DE69818871T2 - 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

The present invention provides one Detergent or detergent tablet, comprising a compressed Portion and a non-compressed, non-encapsulating portion.

background

Detergent compositions in tablet form are known in the prior art. It is said that detergent compositions in tablet form opposite Particulate detergent compositions have numerous advantages such as ease of dosing, handling of transportation and storage.

Detergent tablets most common made by premixing components of a detergent composition and molding the premixed detergent components into one Tablet using a tablet press. Tablets typically by compressing the components of the detergent composition formed into a tablet. However, the applicant has found that some components of a detergent composition by the compression pressure used to form the tablets in disadvantageous Way impaired become. These components previously could not be used in a detergent tablet composition be involved without a loss of performance to suffer. In some cases the components could even become unstable as a result of the compression or become inactive.

Furthermore, as well as the components of the detergent composition are compressed, the components brought in close proximity to each other. A result of the close Near the Components can be certain of the components with each other react, become unstable, inactive or consumed. A solution to this Problem, as seen in the prior art, was the components the detergent composition that potentially react with each other can, when the detergent composition compresses into a tablet form will separate. A separation of the components was for example achieved by producing multilayer tablets in which the components, which can potentially react with each other in different layers the tablet are included. Multi-layer tablets are becoming traditional made using multiple compression steps. layers the tablet, which has undergone more than one compression step become a cumulative and potentially larger total compression pressure exposed. It is known that an increase in compression pressure the tablet press the dissolution rate the tablet decreased, with the result that such a multilayer does not dissolve satisfactorily during use.

Other methods of achieving one Separation of the detergent components have been described. For example EP-A-0 224 135 describes a dishwashing detergent in a form which a hot water soluble Melt comprises, into which a cold water soluble tablet is pressed. The document teaches a detergent composition consisting of two There is dividing, with the first part dissolving in the pre-wash cycle and the second part during the main wash the dishwasher dissolves.

EP-B-0 055 100 describes one Toilet cleaning cube, which by combining a slowly dissolving body with a tablet is formed. The toilet cleaning cube is designed to be in the water tank a toilet is arranged and over a period of days, preferably weeks. This teaches as a means of regulating the dissolution of the toilet cleaning cube Document the admixture of one or more solubility regulators. Examples such solubility regulators are a para-dichlorobenzene, waxes, long chain fatty acids and Alcohols and esters thereof and fatty alkyl amides. Detergent tablets for use in washing or machine dishwashing essentially within one cycle of the washing machine or dishwasher, that is within 30 to 120 minutes.

The applicant has found that through Providing a detergent tablet comprising a compressed one Portion and a non-encapsulating, non-compressed portion, Detergent components, which used to be as unacceptable for Detergent tablets were viewed, placed in a detergent tablet can be. additionally can potentially reactive components of the detergent composition in be separated effectively.

Another advantage of using it a detergent tablet as described herein has the performance advantages which can be achieved by making it possible is to make the detergent tablet so that if necessary the compressed portion and the non-compressed portion differ dissolution rates have. Such performance benefits are achieved through selective Respectively active detergent components in the washing solution at different times.

Summary of the Invention

• (a) einen komprimierten Anteil, umfassend einen aktiven Detergensbestandteil; und
• (b) einen nicht-komprimierten, nicht-einkapselnden Anteil, umfassend einen aktiven Detergensbestandteil, wobei der komprimierte Anteil eine vorgefertigte Mulde vorsieht und der nicht-komprimierte Anteil in Form eines Gels oder einer verfestigten Schmelze vorliegt und mindestens teilweise in der Mulde enthalten ist, und das Gewichtsverhältnis von komprimiertem Anteil zu nicht-komprimiertem Anteil größer als 4 : 1 ist, wobei vorzugsweise die Detergenstablette ein Enzym umfasst.

According to the invention there is provided a detergent tablet comprising:

• (a) a compressed portion comprising an active detergent ingredient; and
• (b) a non-compressed, non-encapsulating portion comprising an active detergent ingredient, the compressed portion providing a prefabricated well and the non-compressed portion being in the form of a gel or a solidified melt and being at least partially contained in the well, and the weight ratio of compressed portion to uncompressed portion is greater than 4: 1, preferably the detergent tablet comprising an enzyme.

In a preferred embodiment the detergent tablet comprises a silicate.

In a preferred embodiment the detergent tablet has a dissolution rate greater than 0.33 g / min measured using the SOTAX dissolution test procedure described herein.

In a further preferred embodiment is the weight of the detergent tablet is less than 40 g and the detergent tablet has a dissolution rate of greater than 0.33 g / min measured using the SOTAX dissolution test procedure described herein.

In addition, there is also a procedure provided for the manufacture of the detergent tablets described herein.

detailed Description of the invention

According to the invention it was found that the active Detergent components a detergent tablet, which used to be how it is used to manufacture the tablets in disadvantageous Way influenced were now contained in a detergent tablet can. Examples of these components belong Bleach and enzymes. Moreover was according to the present Invention found that active Detergent components of a detergent tablet can be separated from each other that a or several compatible components in a pressed portion are included and one or more compatible components in a non-pressed Portion of the tablet are included. Examples of components who can react with each other and therefore must be separated from each other include bleach, bleach activators or catalysts and enzymes; Bleaching agents and bleaching catalysts or activators; Bleaches and surfactants; alkalizing Medium (sources of alkalinity) and enzymes.

It can also be beneficial be the pressed and non-pressed Provide shares so that they dissolve in the wash water at different dissolution rates Check or set the dissolution speed of each Proportion in proportion to the other and by selecting the active detergent components in the respective proportions the order of their approval can be seen the wash water can be checked or controlled and the cleaning ability of the Detergent tablet can be improved. For example, it is frequently preferred enzymes the wash water before the bleach and / or the bleach activator be added. It may also be preferred that an alkaline agent is released into the wash water faster than other components of the detergent tablet. It is also conceivable that it can be advantageous to produce a detergent tablet according to the invention, in the release of certain components of the tablet in relation to other components delayed is.

It is also conceivable that the tablet a variety of pressed or non-pressed Shares can include. For example, a variety of pressed parts be arranged in farm of layers and / or a variety of non-compressed Shares can be in the form of individual sections of the tablet, by a pressed one Share are separated. Thus there can be a first and a second and optionally further pressed and / or non-pressed parts, each of which comprises an active detergent component, and at least the first and the second part can have different active Detergent components or mixtures of components. Such a variety of pressed or non-pressed Proportions can be beneficial as they are making a tablet with for example a first and a second and optionally additional sections allowed so that they have different resolution speeds to have. These benefits are achieved through selective delivery of the active detergent components to the wash water at different times.

The detergent tablets described here preferably have a weight between 15 g and 100 g, in particular between 18 g and 80 g, very particularly preferably between 20 g and 60 g. The detergent tablets, which are suitable for use in textile washing processes, particularly preferably have a weight between 40 g and 100 g, very particularly preferably between 40 and 80 g, most preferably between 40 g and 65 g. The weight ratio between the pressed portion and the non-pressed portion is greater than 4: 1, most preferably at least 5: 1.

The detergent tablets described here have a children's bite resistance (Child Bite Strength CBS), which is generally more than 10 kg, preferably is more than 12 kg, most preferably more than 14 kg. The CBS is tested according to the U.S. Consumer Product Safety Commission Specification determined.

Child bite Strength test procedure

After this test procedure the Tablet placed horizontally between two metal strips / plates. The upper and lower plates are on one side by means of a Joint connected so that the Plates resemble a human jaw. An increasing, after downward force is applied to the top plate, so the closing process mimicking the jaw until the tablet breaks. Slide CBS of the tablet is a measure of strength in kg, which is required to break the tablet.

The detergent tablets described here generally have a dissolution rate from> 0.33 g / min, preferably> 0.5 g / min, particularly preferably from> 1.00 g / min, very particularly preferably from> 2.00 g / mln, most preferably from> 2.73 g / min. The dissolution rate will measured using the SOTAX dissolution test method. For the purposes The present invention is the dissolution of the detergent tablets achieved by using a SOTAX (trade name) machine, model No. AT7 available from the company SOTAX.

SOTAX dissolution test method

The SOTAX test device passes from a water bath closed with a lid with regulated Temperature. There will be 7 pots hung in the water bath. Seven electric stir bars hang from the Bottom of the lid down in positions that match the position of the pots match in the water bath. The lid of the water bath also serves as a lid on the pots.

The SOTAX water bath comes with water filled and the temperature measuring device will open 50 ° C set. Then each pot is filled with 1 liter of deionized water and the stirring is set to 250 rpm. The lid of the water bath is closed taking the temperature of the deionized water in the pots yourself allow to equilibrate with the water in the water bath for 1 h.

The tablets are weighed and a tablet is placed in each pot, then the lid is closed. The tablet is monitored visually until they are completely disbanded The time is recorded when the tablet has completely dissolved. The dissolution rate the tablet is calculated as the average weight (g) the tablet that has dissolved in deionized water per minute.

Pressed portion

The compressed portion of the detergent tablet comprises at least one active detergent component, but it can also comprise a mixture of more than one active detergent component, the pressed will become). Any detergent tablet component that is common Known detergent tablets are used for incorporation in the pressed Proportion of detergent tablets according to the invention suitable. Suitable active detergent components are shown below described. Preferred active detergent components belong a builder (scaffold) connection, a surfactant, a bleach, a bleach activator, a bleach catalyst, an enzyme and an alkalizing compound (source of alkalinity).

The existing in the pressed layer active detergent component (s) can, if necessary in combination with a carrier and / or a binder, for example water, polymer (e.g. PEG), liquid Silicate. The active detergent components are preferably in the form of particles (i.e. in the form of a powder or in grainy Shape) and they can by any known method, for example through conventional spray drying, granulation or agglomeration. The particulate active detergent component (s) is then pressed using a suitable device for manufacturing of pressed Tablets, blocks, Bricks or briquettes are suitable, as described in more detail below becomes.

Not pressed, not encapsulating proportion of

The non-pressed, non-encapsulating portion (hereinafter referred to as "non-pressed portion") comprises at least one active detergent component, but it can also be a mixture of more than an active detergent component. Active detergent components that are suitable for incorporation into the unpressed portion include components that react with one or more of the detergent components contained in the pressed portion. Preferred components of the non-pressed portion are, in particular, those which are adversely affected by the pressing pressure, for example of a tablet press. Examples of such active detergent components include, but are not limited to, a surfactant, a bleach, a bleach activator, a bleach catalyst, an enzyme, a corrosion inhibitor, a perfume, and an alkalinity source. These components are described in more detail below. The active detergent component (s) can be in any form, for example in the form of particles (ie in the form of a powder or in granular form) or in the form of a gel or in liquid form. In addition to an active detergent component, the non-pressed portion can optionally also comprise a carrier component. The active detergent component can be in the form of a solid, gel or liquid before being combined with a carrier component.

The non-compressed portion of the detergent tablet lies as. Gel or in the form of a solidified melt.

The detergent tablet according to the invention requires that the non-pressed Share the pressed Share fed so will that the pressed Portion and the non-pressed Share are in contact with each other. The non-pressed part can the pressed Proportion added in solid or flowable farm become. If the non-pressed Part is in solid form, it is prepared beforehand, if necessary molded and then pressed ge Portion added. The non-pressed part is then in one preformed pressed Fixed portion, for example by adhesion or by inserting the non-pressed portion in a cooperating surface the pressed Share. Preferably includes the pressed one Proportion of a previously created depression or shape into which the non-pressed Share introduced becomes.

The non-pressed portion is preferred in flowable form the pressed one Share fed. The non-pressed one Share is then in the pressed Share fixed, for example, by adhesion, by forming a coating on the non-pressed Layer to him pressed on the To attach portion, or by hardening, for example (i) through cooling down below the melting point at which the flowable composition becomes a solidified melt is; (ii) by evaporating a solvent; (iii) by crystallization; (iv) by polymerizing a polymer Component of the flowable non-pressed portion; (v) by pseudo-plastic properties when the flowable non-pressed portion comprises a polymer and shear forces the non-pressed one Act share; (vi) by combining a binder with the flowable non-pressed portion. In an alternative embodiment the flowable non-pressed portion an extrudate that is fixed to the pressed portion, for example using any of the mechanisms described above or by extending the extrudate to the parameters of a farm (deepening), that of the pressed one Share is formed.

The pressed portion comprises one previously made recess or shape (hereinafter referred to as "shape") in that of the non-pressed Share introduced becomes. In an alternative embodiment, the surface of the pressed Share more than one form (recess) in which the non-pressed portion introduced can be. The shape (s) (recess (s)) are preferably at least partially one or more non-pressed portions. The (the) non-pressed (n) Shares) is then (are) introduced into the mold and the pressed portion fixed as described above.

The non-pressed portion can comprise particles. The particles can can be produced by a known method, for example by conventional spray drying, Granulation, encapsulation or agglomeration. On the pressed part can the particles by incorporating a binder or by formation a coating layer over the non-compressed Proportion to be fixed.

If the detergent tablet more than a non-pressed one Share includes can the first and the second and optionally further non-pressed parts Particles that are substantially different average Have particle sizes. Taking a substantially different average Particle size is here to understand that the Difference between the average particle size of the first and second and / or further compositions by more than 5%, preferably more than 10%, particularly preferably more than 15% or is even 20% larger than the smaller average particle size.

The average particle size here used particulate active detergent components is calculated using a series of van Tyler seven. The series consists of a number of sieves, each with a different sieve opening size. Samples of a composition active detergent components turn into a series sieved by sieves (usually 5 sieves). The weight of a sample the composition retained by the screen is counteracted the opening size of the sieve applied. The average particle size of the composition is defined as the screen opening size that 50% by weight of the sample of the composition is passed through.

In another embodiment, the first and the second and optionally further assign compositions of active detergent components have a substantially different density, so that the difference between the density of the first and second and / or further compositions by more than 5%, preferably by more than 10%, particularly preferably by more than 15% or is even 20% larger than the lower density. The density of the particulate composition of active detergent components can be measured by a known method suitable for measuring the density of a particulate material.

Preferably, the density of the Composition of active detergent components measured using a simple funnel and cup device, which consists of a conical funnel that is rigid at a base is molded and with a flap valve at its lower end is provided so that the Contents of the funnel into an axially aligned cylindrical Cup can be emptied, which is arranged below the funnel is. The funnel is 130 mm high and has an inner diameter of 130 mm and 40 mm at its respective upper and lower ends. He is so attached that lower end is located 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an inner diameter of 84 mm. Its nominal Volume is 500 ml.

A density measurement is carried out by the composition is poured into the funnel by hand. If once the funnel is filled the flap valve is opened and you leave the powder run through the funnel, overflowing the cup. The filled mug is removed from the frame and the excess powder is removed from the cup removed by using a straight wiper element, for example a knife, over its upper edge leads away. The filled one The cup is then weighed and the weight of the powder obtained The value is doubled, giving the bulk density in g / l. The Measurements are repeated as often as necessary.

Tablets in which one or more the non-pressed Proportions of particles include and the average particle size and / or Density of the first and second and possibly further non-pressed parts are substantially different from each other, are preferred if the first and the second and the optionally further non-pressed portions different resolution speeds should have.

If the non-pressed portion comprises a solidified melt, the melt is made by heating a composition, which an active detergent component and optionally one or comprises several carrier components a value above its melting point to form a flowable melt. The flowable melt is then poured into a mold and allowed to cool. When the melt cools, it becomes solid, changing the shape of the shape (depression) at ambient temperature accepts. If the composition comprises one or more carrier components, (can they Carrier component (s) be heated to a temperature above their melting point and then an active detergent component can be added become. Carrier components, the for the production of a solidified melt are suitable in typically non-active components that are at a temperature above their melting point can be heated to form a liquid and the cooled down can be to form an intermolecular matrix that the active Can effectively include detergent components. A preferred non-active Carrier component is an organic polymer that is solid at ambient temperature. The non-active detergent components are preferably used around polyethylene glycol (PEG). The compressed portion of the detergent tablet preferably has a shape (depression), which the melt receives.

The flowable, non-pressed part can be in a form that is a dissolved or suspended active Detergent component includes. The flowable non-pressed part can harden under time Formation of a solid, semi-solid or highly viscous liquid non-pressed portion by any of the methods described above. The flowable non-pressed part can harden particularly by evaporation of a solvent. To solvents the for the use according to the invention are suitable belong any known solvent in which a binder is soluble is. Preferred solvents can be polar or non-polar and they can include water, alcohol (e.g. ethanol, acetone) and alcohol derivatives. An alternative embodiment can also be more than one solvent be used.

The flowable, unpressed portion may comprise one or more binders. Any binder which has the effect of ensuring that the composition becomes solid, semi-solid or highly viscous over time is suitable for the use according to the invention. Without being bound by any theory, it is believed that the mechanisms by which the binder causes a non-solid composition to become solid, semi-solid, or highly viscous include: a chemical reaction (e.g. chemical crosslinking) or the initiation of an interaction between two or more components of the flowable compositions; a chemical or physical interaction between the binder and a component of the composition. Preferred binders include a sugar / gelatin combination, starch, glycerin and organic polymers. The sugar can be any monosaccharide (e.g. glucose), disaccharide (e.g. sucrose or maltose) or polysaccharide. The on most preferred sugar is the commonly available sucrose. Type A or Type B gelatin, such as is available from Sigma, for example, can be used for the purposes of the present invention. Type A gelatin is preferred because it is more stable than Type B under alkaline conditions. A preferred gelatin also has a bloom resistance between 65 and 300, most preferably between 75 and 100. Preferred organic polymers include polyethylene glycol (PEG) with a molecular weight of 500 to 10,000, preferably 750 to 8000, most preferably 1000 to 6000, available from Hoechst.

If the non-pressed portion is an extrudate, the extrudate is made by premixing the active detergent components with any used Carrier components to form a viscous paste. The viscous paste is then using a suitable, commonly available Extrusion device, for example a single-screw or twin-screw extruder, as for example from the company APV Baker, Peterborough, U. K., available is extruded. The extrudate is then cut to the desired size, either after insertion in the pressed Share or before introduction in the pressed Percentage of detergent tablet. The compressed portion of the tablet preferably comprises a shape (recess) into which the extruded non-pressed portion introduced can be.

In a preferred embodiment becomes the non-pressed Share with a coating layer Mistake. The layer can be used to make a non-pressed portion on the pressed To fix share. This can be particularly advantageous if the non-pressed Proportion of flowable particles, Gels or liquids includes.

The coating layer preferably comprises a material that is in contact with the pressed and / or non-pressed portion within preferably less than 15 minutes, particularly preferred less than 10 min, very particularly preferably less than 5 min and most preferably less than 60 s, solid becomes: the coating layer is preferably water soluble. Preferred coating layers include materials selected are from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, Carboxylic acid, dicarboxylic acid, Polyvinyl acetate (PVA), polyvinyl pyrrolidone (PVP), polyacetic acid (PLA), Polyethylene glycol (PEG) and mixtures thereof. Preferred carboxylic acids or dicarboxylic acids preferably comprise an even number of carbon atoms. Preferred carboxylic acids or dicarboxylic acids comprise at least 4, particularly preferably at least 6, very particularly preferably at least 8 and most preferably 8 to 13 carbon atoms. Preferred dicarboxylic acids belong Adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid and Mixtures of these. Preferred fatty acids are those that have a Carbon chain length from C12 to C22, particularly preferably from C18 to C22. The coating layer may also preferably comprise a disintegrant. If the coating layer present, it generally makes up at least 0.05%, preferably at least 0.1%, particularly preferably at least 1%, most preferably at least 2% or even at least 5% of the detergent tablet.

In an alternative embodiment can the coating layer encapsulate the detergent tablet. In this embodiment is the coating layer in an amount of at least 4%, particularly preferably at least 5%, most preferably at least 10% of the detergent tablet in front.

In a preferred embodiment contains the pressed one and / or non-pressed portion and / or the coating layer additionally a disassembling agent. The disintegrant can be a disintegrant or be an effervescent. Suitable disintegrants belong Agents that swell upon contact with water or inflow and / or Drain water easier by forming channels in the pressed and / or non-pressed parts. For the use according to the invention any known disintegrant or effervescent is suitable, that for the use for Suitable for washing or dishwashing purposes is. Suitable disintegrators include starch, starch derivatives, alginates, carboxymethyl cellulose (CMC), CMC-based polymers, sodium acetate, aluminum oxide. To suitable effervescent agents those that form a gas on contact with water. Suitable effervescent can its developing oxygen, nitrogen dioxide or carbon dioxide Links. examples for preferred effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate, Bicarbonate and carboxylic acids like citric acid or maleic acid.

An advantage of adding a cutting agent to the detergent tablet according to the invention the transportation, storage and handling benefits that can be achieved through increase the hardness the detergent tablet without detrimental to the cleaning effectiveness to influence.

method

• (i) einen komprimierten Anteil, umfassend einen aktiven Reinigungsmittelbestandteil; und
• (ii) einen nicht-komprimierten, nicht-einkapselnden Anteil, umfassend einen aktiven Reinigungsmittelbestandteil, wobei der komprimierte Anteil eine vorgefertigte Mulde vorsieht und der nicht-komprimierte Anteil in Form eines Gels oder einer verfestigten Schmelze vorliegt und zumindest teilweise in der Mulde enthalten ist, und das Gewichtsverhältnis von komprimiertem Anteil zu nicht-komprimiertem Anteil größer als 4 : 1 ist, das die Stufen umfaßt:
• a) Pressen einer aktiven Reinigungsmittel-Komponente unter Bildung des gepreßten Anteils und Bilden einer Mulde in dem gepreßten Anteil; und
• b) Einführen eines nicht-gepreßten, nicht-einkapselnden Anteils, der eine aktive Reinigungsmittel-Komponente umfaßt, in die Mulde in dem gepreßten Anteil.

The present invention also relates to a method for producing a detergent tablet for use in washing laundry in a washing machine, which comprises:

• (i) a compressed portion comprising an active detergent ingredient; and
• (ii) a non-compressed, non-encapsulating portion comprising an active detergent ingredient, the compressed portion providing a pre-made trough and the uncompressed portion being in the form of a gel or solidified melt and being at least partially contained in the trough, and the weight ratio of compressed portion to uncompressed portion is greater than 4: 1 comprising the steps:
• a) pressing an active detergent component to form the pressed portion and forming a trough in the pressed portion; and
• b) inserting a non-pressed, non-encapsulating portion comprising an active detergent component into the well in the pressed portion.

As described above the detergent tablets described here are manufactured by separate Production of the composition of active detergent components, each the pressed Portion and the non-pressed Form share, subsequent Introduce or attaching the composition of the unpressed portion on the pressed Proportion of.

The pressed portion is produced by providing at least one active detergent component and optionally mixing it with carrier components. The premixing is carried out in a suitable mixer, for example in a pan mixer, a rotary drum, a vertical mixer or a high shear mixer. Preferably, the dry particulate components are mixed together in a mixer as described above and liquid components are added to the dry particulate components, for example by spraying the liquid components directly onto the dry particulate components. The resulting composition is then molded into a pressed portion in a press stage using any known suitable device. Preferably, the composition is molded into a compressed portion using a tablet press, the tablet being made by pressing the composition between an upper and a lower die. In a preferred embodiment of the invention, the composition is introduced into an embossing die recess of a tablet press and pressed to form a pressed portion using a pressure which is preferably greater than 6.3 kN / cm ² , particularly preferably greater than 9 kN / cm ² , most preferably greater than 14.4 kN / cm ² .

To make a preferred tablet according to the invention, in which the pressed Portion has a shape (depression) that the non-pressed portion picks up, the pressed Portion made using a modified tablet press, which includes modified upper and / or lower dies. The upper and lower dies the modified tablet press are modified so that the pressed portion one or more recesses that gives one or more shapes form, in which the non-pressed portion is introduced.

The non-pressed portion comprises at least an active detergent component. If the non-pressed Proportion comprises more than one active detergent component the components using any known suitable one Mixing device premixed. In addition, the non-pressed portion optionally a carrier include with which the active detergent components are combined become. The non-pressed part can be in solid or flowable form getting produced. Once the composition is made it is pressed to the Share fed. The non-pressed one Share can be pressed Share by manual feed or using a nozzle feeder or an extruder become. If the pressed Portion has a shape (recess), the non-pressed portion preferably given in the mold (well) using a Precision feeder for example a nozzle feeder, for example a weight loss screw feeder, as it is available from the company Optima, Germany, or an extruder.

If the flowable, non-pressed portion is in the form of particles, the method comprises feeding a flowable non-pressed portion to the pressed one Proportion in a feed level and the subsequent one Coating at least a portion of the non-pressed portion with a coating layer, so that the coating layer the effect has the non-pressed portion essentially in the pressed portion to fix.

If the flowable non-pressed portion by curing on the pressed Percentage is fixed the process a feed stage, in which the flowable non-pressed portion the pressed one Share fed and a subsequent conditioning step, in which the non-pressed Portion hardens. Such a conditioning step can include drying the Cooling down, binding, polymerizing and the like of the non-pressed portion, being during this stage of the non-pressed Portion becomes solid, semi-solid or highly viscous. In the drying stage can heat be applied. To polymerize in one polymerization stage can cause heat or exposure to radiation.

It is also conceivable for the pressed part to be produced with a multiplicity of shapes (depressions) becomes. The plurality of shapes (recesses) are then filled with an unpressed portion. It is also conceivable for each mold to be filled with a different non-pressed part or, alternatively, for each mold to be filled with a large number of different non-pressed parts.

Active cleaning agent components

The pressed portion of those described here Detergent tablets are made by pressing the composition of active detergent components. A suitable composition can be a variety of different active detergent components include, for example, builder compounds, surfactants, Enzymes, bleaches, sources of alkalinity, dye, Perfume, Lime soap dispersant, organic polymeric compounds including polymeric ones Dye transfer Inhibierungsagentien, Crystal growth inhibitors, heavy metal ion sequestering agents, metal ion salts, Enzyme stabilizers, corrosion inhibitors, foam suppressors, Solvent, Fabric softeners, optical brighteners and hydrotropic agents.

Strongly preferred active detergent components belong a builder (scaffold) connection, a surfactant, an enzyme and a bleach.

Builder Connection

The cleaning agent tablets according to the invention preferably contain a builder connection, usually in an amount of 1 to 80% by weight, preferably from 10 to 70% by weight, most preferably from 20 to 60 wt .-%, based on the weight of the composition of the active Detergent components.

Water soluble builder compound

To suitable water-soluble Belong to builder connections the water soluble monomeric polycarboxylates or their acid forms, homo- or copolymers polycarboxylic or their salts in which the polycarboxylic acid contains at least two carboxyl radicals comprises separated by no more than two carbon atoms are, carbonates, bicarbonates, borates, phosphates and mixtures of above compounds.

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

Suitable carboxylates, the one Contain carboxy group, belong the water soluble Lactic acid salts, glycolic and their ether derivatives. To polycarboxylates, the two carboxy groups included, belong the water soluble Salts of succinic acid, malonic, (Ethylenedioxy) diacetic acid, maleic acid, diglycolic, Tartaric acid, tartronic and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. To polycarboxylates, which contain three carboxy groups include in particular water-soluble citrates, Aconitrate and citraconate as well as succinate derivatives, for example the carboxymethyloxysuccinates as described in the British patent 1,379,241, lactoxysuccinates as described in the British Patent 1,389,732 and aminosuccinates as described in the Dutch Patent Application No. 7205873 are described, and the oxypolycarboxylate materials, e.g. B. 2-Oxa-1,1,3-propane tricarboxylates as described in the British patent 1,387,447.

To polycarboxylates, the four carboxy groups included, belong Oxydisuccinates as described in British Patent 1,261,829 are 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. To polycarboxylates, which contain sulfo substituents include the sulfosuccinate derivatives, as disclosed in British Patents 1,398,421 and 1,398,422 and in U.S. Patent 3,936,448 and the sulfonated pyrolyzed Citrates as described in British Patent 1,439,000 are.

Alicyclic and heterocyclic Polycarboxylates include Cyclopentane-cis, cis, cis-tetracarboxylates, Cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyhydroxy alcohols, such as sorbitol, Mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives, as described in British Patent 1,425,343.

The preferred polycarboxylates among The above are hydroxy carboxylates, which have up to three carboxy groups per molecule contain, particularly preferred are citrates.

The parent acids (starting acids) of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, such as citric acid or citrate / citric acid mixtures also considered useful builder components.

Borat builders as well as builders who Contain borate-forming materials that are among the detergent storage or washing conditions can form borate can also be used however, they are under washing conditions of less than 50 ° C, especially below 40 ° C, not preferred.

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

Particularly preferred builder compounds for the use according to the 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, Sodium polymeta / phosphate, the degree of polymerization in the range from 6 to 21, and salts of phytic acid.

Specific examples of water soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, Sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta / phosphate, wherein the degree of polymerization is in the range from 6 to 21, and salts of phytic acid.

Partially soluble or insoluble Builder Connection

The detergent tablets according to the invention can 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 laundering processes. Examples of partially water-soluble builder compounds include the crystalline layered silicates as described, for example, in EP-A-0164514, in DE-A-3417649 and in DE-A-3742043. The crystalline layered sodium silicates of the general formula are preferred NaMSi _x O _{2x +} 1yH ₂ O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "layer" structure, e.g. B. the so-called δ-layer structure, as in EP 0 164 514 and in EP 0 293 640 is described. Processes for producing crystalline layered silicates of this type are described in DE-A-34 17 649 and in DE-A-37 42 043. For the purposes of the present invention, x in the general formula given above has a value of 2, 3 or 4, preferably 2.

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

The crystalline layered sodium silicate material lies preferably in granular Detergent compositions as a particulate material intimately Mixture with a solid, water-soluble ionizable material as described in PCT patent application WO92 / 18594. 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 builder substances which are largely insoluble in water include sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites, which have a unit cell of the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] .xH ₂ O, where z and y are at least 6; the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, particularly preferably 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline and contain 10 to 28%, particularly preferably 18 to 22% water in bound form.

The aluminosilicate zeolites can be found in naturally occurring materials, but they are preferred synthetically manufactured. Synthetic crystalline aluminosilicate ion exchange materials are under the names Zeolite A, Zeolite B, Zeolite P, Zeolites X, Zeolites HS and mixtures thereof available.

A preferred method of synthesizing of aluminosilicate zeolites is such as that of Schoeman et al (published in "Zeolithe" (1994), 14 (2), 110-116) is where the author is a method of making colloidal Describes aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should preferably be so big that not more than 5 of the particles have a size of more than 1 μm have a diameter and no more than 5% of the particles have a size of less than 0.05 μm have in diameter. Preferably the aluminosilicate particles have zeolite an average particle diameter between 0.01 and 1 μm, especially preferably between 0.05 and 0.9 μm, most preferably between 0.1 and 0.6 µm.

Zeolite A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O where x stands for a number from 20 to 30, in particular for the number 27.

Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 276H ₂ O. Zeolite MAP, as described in EP-B-0 384 070, is a preferred zeolite builder here.

Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. If as a component a detergent composition can be used the colloidal aluminosilicate zeolites, especially the colloidal Zeolite A, an improved builder performance by providing an improved Allow stain removal. Improved builder performance can also be seen in terms of reduced tissue incrustation and improved fabric whiteness maintenance, Problems believed to be related to detergent compositions associated with low builder content.

Surprised was found to be mixed Aluminosilicate zeolite detergent compositions, the colloidal Zeolite A and colloidal zeolite Y comprise the same calcium ion sequestering performance result as an equal amount of weight from commercial Zeolite A. Another result that was surprisingly found is that mixed Aluminosilicate zeolite detergent compositions such as have been described above, an improved magnesium ion sequestration efficiency result as an equal weight amount of commercially available Zeolite A.

surfactant

Surfactants are preferred active detergent components of the compositions described here. Suitable surfactants selected from anionic, cationic, non-ionic ampholytic and zwitterionic surfactants and mixtures thereof. Automatic dishwasher products should little foam and therefore the Foaming of the surfactant system for use in dishwashing processes repressed be, or most preferably a little foaming system, usually with a non-ionic character. Foaming caused by Causes surfactant systems that are used in washing cleaning processes not to be suppressed to the same extent as with the Wash the dishes is required. The surfactant is usually in an amount of 0.2 to 30 wt .-%, particularly preferably from 0.5 to 10 wt .-%, am most preferably from 1 to 5% by weight based on the weight of the Composition of the active detergent components, before.

A typical list of anionic, non-ionic, ampholytic and zwitterionic Surfactants and species of these surfactants are described in U.S. Patent 3,929,678 (Laughlin and Heuring, published December 30, 1975). A list of suitable cationic surfactants is given in U.S. Patent 4,259,217 (Murphy, released on March 31st 1981). A list of surfactants, usually in automatic Dishwashing detergent compositions are contained, for example, in EP-A-0 414 549 and in PCT patent applications WO 93/08876 and WO 93/08874.

Non-ionic surfactant

It can be practically any non-ionic surfactant that for Cleaning purposes can be used in the detergent tablet be included. Preferred classes of usable non-ionic Surfactants, to which the invention is not limited, are listed below.

Non-ionic ethoxylated alcohol surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 mol ethylene oxide are for the use according to the invention suitable. The alkyl chain of the aliphatic alcohol can either be straight (unbranched) or branched, primary or secondary and generally contain 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols that have an alkyl group have with 8 to 20 carbon atoms, with 2 to 10 moles of ethylene oxide per mole of alcohol.

With end groups provided alkyl alkoxylate surfactant

A suitable, end-capped alkyl alkoxylate surfactant are the poly (oxyalkylated) alcohols with epoxy end groups, 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 with 4 to 18 carbonates men; R _{2 is} a linear or branched aliphatic hydrocarbon radical having 2 to 26 carbon atoms; x is an integer with an average value of 0.5 to 1.5, preferably 1; and y represents an integer with a value of at least 15, preferably at least 20.

The surfactant of formula I contains at least 10 carbon atoms in the terminal epoxy unit [CH ₂ CH (OH) R ₂ ]. Suitable surfactants of formula I according to the present invention are SLF 18B Olin Corporation, for example, in WO 94/22800, published October 13, 1994, Olin Corporation describes the non-ionic surfactants POLYTERGENT ^®.

With ether end groups poly (oxyalkylated) alcohols

Preferred surfactants for use in accordance with the invention include poly (oxyalkylated) alcohols of the formula which have an ether end group: 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 with an average value from 1 to 30, where if x ≥ 2, R ³ can stand for the same or different radicals, and k and j are integers with an average value from 1 to 12, preferably from 1 to 5, represent.

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 those having 8 to 18 carbon atoms being most preferred. N or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms is most preferred for R ³ . X is preferably an integer with an average value of 1 to 20, particularly preferably 6 to 15.

As indicated above, when x is greater than 2 in preferred embodiments, R ^{3 may be the} same or different. That is, R ³ can vary between the alkylene oxide units as described above. For example, if x = 3, R ³ can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and it can vary in the order (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the integer 3 is chosen only as an example and the variation can be much larger with a higher integer for x and it can for example comprise many (EO) units and a much smaller number of (PO) units.

To particularly preferred surfactants, as described above include those that have a low cloud point of less than 20 ° C to have. These low cloud point surfactants can then together with a surfactant with a high cloud point, as below described in detail, to achieve better fat cleaning effects be used.

The most preferred ether terminated poly (oxyalkylated) alcohol surfactants are those where k = 1 and j = 1 so that the surfactants have the formula: R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² wherein R ¹ , R ² and R ^{3 are} as defined above and x represents an integer with an average value from 1 to 30, preferably from 1 to 20 and be particularly preferably from 6 to 18. Most preferred are surfactants wherein R ¹ and R ^{2 are} in the range of 9 to 14 carbon atoms, R ^{3 is} N that forms ethyleneoxy, and x is in the range of 6 to 15.

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

These surfactants have significant Improvements in detaching and filming properties and removing greasy dirt when used with High cloud point surfactants compared to conventional surfactants.

In general, the poly (oxyalkylene) alcohol surfactants with ether end group according to the present invention can be produced by reacting an aliphatic alcohol with an epoxy to form of an ether, which is then reacted with a base to form of a second epoxy. The second epoxy is then alkoxylated Alcohol implemented to form the new invention Links. examples for Process for the preparation of the poly (oxyalkylated) alcohol surfactants with ether end groups are described below.

Preparation of a C _12/14 alkyl glycidyl ether

AC _12/14 fatty alcohol (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol, available from Aldrich) are placed in a 500 ml three-necked round bottom flask made of is equipped with a cooler, an argon inlet, an addition funnel, a magnetic stirrer and an internal temperature probe. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise so as to maintain the temperature between 60 and 65 ° C. After stirring for a further hour at 60 ° C., 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 stirring mechanically. After the addition has ended, the mixture is heated to 90 ° C. for 1.5 hours, cooled and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO ₄ , filtered and concentrated. Distillation of the oil at 100 to 120 ° C (0.1 mm Hg) gives the glycidyl ether in the form of an oil.

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

Neodol ^® 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from the Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) in a 250 ml are three-necked -Round flask combined, which is equipped with a cooler, an argon inlet, an addition funnel, a magnetic stirrer and an internal temperature probe. The mixture is increased to 60 ° C., at which time a C _12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over a period of 15 min. After stirring at 60 ° C. for 18 hours, the mixture is cooled to room temperature and dissolved in an equal amount of dichloromethane. The solution is passed through a 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, 0.5 mm Hg) to give the surfactant in the form of an oil.

Non-ionic ethoxylated / propoxylated Fatty alcohol surfactant

The ethoxylated C ₆ -C ₁₈ fatty alcohols and the mixed C ₆ -C ₁₈ ethoxylated / propoxylated fatty alcohols are suitable surfactants for the use according to the invention, in particular if they are water-soluble. Preferred as ethoxylated fatty alcohols are the C ₁₀ -C ₁₈ -ethoxylated fatty alcohols with a degree of ethoxylation of 3 to 50, most preferred among these are the C ₁₂ -C ₁₈ -ethoxylated fatty alcohols with a degree of ethoxylation of 3 to 40. The mixed ethoxylated ones preferably have / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

Non-ionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base, which are formed by condensation of propylene oxide with propylene glycol, are suitable for the use according to the invention. The hydrophobic part of these compounds preferably has a molecular weight of 1500 to 1800 and is insoluble in water. Examples of compounds of this type include certain commercially available Pluronic ^™ surfactants marketed by BASF.

Non-ionic EO condensation products with propylene oxide / ethylenediamine adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide with ethylenediamine are suitable for use in the present invention. The hydrophobic portion 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 non-ionic surfactant include certain of the commercially available Tetronic ^™ compounds from the company BASF to be brought to the market.

mixed non-ionic surfactant system

In a preferred embodiment of the present invention the detergent tablet is a mixed non-ionic surfactant system, the at least one non-ionic surfactant with a low cloud point and at least one high cloud point nonionic surfactant includes.

The term "cloud point" used here means a generally known property of nonionic surfactants, which is a consequence of the fact that the surfactant increases with temperature becomes less soluble, the temperature at which the appearance of a second phase becoming visible is referred to as the "cloud point" (cf. "Kirk Othmer's Encyclopedia of Chemical Technology", 3rd edition, volume 22, pages 360-379).

A "low cloud point" nonionic surfactant used herein is defined as a nonionic surfactant system component that has a cloud point of less than 30 ° C, preferably less than 20 ° C, and most preferably less than 10 ° C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from a primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reversible block polymers. These nonionic surfactants with low cloud point include for example, ethoxylated-propoxylated alcohol (eg. As Poly-Tergent SLF18 ^® Olin Corporation), having an epoxy terminal group provided poly (oxyalkylated) alcohols (eg. B. non- ionic surfactants of the poly-Tergent SLF18B ^® series from Olin Corporation, as described for example in WO 94/22800, published October 13, 1994, Olin Corporation) are described, and the ether end groups, provided poly (oxyalkylated) alcohol surfactants.

Non-ionic surfactants may be used Contain propylene oxide in an amount of up to 15 wt .-%. Other preferred non-ionic surfactants can be prepared by processes as disclosed in U.S. Patent 4,223,163 (Builloty on September 16, 1980), to which express reference is made here is taken.

Low cloud point nonionic surfactants also include a polyoxyethylene-polyoxypropylene block polymer compound. Polyoxyethylene / polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane and ethylenediamine as a reactive initiator-hydrogen compound. Certain of the block polymer surfactant compounds called PLURONIC ^® ; REVERSED PLURONIC ^® and TETRONIC ^® from BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions according to the invention. Preferred examples include REVERSED PLURONIC ^® 25R2 and TETRONIC ^® 702. These surfactants can generally be used according to the invention as non-ionic surfactants with a low cloud point.

The non-ionic used here "High Cloud point "is defined as a non-ionic surfactant system component with a cloud point from higher than 40 ° C, preferably higher than 50 ° C and particularly preferably from higher than 60 ° C. Preferred is the non-ionic surfactant system, which is an ethoxylated surfactant comprises that of the reaction of a monohydroxy 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 is. To these non-ionic surfactants with a high cloud point belong for example Tergitol 15S9 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhone Poulenc) and Neodol 91-8 (distributed by Shell).

For for the purposes of the present invention, it is also preferred that the nonionic High cloud point surfactant Moreover a hydrophilicity-lipophilicity equilibrium value (HLB value; see Kirk Othmer, as stated above) within the range from 9 to 15, preferably from 11 to 15. About these materials belong for example Tergitol 15S9 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhone Poulenc) and Neodol 91-8 (distributed by Shell).

Another preferred non-ionic surfactant with a high cloud point is derived from a straight chain or preferably branched chain or secondary fatty alcohol containing 6 to 20 carbon atoms (C ₆ -C ₂₀ alcohol) including the secondary alcohols and branched chain primary alcohols. The non-ionic surfactants with a high cloud point are preferably branched or secondary alcohol ethoxylates, particularly preferably mixed C9 / 11 or C11 / 15 branched alcohol ethoxylates, with an average of 6 to 15 mol, preferably 6 to 12 mol, most preferably 6 to 9 mol Ethylene oxide are condensed per mole of alcohol. The ethoxylated non-ionic surfactant derived in this way preferably has a narrow ethoxylate distribution, based on the average value.

In a preferred embodiment comprises the detergent tablet, which is such a mixed surfactant system comprises Moreover a lot of water soluble Salt to electrical conductivity in deionized water, measured at 25 ° C, of higher than 3 mS / cm, preferably from higher than 4 mS / cm, most preferably higher than 4.5 mS / cm, as in the pending British patent application (attorney file number CM 1573F).

In another preferred embodiment, the mixed surfactant system dissolves in water having a hardness of 1.246 mmol / L in any suitable automatic cold fill dishwasher to form a solution with a surface tension of less than 4 dynes / cm ² at less less than 45 ° C, preferably less than 40 ° C, most preferably less than 35 ° C, as described in pending U.S. patent application (Attorney Docket No. 6252).

In another preferred embodiment, the high cloud point and low cloud point surfactants of the mixed surfactant system are separated from one another such that one of the high cloud point surfactants or the low cloud point surfactants is present in a first matrix and the other is in a second matrix, as described in pending US patent application (attorney file number 6252). For the purposes of the present invention, the first matrix can be a first particulate matrix and the second matrix can be a second particulate matrix. A surfactant can be applied to a particulate matrix using any suitable known method, preferably the surfactant is sprayed onto the particulate material. In a preferred aspect, the first matrix is the pressed portion and the second matrix is the non-pressed portion of the detergent tablet according to the invention. The surfactant with a low cloud point is preferably present in the compressed portion and the surfactant with a high cloud point is present in the non-compressed portion of the detergent tablet according to the invention.

anionic surfactant

Any are essentially suitable anionic surfactants for Cleaning purposes are useful. These can include salts (including, for example the sodium, potassium, ammonium and substituted ammonium salts, such as the mono-, di- and triethanolamine salts) of anionic sulfate, Sulfonate, carboxylate and sarcosinate surfactants. The anionic suifate surfactants are preferred.

Other anionic surfactants include the isethionates, for example the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, the monoesters of sulfosuccinate (in particular the saturated and unsaturated C ₁₂ -C ₁₈ monoesters), the diesters of sulfosuccinate (in particular the saturated and unsaturated C ₆ -C ₁₄ diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, e.g. As rosin, hydrogenated rosin and resin acids and hydrogenated resin acids that occur in or are derived from tallow oil.

anionic Sulfate surfactant

Anionic sulfate surfactants suitable for use in the invention include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ - alkyl) - and -N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfates and the sulfates of alkyl polysaccharides, for example the sulfates of alkyl polyglucoside (the non-ionic non-sulfated compounds being described here).

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

Alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C ₁₀ -C ₁₈ alkyl sulfates that have been ethoxylated with 0.5 to 20 times ethylene oxide per molecule. Particularly preferred as the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ , in particular a C ₁₁ -C ₁₅ alkyl sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5 times, ethylene oxide per molecule.

In a particularly preferred aspect The invention provides mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants used. These mixtures are in PCT patent application WO 93/18124 described.

anionic Sulfonate surfactant

Anionic sulfonate surfactants suitable for the use according to the invention include the salts of linear C ₅ -C ₂₀ alkylbenzenesulfonates, alkyl ester sulfonates, primary or secondary C ₆ -C ₂₂ alkanesulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids , Alkylglycerol sulfonates, fatty acylglycerol sulfonates, fatty oleylglycerol sulfonates and any mixtures thereof.

anionic Carboxylate surfactant

Suitable anionic carboxylate surfactants belong the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyl compounds"), especially certain secondary Soaps are described here.

Suitable alkyl ethoxy carboxylates include those having the formula RO (CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , where R is a C ₆ -C ₁₈ alkyl group, x is a number in the range from 0 to 10 and the Ethoxylate distribution is such that, based on the weight, the amount of material where x = 0 is less than 20% and M stands for a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO- (CHR ₁ CHR ₂ -O) -R ₃ , where R is a C ₆ -C ₁₈ alkyl group and x is a number from 1 to 25, R ₁ and R _{2 are} selected from the group consisting of hydrogen, the methyl acid residue, the succinic acid residue, the hydroxy succinic acid residue and mixtures thereof and R _{3 is} selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms and mixtures thereof.

Suitable soap surfactants include secondary Soap surfactants, which are bound to a secondary carbon atom Carboxyl unit included. For the use according to the invention preferred secondary Soap surfactants are water soluble Representative, 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-actanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can may also be included as foam suppressors.

Alkali metal sarcosinate surfactant

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

amphoteric surfactant

For the use according to the invention suitable amphoteric surfactants include the amine oxide surfactants and Alkyl amphocarboxylic acids.

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

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

zwitterionic surfactant

Zwitterionic surfactants can also are incorporated into the detergent compositions. This Surfactants can are generally described as derivatives of secondary and tertiary Amines, as derivatives of heterocyclic secondary and tertiary amines or as derivatives of quaternary Ammonium, quaternary Phosphonium or tertiary Sulfonium compounds. Betaine and sultain surfactants are exemplary zwitterionic surfactants for the use according to the invention.

Suitable betaines are those compounds of the formula R (R ¹ ) ₂ N ⁺ R ² COO ^- , in which R is a C ₆ -C ₁₈ hydrocarbyl group, each of the R ¹ radicals is usually C ₁ -C ₃ alkyl and R ^{2 represent} a C ₁ -C ₅ hydrocarbyl group. Preferred Setaine are C _12-18 dimethylammoniohexanoate and the C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for the use according to the invention.

cationic surfactants

The cationic used in the invention Ester surfactants are preferably water-dispersible compounds, which have surfactant properties and at least one ester (i.e. H. -COO -) - bond and at least one cationically charged group exhibit. Other suitable cationic ester surfactants include choline ester surfactants, such as those described in U.S. Patents 4,228,042, 4,239,660 and 4,260,529.

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

enzymes

In one embodiment of the present invention, an enzyme is an essential feature of the detergent tablet. In other embodiments of the present invention, an enzyme is an optional active detergent component. If the enzymes mentioned are present, who they selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, Amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, laconate or chondroitinase thereof.

Preferred enzymes include Protease, amylase, lipase, peroxidases, cutinase and / or cellulase in combination with one or more a plant cell wall degrading enzymes.

The cellulases which can be used according to the invention include both bacterial and fungi cellulase. They preferably have a pH optimum between 5 and 12 and an activity of> 50 CEVU (cellulose viscosity units). Suitable cellulases are described in U.S. Patent 4,435,307 (Barbesgoard et al.), J61-078384 and WO96 / 02653, which describe fungi cellulases, each made from Humicola insolens, Trichoderma, Thielavia and Sporotrichum , In EP 0 739 982 describes cellulases which have been isolated from new Bacillus species. Suitable cellulases are also described in GB-A-2 075 028; GB-A-2 095 275; DE-OS-2 247 832 and WO95 / 26398.

Examples of such cellulases are Cellulases derived from a strain of Humicola insolens (Humicola grisea var thermoidea), in particular the Humicola strain DSM 1800, be formed. Other suitable cellulases are cellulases that from Humicola insolens, with a molecular weight of 50 KDa, contain an isoelectric point of 5.5 and 415 amino acids; and a ~ 43 kD endoglucanase from Humicola insolens, DSM 1800, which has cellulase activity; a preferred one Endoglucanase component has the amino acid sequence described in PCT patent application WO 91/17243 on. Suitable cellulases are also the EGIII cellulases from Trichoderma Iongibrachiatum, as described in WO94 / 21801 (Genencor, published on September 29, 1994). Particularly suitable cellulases are the cellulases with color care effects, examples of such Cellulases are those in the European Patent Application No. 91202879.2 (Novo), filed November 6 1991) described cellulases. Carezyme and Celluzyme (Novo Nordisk A / S) are particularly useful (see also WO91 / 17244 and WO91 / 21801). Other suitable cellulases for tissue care and / or cleaning properties are in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

The cellulases mentioned are usually the detergent composition in amounts of 0.0001 to 2% active enzyme by weight of the detergent composition.

Peroxidase enzymes are used in combination with oxygen sources, for example a percarbonate, perborate, Persulfate, hydrogen peroxide and the like. They are used for "solution bleaching", d. that is, the transfer of dyes or pigments that are made during washing operations Substrates have been removed to other substrates in the wash solution prevent. Peroxidase enzymes are known from the prior art and belong to it for example horseradish peroxidase, ligninase and haloperoxidase, for example chloro- and bromoperoxidase. Peroxidase containing Detergent compositions are for example in the International PCT patent applications WO 89/099813, WO89 / 09813 and in European patent applications No. 91202882.6 (filed November 6, 1991) and 96870013.8 (filed on February 20, 1996). It is also suitable the lactase enzyme.

Preferred reinforcing agents (improving agents) are substituted phenthiazine and phenoxazine, 10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C ₃ -C ₅ substituted alkylsyringates) and phenols, sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

The cellulases mentioned and / or Peroxidases are usually the detergent composition in amounts of 0.0001 to 2% active enzyme by weight of the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the invention include lipases. Suitable lipase enzymes for use in a detergent include those formed by microorganisms of the Pseudomonas group, for example Pseudomonas stutzeri ATCC 19.154, as described in British Patent 1,372,034. Suitable lipases include those which give a positive immunological cross-reaction with the lipase antibody produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, for example Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., Netherlands, and lipases from Pseudomonas gladioli. Especially suitable lipases are lipases M1 Lipase Lipomax ^{® ®} and (Eactual-Brocades) and Lipolase ^® and Lipolase Ultra ^® (Novo) which have proved to be very effective when used in combination with the compositions of this invention as shown. The lipolytic enzymes as described in EP 0 258 068 , WO 92/05249 and WO 95/22615 (Novo Nordisk) and in WO 94/03578, WO 95/35381 and WO 96/00292 (Unilever).

Cutinases [EC 3.1.150], which can be regarded as a special type of lipase, namely as Lipases that have no interface activation require. The addition of cutinases to detergent compositions is already described for example 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 usually the detergent composition in amounts of 0.0001 up to 2% of the active enzyme, based on the weight of the detergent composition, incorporated.

Suitable proteases are the subtilisins which are available from special strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH-range of 8 to 12 and is developed and sold under the name ESPERASE ^® by Novo Industries A / S of Denmark, hereinafter referred to as Inscribed "Novo". The preparation of this enzyme and of analogous enzymes is described in GB 1 243 784 (Novo). Other suitable proteases include ALCALASE ^® , DURAZYM ^® and SAVINASE ^® from Novo and MAXATASE ^® , MAXACAL ^® , PROPERASE ^® and MAXAPEM ^® (protein-modified Maxacal) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, e.g. B. those as described in European Patent Application No. 87303761.8 (filed on April 28, 1987), particularly on pages 17, 24 and 98, which is referred to there as "Protease B", and in the European patent application 0 199 404 (Venegas, published October 29, 1986), which is referred to here as a modified bacterial serine proteolytic enzyme, here called "Protease A". Also suitable is what is referred to here as "Protease C", which is a variant of an alkaline serine protease from Bacillus, in which lysine in position 27 replaces arginine, thyrosine in position 104 replaces valine, serine replaced asparagine in position 123 and alanine replaced in position 274 threonine. Protease C is in EP 90 915 958 4 , corresponding to WO 91/06637 (published May 16, 1991). Genetically modified variants, in particular of protease C, also belong to the scope of the present invention.

A preferred protease, referred to herein as "Protease D", is a carbonyl hydrolase variant with an amino acid sequence found in nature is not present, which is derived from a precursor carbonyl hydrolase has been through introduction another amino acid instead of a multitude of amino acid residues in one position in said carbonyl hydrolase, which is equivalent to the position +76 is, preferably also in combination with one or more amino acid residue positions, the equivalent to those are 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 after the numbering of the Bacillus amyloliquefaciens subtilisin, such as in WO 95/10591 and in the patent application by C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes "with the US application no. 08/322 677, filed October 13, 1994, described.

Proteases such as those in the patent applications are also suitable for the present invention EP 251 446 and WO 91/06637, protease BLAP ^®, as described in WO 91/02792, and its variants as described in WO 95/23221.

A protease with a high pH from Bacillus sp. NCIMB 40338, as described in WO 93/18140 A (Novo). Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A (Novo). If desired, a protease which has reduced adsorption and increased hydrolysis is available, as described in WO 95/07791 (Procter & Gamble). A recombinant trypsin-like protease for cleaning agents which is suitable according to the invention is described in WO 94/25583 (Novo). Other suitable proteases are in EP 516 200 (Unilever).

To other preferred protease enzymes belong Protease enzymes, which are a carbonyl hydrolase variant, which is an amino acid sequence which is not present in nature, which has been derived is from a precursor carbonyl hydrolase with other amino acids by replacing a variety of the amino acid residues, the said variety of amino acid residues, those in the precursor enzyme position +210 in combination with a corresponds to one or more of the following radicals: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions of a naturally occurring subtilisin of Bacillus amyloliquefaciens correspond or are equivalent to amino acid residues in other carbonyl hydrolases or subtilisins (e.g. Bacillus lentus subtilisin). Preferred enzymes of this type include those the position changes in +210, +76, +103, +104, +156 and +166.

The proteolytic enzymes are the detergent compositions according to the invention in an amount of 0.0001 to 2% by weight, preferably 0.001 to 0.2% by weight, in particular from 0.005 to 0.1% by weight, of pure enzyme, based on the weight of the composition.

Amylases (α- and / or β-amylases) may be included to remove carbohydrate-based stains. WO94 / 02597 (Novo Nordisk A / S, published on February 03, 1994) describes cleaning compositions which contain mutant amylases (see also WO95 / 10603 (Novo Nordisk A / S, published on April 20, 1995) ). Other amylases known for use in cleaning compositions contain both α- and β-amylases. α-Amylases are known in the art and include those as described in U.S. Patent 5,003,257; in EP 252 666 ; in WO 91/00353; in FR 2 676 456; in EP 285 123 ; EP 525 610 ; in EP 368 341 and described in British Patent 1,296,839 (Novo). Further suitable amylases are amylases with improved stability, as described in WO94 / 18314 (published on August 18, 1994) and WO96 / 05295 (Genencor, published on February 22, 1996) and amylase variants with an additional modification in the immediate precursor, available from Novo Nordisk A / S, described in WO 95/10603, published in April 1995. Amylases as described in EP 277 216 , WO95 / 26397 and WO96 / 23873 (all from Novo Nordisk).

Examples of commercially available α-amylysis products are Purafect Ox Am ^® from Genencor and Termamyl ^® , Ban ^® , Fungamyl ^® and Duramyl ^® , all available from Novo Nordisk A / S Denmark. In WO95 / 26397 other suitable amylases are described: α-amylases which are characterized in that they have a specific activity that is higher by at least 25 than the specific activity of Termamyl ^® at a temperature in the range of 25 to 55 ° C and at a pH in the range of 8 to 10 as determined by the Phadebas ^® -α-amylase activity assay. Variants of the above-mentioned enzymes are also suitable, as described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes with improved properties in terms of activity and the combination of heat resistance and higher activity are described in WO95 / 35382.

Preferred amylase enzymes include those as described in WO95 / 26397 and in the pending patent application of Novo Nordisk PCT / DK96 / 00056 are described.

The amylolytic enzymes are the detergent compositions according to the invention in an amount of 0.0001 to 2%, preferably 0.00018 to 0.06%, particularly preferably 0.00024 to 0.048% pure enzyme, based on the weight of the composition.

In a particularly preferred embodiment comprise the detergent tablets according to the invention Amylase enzymes, especially those as described in WO95 / 26397 and in the pending Patent application PCT / DK96 / 00056 from Novo Nordisk described are in combination with a complementary amylase.

“Complementary” here means the addition of one or more amylases which are suitable for cleaning purposes. Examples of complementary amylases (α- and / or β-amylases) are given below. In WO94 / 02597 and WO95 / 10603 (Novo Nordisk A / S) cleaning compositions are described which contain mutant amylases. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those described in U.S. Patent 5,003,257; in EP 252 666 ; in WO 91/00353; in FR 2 676 456; in EP 285 123 ; in EP 525 610 ; in EP 368 341 and described in British Patent 1,296,839 (Novo). Other suitable amylases are amylases with improved stability, as described in WO94 / 18314 and WO96 / 05295 (Genencor), and amylase variants with an additional modification in the immediate precursor, available from Novo Nordisk A / S, described in WO 95 / 10,603th Amylases as described in EP 277 216 (Novo Nordisk) are described. Examples of commercially available α-amylase products are Purafect Ox Am ^® from Genencor and Termamyl ^® , Ban ^® , Fungamyl ^® and Duramyl ^® , all available from Novo Nordisk A / S Denmark. In WO95 / 26397 other suitable amylases are described: α-amylases which are characterized in that they have a specific activity that is higher by at least 25% higher than the specific activity of Termarnyl ^® at a temperature in the range of 25 to 55 ° C and at a pH in the range of 8 to 10, determined according to the Phadebas ^® α-amylase activity assay. Variants of the above-mentioned enzymes, as described in WO96 / 23873 (Novo Nordisk), are also suitable. Further amylolytic enzymes with improved properties in terms of activity and the combination of heat resistance and higher activity are described in WO95 / 35382. Preferred complementary amylases for the present invention are the amylases described in WO 94/18314 under the tradename Purafect Ox Am ^®, WO96 / 05295 sold by Genencor; Termamyl ^® , Fungamyl ^® , Ban ^® and Duramyl ^® , all available from Novo Nordisk A / S, and Maxamyl ^® from Gist-Brocades.

The complementary amylase mentioned is generally the detergent compositions of the invention in an amount of 0.0001 to 2% by weight, preferably 0.00018 to 0.06 % By weight, particularly preferably from 0.00024 to 0.048% by weight of pure Enzyme, based on the weight of the composition, is incorporated. The weight ratio of pure enzyme is preferably one specific amylase to the complementary amylase in the range between 9: 1 and 1: 9, particularly preferably between 4: 1 to 1: 4, most preferably between 2: 1 and 1: 2.

The above enzymes can be of any suitable origin, for example wise of plant, animal, bacterial, fungi and yeast origin. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotropic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic and the like). Purified or unpurified forms of these enzymes can be used. The invention by definition also encompasses mutants of native enzymes. Mutants can be obtained, for example, by protein and / or genetic engineering, chemical and / or physical modifications of native enzymes. A common practice is also expression of the enzyme via host organisms in which the genetic material required for the formation of the enzyme has been cloned.

The enzymes mentioned are usually the detergent composition in amounts from 0.0001 to 2 % By weight of active enzyme, based on the weight of the detergent composition, is incorporated. The enzymes can as separate individual components (prills, granules, stabilized liquids and the like, which contain an enzyme) or in the form of mixtures of two or more enzymes (for example cogranulates) are added.

To other suitable detergent components, that can be added belong Enzyme oxidation scavenger, as in pending European patent application No. 92870018.6, filed January 31, 1992. Examples for such Enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme materials and agents for their incorporation into synthetic detergent compositions are also described in WO 93 / 07263A and WO 93/07260 A (Genencor International), WO 89/08694 A (Novo) and in U.S. Patent 3 553,139 (McCarty et al, January 5, 1971). Additional enzymes are described in U.S. Patent 4,101,457 (Place ei al, July 18, 1978) and U.S. Patent 4,507,219 (Hughes, March 26, 1985). Enzyme materials suitable for liquid detergent formulations and their incorporation into such formulations are described in U.S. Patent 4,261,868 (Hora et al, April 14, 1981). Enzymes for use in detergents can be stabilized using various methods. Enzyme stabilization methods are described and exemplified in U.S. Patent 3,600,319 (Gedge ei al) August 17, 1971) and in EP 199 405 and EP 200 586 (Venegas, October 29, 1986). Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. A suitable Bacillus sp. AC13, which can form proteases, xylanases and cellulases, is described in WO 94/01532 A (Novo).

bleach

A particularly preferred component the composition of the active detergent components a bleach. Suitable bleaches include chlorine and oxygen-releasing bleaches, in a preferred one Aspect contains the oxygen-releasing bleach is a source of hydrogen peroxide and an organic peroxyacid bleach precursor. The formation of the organic peroxyacid takes place in an in situ reaction of the predecessor with a hydrogen peroxide source. Preferred hydrogen peroxide sources belong inorganic perhydrate bleach. In another preferred aspect, one is pre-made organic peroxyacid incorporated directly into the composition. Compositions, the mixtures from a hydrogen peroxide source and an organic peroxyacid precursor in Contain combination with a previously prepared organic peroxyacid, are also suitable.

inorganic Perhydrate bleaches

The compositions of the active Detergent components preferably include a source of hydrogen peroxide as an oxygen releasing bleach. Appropriate sources of hydrogen peroxide belong the inorganic perhydrate salts.

The inorganic perhydrate salts are usually in the form of the sodium salt in an amount of 1 to 40% by weight, preferably 2 to 30% by weight, most preferred from 5 to 25% by weight, based on the weight of the composition, added.

Examples of inorganic perhydrate salts belong Perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be a crystalline solid without additional defense be incorporated. For however certain perhydrate salts are the preferred embodiment such grainy Compositions using a coated form of material, which has a better shelf life for the perhydrate salt in the granular Form.

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

Alkali metal percarbonates, especially sodium percarbonate, are preferred perhydrates for incorporation into the compositions according to the invention. Sodium percarbonate is an addition compound, which has a formula corresponding to 2Na ₂ CO ₃ corresponds .3H ₂ O _2, and is available commercially in the form of a crystalline solid. Sodium percarbonate, which is a hydrogen peroxide addition compound, tends to release the hydrogen peroxide rapidly upon dissolution, increasing the tendency towards localized high bleach concentrations. The percarbonate is most preferably incorporated into these compositions in a coated form that provides stability within the product.

A suitable coating material that provides stability within the product comprises a mixed salt of a water-soluble alkali metal sulfate and carbonate. These coatings, along with the coating processes, have already been described in British Patent 1,466,799 (Interox, March 9, 1977). The weight ratio between the mixed salt coating material and the percarbonate is in the range from 1: 200 to 1: 4, particularly preferably from 1:99 to 1: 9 and most preferably from 1:49 to 1:19. It is preferably for the mixed salt around sodium sulfate and sodium carbonate with the general formula Na ₂ SO ₄ .n. Na ₂ CO ₃ , where n is from 0.1 to 3, preferably from 0.3 to 1.0 and most preferably from 0 , 2 to 4.5.

Another suitable coating material that provides stability within the product comprises sodium silicate with an SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, which is preferably applied in an amount of 2 to 10% by weight (normally 3 to 5% by weight) of SiO ₂ , based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings containing silicate and borate salts or boric acid or other inorganic materials are also suitable.

Other coatings, the waxes, oils, fatty soaps can contain also advantageous according to the invention be used.

Potassium peroxymonopersulfate is a other inorganic perhydrate salt used in the compositions of the invention is usable.

Peroxyacid bleach precursor

worin L für eine austretende Gruppe und X im wesentlichen für eine beliebige Funktionalität steht, so daß bei der Perhydrolyse die Struktur der gebildeten Peroxysäure die folgende ist

Peroxysäure-Bleichmittel-Vorläufer-Verbindungen werden vorzugsweise in einer Menge von 0,5 bis 20 Gew.-%, besonders bevorzugt von 1 bis 10 Gew.- %, am meisten bevorzugt von 1,8 bis 5 Gew.-% den Zusammensetzungen einverleibt.Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form a peroxyacid. In general, peroxyacid bleach precursors can be represented by the formula

where L stands for a leaving group and X essentially for any functionality, so that the structure of the peroxyacid formed is the following in perhydrolysis

Peroxyacid bleach precursor compounds are preferably incorporated into the compositions in an amount of 0.5 to 20%, more preferably 1 to 10%, most preferably 1.8 to 5% by weight ,

Suitable peroxyacid bleach precursor compounds usually contain one or more N- or O-acyl groups, being the precursor selected can be from a wide range of classes of compounds. To suitable Classes belong Anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. examples for suitable materials within these classes are in GB-A-1 886 789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and in EP-A-0170386.

escaping groups

The leaving group, below referred to as the L group, must be sufficient reactively be so the perhydrolysis reaction within the optimal time frame expires (e.g. within a wash cycle). However, if L is too reactive, this activator is difficult to stabilize for use in a bleaching composition.

und Mischungen davon, worin R¹ für eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen, R³ für ein Alkylkette mit 1 bis 8 Kohlenstoffatomen, R⁴ für N oder R³, R⁵ für eine Alkenylkette mit 1 bis 8 Kohlenstoffatomen und Y für H oder eine solubilisierende Gruppe stehen. Jeder der Reste R¹, R³ und R⁴ kann substituiert sein im wesentlichen durch irgendeine beliebige funktionelle Gruppe, z. B. Alkyl-, Hydroxy-, Alkoxy-, Halogen-, Amin-, Nitrosyl-, Amid- und Ammonium- oder Alkylammonium-Gruppen.Preferred L groups are selected from the group consisting of

and mixtures thereof, in which R ¹ for an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ³ for an alkyl chain with 1 to 8 carbon atoms, R ⁴ for N or R ³ , R ⁵ for an alkenyl chain with 1 to 8 Carbon atoms and Y represent H or a solubilizing group. Each of R ¹ , R ³ and R ⁴ may be substituted essentially by any functional group, e.g. B. alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred sofubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O <- (N (R ³ ) ₃ and am Most preferred are -SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ , wherein R ^{3 is} for an alkyl chain having 1 to 4 carbon atoms, M for a cation which gives solubility to the bleach activator, and X for an anion which solubility for 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, methyl sulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds result in Perhydrolysis Perbenzoic acid.

To suitable O-acylated perbenzoic acid precursor compounds belong the substituted and unsubstituted benzoyloxybenzenesulfonates including for example benzoyloxybenzenesulfonate:

Ac = COCH₃; Bz = BenzoylAlso suitable are the benzoylation products of sorbitol, glucose and all saccharides with benzoylation agents, such as. B.

Ac = COCH ₃ ; Bz = benzoyl

To perbenzoic acid precursor compounds of the imide type belong N-benzoyl succinimide, Tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. To suitable perbenzoic acid precursor compounds from Include imidazole type N-benzoylimidazole and N-benzoylbenzimidazole and other suitable perbenzoic acid precursor compounds that have an N-acyl group included, belong N-benzoylpyrrolidone, dibenzoyl taurine and benzoylpyroglutamic acid.

To other perbenzoic acid precursor compounds belong the benzoyldiacyl peroxides, the benzoyltetraacyl peroxides and the Compounds of the formula:

Phthalic anhydride is another suitable perbenzoic acid precursor compound used in the present invention can be:

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

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

Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursors Perbenzoic acids substituted in perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors all include perbenzoic acid precursors described here, in which the benzoyl group essentially by a non-positive charged (i.e. non-cationic) functional group, such as alkyl, Hydroxyl, alkoxy, halogen, amine, nitrosyl and amide groups, is substituted.

worin R¹ für eine Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen, R² für eine Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen und R⁵ für Wasserstoff oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen stehen und L im wesentlichen irgendeine austretende Gruppe sein kann. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann Aryl, substituiertes Aryl oder Alkylaryl sein, das eine Verzweigung, eine Substitution oder beide enthält, und es kann aus irgendeiner synthetischen Quelle oder natürlichen Quelle stammen, beispielsweise aus Talgfett. Für R² sind analoge Strukturvariationen zulässig. Die Substitution kann umfassen Alkyl-, Aryl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen. R⁵ steht vorzugsweise für H oder Methyl. R¹ und R⁵ sollten insgesamt nicht mehr als 18 Kohlenstoffatome enthalten. Amid-substituierte Bleichmittelaktivator-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 for an aryl or alkaryl group having 1 to 14 carbon atoms, R ² for an arylene or alkarylene group having 1 to 14 carbon atoms and R ^{5 is} hydrogen or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms and L can be essentially any leaving group. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be aryl, substituted aryl, or alkylaryl containing branching, substitution, or both, and may be from any synthetic or natural source, such as tallow fat. Analogous structure variations are permitted for R ² . The substitution can include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ preferably represents H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

cationic Peroxyacid precursor

Cationic peroxyacid precursor compounds form cationic peroxyacids during perhydrolysis.

Typical cationic peroxyacid precursors will be formed by substituting the peroxyacid portion of an appropriate one Peroxyacid precursor compound with a positively charged functional group, for example an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are usually in the compositions in the form of a. Salt with a suitable Anion, for example a halide ion or a methyl sulfate ion, in front.

The peroxyacid precursor compound that is so cationic to be substituted can be a peroxyacid or a substituted one Derivative thereof as a precursor compound as described above. Alternatively, the peroxyacid precursor compound an alkyl percarboxylic acid precursor compound or an amide-substituted alkyl peroxyacid precursor compound as follows described.

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

Suitable cationic peroxyacid precursors include all Ammonium or alkylammonium substituted Alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyl-tetraacetylglucose benzoyl peroxides.

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

A preferred cationically substituted one Alkyloxybenzenesulfonate has the formula:

Preferred cationic peroxyacid precursors the class of the N-acylated caprolactams include the trialkylammonium methylenebenzoylcaprolactams, especially trimethylammanium-methylenebenzoylcaprolactam:

worin n für eine Zahl von 0 bis 12, insbesondere von 1 bis 5, steht.Other preferred cationic peroxyacid precursors from the class of the N-acylated caprolactams are, for example, the trialkylammonium methylene alkyl prolactams:

where n is a number from 0 to 12, in particular from 1 to 5.

Another preferred cationic Peroxyacid precursor 2- (N, N, N-trimethyl ammonium) -ethylnatrium 4-sulfophenyl-carbonatchlorid.

Alkyl bleach precursor

Alkyl percarboxylic acid bleach precursors are formed from percarboxylic acids in perhydrolysis. Preferred precursors of this type result in the perhydrolysis peracetic acid.

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

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

Amide substituted Alkyl peroxyacid precursor

worin R¹ für eine Alkylgruppe mit 1 bis 14 Kohlenstoffatomen, R² für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen und R⁵ für H oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen stehen und L im wesentlichen irgendeine austretende Gruppe sein kann. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann geradkettiges oder verzweigtes Alkyl sein, das eine Verzweigung, eine Substitution oder beide aufweist und es kann stammen entweder aus synthetischen Quellen oder aus natürlichen Quellen, z. B. Talgfett. Analoge Strukturvariationen sind möglich für R². Die Substitution kann umfassen Alkyl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen. R⁵ steht vorzugsweise für H oder Methyl. R¹ und R⁵ sollten insgesamt nicht mehr als 18 Kohlenstoffatome enthalten. Amid-substituierte Bleichmittelaktivator-Verbindungen dieses Typs sind in EP-A-0170386 beschrieben.Amide substituted alkyl peroxyacid precursor compounds are also suitable, e.g. B. those of the following general formulas:

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

Benzoxazin-organic Peroxyacid precursor

einschließlich der substituierten Benzoxazine des Typs

worin R₁ für H, Alkyl, Alkaryl, Aryl, Arylalkyl und R₂, R₃, R₄ und R₅ die gleich oder verschieden sein können, für Substituenten, ausgewählt aus N, Halogen, Alkyl, Alkenyl, Aryl, Hydroxyl, Alkoxyl, Amino, Alkylamino, COOR₆ (worin R₆ für N oder eine Alkylgruppe steht) und Carbonyl-Funktionen stehen.Precursor compounds of the benzoazine type, as described for example in EP-A-332 294 and EP-A-482 807, are also suitable, in particular those of the formula:

including the substituted benzoxazines of the type

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

A particularly preferred precursor of the benzoxazine type is

Previously made organic peroxyacid

The organic peroxyacid bleaching system can additionally to or as an alternative to an organic peroxyacid bleach precursor compound a previously prepared organic peroxyacid, usually in one Amount of 0.5 to 25 wt .-%, preferably from 1 to 10 wt .-%, based on the weight of the composition.

worin R¹ für eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen, R² für eine Alkylen-, Arylen- und Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen und R⁵ für H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen stehen. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann geradkeitiges oder verzweigtes Alkyl, substituiertes Aryl oder Alkylaryl, das eine Verzweigung, eine Substitution oder beide enthält, sein und es kann stammen entweder aus synthetischen Quellen oder aus natürlichen Quellen, z. B. Talgfett. Analoge Strukturvariationen sind möglich für R². Die Substitution kann umfassen Alkyl-, Aryl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen. R⁵ steht vorzugsweise für N oder Methyl. R¹ und R⁵ sollten insgesamt nicht mehr als 18 Kohlenstoffatome enthalten. Amid-substituierte 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 for an alkyl, aryl or alkaryl group with 1 to 14 carbon atoms, R ² for an alkylene, arylene and alkarylene group with 1 to 14 carbon atoms and R ⁵ for H or an alkyl, aryl or alkaryl group with 1 are up to 10 carbon atoms. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ can be straight or branched alkyl, substituted aryl or alkylaryl containing a branch, a substitution or both, and it can come either from synthetic sources or from natural sources, e.g. B. tallow fat. Analogous structure variations are possible for R ² . The substitution can include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ preferably represents N or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, in particular diperoxydodecanedicarboxylic acid, diperoxytetradecanedicarboxylic acid and Diperoxyhexadecandicarbonsäure. Dibenzoyl peroxide is an organic peroxy acid preferred according to the invention. mono- and diperazelaic acid, Mono- and diperbrassylic acid and N-phthaloylaminoperoxycaproic acid are also in accordance with the invention suitable.

Means of Control the release rate

A means can be provided to control (control) the rate of release of the bleach, especially the release of the oxygen bleach into the Wash solution.

A means of control The rate of bleach release can be a controlled release of the peroxide compounds in the wash solution. To such means can for example controlling the release of an inorganic perhydrate salt, that acts as a hydrogen peroxide source in the wash solution.

Suitable controlled release agents can include the restriction of the bleach on either the pressed or the unpressed portions. If more than one non-pressed Is present, the bleach can be limited on the first and / or second and / or optionally further non-pressed portions.

Another control mechanism the rate (rate) of release of the bleach can be by coating the bleach with a coating, which is designed to give a controlled release. The coating can therefore comprise, for example, a material which is sparingly soluble in water or he can cover be of sufficient thickness so that the kinetics of the dissolution of the thick coating can give the controlled release rate.

The coating material can under Apply various methods. A coating material is usually in a weight ratio of coating material to bleach from 1:99 to 1: 2, preferably from 1:49 to 1: 9, before.

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

Other suitable coating materials can include the alkali and alkaline earth metal sulfates, silicates and carbonates including Calcium carbonate and silicon dioxide.

A preferred coating material, in particular for an inorganic perhydrate salt bleach source, comprises sodium silicate with an SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 , and / or sodium metasilicate, which is preferably applied in an amount of 2 to 10 wt .-% (normally 3 to 5 wt .-%) SiO ₂ , based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be contained in the coating.

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

Other preferred binders include certain polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 × 10 ⁶ , preferably from 1000 to 400,000, most preferably from 1000 to 10,000. Further examples of polymeric materials which are suitable as binders are copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride making up at least 20 mol% of the polymer. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the above-mentioned C ₁₀ -C ₂₀ alcohol ethoxylates, which contain 5 to 100 moles of ethylene oxide per mole. Other examples of binders include the C ₁₀ -C ₂₀ mono- and diglycerol ethers and also the C ₁₀ -C ₂₀ fatty acids.

More examples of binders, the for the use according to the invention cellulose derivatives such as methyl cellulose and carboxymethyl cellulose are suitable and hydroxyethyl cellulose and homo- or copolymer polycarboxylic acids or their salts.

A method of applying the coating material comprises the agglomeration. Preferred agglomeration methods include the use of any of the organic binders described above. Any conventional agglomerator / mixer can be used such as B. without the invention limited to this is pan, rotary drum and vertical mixer types. It can too molten coating compositions are applied either by direct pouring or spraying a fluid bed of the bleach.

To other means of achieving The required controlled release includes mechanical means change the physical properties of the bleach to its solubility and to control its release rate Experimental arrangements can include pressing, mechanical injection, manual injection and the solubility adjustment the bleach compound by selecting the particle size of each particulate Component.

Although the choice of particle size is both on the composition of the particulate component as well the desire, the desired To meet controlled release kinetics, it is desirable that the particle size be more than 500 μm should preferably be an average particle diameter from 800 to 1200 μm should have.

Further experimental arrangements for Provision of controlled release means include the appropriate selection of the other components of the detergent composition matrix, z. B. the that then when the composition is introduced into the washing solution, the ionic strength of the Environment is provided in it, which is achieving the required controlled release kinetics allowed.

Containing metal Bleach Catalyst

The compositions described herein which contain a bleach as an active detergent tel component can additionally contain as a preferred component a metal-containing bleach catalyst. The bleaching agent catalyst containing a metal is preferably a bleaching agent catalyst containing a transition metal, in particular a bleaching agent catalyst containing manganese or cobalt.

A suitable type of bleach catalyst is a catalyst that has a heavy metal cation with a defined catalytic bleaching activity comprises such as copper, iron cations, an auxiliary metal cation with a low or no catalytic bleaching activity, such as zinc or aluminum cations and a sequestering agent with defined stability constants for the catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminietra (methylenephosphonic acid) and water-soluble Salts thereof. Such catalysts are described in U.S. Patent 4,430,243 described.

Preferred types of bleach catalysts include the manganese-based complexes described in U.S. Patents 5,246,621 and 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), (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₃ and mixtures thereof. Further catalysts are described in published European patent application No. 549 272. Other ligands which are suitable for the use according to the invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4 , 7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

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

Another type of bleach catalyst, as described in U.S. Patent 5,114,606 is a water soluble Complex of manganese (III) and / or (IV) with a ligand in which it is a non-carboxylate polyhydroxy compound deals with at least three successive C-OH groups. Preferred ligands belong Sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof.

worin R¹, R², R³ und R⁴ jeweils ausgewählt werden können aus H, substituierten Alkyl- und Arylgruppen, so daß jedes R¹-N=C-R² und R³-C=N-R⁴ einen fünf- oder sechsgliedrigen Ring bildet. Der genannte Ring kann ferner substituiert sein. B ist eine Brückenbildungsgruppe, ausgewählt aus O und S, CR⁵R⁶, NR⁷ und C=O, worin R⁵, R⁶ und R⁷ jeweils für H, Alkyl- oder Arylgruppen einschließlich der substituierten oder unsubstituierten Gruppen stehen können. Zu bevorzugten Liganden gehören Pyridin-, Pyridazin-, Pyrimidin-, Pyrazin-, Imidazol-, Pyrazol- und Triazol-Ringe. Gegebenenfalls können die genannten Ringe substituiert sein durch Substituenten, wie Alkyl, Aryl, Alkoxy, Halogenid und Nitro. Besonders bevorzugt ist der Ligand 2,2'-Bispyridylamin.U.S. Patent 5,114,611 describes a bleach catalyst comprising a complex of transition metals such as Mn, Co, Fe or Cu with a non (macro) cyclic ligand. The ligands mentioned have the formula:

wherein R ¹ , R ² , R ³ and R ^{4 can} each be selected from H, substituted alkyl and aryl groups, so that each R ¹ -N = CR ² and R ³ -C = NR ⁴ forms a five- or six-membered ring , Said ring can also be substituted. B is a bridging group selected from O and S, CR ⁵ R ⁶ , NR ⁷ and C = O, where R ⁵ , R ⁶ and R ^{7 can} each represent H, alkyl or aryl groups including the substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. If appropriate, the rings mentioned can be substituted by substituents, such as alkyl, aryl, alkoxy, halide and nitro. The ligand 2,2'-bispyridylamine is particularly preferred.

Preferred bleach catalysts include Co, Cu, Mn, Fe-bispyridyl methane and bis-pyridyl amine complexes. Particularly preferred catalysts include Co- (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), tris dipyridylarnine cobalt (II) perchlorate, Co- (2,2-bispyridyiamine) 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, such as N ₄ Mn ^III (uO) ₂ Mn ^IV Na ₄ ) ⁺ and [Bipy ₂ Mn ^III (uO) ₂ Mn ^IV bipy ₂ ] - (ClO ₄ ) ₃ .

Although the structures of the bleach-catalyst manganese complexes according to the invention are not yet enlightened , it can be assumed that it hydrogenated chelates or others Include coordination complexes that result from the interaction between the carboxyl and nitrogen atoms of the ligand with the Manganese cation. The oxidation state of the manganese cation is also while of the catalytic process is not exactly known and it can these are the (+ II) -, (+ III) -, (+ IV) - or (+ V) -valence state. Because of the potential six binding points of the ligands to the manganese cation can be reasonably are believed to be multinuclear Species and / or "cage" structures in the aqueous bleaching media can be present. Independently which is the form of the active Mn ligand species that indeed is present, it acts in an apparently catalytic manner Achieving an improved bleaching effect for stubborn stains, z. B. stains of tea, ketchup, coffee, wine, juice and the like.

Other bleach catalysts are described, for example, in the published European Patent application 408 131 (cobalt complex catalysts), in published European patent applications 384 503 and 306 089 (metal porphyrin catalysts), in US patent 4,728,455 (manganese / multidentate ligand catalyst), in the US U.S. Patent 4,711,748 and published European Patent Application 224,952 (absorbed manganese on an aluminosilicate catalyst), U.S. Patent 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. Patent 4 626,373 (manganese / ligand catalyst), in U.S. Patent 4,119,557 (iron (III) complex catalyst), in German Patent 2,054,019 (cobalt chelating catalyst), in Canadian Patent 866,191 (salts containing a transition metal), in U.S. Patent 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations) and in U.S. Patent 4,728,455 (manganese gluconate catalysts).

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

Preferred cobalt catalysts of this type have the formula: [Co (NH ₃ ) _n (M ') _m ] Y _y where n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M 'represents an unstable coordination residue, which is preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (if m is greater than 1) combinations thereof; m looks for an integer from 1 to 3 (preferably for the number 1 or 2; most preferably for the number 1); m + n = 6; and Y stands for a suitably selected counter anion which is present in the number y, where y is an integer from 1 to 3 (preferably the number 2 to 3; most preferably the number 2) when Y is a simply negatively charged anion), forming a salt with a balanced charge.

The preferred cobalt catalysts of this type which can be used according to the invention are cobalt pentamine chloride salts of the formula [Co (NH ₃ ) ₅ Cl] Y _y and in particular [Co (NH ₃ ) ₅ Cl] Cl ₂ .

The compositions according to the invention in which cobalt (III) bleaching catalyst of the formula are used are particularly preferred: [Co (NH ₃ ) _n (M) _m (B) _b ] T _y wherein cobalt is in the + 3 oxidation state; n represents the number 4 or 5 (preferably the number); M represents one or more ligands coordinated by a site on the cobalt; m stands for the number D, 1 or 2 (preferably for the number 1); B represents a ligand coordinated to the cobalt by two sites; b stands for the number 0 or 1 (preferably for the number 0) and, if b = 0, then m + n = 6, and if b = 1, then m = 0 and n = 4; and T represents one or more suitably selected counter anions which are in number y, where y is an integer to achieve a salt with a balanced charge (preferably y is a number from 1 to 3; particularly preferably for the number 2 if T is a single negatively charged anion) and the said catalyst also has a base hydrolysis rate constant of <0.23 M ^-1 s ^-1 (25 ° C).

Preferred radicals 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. T may optionally be protonated if there is more than one anionic group in T, such as. B. HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- and the like. In addition, T can be selected those from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g. linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES) and the like) and / or anionic polymers (e.g. Polyacrylates, polymethacrylates and the like.).

The M radicals include, but are not limited to, the invention, for example F ^- , SO ₄ ^-2 , NCS ^- , SCN ^- , S ₂ O ₃ ^-2 , NH ₃ , PO ₄ ^{3 -} ) and carboxylates (which are preferably monocarboxylates , but there may also be more than one carboxylate in the residue, as long as the binding to the cobalt occurs only via one carboxylate per residue, in which case the other carbaxylate may be protonated in the M residue or may be in its salt form ). M may optionally be protonated if there is more than one anionic group in M (e.g. HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- , HOC (O) CH ₂ C (O) O-, and the like .). Preferred M radicals are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids of the formula: RC (O) O- wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) alkyl, unsubstituted and substituted C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) -Aryl and unsubstituted and substituted C ₃ -C ₃₀ - (preferably C ₅ -C ₁₈ ) heteroaryl, the substituents being 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 radicals. This substituted R therefore comprises the radicals - (CH ₂ ) _n OH and - (CH ₂ ) NR ' ₄ ⁺ , where n is an integer from 1 to 16, preferably from 2 to 10 and most preferably from 2 to 5, stands.

The most preferred M are carboxylic acids having the formula given above, 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 residues include formic acid, benzoic acid, octanoic acid, nonanoic acid, decanoic acid, dadecanoic acid, malonic acid, maleic acid, succinic acid, adipic acid, phthalic acid, 2-ethylhexanoic acid, naphthenic acid, oleic acid, palmitic acid, triflate, tartrate, stearic acid, butyric acid, butyric acid, butyric acid, butyric acid Acrylic acid, aspartic acid, fumaric acid, lauric acid, linoleic acid, lactic acid, malic acid and especially acetic acid.

The B residues include carbonate, di- and higher Carboxylates (e.g. oxalate, malonate, malic acid, succinate, maleate), picolinic acid and α- and β-amino acids (e.g. B. glycine, alanine, β-alanine, Phenylalanine).

The cobalt bleach catalysts which can be used according to the invention are known and are described, for example, together with their base hydrolysis rates from ML Tobe in "Base Hydrolysis of Transition-Metal Complexes" in "Adv. Inorg. Bioinorg. Mech." (1983), 2, pages 1-94. For example, Table 1 on page 17 shows the base hydrolysis rates (referred to as k _OH therein) for cobalt pentaamine catalysts that are complex-bound with oxalate (k _OH = 2.5 × 10 ^-4 M ^-1 s ^-1 (25 ° C)), NCS ^- (k _OH = 5.0 × 10 ^-4 M ^-1 s ^-1 (25 ° C)), formate (k _OH = 5.8 × 10 ^-4 M ^-1 s ^-1 ( 25 ° C)) and acetate (k _OH = 9.6 x 10 ^-4 M ^-1 s ^-1 (25 ° C)). The most preferred cobalt catalysts which can be used according to the invention are cobalt pentaamine acetate salts of the formula [Co (NH ₃ ) ₅ OAc] T _y in which OAc stands for an acetate radical, and in particular colbalt pentamine acetate chloride [Co (NH ₃ ) ₅ OAc] Cl ₂ and [Co (NH ₃ ) ₅ OAc) ₂ ; [Co (NH ₃ ) ₅ OAc] (PF ₅ ) 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 (referred to here as "PAC").

These cobalt catalysts are light can be produced by known processes, as described, for example, in the above-mentioned Tobe article and in the references mentioned therein, in U.S. Patent 4,810,410 (Diakun et al., published March 7, 1989), in "J. Chem. Ed." (1989), 66, (12), 1043-1045; in "The Synthesis and Characterization of Inorganic Compounds "by W. L. Jolly (Prentice-Hall; 1970), Pp. 461-463; in "Inorg. Chem.", 18, 1497-1502 (1979); in "Inorg. Chem.", 21, 2881-2885 (1982); in "Inorg. Chem.", 18, 2023-2025 (1979); in "Inorg. Synthesis", 173-176 (1960); and in "Journal of Physical Chemistry ", 56, 22-25 (1952), as well as described in the following synthesis examples are.

Cobalt catalysts for incorporation suitable in the detergent tablets according to the invention are, can are prepared according to the synthetic routes as described in the U.S. patents 5 559 261, 5 581 005 and 5 597 936 are given on their disclosure here explicitly Reference is made.

These catalysts can be common treated with addition materials to change the color diminish if this is from aesthetic establish for the Product wanted is. or the particles contained in the enzyme as follows explained should be included, or the compositions can be so that they are manufactured Catalyst "spots" included.

organic polymeric compound

Organic polymeric compounds can be added as preferred components of the detergent tablets according to the invention. An organic polymeric compound is to be understood as meaning essentially any polymeric organic compound which is usually found in cleaning agent compositions, the dispersing, deposit-preventing, dirt-repellent or other Have cleaning properties.

An organic polymeric compound is usually the detergent compositions according to the invention in an amount of 0.1 to 30%, preferably 0.5 to 15%, am most preferably from 1 to 10%, based on the weight of the compositions, incorporated.

Examples of organic polymeric compounds belong the water soluble organic homo- or copolymers polycarboxylic acids, modified polycarboxylates or their salts in which the polycarboxylic acid contains at least two carboxyl radicals comprises separated by no more than two carbon atoms are. Polymers of the latter type are described in GB-A-1 596 756. examples for such salts are polyacrylates with a molecular weight of 2000 to 10,000 and their copolymers with any suitable other Monomer units, e.g. B. modified acrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid 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 commercial, acrylic acid containing polymers having a molecular weight below 15,000 those under the trade names Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 are sold by BASF GmbH, and those sold under the trade name Acusol 45N, 480N, 460N are distributed by the Rohm and Haas company.

Preferred copolymers containing acrylic acid include those which contain as monomer units: (a) 90 to 10% by weight, preferably 80 to 20% by weight of acrylic acid or its salts and (b) 10 to 90% by weight, preferably 20 to 80% by weight of a substituted acrylic monomer or salts thereof having the general formula - [CR ₂ -CR ₁ (CO-OR ₃ )] -, in which at least one of the substituents R ₁ , R ₂ or R ₃ , preferably R ₁ or R _{2 is} a C ₁ -C ₄ alkyl or hydroxyalkyl group, R ₁ or R _{2 may be} a hydrogen atom and R _{3 may be} a hydrogen atom 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 60 to 80% by weight of acrylic acid and 40 to 20% by weight of methacrylic acid.

Among the usable according to the invention Polyamine and modified polyamine compounds include those that of aspartic acid are derived, e.g. B. such as those in EP-A-305282, EP-A-305283 and EP-A-351629.

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

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

Soil release agents

Suitable polymeric soil release agents include those soil release agents that have (a) one or more non-ionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2 or (ii) Oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, said hydrophilic segment comprising an oxypropylene unit only when it is bonded to adjacent residues at each end by ether bonds, or (iii) a mixture of oxyalkylene Units comprising oxyethylene and 1 to 30 oxypropylene units, the hydrophilic segments mentioned preferably at least 25% oxyethylene units and particularly preferably, in particular for those components which have 20 to 30 oxypropylene units, at least 50% oxyethylene Include units; or (b) one or more hydrophobic components which comprise (i) C ₃ -oxyalkylene terephthalate segments, in which, if the said hydrophobic components also contain oxyethylene terephthalate, the ratio of oxyethylene terephthalate to C ₃ -oxyalkylene terephthalate units is 2: 1 or less , (ii) C ₄ -C ₆ alkylene or oxy-C ₄ -C ₈ alkylene segments or mixtures thereof, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, with a degree of polymerization of at least 2 or ( iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents or mixtures thereof, where the substituents mentioned are in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof, or a combination of (a) and (b).

As a rule, the polyoxyethylene segments of (a) (i) have a degree of polymerization of 200, although those with a lower degree of polymerization, preferably from 3 to 150, particularly preferably from 6 to 100, can also be used. Suitable hydrophobic oxy-C ₄ -C ₆ -alkylene segments include, but are not limited to, polymeric soil release agents with terminal groups such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, in which M is sodium and n is an integer from 4 to 6 as described in U.S. Patent 4,721,580 (Gosselink, published January 26, 1988).

Polymeric soil release agents which can be used according to the invention also include cellulo SE derivatives such as hydroxy ether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate and the like. Such agents are commercially available and include hydroxy ethers of cellulose such as METHOCEL (Dow). The cellulosic soil release agents which can be used according to the invention also include those which are selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose (cf. US Pat. No. 4,000,093 (Nicol et al. published December 28, 1976).

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

Another suitable soil release agent is a copolymer with random blocks from Ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The The molecular weight of this polymeric soil release agent lies in that Range from 25,000 to 55,000 (see U.S. Patent 3,959,230 (Hays, published on May 25, 1976) and U.S. Patent 3,893,929 (Basadur) on July 8, 1975)).

Another suitable polymer Soil-Release-Agent is a polyester with repeating units from ethylene terephthalate units, the 10 to 15 wt .-% ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units, derived from an average polyoxyethylene glycol Molecular weight from 300 to 5000 contains.

Another suitable polymer Soil release agent is essentially a sulfonated product linear ester oligomers, consisting of an oligomeric ester backbone of recurring terephthaloyl and oxyalkyleneoxy units and terminal residues that are covalent to the basic structure are bound. These soil release agents are, for example, in U.S. Patent 4,968,451 (J.J. Scheibe) and E.P. Gosselink on November 6, 1990). To other suitable polymers Soil release agents belong the terephthalate polyesters according to US patent 4,711,730 (Gosselink et al, published on B. December 1987), the oligomers provided with anionic end groups US patent esters 4,721,580 (Gosselink, published on January 26, 1988) and the oligomeric block polyester compounds of U.S. Patent 4,702,857 (Gosselink, published on October 27, 1987). To other polymeric soil release agents belong Moreover the soil release agents under US patent 4,877,896 (Maldonado et al on October 31, 1989), in which with anionic, especially sulfoarolyl end groups provided terephthalate esters are described.

Another soil release agent is an oligomer with recurring terephthaloyl, sulfoisoterephthaloyl, Oxyethyleneoxy and oxy-1,2-propylene units. The recurring units form the basic framework of the oligomer and they preferably have modified isethionate end groups on. A particularly preferred soil release agent of this type contains one Sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a relationship from 1.7 to 1.8 and two terminal group units made from sodium 2- (2-hydroxyethoxy) ethanesuffonate.

Heavy metal metal ion sequestrant

The detergent tablets according to the invention preferably contain a heavy metal ion sequestering agent as an optional component. Components are here under a heavy metal ion sequestering agent to understand that act as a sequester (chelate) for heavy metal ions. These components can also a chelation educational ability for calcium and have magnesium, but preferably they have a selective one binding capacity across from Heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrant are generally in an amount of 0.005 to 20% by weight, preferably from 0.1 to 10% by weight, particularly preferably from 0.25 to 7.5% by weight and most preferably from 0.5 to 5% by weight based on the weight of the compositions, available.

Heavy metal ion sequestrant, which are acidic in nature and which have, for example, phosphonic acid or carboxylic acid functionalities, can either in their acid form or as a complex salt with a suitable counter cation, for example an alkali or alkaline earth metal ion, ammonium or substituted ammanium ionian or mixtures thereof.

Preferred salts / complexes are water soluble. The molar ratio between the counter cation and the heavy metal ion sequestering agent is preferably at least 1: 1.

Suitable heavy metal ion sequestrants that can be used according to the invention belong organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), Alkali metal ethane-1-hydroxy-diphosphonates and nitrilotrimethylene phosphonates. Preferred among the abovementioned compounds are diethylene triamine penta (methylene phosphonate), Ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids, e.g. B. ethylenediaminetetraacetic acid, ethylenetriamine pentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid or any salts thereof.

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

Crystal growth inhibitor component

The detergent contains tablets preferably a crystal growth inhibitor component, preferably an organodiphosphonic acid component, preferably in an amount of from 0.01 to 5% by weight, in particular from 0.1 to 2% % By weight, based on the weight of the compositions, is incorporated.

Taking an organodiphosphonic acid is here an organodiphosphonic acid understand that no nitrogen is part of their chemical structure contains. This definition closes hence the organoaminophosphonates, but in the compositions according to the invention be included as heavy metal ion sequestering agent components can.

The organodiphosphonic acid is preferably a C ₁ -C ₄ -diphosphonic acid, particularly preferably a C ₂ -diphosphonic acid, e.g. B. ethylenediphosphonic acid, or most preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP) and it can be contained in partially or fully ionized form, especially as a salt or complex.

water-soluble sulfate salt

The detergent tablet may contain a water soluble Sulfate salt. If present, the water-soluble sulfate salt is in one Amount of 0.1 to 40 wt .-%, preferably from 1 to 30 wt .-%, am most preferably from up to 25% by weight, based on the weight of the Compositions, before.

The water-soluble sulfate salt can essentially be any sulfate salt with any counter cation. Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, in particular Sodium sulfate.

alkali metal

In one embodiment of the 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 with an SiO ₂ : Na ₂ O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, particularly preferably 2.0. Sodium silicate is preferably present in an amount of less than 20% by weight, particularly preferably from 1 to 15% by weight, most preferably from 3 to 12% by weight, calculated as SiO ₂ . The alkali metal silicate can be in the form of the anhydrous salt or in the form of a hydrated salt.

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

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

dye

The term "colorant" as used herein means any substance, the light of a specific wavelength from the visible light spectrum absorbed. Such colorants have when added to a detergent composition the effect, the visible color and thus the appearance change the detergent composition. For example, colorants can either Dyes or pigments. The colorants are preferred in the composition in which they are to be incorporated, stable. In a composition with a high pH this is dye thus preferably alkali-stable and in a composition with at a low pH, the colorant is preferably acid-stable.

The pressed part and / or the non-pressed part can a colorant, a mixture of colorants, colored Contain particles or a mixture of colored particles, so that the pressed Portion and the non-pressed Share have a different visual appearance. Preferably contains either just the pressed one Proportion or only the non-pressed Share a colorant.

If the non-pressed portion two or more compositions of active detergent components contains contains preferably at least one of them, either the first and the second and / or other compositions, a colorant. If both the first and the second and / or the others Compositions a colorant included, it is preferred that the dye have a different visual appearance.

If present, the coating layer contains preferably a colorant. If the pressed Share and the coating layer a colorant included, it is preferred that the dye give a different visual effect.

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

The colorant can be the pressed and / or non-compressed Portion may be incorporated by any suitable method. Appropriate procedures include mixing all or selected ones active detergent components with a colorant in a drum or spraying all or selected active detergent components together with the colorant in a rotating drum.

The colorant lies when it is as a component of the pressed Share is present, in an amount of 0.001 to 1.5%, preferably from 0.01 to 1.0%, most preferably from 0.1 to 0.3%. If it is present as a component of the unpressed portion the colorant generally in an amount of 0.001 to 0.1%, preferably of 0.005 to 0.05%, most preferably 0.007 to 0.02%. If it is as a component of the coating layer the colorant is present in an amount of 0.01 to 0.5%, preferably 0.02 to 0.1%, most preferably from 0.03 to 0.06%.

Hydrocarbon oils

Another preferred active detergent component for use in the present invention is a hydrocarbon oil, usually a predominantly long chain aliphatic hydrocarbon with a number of carbon atoms in the range from 20 to 50; preferred hydrocarbons are saturated and / or branched hydrocarbons; a preferred hydrocarbon oil is selected from predominantly branched C ₂₅ -C ₄₅ compounds with a ratio of cyclic to non-cyclic hydrocarbons of 1:10 to 2: 1, preferably 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin. A paraffin oil that meets the above requirements and has a ratio of cyclic to non-cyclic hydrocarbons of 32:68 is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Enzyme stabilizing systems

The enzyme containing preferred according to the invention Compositions can 0.001 to 10% by weight, preferably 0.005 to 8% by weight, most preferably 0.01 to 6% by weight of an enzyme-stabilizing system containing. The enzyme stabilizing system can be any stabilizing system System that is compatible with the detergent enzyme. This stabilizing Systems can include calcium ions, boric acid, Propylene glycol, a short chain carboxylic acid, a boron acid, chlorine bleach scavenger and mixtures thereof. These stabilizing systems can too reversible enzyme inhibitors, e.g. B. reversible protease inhibitors, contain.

Lime soap dispersant compound

The compositions of active Detergent components can contain a lime soap dispersant compound, preferably in an amount of 0.1 to 40% by weight, particularly preferably 1 up to 20% by weight, on most preferably from 2 to 10% by weight based on the weight of the Compositions.

A lime soap dispersant is a material that precipitates of alkali metal, ammonium or amine salts of fatty acids Prevents calcium or magnesium ions. Preferred lime soap dispersant compounds are in PCT application WO93 / 08877.

The foaming suppressive systems

The detergent tablets according to the invention included if for formulated for use in washing machine compositions, preferably a system which suppresses the formation of foam, which in one Amount from 0.01 to 15% by weight, preferably from 0.05 to 10% by weight, most preferably from 0.1 to 5% by weight based on weight the composition.

For the use according to the invention Suitable systems that suppress foam formation can be found in essentially comprise a known anti-foam compound, e.g. B. Silicone anti-foam compounds, 2-alkyl and alkanol anti-foam compounds. Preferred anti-foaming systems and anti-foam compounds are described in PCT application WO93 / 08876 and in EP-A-0 705 324.

Polymeric dye transfer inhibitors

The detergent tablets according to the invention can also 0.01 to 10% by weight, preferably 0.05 to 0.5% by weight, of polymer Dye transfer inhibiting agents contain. The polymeric dye transfer inhibiting agents are preferred selected made of polyamine N-oxide polymers, Copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

Optical brighteners

For use in washing processes, suitable detergent tablets as described here can optionally 0.005 to 5% by weight of certain types of hydrophilic optical brighteners included.

worin R₁ ausgewählt wird aus Anilino, N-2-Bis-hydroxyethyl und NH-2-Hydroxyethyl; R₂ ausgewählt wird aus N-2-Bishydroxyethyl, N-2-Nydroxyethyl-N-meihylamino, Morpholino, Chloro und Amino; und M ein salzbildendes Kation, beispielsweise Natrium oder Kalium, darstellt.The hydrophilic optical brighteners which can be used according to the invention 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-bishydroxyethyl, N-2-Nydroxyethyl-N-meihylamino, morpholino, chloro and amino; and M represents a salt-forming cation, for example sodium or potassium.

In the above formula, when R _{1 is} anilino, R _{2 is} N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2-bishydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid and the disodium salt. This special brightener compound is commercially available under the trade name Tinopal-UNPA-GX from Ciby-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener used in the detergent compositions according to the invention.

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 special brightener compound is commercially available under the trade name Tinopal 5BM-GX from Ciba-Geigy Corporation.

In the above formula, when R _{1 is} anilino, R _{2 is} morpholino and M is katian such as sodium, the brightener is 4,4'-bis [(anilino-6-morpholino-s-triazine-2- yl) amino] -2,2'-stilbenedisulfonic acid, sodium salt. This special brightener compound is commercially available under the trade name Tinopal AMS-GX from Ciby Geigy Corporation.

Clay softening system

For use in washing-cleaning processes Suitable detergent tablets can be a clay-plasticizer system contain a clay mineral compound and optionally one Tone precipitating contains.

The clay mineral compound is preferably a smectite-clay compound. Smectite clays are described in U.S. Patents 3,862,058, 3,948,790, 3,954,632 and 4,062,647. Suitable organic polymers are found in European patents EP-A-299 575 and EP-A-313 146 (both Procter and Gamble Company) Clay flocculant described.

cationic Fabric softening compounds

Cationic fabric softener compounds can also the compositions of the invention which are suitable for use in processes for washing in a washing machine. Suitable cationic fabric softener compounds belong the water-insoluble tertiary Amines or di-long chain amide materials as described in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softener compounds are usually in total amounts of 0.5 to 15 wt .-%, normally from 1 to 5% by weight.

Other optional components

To other optional components, the for the incorporation into the compositions according to the invention is suitable are belong perfumes and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions

The detergent tablets according to the invention are preferably formulated so that they are not excessively high have pH, preferably they have a pH measured as 1% solution in distilled water, from 8.0 to 12.5, particularly preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.

According to another aspect of Invention are the pressed and the non-pressed ones Shares formulated so that they result in different pH values.

Washing machine washing process

Under washing machine washing process is usually understood to mean the treatment of soiled Laundry with an aqueous wash solution in a washing machine in which an effective amount of a washing machine detergent tablet according to the invention solved or is distributed. Taking an effective amount of detergent Tablet composition is 40 to 300 g of product, dissolved or dispersed in a washing solution with a volume of up to 65 l as typical product dosages and wash solution volumes, like they usually do used in conventional washing machine washing processes, too understand.

With a preferred application aspect a distribution device is used in the washing process. The distribution device comes with the detergent product and it is used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Your volume capacity should be be such that they usually enough Detergent product can take up as it normally does in the washing process is used.

Once the washing machine with the laundry has been loaded, the distribution device containing the detergent product contains arranged inside the drum. At the beginning of the wash cycle the Water is introduced into the drum and the drum rotates periodically. The shape of the distribution facility should be such that she the inclusion of the dry detergent product allows it, however depending on the release of this product during the wash cycle of the movement when the drum is spinning, and also as a result their contact with the wash water.

To release the detergent product while To allow washing, the device can have a number of openings through which the product can pass. Alternatively, you can the device must be made of a material suitable for liquid permeable is, however, for the solid product impermeable is so that it the release of the solved Product allowed. Preferably the detergent product Released quickly at the start of the wash cycle, which temporarily high local concentrations of product in the drum of the washing machine be obtained at this stage of the wash cycle.

Preferred distribution facilities are reusable and built so that the integrity of the container is both in the dry state as well as during the washing cycle is maintained.

Alternatively, the distribution device can be a flexible container, for example a bag or a bag. The pouch may be of a fibrous construction coated with a waterproof protective material so as to retain the contents as described in published European patent application 0018678. Alternatively, it can be made from a water-insoluble synthetic polymeric material be produced, which is provided with an edge seal or an edge closure, which is intended to break open in aqueous media, as described in the published European patent applications 0011500, 0011501, 0011502 and 0011968. A suitable form of water-dissolvable closure includes a water-soluble adhesive that seals along and seals an edge of a pocket made of a water-impermeable polymeric film such as polyethylene or polypropylene.

Claims (24)

Detergent tablet for use in washing of laundry in a washing machine comprising: (a) a compressed one Portion comprising an active detergent ingredient; and (B) comprising an uncompressed, non-encapsulating portion an active detergent ingredient, the compressed portion provides a prefabricated trough and the non-compressed portion is in the form of a gel or a solidified melt and is at least partially contained in the trough, and the weight ratio of compressed portion to uncompressed portion greater than Is 4: 1. The detergent tablet of claim 1, wherein the non-compressed Portion of the compressed portion is attached by adhesion or hardening. Detergent tablet according to claim 1 or claim 2, the tablet being a plurality of layers arranged includes non-compressed portions. Detergent tablet according to any preceding Claim, wherein the tablet is a variety of non-compressed Shares includes, and wherein the compressed portion is a plurality of troughs and any uncompressed portion at least is partially contained in a trough. Detergent tablet according to any preceding Claim, wherein the non-compressed portion is a solidified melt is. Detergent tablet according to any preceding Claim, wherein the uncompressed portion comprises a binder, selected from the group consisting of sugar, starch, gelatin and organic polymers. A detergent tablet according to claim 6, wherein the non-compressed Portion comprises a binder which is an organic polymer. Detergent tablet according to any preceding Claim, wherein the dissolution rate of the uncompressed portion is larger than the resolution speed of the compressed portion measured using that herein SOTAX dissolution test procedure described. Detergent tablet according to any one of claims 1 to 7, the dissolution rate of the compressed portion is larger than the dissolution rate of the uncompressed portion measured using that herein SOTAX dissolution test procedure described. Detergent tablet according to any preceding Claim comprising an enzyme. A detergent tablet according to claim 10, wherein the enzyme selected is from the group consisting of amylases, proteases, cellulases, Hemicellulases, peroxidases, lipases, phospholipases and mixtures thereof. Detergent tablet according to any preceding Claim, wherein the active detergent component of the non-compressed Share selected is made of surfactant, bleach, bleach activator, bleach catalyst, Enzyme, corrosion inhibitor, fragrance and a source of alkalinity. Detergent tablet according to any preceding Claim, wherein the active detergent component of the non-compressed Is an enzyme. Detergent tablet according to any preceding Claim, wherein the active detergent component of the compressed Share selected is made of builder compound, surfactant, bleach, bleach activator, Bleaching catalyst, enzyme and a source of alkalinity. Detergent tablet according to any preceding Claim, wherein the active detergent component of the compressed Portion is a bleach. Detergent tablet according to any preceding Claim comprising an alkali metal silicate. Detergent tablet according to any preceding Claim, wherein the detergent tablet comprises silicate and the detergent tablet comprises at least 20% by weight of builder compounds based on active detergent ingredients. Detergent tablet according to any preceding Claim, wherein the non-compressed portion with a coating layer is coated. Detergent tablet according to any preceding Claim, wherein the detergent tablet additionally a disrupting agent which comprises a disintegrant, an effervescent or mixtures thereof. A detergent tablet according to claim 19, wherein the disrupting agent selected is from the group consisting of starch, starch derivatives, alginate, carboxymethyl cellulose (CMC) -based Polymers, sodium acetate, aluminum oxide, carbonate, bicarbonate, carboxylic acids and Mixtures of these. A method of washing laundry comprising the treatment of dirty laundry with an aqueous wash solution in a washing machine in which a detergent tablet after some of claims 1 to 20 resolved or is dispensed. Use of a detergent tablet in a procedure for washing laundry in a washing machine, the tablet comprising: (a) one compressed portion comprising an active detergent ingredient; and (b) a non-compressed, non-encapsulating portion, comprising an active detergent ingredient, the compressed one Share provides a prefabricated trough and the non-compressed Share is in the form of a gel or a solidified melt and is at least partially contained in the trough, and the weight ratio of compressed portion to uncompressed portion greater than Is 4: 1. Use according to claim 22, wherein the tablet any of the claims 2 to 20 mentioned additional Has characteristics. Process for making a detergent tablet for use in washing laundry in a washing machine that includes: (a) a compressed one Portion comprising an active detergent ingredient; and (B) comprising an uncompressed, non-encapsulating portion an active detergent ingredient, the compressed portion provides a prefabricated trough and the non-compressed portion is in the form of a gel or a solidified melt and is at least partially contained in the trough, and the weight ratio of compressed portion to uncompressed portion is larger as 4: 1, the method comprising the steps: (i) Compress an active detergent ingredient to the compressed portion to form and mold a trough in the compressed portion; and (Ii) Respectively a non-compressed, non-encapsulating portion an active detergent ingredient, to the well in the compressed Proportion of.