DE69801735T3 - detergent composition - Google Patents

Abstract

According to the present invention there is provided a washing detergent in the form of a tablet comprising one or more detergent compositions and wherein at least one detergent composition dissolves in a dishwashing machine in less than 3 minutes.

Description

The The present invention relates to machine dishwashing detergents in the form of a multilayer tablet.

Detergent compositions in tablet form are known in the art. It goes without saying that detergent compositions in tablet form several advantages, such as easy handling, transporting and storage, compared to detergent compositions in Have particle shape.

Detergent tablets become the most common by premixing the components of a detergent composition and molding the premixed detergent components into one Tablet made using a tablet press. tablets typically by compressing the detergent components produced to a tablet. Tablets must be with a sufficient Compression pressure are compressed, so that the advantages described above with regard to handling, transport and storage can be. An associated with the compression of the detergent components Problem is, however, that yourself the dissolution rate slows down the tablet as the compaction pressure is increased.

The The aim of the present invention is to provide a detergent tablet, comprising compressed detergent components that rapidly dissolve.

Also posed Applicant states that components a detergent composition which improves the dissolution of the Improve detergent composition, sometimes are unstable and inactivated or used up. While the present invention Providing tablets that dissolve quickly, she also sees a solution to this Problems of instability in front.

According to the invention there is provided a machine dishwashing detergent in the form of a multilayer tablet having a compressed area with a density of from 1.3 g / cm ³ to 1.9 g / cm ³ , each layer of the tablet comprising a detergent composition wherein at least one detergent composition is compressed and dissolves in a dishwashing machine in less than 3 minutes, and wherein at least one detergent composition comprises an enzyme and a dissociating detergent-releasing component, and further wherein the tablet comprises an oxygen-releasing bleach and the enzyme is released from the oxygen-releasing bleach.

Preferably dissolves the detergent composition in less than 2.5 minutes, most preferably less than 2 minutes and also less than 1 minute, determined according to DIN 44990 using a dishwasher available from Bosch with the 65 ° C normal wash program at a water hardness from 18 ° H.

The present tablets comprise one or more detergent compositions, which are compressed and dissolve in less than 3 minutes. The Tablet is a multilayer tablet, with each layer containing a detergent composition includes. Optional additional Layers can can be formed by compressing or can not be uncompressed layers be.

At the Compressing a detergent composition to a tablet the components are in close proximity to each other brought. One result of the immediate neighborhood is that certain the components can react with each other, unstable, inactive or be used up. A solution this problem, as in the state the art, the separation of detergent components, which possibly can react with each other, especially when the components are compressed into a tablet form become. The separation of the components was done, for example, by manufacturing scores of multi-layer tablets, with the possible components can react with each other, contained in different layers of the tablet. Multilayer tablets are traditionally using multiple compression steps produced.

In dissolves the present tablets at least one layer of the compressed detergent composition in less than 3 minutes, preferably less than 2 minutes or also less than 1 minute up. Such an embodiment provides performance benefits because they require the rapid delivery of selected specific detergent components into the wash liquor. In the tablets according to the invention shut down specific detergent components enzymes.

The rapidly dissolving Detergent composition (i.e., the detergent composition, which dissolves in less than 3 minutes) includes an explosive, Detergent releasing component. Preferably dissolve the slower dissolving ones Layers in a dishwasher also in less than 3 minutes, but dissolve more slowly than that rapidly dissolving Shift up. In this way, a sequential release the detergent components are effected. According to the invention Enzyme released before the oxygen-releasing bleach.

The resolution of the detergent composition in less than 3 minutes by introducing a blasting detergent releasing component causes. The term conflicting, Detergent-releasing component includes gas-generating reactants, preformed and trapped gas, breaker and Mixtures thereof.

In The present detergent tablets include the explosive, Detergent-releasing component preferably gas-generating Reactants. The gas-generating reactants react with each other, being in contact with water in a dishwasher a gas is formed in situ. Alternatively, the gas in a or more detergent compositions of the tablet and be included, so that as the detergent composition begins to dissolve, the gas is released, whereby the dissolution rate of the detergent composition is increased. Examples of suitable gases include carbon dioxide, nitrogen dioxide, Oxygen and / or any other non-toxic, non-flammable Gas on. When incorporated into a detergent composition which forming all or part of the detergent tablet, gives the diverging, detergent-releasing Component consequently a rapid dissolution of the detergent composition, which are preferably in a dishwasher in less than 3 Minutes dissolves.

To form the gas in situ, the detergent tablet may contain gas generating reactants such as an acid and an alkali. Suitable acids include mono-, di- or tri- protic acids having a pK _a in the range of 1.0 to 6.9. Preferred acids include amino sulfonic acids, organophosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP acid), and polycarboxylic acids. Preferred polycarboxylic acids may include citric, malic, maleic, malonic, itaconic, tartaric, oxalic, glutaric, glutamic, lactic, fumaric, glycolic and mixtures thereof. Citric acid and / or HEDP acid are particularly preferred acids. The most preferred citric acid is particulate having an average particle size of less than 1000 microns, more preferably less than 600 microns, most preferably less than 400 microns. Other preferred polycarboxylic acids are selected from the group consisting of homopolymers or copolymers of acrylic acid, maleic acid, carboxyvinyl polymeric auxiliaries, carbomers, and mixtures thereof having a molecular weight in the range of 2,000 to 200,000. Particularly preferred polycarboxylic acids include homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid. Suitable alkalis include alkali metal silicate, carbonate, bicarbonate and sesquicarbonate and mixtures thereof. Metasilicate and / or carbonate and especially bicarbonate are preferred. The most preferred bicarbonate is particulate and has an average particle size of less than 1000 microns, more preferably less than 700 microns, most preferably less than 400 microns. Sodium or potassium salts of the above are particularly preferred. Other gas generating reactants include perborate, especially perborate-0 (PB-0) and / or percarbonate. Preferably, the gas generating reactants are present in a proportion of at least 10%, preferably at least 20%, of the detergent composition.

The explosive, detergent-releasing component may include a breakup means. Suitable break apart agents shut down Agents that swell on contact with water or are more rapid dissolve as surrounding components, causing the influx and / or outflow facilitated by water through the formation of channels in the tablet becomes. Any known break apart means of use in detergent or dishwashing detergent applications is contemplated for use herein, for example, those available from Lowenthal W., Journal of Pharmaceutical Sciences, Vol. 61, No. 11 (November 1972). Suitable break apart agents include starch, starch derivatives (e.g., primrose and / or Primojel available available from Auebe, or Avicel from FMC), alginic acids or salts thereof (available from Kelco), carboxymethylcellulose (CMC), CMC-based polymers (for example, Nymcel, available available from Metsa-Serla, Explotab available from Mendell, or Ac-di-sol from FMC), polyvinyl pyrrolidone (PVP), cross-linked PVP, sodium acetate, Potassium carbonate, potassium sulfate, Glauber salts, sugar, in particular Mannitol and sorbitol, alumina and mixtures thereof.

According to a preferred aspect of the present invention have at least 80%, vorzugswei At least 85% or even 90% of the particles of the detergent composition which dissolves in less than 3 minutes have a particle size of more than 200 μm.

Preferably is the free moisture content of the rapidly dissolving detergent composition below 4% by weight, stronger preferably below 2% by weight and more preferably below 1% by weight.

According to one another aspect of the invention is a particulate Component of the detergent composition with a hydrophobic Coated coating material. The particulate component may be a selected Be detergent component, such as the gas-generating acid and / or Alkali reactants of preamplifying, detergent-releasing Component, or can to substantially all components of the detergent composition lock in.

The Coating material containing the particulate component at least partially covered, is preferably a paraffin oil, wax and / or solid, preferably having a melting point in the range of 20 ° C to 60 ° C, more preferably 35 ° C to 45 ° C, especially preferably 42 ° C up to 44 ° C, to which a nonionic surfactant may be added.

alternative For example, the coating material may be an organic polymer, for Example, polyethylene glycol (PEG), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), methylcellulose (MC) or derivatives thereof, especially carboxymethylcellulose (CMC) and / or hydroxypropyl methylcellulose (HPMC).

The particulate (s) Component (s) can (can) with the hydrophobic coating material using each known, suitable type of apparatus to be coated. Preferably the hydrophobic coating material is in a liquid or molten form and is applied to the particulate component sprayed.

each Detergent tablet component conventionally known in the art Detergent tablets is used for placing in the compressed Range of detergent tablets according to the invention suitable. Suitable detergent components are described below described.

The in the tablet existing (s) detergent component (s) can (can) optionally in combination with a carrier and / or binder, for For example, water, a polymer (e.g., PEG or a polyacrylate homo- or copolymer) or liquid Silicate. The detergent components are preferably in a particulate form (i.e., in a powdery or granular Form) and can by a known method, for example conventional spray-drying, Granulating or agglomerating.

The particulate (s) Detergent component (s) are (are) using any apparatus, which leads to the formation of compressed tablets, blocks, bricks or briquettes is compressed, as described in more detail below is described.

In a particularly preferred embodiment of the invention the detergent tablet is a phosphate builder, preferably Sodium tripolyphosphate (STPP). Preferably, the STPP is in the rapidly dissolving Detergent composition. Preferably, it is in a detergent composition with citric acid and Sodium bicarbonate combined.

The density of the compressed area of the tablet is in the range of 1.3 g / cm ³ to 1.9 g / cm ³ , more preferably 1.4 g / cm ³ to 1.8 g / cm ³ , most preferably 1, 4 g / cm ³ to 1.7 g / cm ³ .

The Density is calculated by dividing the weight (mass) of the compressed one Range calculated by the volume of the compressed range. The volume is calculated by multiplying the length by the thickness by the width the compressed layer is calculated.

If the detergent tablet of the present invention comprises an uncompressed layer of a detergent composition, the non-compressed layer may include components that interact with one or more of the detergent components present in the compressed layer. If additional detergent components are present in the non-compressed layer, preferred components include those which are affected by the compaction pressure of the Example of a compression tablet press can be adversely affected. Examples of such detergent components include, but are not limited to, enzymes, corrosion inhibitors, and perfume. These components will be described in more detail below.

The optionally (n) detergent component (s) may in of any shape, for example in a particulate (i.e. powdery or granular), gel or liquid Form, present. The non-compressed layer may also be optional a carrier component include. The detergent component may be before the combination with a carrier component in the form of a solid, gel or liquid.

The Uncompressed layer may be the detergent tablet in the form of a solid, gel or liquid.

The uncompressed layer is distributed on the compressed layer, So that the compressed layer and the non-compressed layer are in contact to each other. The non-compressed layer may be on the compressed layer are distributed in a solid or flowable form. If the non-compressed layer is in a solid form, it is prepared beforehand, optionally shaped and then compressed Layer abandoned. The uncompressed layer will then open attached to a preformed compressed layer, for example through adhesion or by introducing the non-compressed layer into a cooperating one surface the compressed layer. Preferably, the compressed layer comprises a previously prepared depression or mold into which the non-compressed Layer is introduced.

The non-compressed layer is preferably on the compressed layer in a flowable form distributed. The uncompressed layer is then compressed on the Layer attached, for example by adhesion, by forming a coating over the uncompressed layer to put it on the compressed layer or by solidification, for example (1) by cooling below the melting point at which the flowable composition solidified Melt forms; (ii) by evaporation of the solvent; (iii) by crystallization; (iv) by polymerizing a polymeric component of the flowable, non-compressed Layer; (v) by pseudoelastic properties, wherein the flowable, uncompressed Layer comprises a polymer and shear forces be exerted on the non-compressed layer; (vi) or by Combining a binder with the flowable, non-compressed layer. In another embodiment can be the flowable, uncompressed Layer be an extrudate which is on the compressed layer is fastened, for example by one of the above-described Mechanisms or by expansion of the extrudate on the parameters a mold, which is provided by the compressed layer.

Preferably comprises the compressed layer of a previously prepared recess or Mold (hereafter as "form"), in which the non-compressed layer is introduced. In a another embodiment comprises the surface the compressed layer more than one form into which the uncompressed Layer can be introduced. The form (s) preferably take at least partially to one or more non-compressed layers on. The non-compressed layer (s) will then be in the mold is inserted and fixed on the compressed layer, as described above.

The non-compressed layer may include particulates. The solid particles can by a known method, for example conventional spray-drying, Granulating, encapsulating or agglomerating. The solid particles can on the compressed layer by the introduction of a binder or by forming a cover over the uncompressed one Layer are attached.

If the non-compressed layer comprises a solidified melt, the melt is prepared by heating a composition comprising the finishing additive and an optional cleaning agent and / or carrier component (s) to form a flowable melt above its melting point. The flowable melt is then poured into a mold and allowed to cool. As the melt cools, it solidifies, assuming the shape of the mold at ambient temperature. If the composition comprises one or more carrier components, the carrier components may be heated above their melting point and then an effective detergent component may be added. Carrier components suitable for producing a solidified melt are typically non-active components which can be heated to form a liquid above the melting point and allowed to cool to form an intermolecular matrix containing the finishing additive and optionally may effectively include detergent components. A preferred carrier component is an organic polymer which is solid at ambient temperature. Preferably, the carrier component is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP) having a molecular weight of 10,000 to 360,000. The compressed layer of the detergent tablet preferably provides a mold to receive the melt.

The flowable, non-compressed Layer may be in a form which has a dissolved or suspended Additive additive and an optional detergent component comprises. The flowable, non-compressed Layer can be to form a solid, semi-solid or a high viscosity liquid by any of the methods described above Hardened the time become. In particular, the flowable, non-compressed layer by evaporation of a solvent hardened become. Any solvents suitable for use herein may be any known solvent lock in, in which a binding or gelling agent is soluble. Preferred solvents can polar, nonpolar, non-aqueous or be anhydrous and can for example, water, glycerol, alcohol (for example, ethanol or Acetone) and alcohol derivatives. In another embodiment can be more than a solvent be used.

The flowable, non-compressed Layer may comprise one or more binders or gelling agents. each Binding or gelling agent which can cause the composition becomes solid, semisolid or highly viscous with time, becomes here Use considered. Without being tied to a theory be, one assumes that the Mechanisms by which the binding or gelling agent causes that one Composition solid, semi-solid or highly viscous, the following lock in: a chemical reaction (like a chemical cross linking) or the Effecting an interaction between two or more components the flowable compositions; or the chemical or physical interaction of the binder with a component of the composition.

According to one preferred aspect of the present invention comprises the uncompressed Layer a gel. According to this Aspect is the gel on the compressed layer of the detergent tablet but preferably is in one of the compressed layer provided form introduced.

The Gel covered additionally to the optional detergent components a thickening system. In addition, can The gel also includes solid ingredients to regulate the viscosity of the gel in conjunction with the thickening system. firm Ingredients can also serve to selectively destroy the gel to the dissolution of the To support gels. If included, included the gel typically at least 15% solids, more preferably at least 30% solids, and most preferably at least 40% solids. However, the gel is pumpable or otherwise processable have to be, includes the gel typically does not contain more than 90% solids.

As already mentioned, comprises the gel is a thickening system to the required viscosity or thickness of the gel. The thickening system typically comprises a nonaqueous, liquid thinner and an organic or polymeric gelling additive:

a) Liquid diluent

Of the Term "solvent" or "diluent" is used herein around the liquid Share of thickening system to include. While some of the components The non-compressed layer can actually dissolve in the "solvent" containing phase, others can Components as particulate Material present, which in the "solvent" containing phase is dispersed. Consequently, the term "solvent" does not require that the components the non-compressed layer must be able to indeed in the solvent to solve. Suitable types of solvents, which in the present non-aqueous thickening systems are usable close Alkylenglykolmononiederalkylether, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol ester, glycerol triacetate, low molecular weight polyethylene glycols, low molecular weight Methyl esters and amides.

A preferred type of non-aqueous solvent for use herein comprises the mono-, di-, tri- or tetra-C ₂ -C ₃ alkylene glycol mono C ₂ -C ₆ alkyl ethers. The specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly preferred. Compounds of this type are commercially available under the trade Dowanol, Carbitol and Cellosolve.

One another preferred type of nonaqueous solvent usable herein comprises the low molecular weight polyethylene glycols (PEGs). Such Close materials those with molecular weights of at least 150. PEGs with one Molecular weights in the range of 200 to 600 are most preferred.

Still another preferred type of non-aqueous solvent comprises low molecular weight methyl esters. Such materials include those of the general formula: R ¹ -C (O) -OCH ₃ , wherein R ^{1 has} a value in the range of 1 to 18. Examples of suitable low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.

The the solvent (s) used should (of course) with the other optional detergent components, e.g. enzymes compatible and be non-reactive. Such a solvent component is used in generally used in an amount of 10 to 60 wt .-% of the gel fraction. Stronger preferably comprises the non-aqueous, organic solvent with a low polarity From 20 to 50% by weight of the gel, more preferably from 30 to 50% by weight of the gel.

b) gelling additive

One Gelling agent or additive becomes the nonaqueous solvent of the present invention added to complete the thickening system. To create the gel, which for a suitable phase stability is necessary, and an acceptable rheology of the gel lies the organic gelling agent is generally present to the extent that the ratio of Solvent to gelling agent in the thickening system typically in the range of 99: 1 to 1: 1 is. Stronger preferably the conditions are in the range 19: 1 to 4: 1.

The preferred gelling agents are selected from castor oil derivatives, Polyethylene glycol, sorbitols and related organic thixatropes, organomineral clays, cellulose and cellulose derivatives, Pluronic (RTM) species, stearates and stearate derivatives, sugar / gelatin combinations, Strengthen, Glycerol and derivatives thereof, organic acid amides such as N-lauryl-L-glutamic acid di-n-butylamide, Polyvinylpyrrolidone and mixtures thereof.

The close preferred gelling agent castor oil derivatives one. castor oil is a natural one occurring triglyceride, which is derived from the seeds of Ricinus communis a plant which is found in most tropical and subtropical areas is growing. The primary fatty acid moiety in the castor oil triglyceride is ricinoleic acid (12-hydroxyoleic acid). It makes up 90% of the fatty acid units out. The remainder consists of dihydroxystearin, plamitine, stearin, Olein, linoleic, linolenic and eicosanoic acid units. The hydrogenation of the oil (e.g. by hydrogen under pressure) converts the double bonds in the fatty acid moieties in single bonds, in this way the oil is "hardened". The hydroxyl groups are not affected by this reaction.

The thus obtained hydrogenated castor oil therefore has an average of about 3 hydroxyl groups per molecule. you assumes that the Presence of these hydroxyl groups greatly enhances the excellent structuring properties which are given to the gel, compared with similar ones liquid detergent compositions, the no castor oil containing hydroxyl groups in their fatty acid chains. For use in the compositions of the invention should the castor oil up to an iodine value of less than 20 and preferably less be hydrogenated as 10. The iodine value is a measure of the degree of unsaturation of the oil and is measured by the "Wijis method" on well known in the art. Unhydrogenated castor oil has an iodine value of 80 to 90 on.

hydrogenated castor oil is a commercially available one Goods, for example, in different qualities under the trademark CASTORWAX (RTM) of NL Industries, Inc., Highstown, New Jersey, is distributed. Other suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, manufactured by Rheox, Laporte. Particularly preferred is thixatrol ST.

Polyethylene glycols, if used as a gelling agent, in contrast to the solvents low molecular weight materials having a molecular weight ranging from 1,000 to 10,000, with 3,000 to 8,000 being the most is preferred.

Cellulose and cellulose derivatives, when used in the present invention, preferably comprise: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropyl methylcellulose (HPMC); iii) carboxymethylcellulose (CMC); and mixtures thereof. The hydroxypropylmethylcellulose polymer preferably has a number average molecular weight of 50,000 to 125,000 and a viscosity of a 2% by weight aqueous solution at 25 ° C (ADTMD2363) of 50,000 to 100,000 cps. An especially preferred hydroxypropyl cellulose is Methocel ^® J75MS-N wherein a 2 wt .-% having aqueous solution at 25 ° C a viscosity of about 75,000 cps.

Of the Sugar can be any monosaccharide (e.g., glucose), disaccharide (e.g., sucrose or maltose) or polysaccharide. The most preferred sugar is the commonly available sucrose. According to the invention, gelatin of the type A or B, which, for example, Sigma available is. Type A gelatin is preferred as it provides greater stability alkaline conditions compared to type B has. preferred Gelatine also has a swab strength between 65 and 300, most preferably between 75 and 100.

The Gel can additionally to the thickener as described above and the following in more detail described finishing additive a variety of other ingredients lock in. Ingredients, such as dyes, as well as structurants may be included be. Structural Modifiers shut down various polymers and blends of polymers containing polycarboxylates, Carboxymethylcelluloses and starches lock in, to the absorption of the excess solvent to promote and / or "evaporating" or exiting of the solvent from the gel fraction to reduce or prevent the shrinkage or to reduce breakage of the gel fraction or dissolution or break-up to support the gel fraction during washing. In addition, hardness modifiers can be incorporated into the thickening system are introduced to adjust if necessary, the hardness of the gel. These Hardness control agent are typically selected from various polymers, such as polyethylene glycols, polyethylene oxide, Polyvinylpyrrolidone, polyvinyl alcohol, hydroxystearic acid and polyacetic and, if included, typically in proportions of less than 20% by weight and stronger preferably less than 10% by weight of the solvent in the thickening system used.

The Gel is prepared so that it a pumpable, flowable gel at slightly elevated Temperatures of about 30 ° C or are more to an increased flexibility to allow in the preparation of the detergent tablet but becomes highly viscous at ambient temperatures or hardens, so that this Gel on the compressed layer of the detergent tablet during the Shipping and handling of the detergent tablet at the is held in the right place. Such curing of the gel can be achieved, for example are cooled by (i) below the flow temperature of the gel or raising the shear force, (ii) by solvent transfer, for example, to each medium of the compressed volume range; or (iii) by polymerizing the gelling agent. Preferably the gel is prepared so that it sufficiently hardened, So that the maximum force required to place a probe in the uncompressed To push layer preferably in the range of 0.5 N to 40 N. This power can by measuring the maximum force required to get one Probe equipped with a strain gauge is to push a set distance into the gel. The set route can be between 40 and 80% of the total money. This power can with a QTS-25 test device using a probe be measured with a diameter of 5 mm. Typical measured personnel lie in the range of 1 N to 25 N.

If the non-compressed layer is an extrudate becomes the extrudate by premixing the detergent components of the non-compressed Layer with optional carrier components produced to form a viscous paste. The viscous paste is then made using a suitable, commonly available extrusion device, such as a single or twin screw extruder, available for example extruded from APV Baker, Peterborough, UK. The extrudate will then either after insertion into the compressed layer or before tailored for insertion into the compressed layer of the detergent tablet. The compressed layer of the tablet preferably comprises a mold into which the extruded, non-compressed layer is introduced can be.

In a preferred embodiment For example, the non-compressed layer is coated with a coating layer. The coating can be used to remove the uncompressed Layer on the compressed layer to attach. This can be special be advantageous if the non-compressed layer flowable solid particles, Gels or liquids includes.

The overcoat layer preferably comprises a material which, upon contact with the compressed and / or uncompressed layers, is more preferably within less than 15 minutes less than 10 minutes, even more preferably less than 5 minutes, more preferably less than 60 seconds. Preferably, the coating layer is water-soluble. Preferred coating layers include materials selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acids, dicarboxylic acids, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA), polyethylene glycol (PEG) and Mixtures thereof. Preferred carboxylic or dicarboxylic acids preferably comprise an even number of carbon atoms. Preferably, the carboxylic and dicarboxylic acids comprise at least 4, more preferably at least 6, even more preferably at least 8 carbon atoms, most preferably between 8 and 13 carbon atoms. Preferred dicarboxylic acids include adipic acid, suberic acid, azelaic acid, subacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and mixtures thereof. Preferred fatty acids include those having a carbon chain length of C12 to C22, most preferably C18 to C22. The coating layer may also preferably comprise a break apart agent. If present, the coating layer is generally present at a level of at least 0.05%, preferably at least 0.1%, more preferably at least 1%, most preferably at least 2%, and also at least 5% of the detergent tablet.

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

The density of the non-compressed layer is generally 0.7 g / cm ³ to 1.2 g / cm ³ , more preferably 0.8 g / cm ³ to 1.2 g / cm ³ , particularly preferably 0.9 g / cm ³ to 1.1 g / cm ³ . The density of the non-compressed layer is preferably at least 0.2 g / cm ^3, more preferably at least 0.3 g / cm ^3, more preferably at least 0.4 g / cm ³ less than the density of the compressed layer.

density measurement the non-compressed layer

Preferably The density of the uncompressed area is used a simple funnel and a cup-shaped device, which consists of a conical funnel, which is rigid at its base is shaped and at its lower end with a flap is equipped, which allows the Contents of the funnel in an axially aligned, cylindrical cup of known volume, which is located under the funnel, can be emptied. The funnel is 130 mm high and instructs its upper and lower end an inner diameter of 130 mm or 40 mm. It is fixed so that the lower end 140 mm above the surface the base area located. The cup has a total height of 90 mm, an interior height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

to execution The density measurement will manually enter the uncompressed area filled the funnel, the flap will be opened and you leave the powder flow into the cup until he overflows. The filled cup is removed from the rack, and the excess uncompressed area is treated with a straight-edged article, e.g. a knife that you can over the moved away from the top of the cup. The filled cup is then weighed. The weight of the uncompressed area becomes by subtracting the weight of the cup from the weight of the cup Bechers plus the uncompressed range calculated. The concentration is then divided by dividing the weight (mass) of the uncompressed Area calculated by the volume of the mug. Possibly repeat attempts are made.

Detergent components

The Tablets are made by compressing a detergent composition produced. A suitable composition can be a variety of others Include detergent components, including builder compounds, Surfactants, alkalinity sources, colorants, Perfume, Lime soap dispersants, organic polymeric compounds, including polymeric agents that inhibit dye transfer, crystal growth inhibitors, Heavy metal ion sequester, metal ion salts, enzyme stabilizers, Corrosion inhibitors, foam inhibitors, solvents and hydrotropes.

builder compound

The Detergent tablets according to the invention preferably contain a builder compound, which typically in a proportion of 1 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight of the composition of effective Detergent components is present.

Water-soluble builder compound

suitable water-soluble Close builder compounds the water-soluble monomeric polycarboxylates or their acid forms, homopolymers or copolymers polycarboxylic or their salts, wherein the polycarboxylic acid has at least two carboxyl groups comprises which are separated from each other by not more than two carbon atoms are, carbonates, bicarbonates, borates, phosphates and mixtures any of the above.

Of the Carboxylate or polycarboxylate builder can be monomeric or oligomeric although monomeric polycarboxylates are generally derived from cost and performance reasons to be favoured.

suitable Carboxylates having a carboxyl group include the water-soluble ones Salts of lactic acid, glycolic acid and Ether derivatives thereof. Polycarboxylates with two carboxyl groups shut down the water-soluble Salts of succinic acid, malonic, (Ethylenedioxy) diacetic acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. polycarboxylates with three carboxyl groups especially water-soluble Citrates, aconitrates and citraconates as well as succinate derivatives, such as the carboxymethyloxysuccinates described in the British patent No. 1,379,241, the lactoxysuccinates described in the British Patent No. 1,389,732, and the amino-succinates described in U.S. Pat Dutch Application 7205873, and the oxypolycarboxylate materials, such as 2-oxa-1,1,3-propanetricarboxylates, described in British Patent No. 1,387,447.

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

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-tetrahydrofurantetracarboxylates, 1,2,3,4,5,6-Hexanhexacarboxylate and Carboxymethylderivate polyvalent Alcohols such as sorbitol, mannitol and xylitol, a. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343 one.

The Among the above preferred polycarboxylates are the hydroxycarboxylates with up to 3 carboxyl groups per molecule, more preferably citrates.

The parent acids the monomeric or oligomeric polycarboxylate complexing agent or Mixtures thereof with their salts, e.g. Citric acid or Citrate / citric acid mixtures, are also considered to be useful builder components.

borate builders and builders containing borate-producing materials, which Produce borate under detergent storage and washing conditions can, can can also be used, but are below washing conditions of 50 ° C, especially below 40 ° C not preferred.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including Sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine Calcium carbonate, as in German Patent Application No. 2,321,001, released on November 15, 1973, disclosed.

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

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

Partially soluble or insoluble builder compound

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

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

The crystalline layered sodium silicate material is preferably in granular Detergent compositions as a solid in intimate Mixing with a solid, water-soluble, ionizable material as described in PCT Patent Application No. WO 92/18594 is. The solid, water-soluble, ionizable material is made up of organic acids, organic and inorganic Hydrogen salts and mixtures thereof, with citric acid being preferred becomes.

Examples of mostly water-insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na ₂ [(AlO ₂ ) _z (SiO ₂ ) _y ] .xH ₂ O wherein z and y are at least 6; the molar ratio of z to y is 1.0 to 0.5; and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline with 10 to 28%, more preferably 18 to 22% of water in bound form.

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

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

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

Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When used as a component of a detergent composition, colloidal aluminosilicate zeolites, particularly colloidal zeolite A, provide improved builder performance with a view to providing improved stain removal. Improved builder performance is also observed in terms of reduced tissue encrustation and improved white tone maintenance of the tissue; which present problems believed to be associated with improperly assembled detergent compositions Related.

A surprising The finding is that detergent compositions mixed aluminosilicate zeolite comprising colloidal zeolite A and colloidal zeolite Y, equivalent calcium ion sequestration performance compared to the corresponding weight of the commercially available available zeolites A. Another surprising Statement is that the mixed detergent compositions described above Aluminosilicate zeolites improved magnesium ion sequestration performance provide compared to the equivalent Weight of the commercially available Zeolite A.

surfactant

surfactants Preferred detergent components are those described herein Compositions. Suitable surfactants are anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and Mixtures thereof selected. Products for automatic dishwasher should be low-foaming be, and so must the Foaming of the surfactant system for use in dishwashing processes repressed more preferably, the surfactant system should be low foaming, typically nonionic be. The foaming used by those in laundry washing processes Does not have to be suppressed to the same extent as required for dishwashing is. The surfactant is typically in a proportion of 0.2 to 30% by weight, stronger preferably 0.5 to 10% by weight, particularly preferably 1 to 5 wt .-% of the composition of effective Detergent components before.

A Typical list of anionic, nonionic, ampholytic and zwitterionic classes and species of these surfactants is described in US patent 3,929,678, issued to Laughlin and Heuring on December 30, 1975, specified. A list of suitable cationic surfactants is in U.S. Patent 4,259,217 issued to Murphy on March 31, 1981. A list of surfactants, which are typically used in detergent compositions for automatic dishwashing are included, for example, in EP-A-0-414 549 and the PCT Application Nos. WO 93/08876 and WO 93/08874.

nonionic surfactant

in the essentially any nonionic surfactant which is used for cleaning purposes can be included in the detergent tablet be. Preferred non-limiting classes of useful nonionic Surfactants are listed below.

nonionic ethoxylated alcohol surfactant

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

endcapped alkyl alkoxylate

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

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

Ether-capped, poly (oxyalkylated) alcohols

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

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

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

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

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

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

These Surfactants show significant improvements in stain- and film formation characteristics and removal of greasy soil, when used in conjunction with high cloud point surfactants, compared to conventional Surfactants.

Generally can prepared the ether-capped, poly (oxyalkylated) alcohol surfactants are made by reacting an aliphatic alcohol with an epoxide to form an ether, which is then reacted with a base to form a second epoxide. The second epoxide then becomes reacted with an alkoxylated alcohol to the novel compounds of the invention to build. Examples of Methods for Making the Ether-capped, Poly (oxyalkylated) alcohol surfactants are described below.

Preparation of a C _12/14 alkyl glycidyl ether

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

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

Neodol ^® 91-8 (20.60 g, 0.0393 mol, an ethoxylated alcohol, available from Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) in a 250 ml three-necked round bottom flask equipped with condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C, at which time a C _12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 min. After 18 hours of stirring at 60 ° C, the mixture is cooled to room temperature and dissolved in a similar portion of dichloromethane. The solution is passed through a 25.4 mm (1 inch) thick silica gel pad 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 as an oil.

Nonionic ethoxylated / propoxylated fatty alcohol

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

Nonionic EO / PO condensates with propylene glycol

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

Nonionic EO condensation products with propylene oxide / ethylenediamine adducts

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

mixed nonionic surfactant system

In a preferred embodiment of the invention comprises the detergent tablet is a mixed nonionic surfactant system, which is at least one nonionic surfactant with a low cloud point and at least one nonionic surfactant having a high cloud point includes.

The "cloud point" as used here refers to a well-known property of nonionic Surfactants, which results from the fact that the surfactant with increasing Temperature becomes less soluble; the temperature at which the occurrence of a second phase is perceptible is called the "cloud point" (cf. Kirk Othmer's Encyclopedia of Chemical Technology, 3rd edition, Vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is not one tion component of a surfactant system having a cloud point of less than 30 ° C, preferably less than 20 ° C and more preferably less than 10 ° C defined. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and reverse polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) block polymers. Also include those nonionic surfactants having a low cloud point, for example, ethoxylated-propoxylated alcohols (for example, Poly-Tergent ^® SLF-18 of Olin Corporation), epoxy-capped poly (oxyalkylated) alcohols (eg, the Poly-Tergent ^® SLF-18B series nonionic species of Olin Corporation, as described, for example, in WO 94/22800, published October 13, 1994, by Olin Corporation) and the ether-capped, poly (oxyalkylated) alcohol surfactants.

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

Low cloud point nonionic surfactants additionally comprise a polyoxyethylene / polyoxypropylene block polymer compound. Polyoxyethylene / polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine as the reactive hydrogen starter compound. Certain of the block polymer surfactant compounds designated PLURONIC ^®, REVERSED PLURONIC ^® and Tetronic ^® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable herein. Preferred examples include REVERSED PLURONIC ^® 25R2 and Tetronic ^® a 702nd Such surfactants are typically useful herein as low cloud point nonionic surfactants.

So As used herein, a "high cloud point" nonionic surfactant is nonionic Component of a surfactant system having a cloud point of more than 40 ° C, preferably more than 50 ° C and stronger preferably more than 60 ° C Are defined. Preferably comprises the nonionic surfactant system is an ethoxylated surfactant which from the reaction of a monohydroxy alcohol or alkylphenol with 8 to 20 carbon atoms with 6 to 15 moles of ethylene oxide per mole Alcohol or alkylphenol on an average basis. Such nonionic surfactants with a high cloud point close to Example Tergitol 15S9 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhone Poulenc) and Neodol 91-8 (sold from Shell).

Also according to the invention preferred that the Nonionic surfactant with a high cloud point continues to have one Value for the hydrophilic-lipophilic balance ("HLB", see. Kirk Othmer, supra) within the range of 9 to 15, preferably 11 to 15. Such materials include Example Tergitol 15S9 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhone Poulenc) and Neodol 91-8 (sold from Shell).

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

In a preferred embodiment comprises the detergent tablet containing such a mixed surfactant system comprises also a share of a water-soluble Salt to give a specific electrical conductivity in deionized water, measured at 25 ° C, of more than 3 millisiemens / cm, preferably more than 4 millisiemens / cm, more preferably provide more than 4.5 millisiemens / cm.

In another preferred embodiment, the mixed surfactant system dissolves in water having a hardness of 1.246 mmol / l in a suitable cold water filling dishwashing machine so that a solution having a surface tension of less than 4 dynes / cm ² at less than 45 ° C, preferably less than 40 ° C, more preferably less than 35 ° C is provided.

In another preferred embodiment, the surfactants having a high cloud point or low cloud point of the mixed surfactant system are separated so that either the high cloud point surfactant or the low cloud point surfactant in a first cloud point Matrix is present and the other is present in a second matrix. According to the invention, the first matrix may be a first particulate and the second matrix may be a second particulate. A surfactant may be applied to a particulate by a suitable known method, preferably the surfactant is sprayed onto the particulate. According to a preferred aspect, the first matrix is the compressed area, and the second matrix is the non-compressed area of the detergent tablet according to the invention. Preferably, the low cloud point surfactant is present in the compressed area and the high cloud point surfactant is present in the non-compressed area of the detergent tablet of the present invention.

anionic surfactant

in the essentially any anionic surfactant which is useful for cleaning purposes is is suitable. these can Salts (including for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of the anionic sulphate, Include sulfonate, carboxylate and sarcosinate surfactants. anionic Sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ C ₁₄ diester) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present or derived from tallow oil.

anionic sulphate

Suitable anionic sulfate surfactants for use herein include the linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates containing C ₇ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) - and -N- (C C ₁ -C ₂ hydroxyalkyl) glucamine sulfates and sulfates of alkyl polysaccharides, such as the sulfates of alkyl polyglucoside (the nonionic, non-sulfated compounds described herein).

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

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

One particularly preferred aspect of the invention uses mixtures the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such Mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

anionic sulfonate

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

anionic carboxylate

to suitable anionic carboxylate surfactants herein include Alkyl ethoxycarboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps ('alkylcarboxyls'), especially certain secondary soaps, as described here, a.

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

suitable Close soap surfactants the secondary ones Soap surfactants having one associated with a secondary carbon Carboxylyl unit included. Preferred secondary soap surfactants to the present Use are water-soluble Representatives, selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain Soaps can also included as foam inhibitors.

Alkali

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

amphoteric surfactant

to The present use of suitable amphoteric surfactants includes Amine oxide surfactants and the alkylamphocarboxylic acids.

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

One suitable example of an alkylamphodicarboxylic acid is Miranol (TM) C2M Conc. which is manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

zwitterionic Surfactants can also incorporated into the present detergent compositions become. These surfactants can generally 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 are described. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

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

cationic surfactants

Used according to the invention Cationic ester surfactants are preferably water-dispersible compounds with surfactant properties containing at least one ester linkage (i.e. -COO-) and at least one cationically charged group. Other suitable cationic ester surfactants, including choline ester surfactants for example, in U.S. Patent Nos. 4228042, 4239660 and 4260529 disclosed.

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

enzymes

to Suitable enzymes for use herein are selected from Cellulases, hemicellulases, peroxidases, proteases, glycoamylases, Amylases, xylanases, lipases, phospholipases, esterases, cutinases, Pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, Ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, Arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures hereof.

preferred Close enzymes Proteases, amylases, lipases, peroxidases, cutinases and / or cellulases in conjunction with one or more enzymes which degrade plant cell walls, one.

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

Examples Such cellulases are cellulases derived from a strain of Humicola insolens (Humicola grisea, Var. thermoidea), especially the Humicola strain DSM 1800 are produced Other suitable cellulases are cellulases, which originate from Humicola insolens, with a molecular weight of 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; and a 43 kD endoglucanase obtained from Humicola insolens DSM 1800, which is a cellulase activity shows; wherein a preferred endoglucanase component is that described in U.S. Pat PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum, which is published in WO 94/21801, Genencor on September 29, 1994. Particularly suitable cellulases are the cellulases that have color care benefits. Examples Such cellulases are cellulases which are described in the European patent application No. 91202879.2, filed on Nov. 6, 1991 (Novo) are. Carenzyme and Celluzyme (Novo Nordisk A / S) are special useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases for textile care and / or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

These Cellulases are normally added to the detergent composition at levels of 0.0001 to 2% active enzyme by weight of the detergent composition.

peroxidase are used in conjunction with oxygen sources, e.g. Percarbonate, perborate, Persulfate, hydrogen peroxide, etc. used. They are used for "bleaching in solution", i. to the transfer of dyes or pigments made from substrates during washing processes were removed to prevent other substrates in the wash liquor. Peroxidase enzymes are known in the art and include Example horseradish peroxidase, ligninase and haloperoxidase, such as chlorine and bromine peroxidase, a. Peroxidase-containing detergent compositions are, for example, in PCT International Application WO 89/099813 and WO 89/09813 and in the European patent application with the EP no. 91202882.6, filed November 6, 1991, and EP-No. 96870013.8, filed on February 20, 1996. Also suitable the laccase enzyme.

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

These Cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001 to 2% active enzyme by weight of the detergent composition.

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

Also suitable are cutinases [EC 3.1.1.50] which are considered to be a particular Type of lipase can be considered, namely lipases, the no interfacial activation require. The addition of cutinases to detergent compositions was e.g. in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System); and WO 94/14963 and WO 94/14964 (Unilever).

The Lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001 to 2% active enzyme by weight of the detergent composition.

Suitable proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, this was by Novo Industries A / S of Denmark, hereinafter "Novo", developed and sold as ESPERASE ^®. The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE ^®, DURAZYM ^® and SAVINASE ^® from Novo and MAXATASE a ^®, MAXACAL ^®, PROPERASE® ^® and MAXAPEM ^® (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application No. 87303761.8, filed April 28, 1987 (especially pages 17, 24 and 98), referred to herein as "Protease B" and that described in European Patent Application 199,404, Venegas, published October 29, 1986, which relates to a modified bacterial serine protease enzyme, referred to herein as "Protease A". Also suitable herein is the protease designated "protease C", which is a variant of an alkaline serine protease from Bacillus, wherein arginine at position 27 is by lysine, valine at position 104 by tyrosine, asparagine at position 123 by serine and threonine at position 274 Alanine was replaced. Protease C is described in EP-90915958.4 which corresponds to WO 91/06637 published May 16, 1991. Genetically modified variants, especially protease C, are also included here.

A preferred protease, termed "protease D", is a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence which is derived from a Precursor carbonyl by substituting a plurality of amino acid residues with another amino acid in a position in this carbonyl hydrolase that is the position +76, preferably in combination with one or several amino acid residues, which correspond to the positions selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274, according to the numbering of Bacillus amyloliquefaciens subtilisin, as in WO 95/10591 and in the patent application of Ghosh C. et al., "Bleaching Compositions Comprising Protease Enzymes ", with the US Application Serial No. 08 / 322,677, filed October 13, 1994, is described.

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

See also an effective at high pH protease from Bacillus sp. NCIMB 40338, which is described in WO 93/18140 A to Novo. Enzymatic detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo ben. Optionally, a protease is available which has reduced adsorption and increased hydrolysis, as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergent, which is suitable here, is described in WO 94/25583 to Novo. Other suitable proteases are described in Unilever EP-516,200.

Other preferred protease enzymes include protease enzymes which a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence which are by replacing a variety of amino acid residues a precursor carbonyl hydrolase through other amino acids wherein the plurality of amino acid residues present in the precursor enzyme be replaced, the position +210 in combination with one or more of the following are: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions of course occurring subtilisin from Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those which exchanges in the positions +210, +76, +103, +104, +156 and +166.

The proteolytic enzymes are incorporated into the detergent compositions of the invention in in a proportion of 0.0001 to 2%, preferably 0.001 to 0.2%, more preferably 0.005 to 0.1% pure enzyme by weight of the composition brought in.

amylases (α and / or β) can be used for Removal of carbohydrate spots are included. WO 94/02597, Novo Nordisk A / S, published on February 3, 1994, describes detergent compositions, which include mutated amylases. See also WO 95/10603, Novo Nordisk A / S, published on April 20, 1995. Other amylases suitable for use in detergent compositions are known, close both α- as well as β-amylases one. α-amylases are known in the art and include those which in U.S. Patent No. 5,003,257; EP 252,666; WO 91/00353; FR-2,676,456; EP-285,123; EP-525,610; EP-368,341; and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are amylases having improved stability in WO94 / 18314 on August 18, 1994, and WO 96/05295, Genencor on February 22, 1996, and amylase variants with an additional one Modification in the immediate parent form, that of Novo Nordisk A / S available are and WO 95/10603, published in April 95, are disclosed. Also suitable are amylases which in EP 277,216; WO 95/26397; and WO 96/23873 (all to Novo Nordisk) are described.

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

preferred Close amylase enzymes those described in WO 95/26397 and in the co-pending application PCT / DK96 / 00056 by Novo Nordisk.

The amylolytic enzymes are incorporated in the detergent compositions of the invention in an amount of 0.0001 to 2%, preferably 0.00018 to 0.06%, stronger preferably 0.00024 to 0.048% pure enzyme by weight introduced the composition. In a particularly preferred embodiment include detergent tablets according to the invention Amylase enzymes, especially those described in WO 95/26397 and in U.S. Pat simultaneously pending Application PCT / DK96 / 00056 by Novo Nordisk are described in combination with a complementary one Amylase.

By "complementary" is meant the addition of one or more amylases suitable for purification purposes. Examples of complementary amylases (α and / or β) are described below. WO 94/02597 and WO 95/10603, Novo Nordisk A / S, describe detergent compositions which include mutated amylases. Other amylases known for use in detergent compositions include both α- and β-amylases. α-Amylases are known in the art and include those described in US Pat. Nos. 5,003,257; EP 252,666; WO 91/00353; FR-2,676,456; EP-285,123; EP-525,610; EP-368,341; and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are improved stability amylases described in WO 94/18314 and WO 96/05295, Genencor, and amylase variants with additional modification in the immediate parent form, disclosed in WO 95/10603, published by Novo Nordisk A / S are available. Also suitable are amylases described in EP 277,216 (Novo Nordisk). Examples of commercially available α-amylases products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, all of which are available from Novo Nordisk A / S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl ^® at a temperature range of 25 ° C to 55 ° C and a pH in the range 8 to 10, measured by the Phadebas ^{® -α-amylase} activity assay is. Suitable variants of the above enzymes are those described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes having improved properties with regard to the level of activity and the combination of heat stability and a higher level of activity are described in WO 95/35382. Preferred complementary amylases according to the invention are the amylases, which are described in WO 94/18314 and WO 96/05295, sold by Genencor under the tradename Purafect Ox Am ^®; Termamyl ^®, Fungamyl ^®, Ban ^® and Duramyl ^®, which are all available from Novo Nordisk A / S; and Maxamyl ^® by Gist-Brocades.

The complementary Amylase is in the Reinigungsmittelzusanunensetzungen in the invention general in a proportion of 0.0001 to 2%, preferably 0.00018 up to 0.06%, stronger preferably 0.00024 to 0.048% pure enzyme by weight introduced the composition. Preferably, the ratio of Weight of the pure enzyme of the specific amylase to the complementary amylase between 9: 1 to 1: 9, stronger preferably between 4: 1 to 1: 4 and more preferably between 2: 1 to 1: 2.

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

These Enzymes are normally added to the detergent composition at levels of 0.0001 to 2% active enzyme by weight of the detergent composition. The enzymes can be considered as separate individual ingredients (prills, granules, stabilized liquids etc., contain an enzyme) or as mixtures of two or more Enzymes (e.g., cogranules) are added.

Other suitable detergent ingredients that may be added are Enzyme oxidation scavengers, which in the co-pending European patent application 92870018.6, filed January 31, 1992. Examples such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A Series of enzyme materials and agents for their incorporation into synthetic Detergent compositions are also described in WO 93/072263 A and WO 93/07260 A to Genencor International; WO 89/08694 A to Novo; and 3,553,139, January 5, 1971 to McCarty et al. enzymes are further described in U.S. 4,101,457, Place et al., July 18, 1978; and in US 4,507,219, Hughes, March 26 1985 disclosed. For liquid Detergent preparations usable enzyme materials and their Admixtures in such preparations are described in US 4,261,868, Hora et al., Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques in U.S. 3,600,319, August 17, 1971, Gedge et al .; EP-199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US 3,519,570. The useful one Bacillus sp. AC13 strain containing proteases, xylanases and cellulases is described in WO 94/01532 A to Novo.

bleach

A another component of the composition of detergent components is an oxygen-releasing bleach.

According to one contains preferred aspect the oxygen-releasing bleach is a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid takes place by an in situ reaction of the precursor with a source for Hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic ones Perhydrate bleaching. According to one another aspect is a preformed organic peroxyacid directly introduced into the composition. Compositions containing Mixtures of a hydrogen peroxide source and an organic Peroxyacid precursors in Compound with a preformed organic peroxyacid also considered.

inorganic Perhydratbleichen

The Compositions of detergent components preferably include a source of hydrogen peroxide as an oxygen-releasing bleach one. Suitable sources of hydrogen peroxide include the inorganic perhydrate salts one.

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

Examples inorganic perhydrate salts include perborate, percarbonate, Perphosphate, persulfate and persilicate salts. The inorganic ones Perhydrate salts are usually in the form of the alkali metal salts. The inorganic perhydrate salt may be in the form of a crystalline solid without additional Protection included. For however, certain perhydrate salts use the preferred embodiments such granular Compositions A coated form of material containing a better shelf life for the perhydrate salt in the granular Product provides.

Sodium perborate may be in the form of the monohydrate of nominal formula NaBO ₂ H ₂ O ₂ or of the tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O. Alkali metal percarbonates, especially sodium percarbonate, are preferred perhydrates for inclusion in compositions of the invention. Sodium percarbonate is an additional compound of the formula 2Na ₂ CO ₃ .3H ₂ O _2, and is available commercially as a crystalline solid. Sodium percarbonate, which is a hydrogen peroxide addition compound, upon dissolution, tends to release the hydrogen peroxide very rapidly, increasing the tendency for localized high levels of bleach that may occur. The percarbonate is more preferably incorporated into such compositions in a coated form which provides stability in the product.

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

Another suitable coating material which provides product stability comprises sodium silicate having a SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 and / or Sodium metasilicate, preferably used in a proportion of 2 to 10% (normally 3 to 5%) SiO ₂ based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings containing silicate and borate salts or boric acids or other inorganic species are also suitable.

Other Coatings, which waxes, oils or fat soaps can advantageously also according to the invention be used.

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

Peroxyacid bleach precursor

worin L eine Abgangsgruppe bedeutet und X im wesentlichen irgendeine Funktionalität ist, so daß bei der Perhydrolyse die Struktur der erzeugten Peroxysäure wie folgt ist

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrol sereaktion react to form a peroxy acid. In general, peroxyacid bleach precursors can be represented as

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

Peroxyacid bleach precursor compounds are preferably in a proportion of 0.5 to 20 wt .-%, more preferably 1 to 10 wt .-%, more preferably 1.5 to 5 wt .-% of the compositions introduced.

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

leaving groups

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

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

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

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

Perbenzoic

perbenzoic acid precursor envisage perbenzoic acid in perhydrolysis.

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

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

perbenzoic acid precursor close the imid type N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl-substituted ones Ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl groups containing perbenzoic acid precursors include N-benzoylpyrrolidone, Dibenzoyltaurine and benzoylpyroglutamic acid.

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

Phthalic anhydride is another suitable perbenzoic acid precursor compound:

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

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

Perbenzoesäurederivatvorläufer

See perbenzoic acid derivative precursor in perhydrolysis substituted perbenzoic acids.

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

worin R¹ eine Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen bedeutet und R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist und L im wesentlichen irgendeine Abgangsgruppe ist. R' enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R' kann Aryl, substituiertes Aryl oder Alkylaryl, enthaltend eine Verzweigung, Substitution oder beides, darstellen und kann aus entweder synthetischen Quellen oder natürlichen Quellen, einschließlich zum Beispiel Talgfett, abgeleitet sein. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Aryl-, Halogen-, Stickstoff, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen einschließen. R⁵ hat vorzugsweise die Bedeutung H oder Methyl. R¹ und R⁵ sollten nicht mehr als 18 Kohlenstoffatome insgesamt enthalten. Amid-substituierte Bleichaktivatorverbindungen dieses Typs sind in EP-A-0170386 beschrieben.A preferred class of substituted perbenzoic acid precursor compounds are the amide-substituted compounds of the following general formulas:

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

Cationic peroxyacid precursors

cationic peroxyacid precursor compounds produce perhydrolysis cationic peroxyacids.

typically, Cationic Peroxyacid Precursors Substitution of Peroxysäureanteils a suitable peroxyacid precursor compound by a positively charged, functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, educated. Cationic peroxyacid precursors are present typically in the compositions in the form of a salt with a suitable anion, such as a halide ion or a methylsulfate ion, in front.

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

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

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

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

A preferred cationically substituted alkyloxybenzenesulfonate has the formula:

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

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

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

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

Alkyl bleach precursor

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

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

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

Amide-substituted alkyl peroxyacid precursors

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

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

Organic benzoxazine peroxyacid precursors

einschließlich der substituierten Benzoxazine des Typs

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

including the substituted benzoxazines of the type

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

A particularly preferred benzoxazine-type precursor is:

Pre-formed organic peroxy

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

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

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

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is a preferred organic peroxyacid here. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxycaproic acid are also suitable here.

Means for release at controlled speed

One Means can for a release of oxygen bleach at a controlled rate be provided in the wash liquor.

medium for one Release of bleach at a controlled rate may allow controlled release of peroxide species in the wash liquor. Such funds could be used for Example the control of the release of an inorganic perhydrate salt, which is effective as a source of hydrogen peroxide, into the wash liquor lock in.

suitable Funds for a controlled release the restriction bleaching on either the compressed or the uncompressed Include area. If more than one uncompressed area exists, then bleaching at first and / or second and / or optionally following be restricted to uncompressed area.

One another mechanism for controlling the rate of release bleaching can be achieved by coating the bleach with a coating, which is so laid out that she a controlled release provides. The coating may therefore comprise, for example, a hardly water-soluble material or a Be coating with a sufficient thickness so that the kinetics the resolution the thick coating release with a controlled Speed provides.

The Coating material may be prepared using various methods be applied. Each coating material is typically in a weight ratio from coating material to the bleach from 1:99 to 1: 2, preferably 1:49 to 1: 9 before.

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

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

A preferred coating material, especially for an inorganic perhydrate salt bleach, comprises sodium silicate having a SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably coated in a proportion of 2 to 10% (normally 3 to 5%) SiO ₂ based on the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

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

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones having an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) having an average molecular weight of 600 to 5 x 10 ⁶ , preferably 1,000 to 400,000, more preferably 1,000 to 10,000, are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein the maleic anhydride constitutes at least 20 mole percent of the polymer, are further examples of polymeric materials useful as binders. These polymeric materials may be used as such or in conjunction with solvents such as water, propylene glycol and the aforementioned C ₁₀ -C ₂₀ alcohol ethoxylates with 5 to 100 moles of ethylene oxide per mole of alcohol. Further examples of binders include the C ₁₀ -C ₂₀ mono- and diglycerol ethers and also the C ₁₀ -C ₂₀ fatty acids.

Cellulose derivatives, such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or their salts other examples of Binders suitable for use herein.

One Method for applying the coating material completes the agglomeration one. Preferred agglomeration methods include the use of any the organic binder materials described above one. Any conventional Agglomeration / mixing apparatus may be used, including, but not limited to pan, rotary and vertical mixers. Molten coating compositions may also be formed either by casting or spraying on a moving layer of the bleaching agent are applied.

Other Means for providing the required controlled release shut down mechanical means of change the physical properties of the bleach to its solubility and to control release rate. Suitable protocols could Compression, mechanical injection, manual injection and Adjustment of solubility the bleaching compound by the choice of the particle size of a every particulate Include component.

While the Choice of particle size of both the composition of the particulate component as well from the wish, the desired Kinetics of controlled release, it is desirable to that the Particle size more than 500 μm, preferably with an average particle diameter of 800 to 1200 μm, should be.

Further Protocols for the provision of controlled release means shut down the appropriate choice of any other components of the matrix of the detergent composition such that when the composition is introduced into the wash liquor, the ionic strength environment provided therein allows that the required kinetics of controlled release can be achieved can.

Metal-containing bleach catalyst

The Compositions described herein which contain a bleach as one Detergent component may additionally be considered as a preferred Component containing a metal-containing bleach catalyst. Preferably For example, the metal-containing bleach catalyst is a transition metal-containing one Bleach catalyst, stronger preferably a manganese or cobalt-containing bleach catalyst.

One Suitable bleach catalyst type is a catalyst which is a Heavy metal cation with a defined bleaching catalytic activity, such as copper or iron ions, an additional one Metal cation with little or no pale catalytic Activity, such as zinc or aluminum cations, and a sequestrants with defined stability constants for the catalytic and additional Metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water soluble Salts thereof. Such catalysts are disclosed in U.S. Patent 4,430,243.

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

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

One still another type of bleach catalyst, as in U.S. Patent 5,114,606 discloses is a water-soluble Complex of manganese (III) and / or (IV) with a ligand, which a noncarboxylate polyhydroxy compound having at least three consecutive C is -OH groups. Preferred ligands include sorbitol, iditol, dulsitol, Mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, Lactose and mixtures thereof.

worin R¹, R², R³ und R⁴ jeweils gewählt sein können aus H, substituierten Alkyl- und Arylgruppen, so daß jedes R¹-N=C-R² und R³-C=N-R⁴ einen 5- oder 6-gliedrigen Ring bildet. Dieser Ring kann weiter substituiert sein. B ist eine Brückengruppe, gewählt aus O, S, CR⁵R⁶, NR⁷ und C=O, worin R⁵, R⁶ und R⁷ jeweils H, Alkyl- oder Arylgruppen, einschließlich substituierter oder unsubstituierter Gruppen, sein können. Bevorzugte Liganden schließen Pyridin-, Pyridazin-, Pyrimidin-, Pyrazin-, Imidazol-, Pyrazol- und Triazolringe ein. Wahlweise können diese Ringe durch Substituenten, wie Alkyl, Aryl, Alkoxy, Halogenid und Nitro, substituiert sein. Besonders bevorzugt wird der Ligand 2,2'-Bispyridylamin. Bevorzugte Bleichkatalysatoren schließen Co-, Cu-, Mn-, Fe-Bispyridylmethan- und -Bispyridylamin-Komplexe ein. Besonders bevorzugte Katalysatoren schließen Co(2,2'-Bispyridylamin)Cl₂, Di(isothiocyanato)bispyridylamin-cobalt(II), Trisdi pyridylamin-cobalt(II)-perchlorat, Co(2,2'-Bispyridylamin)₂O₂ClO₄, Bis-(2,2'-Bispyridylamin)-kupfer(II)-perchlorat, Tris(di-2-pyridylamin)-eisen(II)-perchlorat und Mischungen hiervon ein. Bevorzugte Beispiele schließen zweikernige Mn-Komplexe mit N-vierzähnigen und N-zweizähnigen Liganden, einschließlich N₄Mn^III(u-O)ZMn^IVN₄)⁺ und [Bipy₂Mn^III(u-O)₂Mn^IVbipy₂]-(ClO₄)₃, ein.U.S. Patent 5,114,611 proposes a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a non (macro) cyclic ligand. These ligands have the formula:

wherein R ¹ , R ² , R ³ and R ^{4 may} each be selected from H, substituted alkyl and aryl groups such that each R ¹ -N = CR ² and R ³ -C = NR ^{4 is} a 5- or 6-membered one Ring forms. This ring can be further substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C = O, wherein R ⁵ , R ⁶ and R ^{7 may} each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, these rings may be substituted by substituents such as alkyl, aryl, alkoxy, halide and nitro. More preferably, the ligand is 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe-bis-pyridylmethane and bis-pyridylamine complexes. Particularly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), tris-pyridylamine cobalt (II) perchlorate, Co (2,2'-bispyridylamine) ₂ O ₂ ClO ₄ , bis (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate, and mixtures thereof. Preferred examples include binuclear Mn complexes with N-tetradentate and N-bidentate ligands, including N ₄ Mn ^III (uO) ZMn ^IV N ₄₎ ⁺ and [Bipy ₂ Mn ^III (uO) ₂ Mn ^IV bipy _2] - (ClO ₄ ) ₃ , a.

Even though the structures of the bleaching-catalyzing manganese complexes not cleared up one can assume that they are Include chelates or other hydrated coordination complexes, which from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. The same is the case Oxidation stage of the manganese cation during the catalytic process not known with certainty which the (+ II), (+ III), (+ IV) - or (+ V) skill level. Since the ligand at six possible It can be reasonably attached to the manganese cation assume that polynuclear Species and / or "cage" structures in the aqueous bleaching medium may be present. In which form the active Mn ligand species also always is present, it is effective in a seemingly catalytic manner, for improved bleaching performance on stubborn stains such as tea, ketchup, Coffee, wine, juice and the like, provided.

Other Bleach catalysts are described, for example, in the European patent application No. 408,131 (cobalt complex catalysts); the European patent applications Nos. 384,503 and 306,089 (metalloporphyrin catalysts); US 4,728,455 (Manganese / multidentate Ligand catalyst); US-4,711,748 and the European patent application with the publication number 224,952 (aluminosilicate adsorbed manganese catalyst); US 4,601,845 (aluminosilicate with manganese and zinc or magnesium salt); U.S. 4,626,373 (manganese / ligand catalyst); U.S. 4,119,557 (ferric complex catalyst); German Patent Application 2,054,019 (cobalt chelate catalyst); Canadian Patent 866,191 (transition metals containing salts); US 4,430,243 (Chelators with manganese cations and noncatalytic metal cations); and U.S. 4,728,455 (manganese gluconate catalysts).

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

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

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

More preferred are the compositions of the invention which use cobalt (III) bleach catalysts of the formula: [Co (NH ₃ ) _n (M) _m (B) _b ] T _y wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M represents one or more ligands coordinated to the cobalt via a site; m is 0, 1 or 2 (preferably i); B is a ligand coordinated to the cobalt over two sites; b is 0 or 1 (preferably 0), and if b = 0, then m + n = 6, and if b = 1, then m = 0 and n = 0; and T are one or more suitably selected counter anions which are in a number of y, where y is an integer, to obtain a charge balanced salt (preferably, y is 1 to 3, more preferably 2, if T is a). 1-charged anion); and further wherein the catalyst has a base hydrolysis rate constant of less than 0.23 M ^-1 s ^-1 (25 ° C).

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

The M moieties include, but are not limited to, F ^-, SO ₄ ^-2, NCS ^-, SCN ^-, S ₂ O ₃ ^-2, NH _3, PO ₄ ^3- and carboxylate groups (which preferably are Monocarboxylatgruppen, but more than one carboxylate group may be present in the moiety as long as binding to the cobalt occurs only via one carboxylate moiety per moiety, in which case the other carboxylate moiety in the M moiety may be protonated or in its salt form). Alternatively, M may be protonated if more than one anionic group is present in M (eg, HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- , HOC (O) CH ₂ C (O) O-, etc.). Preferred M units are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids of the formula: RC (O) O wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) alkyl, unsubstituted and substituted C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) aryl and unsubstituted and substituted C ₃ -C ₃₀ (preferably C ₅ -C ₁₈ ) heteroaryl, wherein substituents are selected from the group consisting of -NR ' ₃ , -NR' ₄ ⁺ , -C (O) OR ', - OR 'or -C (O) NR' ₂ , wherein R 'is selected from the group consisting of hydrogen and C ₁ -C ₆ units. Such substituted R radicals therefore include the moieties - (CH ₂ ) _n OH and - (CH ₂ ) _n NR ' ₄ ⁺ wherein n is an integer from 1 to about 16, preferably 2 to 10, and more preferably 2 to 5 is.

More preferably, the M units are carboxylic acids of the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C ₄ -C ₁₂ alkyl and benzyl. R particularly preferably has the meaning of methyl. Preferred carboxylic acid M units include formic, benzoic, octanoic, nonaneic, decane, dodecane, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexane, naphthenic, oleinic, , Palmitic, triflate, wine, stearic, butter, citric, acrylic, asparagine, fumar, lauric, linoleic, lactic, malic and especially acetic acid.

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

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

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

Cobalt catalysts which are suitable for incorporation into the detergent tablets according to the invention are, can according to the in U.S. Patent Nos. 5,559,261; 5,581,005 and 5,597,936 disclosed synthetic routes getting produced.

These Catalysts can be processed together with additional materials, if necessary, the color impairment because of the aesthetics of the product or enclosed in enzyme-containing particles as exemplified below, or the compositions can be prepared so that they Catalyst "stains" included.

organic polymeric compound

organic polymeric compounds can as preferred components of the detergent tablets according to the invention be added. With "organic polymeric compound " essentially any polymeric organic compound which is commonly used in detergent compositions, with dispersion, Anti redeposition or dirt repellency properties or others Meant detergent properties.

The Organic polymeric compound is typically incorporated in the detergent compositions in a proportion of 0.1 to 30% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10 wt .-% of the compositions introduced.

Examples organic polymeric compounds include the water-soluble, organic, homo- or copolymeric polycarboxylic acids and modified polycarboxylates or their salts, wherein the polycarboxylic acid has at least two carboxyl groups comprises which are separated by not more than two carbon atoms are a. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight from 2,000-10,000 and their copolymers with any others suitable monomer units, including modified acrylic, Fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, Acrylamide, alkylene, vinyl methyl ether, styrene and any mixtures hereof. Preference is given to the copolymers of acrylic acid and maleic anhydride with a molecular weight of 20,000 to 100,000.

preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 shut down under the trade name Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 from BASF GmbH and those under the trade name Acusol 45N, 480N and 460N from Rohm and Haas marketed.

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

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

Other optionally polymers can Polyvinyl alcohols and acetates, both modified and unmodified, Cellulose derivatives and modified cellulose derivatives, polyoxyethylenes, Polyoxypropylenes and copolymers thereof, both modified as also unmodified, terephthalate ester of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.

suitable Examples are disclosed in U.S. Patent Nos. 5,591,703, 5,597,789 and 4,490,271.

soil

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

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

Useful polymeric soil release agents herein also include cellulosic derivatives, such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose; see. U.S. Patent 4,000,093, issued December 28, 1976 to Nicol et al.

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

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

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

One another suitable polymeric soil release agent is a sulfonated Product of a substantially linear ester oligomer consisting from an oligomeric ester backbone of recurring terephthaloyl and oxyalkyleneoxy units and covalently bonded to the backbone End groups. These soil release agents are described in U.S. Patent 4,968,451, issued November 6, 1990 to Scheibel J.J. and Gosselink E.P., in detail described. Other suitable polymeric soil release agents include Terephthalate polyester of U.S. Patent 4,711,730 issued December 8 1987 to Gosselink et al .; the anionic, end-capped, oligomeric Ester of U.S. Patent 4,721,580 issued January 26, 1988 to Gosselink, and the block polyester oligomer compounds of U.S. Patent 4,702,857, granted to Gosselink on October 27, 1987. Other polymeric soil release agents shut down also the soil release agents of U.S. Patent 4,877,896 issued to October 31, 1989 to Maldonado et al. which is anionic, in particular Sulfoarolyl end-capped terephthalate esters disclosed.

One other soil release agent is an oligomer with recurring Units of terephthaloyl units, sulfoisoterephthaloyl units, Oxyethyleneoxy and oxy-1,2-propylene units. The recurring Units form the backbone of the oligomer and are preferably modified with isethionate endcaps terminated. A particularly preferred soil release agent this Type includes about 1 sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to about 1.8 and two end-cap units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

Heavy metal

The Detergent tablets according to the invention preferably contain a heavy metal ion sequester as an optional component. By heavy metal ion sequestrant here are meant components which are effective in that they Heavy metal ions sequester (complex). These components can also have calcium and magnesium chelating power, but preferably show a selectivity for the Binding of heavy metal ions such as iron, manganese and copper.

heavy metal ion are generally in a proportion of 0.005 to 20 wt .-%, preferably 0.1 to 10 wt%, stronger preferably 0.25 to 7.5 wt .-% and particularly preferably 0.5 to 5 wt .-% of the compositions.

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

to suitable heavy metal ion sequestering agents shut down organic phosphonates, such as the aminoalkylenepoly (alkylenephosphonates), Alkali metal ethane 1-hydroxy diphosphonates and nitrilo trimethylene phosphonates, one. Preferred species among the above are diethylene triamine penta (methylene phosphonate), Ethylenediaminetri (methylenephosphonate), hexamethylenediamine tetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for use herein shut down nitrilotriacetic and polyaminocarboxylic acids, such as ethylenediaminetetraacetic acid, Ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any Salts thereof, a.

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

Crystal growth inhibitor component

The Detergent tablets preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, which is preferably in a proportion of 0.01 to 5% by weight, more preferably 0.1 to 2 wt .-% of the compositions is introduced.

With organo here is an organodiphosphonic acid meant that does not contain nitrogen as part of their chemical Contains structure. This definition concludes Therefore, the organoaminophosphonates, which in the compositions of the invention however, included as heavy metal ion sequestrants components could be.

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

water-soluble sulfate salt

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

The water-soluble Sulfate salt can be essentially any salt of a sulfate with each To be a countercation. Preferred salts are selected from the sulfates of the alkali metal and alkaline earth metals, especially sodium sulfate.

alkali metal

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

The Alkali metal silicate may also be used as a component of an alkalinity system available.

The alkalinity system also preferably contains sodium metasilicate which is present in a proportion 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 of sodium silicate to sodium metasilicate, measured as SiO ₂ , is preferably 50: 1 to 5: 4, more preferably 15: 1 to 2: 1, most preferably 10: 1 to 5: 2.

dye

Of the Term "colorant" as used herein refers to a substance that has specific wavelengths of Absorbed light from the visible light spectrum. Such colorants when added to a detergent composition have the Effect, the visible color and in this way the appearance of the Change detergent composition. For example, colorants can either Be dyes or pigments. Preferably, the colorants in the composition into which they are to be incorporated stable. Such is the colorant in a composition having a high pH, preferably alkali-resistant, and in a composition having a low pH, the colorant is preferred acid-resistant.

Of the Compressed area and / or uncompressed area can be one dye, a mixture of colorants, colored Contain particles or a mixture of colored particles, so that the compressed area and the non-compressed area a different one have visual appearance. Preferably, either the compressed one Area or the non-compressed area a colorant.

If the non-compressed area has two or more effective cleaning compositions Preferably, at least one of the first and second and / or subsequent compositions comprises a dyeing agent. When both the first and second compositions and / or subsequent compositions comprise a colorant, it is preferred that the colorants have a different visual appearance.

If present, included the coating layer preferably a colorant. If the compressed area and the overcoat layer are a colorant It is preferred that the dye provide a different visual effect.

Examples close suitable dyes Reaction dyes, direct dyes or azo dyes. preferred Close dyes Phthalocyanine dyes, anthraquinone dyes, quinoline dyes, Monoazo, disazo and polyazo dyes. More preferred dyes shut down Anthraquinone, quinoline and monoazo dyes. Preferred dyes shut down SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (Trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name), all available from Clariant, GB, HEXACOL QUINOLINE YELLOW (trade name) and HEXACOL BRILLIANT BLUE (Trade name), both available from Pointings, GB, ULTRA MARINE BLUE (trade name), available from Holliday, or LEVAFIX TURQUOISE BLUE EBA (trade name), available from Bayer, USA.

The dye can be in the compressed and / or uncompressed area by a suitable method can be introduced. Suitable methods shut down mixing all or selected effective detergent components with a colorant in a drum or spraying all or selected effective detergent components with the colorant in a rotary drum one.

If the colorant is a component of the compressed area, it lies in one Proportion of 0.001 to 1.5%, preferably 0.01 to 1.0%, especially preferably 0.1 to 0.3% before. If the colorant is a component of is uncompressed area, it is generally in one Proportion of 0.001 to 0.1%, stronger preferably 0.005 to 0.05%, more preferably 0.007 to 0.02% before. If the colorant a component of the overcoat layer is in a proportion of 0.01 to 0.5%, more preferable 0.02 to 0.1%, more preferably 0.03 to 0.06% before.

Corrosion inhibitor compound

The Detergent tablets can Contain corrosion inhibitors, which are preferably made of organic Silver coating agents, especially paraffin, nitrogenous Corrosion inhibitor compounds and Mn (II) compounds, especially Mn (II) salts organic Ligands selected are.

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

The Organic silver coating agent may be present in a proportion of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-% of the total composition be introduced.

The Function of the silver coating agent is a protective coating on any silverware components of the washload to which the compositions are added to form in use. The silver coating agent should therefore have a high affinity for attachment on solid silver surfaces especially if it is used as a component of an aqueous washing and bleach solution present, with which the solid silver surfaces are treated.

suitable Organic silver coating agents here include fatty esters of monohydric or polyhydric alcohols having 1 to 40 carbon atoms in the hydrocarbon chain.

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

Of the Fatty alcohol residue in the fatty ester can be replaced by monovalent or polyvalent Alcohols with 1 to 40 carbon atoms in the hydrocarbon chain be reproduced. Examples of suitable fatty alcohols include behenyl, Arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, Ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, Erythritol, pentaerythritol, sorbitol or sorbitan.

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

preferred Fatty esters here are ethylene glycol, glycerol and sorbitan esters, in which the fatty acid portion of the ester normally comprises a species consisting of behenic acid, stearic acid, oleic acid, palmitic acid or myristic selected is.

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

specific Examples of fatty alcohol esters for use herein include stearyl acetate, palmityl dlactate, Cocoyl isobutyrate, oleyl maleate, oleyl dimaleate and tallowyl propionate one. Here usable fatty acid esters shut down Xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, Glycerol monostearate, ethylene glycol monostearate and sorbitan esters one. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, Sorbitan monolaurate, sorbitan monomyristate, sorbitan mono behenate, sorbitan monooleate, Sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and also mixed tallow alkyl sorbitan mono- and diesters.

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

suitable Organic silver coating agents include triglycerides, mono- or diglycerides and completely or partially hydrated derivatives thereof and any mixtures one of them. Suitable sources for fatty acid ester shut down Vegetable and fish oils and animal Fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.

waxes, including microcrystalline waxes are suitable organic silver coating agents herein. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise 12 to 70 carbon atoms. To be favoured the petroleum waxes of the paraffin and microcrystalline type, which consists of long-chain, saturated Hydrocarbon compounds exist.

alginates and gelatin are suitable organic silver coating agents herein.

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

Other suitable organic silver coating agents include certain polymeric materials.

polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, Polyethylene glycols (PEG) with an average molecular weight from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole and cellulose derivatives, such as methylcellulose, Carboxymethylcellulose and hydroxyethylcellulose are examples such polymeric materials.

Certain Perfume materials especially those which show a high substantivity for metal surfaces, are also useful herein as organic silver coating agents.

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

A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched, aliphatic hydrocarbon having a number of carbon atoms in the range of 20 until 50; Preferred paraffin oils are selected from predominantly branched C _25-45 species having a ratio of cyclic to noncyclic hydrocarbons of 1:10 to 2: 1, preferably 1: 5 to 1: 1. A paraffinic oil meeting these properties with a 32:68 ratio of cyclic to noncyclic hydrocarbons is sold by Wintershall, Salzbergen, Germany, under the trade designation WINOG 70.

nitrogenous Corrosion inhibitor compounds

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

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

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

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

Mn (II) -Korrosionsinhibitorverbindungen

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

The Mn (II) compound may be an inorganic salt in an anhydrous one or hydrated form. Suitable salts include manganese sulfate, Manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride one. The Mn (II) compound may be a salt or complex of an organic Fatty acid, like Manganese acetate or manganese stearate.

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

Other corrosion inhibitor compounds

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

For copolymers from butadiene and maleic acid, especially those under the trade reference no. 07787 from Polysciences, Inc., have been found to act as corrosion inhibitor compounds especially useful are.

Hydrocarbon oils

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

Water-soluble bismuth compound

The Detergent tablets can a water-soluble Contain bismuth compound, which preferably in a proportion from 0.005 to 20% by weight, stronger preferably 0.01 to 5 wt .-%, particularly preferably 0.1 to 1 wt .-% the compositions is present.

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

enzyme Stabilizing system

The present enzyme-containing compositions may be from 0.001 to 10% by weight, preferably 0.005 to 8 wt .-%, particularly preferably 0.01 to 6 wt .-% of an enzyme-stabilizing Systems include. The enzyme stabilizing system may be any be stabilizing system, which with the detergent enzyme compatible is. Such stabilizing systems may include calcium ions, boric acid, propylene glycol, short chain Carboxylic acids, Boronic acid, Chlorine bleach free radical scavengers and mixtures thereof. Such stabilizing systems can also reversible enzyme inhibitors, such as reversible protease inhibitors, include.

pH of the compositions

The Detergent tablets according to the invention are preferably not prepared to be excessively high Have pH, but preferably a pH, measured as 1% solution in distilled water, from 8.0 to 12.5, more preferably 9.0 to 11.8, more preferably 9.5 to 11.5.

According to one another aspect of the invention the compressed and non-compressed areas are prepared, so that you provide a different pH.

machine dishwashing

All suitable methods for machine washing or cleaning of contaminated Dishes are considered. A preferred machine dishwashing comprises treating the soiled items selected from stoneware, glassware, Silverware, metal objects, Cutlery and mixtures thereof, with an aqueous liquid, which is an effective Quantity of a detergent tablet according to the invention solved in it or dispersed. With an effective amount of detergent tablet It is meant 8 g to 60 g of the product which is in a wash liquor from 3 to 10 liters or dispersed, giving typical product dosages and wash liquor volumes are, which are usually in conventional automatic dishwashing process be used. Preferably, the detergent tablets a weight of 15 g to 40 g, more preferably 20 g to 35 g on.

Examples

In the examples used abbreviations

In the detergent compositions, the abbreviated designations of the components have the following meanings: STPP: sodium tripolyphosphate bicarbonate sodium citric acid: Anhydrous citric acid carbonate: Anhydrous sodium carbonate Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 1.6: 3.2) PB1: Anhydrous sodium perborate monohydrate PB4: Sodium perborate tetrahydrate of nominal formula NaBO ₂ · 3H ₂ O · H ₂ O ₂ TAED: tetraacetylethylenediamine HEDP: Ethane-1-hydroxy-1,1- protease: Proteolytic enzyme amylase: Amylolytic enzyme BTA: benzotriazole PA30: Polyacrylic acid with an average molecular weight of about 4,500 pH: Measured as a 1% solution in distilled water at 20 ° C

Examples

The following two-layer detergent tablet compositions M, N and P were prepared according to the invention. The first layer is made by compressing a particulate detergent composition in a usual Tablet press, which is suitable for the production of detergent tablets is manufactured. The second layer is made by pouring a particulate Detergent composition on top of the compressed first Layer and recompressed produced. The first and second Layer can be replaced. The proportions are given as wt .-% of the layer.

Claims (14)

A machine dishwashing detergent in the form of a multilayer tablet having a compressed area with a density of from 1.3 g / cm ³ to 1.9 g / cm ³ , each layer of the tablet comprising a detergent composition wherein at least one detergent composition is compressed and contained in one Dishwashing machine dissolves in less than 3 minutes, (using a Bosch dishwasher according to DIN 44990, 65 ° C normal washing program, 18 ° H water hardness), and wherein the at least one detergent composition comprises an enzyme and an explosive, detergent-releasing component, and further wherein the tablet comprises oxygen-releasing bleach and the enzyme is released from the oxygen-releasing bleach. Dishwashing liquid according to claim 1, wherein at least one detergent component yourself in a dishwasher dissolves in less than 2 minutes. Dishwashing liquid according to claim 1 or 2, wherein the at least one detergent composition includes a phosphate builder. Dishwashing liquid according to at least one of the claims 1 to 3, wherein the diverging, detergent-releasing Component a gas trapped in the detergent composition includes. Dishwashing liquid according to at least one of the claims 1 to 3, wherein the diverging, detergent-releasing Component gas generating reactants, which on contact with water in the dishwasher react to form a gas. Dishwashing liquid according to claim 5, wherein the gas generating reactants are an acid and include an alkali. Dishwashing liquid according to claim 6, wherein the acid citric acid and the alkali is selected from the group sodium carbonate, bicarbonate, sesquicarbonate or mixtures thereof. Dishwashing liquid according to claim 5, wherein the gas-generating reactants in a proportion of at least 10%, preferably at least 20%, of the detergent composition available. Dishwashing liquid according to at least one of the claims 6 to 8, wherein the alkali is present in a stoichiometric excess. Dishwashing liquid according to at least one of the preceding claims, wherein the divisive, Detergent releasing agent is a disintegrating agent includes. Dishwashing liquid according to at least one of the claims 1 to 10, wherein the detergent composition, which is a explosive, detergent-releasing component comprises dissolve faster as a detergent composition which is not a conflicting, Detergent releasing component comprises. Dishwashing liquid according to claim 11, wherein the content of free moisture is faster dissolving Detergent composition below 4 wt .-% of the detergent composition lies. Dishwashing liquid according to at least one of the preceding claims, wherein at least one detergent composition a particulate component coated with a hydrophobic coating material includes. Dishwashing liquid according to claim 13, wherein the hydrophobic coating material is a Paraffin oil, wax and / or solid.