the wash cycle is maintained.

When Alternatively, the dispenser can be an elastic container like to be a bag. The bag can be of fibrous construction and with a water-impermeable Protective material coated be to hold back the content, as published in the European Patent Application No. 0018678. As an alternative, he can out a water-insoluble be made of synthetic polymer material, with an edge seal or an edge closure is provided, the or so designed is that she or he is in watery Medium breaks, as in the published European Patent Applications Nos. 0011500, 0011501, 0011502 and 0011968. A suitable form of water-tearable closure comprises a water-soluble Adhesive along an edge of one of a water impermeable polymer film, arranged like polyethylene or polypropylene, formed bag is and closes this.

Examples

In examples used abbreviations

STPP:

Natriumtripolyphosphat

Citrat:

Trinatriumcitratdihydrat

Bicarbonat:

Natriumhydrogencarbonat

Citronensäure:

Wasserfreie Citronensäure

Carbonat:

Wasserfreies Natriumcarbonat

Silikat:

Amorphes Natriumsilikat (SiO₂:Na₂O-Verhältnis = 1,6–3,2)

Metasilikat:

Natriummetasilikat (SiO₂:Na₂O-Verhältnis = 1,0)

PB1:

Wasserfreies Natriumperboratmonohydrat

PB4:

Natriumperborattetrahydrat der nominalen Formel NaBO₂·3H₂O·H₂O₂

Plurafac:

Gemischter ethoxylierter/propoxylierter C₁₃-C₁₅-Fettalkohol mit einem durchschnittlichen Ethoxylierungsgrad von 3,8 und einem durchschnittlichen Propoxylierungsgrad von 4,5, vertrieben unter der Handelsbezeichnung Plurafac von BASF.

Tergitol:

Nichtionisches Tensid, erhältlich unter der Handelsbezeichnung Tergitol 15S9 von Union Carbide

SLF18:

Epoxyverkappter, poly(oxyalkylierter) Alkohol aus Beispiel III von WO 94/22800, worin 1,2-Epoxydecan durch 1,2-Epoxydodecan substituiert ist, erhältlich unter der Handelsbezeichnung Polytergent SLF18D von OLIN.

TAED:

Tetraacetylethylendiamin

HEDP:

Ethan-1-hydroxy-1,1-diphosphonsäure

DETPMP:

Diethyltriaminpenta(methylen)phosphonat, vermarktet von Monsanto unter der Handelsbezeichnung Dequest 2060

PAAC:

Pentaaminacetat-Kobalt(III)-Salz

BzP:

Benzoylperoxid

Paraffin:

Paraffinöl, vertrieben unter der Handelsbezeichnung Winog 70 von Wintershall

Protease:

Proteolytisches Enzym

Amylase:

Amylolytisches Enzym

BTA:

Benzotriazol

PA30:

Polyacrylsäure mit einem durchschnittlichen Molekulargewicht von ungefähr 4.500

480 N:

Statistisches Copolymer aus 7:3 Acrylat/Methacrylat, durchschnittliches Molekulargewicht 3.500

Sulfat:

Wasserfreies Natriumsulfat

PEG 3000:

Polyethylenglycol, Molekulargewicht ungefähr 3000, erhältlich von Hoechst

PEG 6000:

Polyethylenglycol, Molekulargewicht ungefär 6000, erhältlich von Hoechst

Zucker:

Haushaltsaccharose

Gelatine:

Gelatine Typ A, Bloom-Festigkeit 65, erhältlich von Sigma

CMC:

Carboxymethylcellulose

Dodecandisäure:

C12-Dicarbonsäure

Adipinsäure:

C6-Dicarbonsäure

Laurinsäure:

C12-Monocarbonsäure

pH:

Gemessen als 1%ige Lösung in destilliertem Wasser bei 20°C

In the detergent compositions, the abbreviated component designations have the following meanings:

STPP:

sodium tripolyphosphate

citrate:

trisodium

bicarbonate

sodium

citric acid:

Anhydrous citric acid

carbonate:

Anhydrous sodium carbonate

Silicate:

Amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 1.6-3.2)

metasilicate:

Sodium metasilicate (SiO ₂ : Na ₂ O ratio = 1.0)

PB1:

Anhydrous sodium perborate monohydrate

PB4:

Sodium perborate tetrahydrate of nominal formula NaBO ₂ · 3H ₂ O · H ₂ O ₂

Plurafac:

Mixed ethoxylated / propoxylated C ₁₃ -C ₁₅ fatty alcohol having an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac by BASF.

Tergitol:

Nonionic surfactant, available under the trade name Tergitol 15S9 from Union Carbide

SLF18:

Epoxy-capped poly (oxyalkylated) alcohol of Example III of WO 94/22800, wherein 1,2-epoxydecane is substituted by 1,2-epoxydodecane, available under the tradename Polytergent SLF18D from OLIN.

TAED:

tetraacetylethylenediamine

HEDP:

Ethane-1-hydroxy-1,1-

DETPMP:

Diethyltriamine penta (methylene) phosphonate, marketed by Monsanto under the trade name Dequest 2060

PAAC:

Pentaamine acetate cobalt (III) salt

BZP:

benzoyl peroxide

Paraffin:

Paraffin oil, sold under the trade name Winog 70 by Wintershall

protease:

Proteolytic enzyme

amylase:

Amylolytic enzyme

BTA:

benzotriazole

PA30:

Polyacrylic acid with an average molecular weight of about 4,500

480 N:

Statistical copolymer of 7: 3 acrylate / methacrylate, average molecular weight 3,500

Sulfate:

Anhydrous sodium sulfate

PEG 3000:

Polyethylene glycol, molecular weight about 3000, available from Hoechst

PEG 6000:

Polyethylene glycol, molecular weight about 6000, available from Hoechst

Sugar:

household sucrose

Gelatin:

Gelatin Type A, Bloom Strength 65, available from Sigma

CMC:

carboxymethylcellulose

dodecanedioic:

C12 dicarboxylic acid

adipic acid:

C6 dicarboxylic acid

Lauric acid:

C12 monocarboxylic acid

pH:

Measured as a 1% solution in distilled water at 20 ° C

In Example 1 are all proportions as wt .-% of the compressed part, of the uncompressed part or coating layer. The Total weight (g) of the compressed part, the non-compressed part and the coating layer is also indicated.

example 1

below will be examples of Detergent tablets of the present invention for use in a dishwasher are suitable, illustrated.

The compressed portion is prepared by delivering the composition of active detergent components in a Stempelhöhlung a modified 12 head rotary tablet press and compressing the composition at a pressure of 13 KN / cm ^2. The modified tablet press provides tablets in which the compressed part has a shape. For the purposes of Examples A to F, the uncompressed part is in particulate form. The non-compressed part is dispensed by means of a metering precisely into the shape of the compressed part. The uncompressed part is adhered to the compressed part by coating the uncompressed part with a coating layer contacting the compressed part.

Claims (21)

Detergent tablet for use in a washing machine or dishwasher, wherein the tablet comprises an enzyme and: (a) one compressed part comprising a detergent active; (B) a non-compressed, non-encapsulating part which is a detergent active includes, and (c) a coating layer on the non-compressed, non-encapsulating part, causing the uncompressed, non-encapsulating part on the compressed part attached or attached. A detergent tablet according to claim 1, wherein the compressed Part delivers an already established form and the non-compressed Part is at least partially contained in the form. Detergent tablet according to claim 1 or claim 2, which includes several compressed parts arranged in layers are. Detergent tablet according to one of the preceding claims, which includes a plurality of non-compressed parts, wherein the compressed Part delivers several forms and every non-compressed part at least partially contained in a mold. Detergent tablet according to one of the preceding claims, wherein the non-compressed part is in flowable form. Detergent tablet according to one of the preceding claims, wherein the coating layer is water-soluble. Detergent tablet according to one of the preceding claims, wherein the coating layer a component selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, Carboxylic acid, dicarboxylic acids, Polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA), Polyethylene glycol (PEG) and mixtures thereof. Detergent tablet according to one of the preceding claims, wherein the dissolution rate of the not compressed part is larger as the dissolution rate of the compressed part measured using the one described herein SOTAX dissolution test method. Detergent tablet according to one of claims 1 to 7, where the dissolution rate the compressed part is larger as the dissolution rate of the uncompressed part, measured using the here described SOTAX dissolution test method. Detergent tablet according to one of the preceding Claims, wherein the enzyme is selected from the group consisting of amylases, proteases, Cellulases, hemicellulases, peroxidases, lipases, phospholipases and mixtures thereof is. A detergent tablet according to any one of the preceding claims, wherein the detergent agent is the non-compressed portion of surfactant, bleach, bleach activator, bleach catalyst, enzyme, inhibitor of corrosion tor, fragrance and an alkalinity source. Detergent tablet according to one of the preceding Claims, wherein the detergent active of the non-compressed part Surfactant is. Detergent tablet according to one of the preceding Claims, which comprises an alkali metal silicate. Detergent tablet according to one of the preceding Claims, the weight ratio from compressed to uncompressed parts is greater than 0.5: 1 and the detergent tablet includes silicate and the detergent tablet at least 20 wt .-% builder compounds based on detergent ingredients. Detergent tablet according to one of the preceding Claims, wherein the coating layer encapsulates the detergent tablet. Detergent tablet according to one of the preceding Claims, wherein the detergent tablet further comprises a disruptor, the decomposing agent, foaming agent or mixtures thereof is. A detergent tablet according to claim 16, wherein the Disruptor from the group consisting of starch, starch derivatives, alginate, polymers based on carboxymethylcellulose (CMC), sodium acetate, aluminum oxide, Carbonate, bicarbonate, carboxylic acids and mixtures thereof is. Process for the preparation of a detergent tablet for use in a washing machine or dishwasher, wherein the tablet comprises an enzyme and wherein the method is as follows Steps includes: (a) Compressing a composition containing a detergent active, to form a compressed Part; (b) Feeding a composition comprising a detergent active the compressed part to form an uncompressed, not encapsulating part; and subsequently (c) coating of at least part of the uncompressed part with a coating layer, to attach the uncompressed part to the compressed part or attach. Process for the preparation of a detergent tablet for use in a washing machine or dishwasher, wherein the tablet comprises an enzyme and wherein the method is as follows Steps includes: (a) Compressing a composition containing a detergent active, to form a compressed Partly with a mold; (b) supplying a composition, which comprises a detergent active, to the mold for forming a non compressed, non-encapsulating part, leaving the uncompressed Part is at least partially contained in the form, and then (C) Coating at least part of the uncompressed part with a coating layer, to attach the uncompressed part to the compressed part or attach. The method of claim 19, wherein the compressed Part made using a modified tablet press which includes upper and / or lower stamps, thus modifying are that the compressed part one or more wells supplies that form the mold. A method according to any one of claims 18 to 20, wherein the Tablet any of the additional features, those in the claims 3 to 17 are, has.