ES2309015T3 - DETERGENT COMPOSITIONS. - 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

Detergent compositions.

Technical field

The present invention relates to a detergent wash tablet comprising one or more compositions detergents and wherein at least one detergent composition is Dissolve in a dishwasher in less than three minutes.

Background of the invention

Detergent compositions in the form of tablet are known in the art. It is known that the compositions tablet-shaped detergents have some advantages over detergent compositions in the form of particles, such as their ease of handling, transport and storage.

Detergent tablets are usually prepare premixing components of a detergent composition and forming the detergent components previously mixed in a tablet using a tablet press. The pills are typically form compressing detergent components to get a pill The pills should be compressed with enough compression pressure so that they can be achieved the advantages of handling, transport and storage previously mentioned. However, a problem associated with the compression of detergent components is that the speed of dissolution of the tablet is reduced as the compression pressure

The object of the present invention is provide a detergent tablet comprising components compressed detergents that have a rapid rate of dissolution.

In addition, the applicant has discovered that components of a detergent composition that improves dissolution of the detergent composition are sometimes unstable and are deactivated or deplete The present invention, in addition to providing tablets that dissolve quickly, it also solves this problem of instability.

Summary of the invention

In accordance with the present invention, provides a tablet-shaped detergent for a washing machine clothing as described in claim 1.

Preferably the detergent composition is dissolves in less than 2.5 minutes and most preferably in less 2 minutes or even in less than 1 minute, the time being determined according to DIN 44990 using a commercial dishwasher Bosch in a normal wash program at 65ºC with water hardness at 18ºH.

Detailed description of the invention

For the purposes of the present invention one or more detergent compositions are compressed and dissolve rapidly in less than 3 minutes. The tablet is a multilayer tablet in which each layer comprises a detergent composition. Additional optional layers may be formed by compression or these may be layers not
compressed

By compressing a detergent composition into a tablet components are very close to each other. A consequence of this close proximity is that certain components they can react with each other by becoming unstable, inactive or running out A solution for this problem, as seen in the state of the art, has been to separate the detergent components that can react with each other, especially when the components  They compress to form pills. The separation of components has been achieved, p. eg preparing pills multilayer where the components that can react with each other They are contained in different layers of the tablet. Pills Multilayer are traditionally prepared in several stages of compression.

If the tablet is a multilayer tablet, at less a layer of compressed detergent composition dissolves in less than three minutes, preferably in less than two minutes or Even in a minute. This embodiment may provide advantages. of performance since it allows a rapid supply of components specific detergents selected to the wash solution. In a preferred aspect of the present invention, the components Specific detergents include surfactant, enzymes, source of alkalinity, bleach and detergent builder additive.

The fast dissolving detergent composition (eg the detergent composition that dissolves in less than three minutes), preferably comprises a releasing component of explosive detergent Preferably the dissolution layers more slow will also dissolve in a dishwasher in less than three minutes, but they do it more slowly than the fast layer dissolution. Therefore, a sequential release of detergent components Preferred aspects of the invention include the following: (i) the detergency builder additive it is released before the bleach; (ii) the enzyme is released before the bleach.

The dissolution of the detergent composition may be done in less than three minutes, for example by incorporating (i) an explosive detergent releasing component; (ii) selecting components that have a particle size range that improves the rapid dissolution of the component or mixtures of same. The expression "detergent-releasing component explosive "includes reagents that produce gas, formed gas previously and trapped, disintegrating agents and mixtures of same.

In a detergent tablet comprising an explosive detergent releasing component, the explosive detergent releasing component preferably comprises reagents that produce gas. Reagents that produce gas react with each other to form a gas in situ when it comes into contact with water in a dishwasher. Alternatively, the gas can be pre-formed and trapped in one or more detergent compositions of the tablet so that when the detergent composition begins to dissolve, the gas is released, increasing the dissolution rate of the detergent composition. Examples of suitable gases include carbon dioxide, nitrogen dioxide, oxygen and / or any other non-toxic and non-flammable gas. Therefore, the explosive detergent-releasing component when incorporated into a detergent composition that forms all or part of the detergent tablet produces a compound
Quick dissolving detergent position that preferably dissolves in a dishwasher in less than three minutes.

To form the gas in situ , the detergent tablet may contain reagents that produce gas such as an acid and an alkali. Suitable acids include monobasic, dibasic or tribasic acids that have a pka value in the range of 1.0 to 6.9. Preferred acids include aminosulfonic acids, organophosphonic acids such as 1-hydroxy ethane-1,1-diphosphonic acid (HEDP acid) and polycarboxylic acids. Preferred polycarboxylic acids may include citric acid, malic acid, maleic acid, malonic acid, itaconic acid, tartaric acid, oxalic acid, glutaric acid, glutamic acid, lactic acid, fumaric acid, glycolic acids and mixtures thereof. Citric acid and / or HEDP acid are especially preferred acids. The especially preferred citric acid is in the form of particles with an average particle size of less than 1000 µm, more preferably less than 600 µm and most preferably less than 400 µm. Preferred alternative polycarboxylic acids are selected from the group consisting of homopolymers or copolymers of acrylic acid, maleic acid, polymeric carboxyvinyl adjuvants, carbomers and mixtures thereof having a molecular weight in the range of 2000 to 200,000. Especially preferred polycarboxylic acids include homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid. Suitable alkalis include silicate, carbonate, bicarbonate and alkali metal sesquicarbonate and mixtures thereof. Metasilicate and / or carbonate and especially bicarbonate are preferred. The especially preferred bicarbonate is in the form of particles with an average particle size of less than 1000 µm, more preferably less than 700 µm and most preferably less than 400 µm. The sodium or potassium salts of the foregoing are especially preferred. Other reagents that produce gas include perborate, especially perborate 0 (PB-0) and / or percarbonate. Preferably the reagents that produce gas are present at a level of at least 10%, preferably at least 20%, of the detergent composition.

The explosive detergent releasing component Can comprise a disintegrating agent. Disintegrating agents Suitable include agents that swell upon contact with water or dissolve faster than components surrounding thus facilitating the influx and / or efflux of water to form channels in the pill. Any suitable known disintegrant for use in laundry or dishwashing applications is contemplated for use in the present invention, for example those analyzed by W. Lowenthal in the Journal of Pharmaceutical Sciences, volume 61, No. 11 (November 1972). The agents Suitable disintegrants include starch, starch derivatives, by Primellose and / or Primojel example (marketed by Auebe), Avicel (marketed by FMC), alginic acid or salts thereof (marketed by Kelco), carboxymethyl cellulose (CMC), polymers based on CMC, for example Nymcel (marketed by Metsa-Serla), Explotab (marketed by Mendell),  Ac-di-sol (marketed by FMC), polyvinylpyrrolidone (PVP), crosslinked PVP, sodium acetate, potassium carbonate, potassium sulfate, glaubers salts, sugars, especially mannitol and sorbitol, aluminum oxide and mixtures thereof.

Alternatively, the rapid dissolution of the detergent composition can be achieved by selecting components detergents with a certain particle size range. In a preferred aspect of the present invention, at least 80%, preferably at least 85% or even 90%, of the particles of the detergent composition that dissolves in less than 3 minutes has a particle size greater than 200 µm.

In a preferred embodiment of the invention, the tablet comprises a multilayer tablet comprising at least a compressed layer of quick dissolving detergent composition with other layers that dissolve more slowly.

Preferably the moisture free content of the quick dissolving detergent composition is less than 4% in weight, more preferably less than 2% by weight and with maximum preference less than 1% by weight.

In another aspect of the present invention, a particulate component of the detergent composition is coated with a hydrophobic coating material. The component in particulate form it can be a detergent component selected such as reagents that produce acid gas and / or alkaline of the explosive detergent releasing component or may include even virtually all components of the composition Detergent.

The coating material, which covers the less partially to the particulate component, is preferably a paraffin oil, wax and / or solid, preferably with a melting point in the range of 20 ° C to 60 ° C, more preferably from 35 ° C to 45 ° C and most preferably 42 ° C to 44 ° C, to which non-ionic surfactant can be added.

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

The component (s) in the form of particles can be coated with the coating material hydrophobic using any suitable known method and equipment. Preferably the hydrophobic coating material is in liquid or molten form and is sprayed on the component in particle shape

Any tablet detergent component conventional used in known detergent tablets is suitable for incorporation into the compressed part of the tablet of detergent of this invention. They are described below. suitable detergent components. Detergent components Preferred include detergency builder compound, surfactant, bleaching agent, bleach activator, bleaching catalyst, enzyme and alkalinity source.

The detergent component (s) present (s) in the tablet may optionally be prepared together with a vehicle and / or a binder as per example water, polymer (eg PEG or homopolymer or copolymer of polyacrylate) or liquid silicate. The detergent components are they preferably prepare in the form of particles (ie, in the form of powder or granulate) and can be prepared by any method known, for example, spray drying, granulation or agglomeration.

The detergent component (s) in the form of particles are compressed using any equipment suitable for forming compressed tablets, blocks, bricks or Briquettes as described below in detail.

In an especially preferred embodiment of the invention, the detergent tablet comprises a reinforcing agent of the phosphate type detergency, preferably tripolyphosphate sodium (STPP). Preferably the STPP is comprised in the detergent composition that dissolves rapidly so that it dissolve in the dishwasher in less than 3 minutes. Preferably is combined in a detergent composition with the component of release of explosive detergent and most preferably acid citric and sodium bicarbonate.

The density of the tablet or the composition detergent that forms the pill is generally in the range from 1.3 g / cm 3 to 1.9 g / cm 3, more preferably 1.4 g / cm3 at 1.8 g / cm3 and most preferably 1.4 g / cm 3 to 1.7 g / cm 3.

Density is calculated by dividing weight (mass) of the compressed part between the volume of the compressed part. He volume is calculated by multiplying the length by the width and by the height of the compressed layer.

If the detergent tablet is present invention comprises an uncompressed layer of the composition detergent, the uncompressed layer may include components that interact with one or more detergent components present in the compressed layer If other detergent components are present in the uncompressed layer, preferred components include those that are negatively affected by the compression pressure of, for example, a press to compress pills. Examples of these detergent components include, but are not limited to, enzyme, corrosion inhibitor and perfume. These components are described in more detail below.

The component (s) optional detergents (s) can be in any form, for example in the form of particles (eg powder or granulated), gel or liquid. The uncompressed layer can also optionally comprise a vehicle component. The component detergent may be present in the form of solid, gel or liquid before being mixed with a vehicle component.

The uncompressed layer of the tablet Detergent can be in the form of solid, gel or liquid.

The detergent tablet of the present invention requires that the uncompressed layer be supplied to the compressed layer so that the compressed layer and the uncompressed layer come into contact with each other. The uncompressed layer can be supplied to the compressed layer in solid or fluid form. If the uncompressed layer is in solid form, it is prepared previously, optionally shaped and then supplied to the compressed layer. The uncompressed layer is then fixed to a previously formed compressed layer, for example by adhesion or by insertion of the uncompressed layer to a cooperating surface of the compressed layer. Preferably the compressed layer comprises a depression or a previously prepared mold to which the non-supplied layer is supplied.
compressed

The uncompressed layer is preferably supplied to the compressed layer in fluid form. Layer no compressed is then fixed to the compressed layer, for example, by adhesion, forming a coating on the uncompressed layer to fix it to the compressed layer, or by hardening, for example (i) cooling to a temperature below the melting point in which the fluid composition becomes a melt solidified; (ii) by evaporation of a solvent; (iii) by crystallization; (iv) by polymerization of a polymer component of the fluid uncompressed layer; (v) through properties pseudo-plastics where the uncompressed layer fluid comprises a polymer and shear forces are applied to the uncompressed layer; (vi) combining a binder with the layer not compressed fluid. In an alternative embodiment, the layer does not fluid tablet can be an extrudate that is fixed to the layer compressed by, for example, any of the mechanisms described above or by expansion of the extrudate to the parameters of a mold provided by the compressed layer.

Preferably the compressed layer comprises a depression or a previously prepared mold (hereinafter referred to as "mold") into which the uncompressed layer is introduced. In an alternative embodiment, the surface of the compressed layer comprises more than one mold into which the uncompressed layer can be introduced. They
Mold (s) preferably accommodate at least partially one or more uncompressed layers. The uncompressed layers are then introduced into the mold and fixed to the compressed layer as described above.

The uncompressed layer may comprise material in the form of particles. The particulate material can be prepared by any known method, for example conventional methods of spray drying, granulation, encapsulation or agglomeration. The particulate material it can be fixed to the compressed layer by incorporating a binder or forming a coating layer on the uncompressed layer.

If the uncompressed layer comprises a solidified melt, the melt is prepared by heating a composition comprising the finishing additive and any detergent component and / or optional vehicle above its melting point to form a fluid melt. The fluid melt is then incorporated into a mold and allowed to cool. As the melt cools, it solidifies and adopts the shape of the mold at room temperature. When the composition comprises one or more vehicle components, the component (s)
The vehicle can be heated to a temperature above its melting point and then an active detergent component can be added. Suitable vehicle components for preparing a solidified melt are typically non-active components that can be heated above the melting point to form a liquid and cooled to form an intermolecular matrix that can effectively trap the finishing additive and Optional detergent components. A preferred vehicle component is an organic polymer that is solid at room temperature. Preferably the carrier component is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP) with a molecular weight of 10,000 to 360,000. The compressed layer of the detergent tablet preferably provides a mold to accommodate the melt.

The fluid uncompressed layer may be in a form comprising a dissolved or suspended finishing additive and optional detergent components. The fluid uncompressed layer it can harden over time to form a solid, a semi-solid or a very viscous liquid by any of the methods described above. In particular, the layer does not fluid tablet can be hardened by evaporation of a solvent Suitable solvents for use herein invention may include any known solvent in which a binder or gelling agent is soluble. Solvents Preferred may be polar, non-polar, non-aqueous or anhydrous and they can include, for example, water, glycerin, alcohol (for example, ethanol, acetone) and alcoholic derivatives. In one embodiment alternatively more than one solvent can be used.

The fluid uncompressed layer may comprise one or more binding or gelling agents. At the moment invention is considered useful any binding agent or gelling agent that has the effect of making the composition Become solid, semi-solid or highly viscous over time. Without pretending to impose any theory, it is believed that the mechanisms whereby the binder or gelling agent causes a non-solid composition become solid, semi-solid or highly viscous include: chemical reaction (as crosslinking chemistry) or interaction of effect between two or more components of the fluid compositions; chemical or physical agent interaction binder with a component of the composition.

In a preferred aspect of the present invention, the uncompressed layer comprises a gel. In this aspect the gel is supplied to the compressed layer of the tablet detergent but preferably supplied in a mold provided by the compressed layer.

The gel comprises a thickening system in addition to Optional detergent components. In addition, the gel can also comprise solid ingredients to facilitate the control of the viscosity of the gel together with the thickener system. The solid ingredients can also act by optionally altering the gel and thus favoring its dissolution. If included, the gel typically comprises at least 15% ingredients solids, more preferably at least 30% solid ingredients and most preferably at least 40% solid ingredients. Without However, due to the need to be able to pump or process another form the gel, this typically does not include more than 90% of solid ingredients

As indicated above, the gel comprises a thickener system to provide viscosity or gel thickness needed. The thickener system comprises typical a non-aqueous liquid diluent and a gelling additive organic or polymeric:

a) Liquid diluent: the term "solvent" or "diluent" is used herein memory to refer to the liquid part of the thickener system. Although some of the components of the uncompressed layer may actually dissolve in the phase containing "solvent", other components may be present as material in the form of particles dispersed within the phase that contains "solvent." Therefore, the term "solvent" does not implies that the components of the uncompressed layer are capable of really dissolve in the solvent. Suitable types of solvents useful in the non-aqueous thickener systems of the present invention include lower monoalkyl ethers of alkylene glycol, propylene glycols, ethylene or ethoxylated propylene or propoxylated, glycerol esters, glycerol triacetate, low molecular weight polyethylene glycols, esters and amides of low molecular weight methyl.

A preferred type of non-aqueous solvent for use in the present invention comprises monoalkyl C 2 -C 6 monoalkylene glycol ethers, dialkylene glycol, trialkylene glycol or tetralkylene glycol C_ {2} -C_ {3}. The specific examples of such Compounds include diethylene glycol monobutyl ether, monobutyl ether of tetraethylene glycol, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Especially preferred is the diethylene glycol monobutyl ether and monobutyl ether dipropylene glycol. Compounds of this type are sold with trade names Dowanol, Carbitol and Cellosolve.

Another preferred type of useful non-aqueous solvent in the present invention comprises polyethylene glycols (PEG) of low molecular weight These materials are the ones that have a weight molecular weight of at least 150. The most preferred are PEGs with a molecular weight of 200 to 600.

Another preferred type of non-aqueous solvent It comprises low molecular weight methyl esters. Sayings Materials have the general formula: R 1 -C (O) -OCH 3 in where R1 is 1 to 18. Examples of methyl esters of Suitable low molecular weight include methyl acetate, propionate of methyl, methyl octanoate and methyl dodecanoate.

The organic solvent (s) non-aqueous (s) used should logically be compatible and not react with the other detergent components optional, p. ex. enzymes This type of solvent component is will generally use in an amount of 10% to 60% by weight of the gel part More preferably, the non-aqueous organic solvent Low polarity will comprise 20% to 50% by weight of the gel and with maximum preference of 30% to 50% by weight of the gel.

b) Gelling additive: an agent or additive gelling agent is added to the non-aqueous solvent to complete the thickener system. To form the required gel and get a adequate phase stability and acceptable gel rheology, the organic gelling agent is generally present in a solvent ratio: gelling agent in the thickener system of typical form of 99: 1 to 1: 1. More preferably, the ratio is 19: 1 to 4: 1.

Preferred gelling agents are selected from castor oil derivatives, polyethylene glycol, organic sorbitols and related thixaptrops, organo-clays, cellulose and cellulose derivatives, Pluronics®, stearates and stearate derivatives, sugar / gelatin combination, starches, glycerols and derivatives thereof, organic acid amides such as di-n-butyl amide acid N-lauryl-L-glutamic, polyvinylpyrrolidone and mixtures thereof.

Preferred gelling agents include castor oil derivatives. Castor oil is a natural triglyceride obtained from the seeds of Ricinus communis , a plant that grows in most tropical or subtropical areas. The rest of the primary fatty acid in the triglyceride of castor oil is ricinoleic acid (12-hydroxyoleic acid) and is responsible for 90% of the fatty acid residues. The rest up to 100% consists of dihydroxystearic, palmitic, stearic, oleic, linoleic, linolenic and eicosanoic acid residues. Hydrogenation of the oil (eg, by hydrogen under pressure) converts the double bonds of the fatty acid residues into single bonds, which "hardens" the oil. The hydroxyl groups are not affected by this reaction.

The resulting hydrogenated castor oil, by therefore, it has an average of approximately three hydroxyl groups per molecule It is believed that in the presence of these hydroxyl groups the excellent structural properties of the gel compared to liquid detergent compositions similar that do not contain castor oil with hydroxyl groups in its fatty acid chains. For use in the compositions of the present invention castor oil should be hydrogenated to a Iodine index less than 20 and preferably less than 10. The Iodine index is a measure of the degree of unsaturation of the oil and it is measured by the "Wijis Method", well known in the technique. Non-hydrogenated castor oil has an iodine index from 80 to 90.

Hydrogenated castor oil is an article commercially available, for example, in various qualities with the CASTORWAX.RTM brand by NL Industries, Inc., Highstown, New Jersey. Other castor oil derivatives Suitable hydrogenated are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, manufactured by Rheox, Laporte. It preferred especially Thixatrol ST.

When polyethylene glycols are used as gelling agents instead of as solvents, these are low molecular weight materials that have a molecular weight in the 1,000 to 10,000 range, the most preferred being 3,000 to 8,000

When cellulose and cellulose derivatives are used in the present invention, these include preferably: i) Cellulose acetate and cellulose acetate phthalate (CAP); ii) Hydroxypropyl methylcellulose (HPMC); iii) Carboxymethylcellulose (CMC) and mixtures thereof. The hydroxypropyl methylcellulose polymer preferably it has an average molecular weight in number of 50,000 to 125,000 and a viscosity in a 2% aqueous solution in weight at 25 ° C (ADTMD2363) from 50 to 100 Hz (from 50,000 to 100,000 cps). An especially preferred hydroxypropylcellulose polymer is Methocel® J75MS-N where an aqueous solution at 2.0% by weight at 25 ° C has a viscosity of approximately 75 Hz (75,000 cps).

       \ newpage
    

The sugar can be any monosaccharide (e.g. eg glucose), disaccharide (eg, sucrose or maltose) or polysaccharide. The most preferred sugar is common sucrose. For For the purposes of the present invention, type A gelatin can be used or type B, marketed, for example by Sigma. The Type A jelly since it has greater stability in alkaline conditions than type B. The preferred gelatin It also has a consistency of 65 to 300 and most preferably from 75 to 100

The gel may include other ingredients in addition of the thickener, as described hereinabove memory, and the finishing additive, described in more detail at continuation. Ingredients such as dyes can be included as well as agents modifying the structure. The agents structure modifiers include various polymers and polymer blends, including polycarboxylates, carboxymethyl celluloses and starches, to facilitate adsorption of excess solvent and / or reduce or avoid "purging" or leaking solvent from the gel fraction, reduce shrinkage or cracking the gel fraction or facilitate dissolution or breakage of the gel fraction in the wash water. Also, if if desired, hardness modifying agents can be incorporated into the thickening system to adjust the hardness of the gel. These agents hardness controllers are typically selected from various polymers, such as polyethylene glycols, poly (ethylene oxide), polyvinylpyrrolidone, polyvinyl alcohol, acid hydroxystearic and polyacetic acid and when they are included typically used in amounts less than 20% and more preferably less than 10%, by weight of the solvent in the system thickener

The gel is formulated to be a gel pumpable and fluid at slightly elevated temperatures of approximately 30 ° C or higher to increase the flexibility in the production of the detergent tablet, but of so that at the same time it can become highly viscous or harden at room temperature so that the gel remains fixed on the compressed part of the detergent tablet for The whole process of transporting and handling the tablet Detergent. This gel hardening can be achieved by example, (i) cooling to a temperature below the fluidity temperature of the gel or eliminating shear; (ii) transferring the solvent, for example to the atmosphere of the part of the compressed body; or (iii) polymerizing the gelling agent. Preferably, the gel is formulated so that it hardens. enough so that the maximum force necessary to introduce a probe in the uncompressed layer is preferably 0.5 N a 40 N. This force can be calculated by measuring the maximum force needed to push a probe, equipped with a tape elastometric, along a certain distance in the gel inside. The established distance can be between 40% and 80% of the total gel depth. This force can be measured.  in a QTS 25 analyzer using a 5 mm diameter probe. Typical forces measured are in the range of 1 N to 25 N.

If the uncompressed layer is an extrudate, the Extruded is prepared by premixing detergent components of the layer not compressed with optional vehicle components to form a viscous paste The viscous paste is then extruded using any common extrusion equipment such as a single or double screw extruder marketed, p. eg, by APV Baker, Peterborough, United Kingdom. The extrudate is then cut to its size after delivery to the compressed layer or before its supply to the compressed layer of the detergent tablet. The compressed layer of the tablet preferably comprises a mold in which can be introduced the extruded uncompressed layer.

In a preferred embodiment, the layer does not Compressed is coated with a coating layer. He coating can be used to fix an uncompressed layer to the compressed layer This can be especially advantageous if the uncompressed layer comprises fluid particles, gels or liquids

The coating layer preferably comprises a material that becomes solid upon contacting the compressed and / or uncompressed layers within a period of preferably less than 15 minutes, more preferably less than 10 minutes, even more preferably less than 5 minutes and most preferably less than 60 seconds. Preferably the coating layer is water soluble. Preferred coating layers comprise materials selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA) , polyethylene glycol (PEG) and mixtures thereof. Preferred carboxylic or dicarboxylic acids preferably comprise an even number of carbon atoms. Preferably the carboxylic or dicarboxylic acids comprise at least 4, more preferably at least 6, even more preferably at least 8, carbon atoms and most preferably from 8 to 13 carbon atoms. Preferred dicarboxylic acids include adipic acid, subic acid, azelaic acid, sub-chaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof. Preferred fatty acids are those having a chain length of C12 to C22 and most preferably C18 to C22. The coating layer may also preferably comprise a disruptive agent. When the coating layer is present, it is generally present in an amount of at least 0.05%, preferably of at least 0.1%, more preferably of at least 1% and most preferably of at least 2% or even of at least 5% of the tablet
of detergent

In an alternative embodiment the layer of coating can encapsulate the detergent tablet. In this embodiment the coating layer is present in an amount of at least 4%, more preferably of at least 5% and with maximum preference of at least 10% of the tablet Detergent.

The density of the uncompressed layer is generally from 0.7 g / cm 3 to 1.2 g / cm 3, more preferably  from 0.8 g / cm 3 to 1.2 g / cm 3 and most preferably 0.9 g / cm3 to 1.1 g / cm3. The density of the uncompressed layer it is preferably at least 0.2 g / cm3, more preferably at minus 0.3 g / cm3 and most preferably at least 0.4 g / cm3, lower than the density of the compressed layer.

Density measurement of the uncompressed layer : Preferably the density of the uncompressed part is measured using a simple funnel and cup device consisting of a conical funnel rigidly molded into a base and equipped with a flap valve at its lower end to allow the funnel to be emptied into an axially aligned cylindrical cup of known volume that is arranged below the funnel. The funnel has a height of 130 mm and an internal diameter of 130 mm and 40 mm at its upper and lower ends, respectively. It is mounted so that the lower end is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

Density measurement is done by pouring manually the uncompressed part in the funnel. When the funnel is full, the flap valve is opened and the powder is allowed to flow to through the funnel to fill until the cup overflows. Full cup it is removed from the base and the excess of uncompressed part is removed of the cup passing a straight blade utensil, p. eg a knife, by its upper edge. Then the full cup is weighed. He The weight of the uncompressed part is calculated by subtracting the weight of the cup the weight of the cup plus the uncompressed part. Then Density is calculated by dividing the weight (mass) of part no compressed between the volume of the cup. If necessary, it Repeat the measurements.

Detergent components

The tablet of the present invention is prepared compressing a detergent composition. A suitable composition may include different detergent components including detergency builders, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfumes, limestone soap dispersants, organic polymeric compounds including dye transfer inhibitors polymeric, crystal growth inhibitors, sequestrants of heavy metal ions, metal ion salts, enzymes stabilizers, corrosion inhibitors, suppressants soaps, solvents, fabric softening agents, optical and hydrotropic brighteners.

The most preferred detergent components include a detergency builder compound, a surfactant, an enzyme and a bleaching agent.

Detergency builder compound

The detergent tablet of the present invention preferably contains a reinforcing compound of the detergency, typically present at a level of 1% to 80% in weight, preferably from 10% to 70% by weight and most preferably from 20% to 60% by weight, of the composition of detergent components assets.

Soluble detergency additive compound soluble in Water

Strengthening compounds of detergency Suitable water soluble include monomeric polycarboxylates  soluble in water, or its acidic forms, polycarboxylic acids homopolymers or copolymers or their salts wherein the acid polycarboxylic comprises at least two carboxylic radicals separated from each other by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the previous.

The detergency reinforcing additive of type carboxylate or polycarboxylate can be monomeric type or oligomeric although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing a carboxy group include water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. The polycarboxylates containing two carboxy groups include the water soluble salts of succinic acid, malonic acid, acid (ethylenedioxy) diacetic, maleic acid, diglycolic acid, acid tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. The polycarboxylates that they contain three carboxy groups include, in particular, citrates, water soluble aconitrates and citraconates, as well as derivatives of succinate as the carboxymethyloxysuccinates described in GB- 1,379.24l, the lactoxysuccinates described in GB-1,389,732, and the aminosuccinates described in NL-7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-1,387,447.

Polycarboxylates containing four groups carboxy include the oxidisuccinates described in GB-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. The polycarboxylates containing sulfo substituents include the sulphosuccinate derivatives described in the patents GB-1,398,421 and GB-1,398,422 and in US 3,936,448 and sulfonated pyrolyzed citrates described in GB-1,439,000.

Alicyclic polycarboxylates and heterocyclic include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid and derivatives of phthalic acid described in GB-1,425,343.

Of the above, polycarboxylates Preferred are hydroxycarboxylates containing up to three carboxy groups per molecule, more especially citrates.

The precursor acids of chelating agents monomeric or oligomeric polycarboxylate type or mixtures of the themselves with their salts, p. ex. citric acid or mixtures of citrate / citric acid are also considered as components useful detergency builders.

Additives strengthening detergency borate type as well as detergency builder additives that they contain borate-forming materials that can produce borate in Detergent or wash storage conditions they can also be used but are not preferred in conditions wash below 50 ° C, especially below 40 ° C.

Examples of additives reinforcing the carbonate type detergency are alkali metal carbonates and alkaline earth, including sodium carbonate and sesquicarbonate sodium and mixtures thereof with ultrafine calcium carbonate as described in DE-2,321,001 published on 15 November 1973

Strengthening compounds of detergency Highly preferred for use in the present invention are the phosphate type detergency builders soluble in Water. Specific examples of detergency builders Water soluble phosphate type are metal tripolyphosphates alkaline, sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, sodium orthophosphates and potassium, sodium polymeta / phosphates with a degree of polymerization from 6 to 21 and salts of phytic acid.

Specific examples of reinforcing agents of Water soluble phosphate type detergency are the alkali metal tripolyphosphates, sodium, potassium and pyrophosphates ammonium, sodium, potassium and ammonium pyrophosphates, orthophosphates sodium and potassium, sodium polymeta / phosphates in which the degree of polymerization is 6 to 21 and salts of phytic acid.

Partially soluble detergent builder additive or insoluble

The detergent tablets of the present invention may contain a detergency builder compound partially soluble or insoluble. The reinforcing compounds of the partially soluble and insoluble detergents are especially suitable for use in tablets prepared for use in methods of laundry. Examples of additives reinforcing the partially water soluble detergency include silicates crystalline sodium laminar as described, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043.

Crystalline laminar silicates are preferred sodium of general formula

NaMSi_ {x} O_ {2 + 1}. And H2O

where M is sodium or hydrogen, x is a number from 1.9 to 4 and is a number from 0 to 20. Silicates crystalline sodium laminators of this type preferably have a two-dimensional "laminar" structure, such as the structure called δ-laminar, as described in EP-0 164514 and EP-0 293640. Methods to prepare crystalline laminar silicates of this type, described in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the above general formula has a value of 2, 3 or 4 and is preferably 2.

The crystalline laminar silicate compound of most preferred sodium has the formula δ-Na_ {2} Si_ {2} O_ {5}, is known as NaSKS-6 (trade name) and marketed by Hoechst AG.

The crystalline laminar silicate material of sodium is preferably present in detergent compositions  particle-shaped granules in an intimate mixture with a solid water soluble and ionizable material as described in PCT WO-92/18594. The water soluble ionizable material solid is selected from organic acids, salts of organic acids and inorganic and mixtures thereof, the acid being preferred citric.

Examples of reinforcing additives of the very water insoluble detergency include aluminosilicates of sodium. Suitable aluminosilicates include zeolites of aluminosilicate having the cell unit formula Na_ {z} [(AlO2) z (SiO2) y]. xH 2 O where z e y are at least 6; the molar relationship between z e y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials they are in hydrated form and are preferably crystalline and they contain 10% to 28%, more preferably 18% to 22%, of water of hydration.

The aluminosilicate zeolites can be natural materials but preferably they are derived by synthesis. The synthetic ion exchange materials of crystalline aluminosilicate are marketed under the names of Zeolite A, Zeolita B, Zeolita P, Zeolita X, Zeolita HS and mixtures of the same.

A preferred method of synthesizing aluminosilicate zeolites has been described by Schoeman et al. (published in Zeolite (1994) 14 (2), 110-116), where the author describes a method for preparing colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles have a diameter greater than 1 µm and no more than 5% of particles have a diameter less than 0.05 µm. Preferably aluminosilicate zeolite particles have an average particle size diameter.
from 0.01 µm to 1 µm, more preferably from 0.05 µm to 0.9 µm and most preferably from 0.1 µm to 0.6 µm.

Zeolite A has the formula

Na_ {12} [AlO 2) 12 (SiO 2) 12]. xH_ {2} O

where x is from 20 to 30, especially 27. Zeolite X has the formula Na 86 [(AlO 2) 86 (SiO 2) 106]. 276 H2O. The zeolite MAP, as described in EP-B-384.070, is a reinforcer of the zeolite detergency preferred herein invention.

Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. If they are used as a component of a zeolite detergent composition of colloidal aluminosilicate, especially colloidal zeolite A, provide better detergency reinforcing action in terms of better stain removal. There is also an increase of the strengthening capacity of detergency in terms of reduction of tissue embedding and better maintenance of the whiteness of the tissues, problems that are believed to be associated to compositions with poor reinforcing power of the detergency

A surprising finding is that mixed aluminosilicate zeolite detergent compositions that comprise colloidal zeolite A and colloidal zeolite Y provide the same chelating action of calcium ion as an equal weight of zeolite A commercial. Another surprising finding is that the compositions mixed aluminosilicate zeolite detergents described previously provide better chelating action of magnesium ion than an equal weight of commercial zeolite A.

Surfactant

Surfactants are detergent components preferred of the compositions described herein. Suitable surfactants are selected from surfactants anionic, cationic, nonionic, ampholytic and hybrid ion and mixtures thereof. Dishwasher products should be low foam and therefore the foam should be removed from the system surfactant for use in dishwashing methods or more preferably these should be low foaming, typically Non-ionic character. Soap formation caused by the surfactant systems used in the washing methods of clothing does not need to be suppressed at the same level as in the case of dishwasher. The surfactant is typically present at a 0.2% to 30% by weight level, more preferably 0.5% to 10% in weight and most preferably from 1% to 5% by weight, of the composition of the active detergent components.

A typical list of classes and types of these anionic, nonionic, amphoteric and hybrid ion surfactants are includes in US-3,929,678, granted to Laughlin and Heuring on December 30, 1975. A list of surfactants Suitable cationics are included in US 4,259,217, granted to Murphy on March 31, 1981. A list of the surfactants typically included in the compositions dishwashing detergents are presented, for example, in EP-A-0414 549 and in PCT WO-93/08876 and WO-93/08874.

Nonionic Surfactant

Virtually any non-ionic surfactant Useful for detersive purposes can be included in the tablet Detergent. Preferred, non-limiting classes of surfactants Useful nonionics are included below.

Nonionic surfactant of ethoxylated alcohol type

Alkylethoxylated condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol can be linear or branched, primary or secondary and generally contains 6 to 22 carbon atoms. Especially preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 atoms carbon with 2 to 10 moles of ethylene oxide per mole of alcohol.

Surfactant of alkyl alkoxylate type with ends protected

An alkyl alkoxylate surfactant with Suitable protected ends are poly (alcohols oxyalkylated) terminally protected with epoxy groups represented by the formula:

(I) R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R2

where R_ {1} is a radical aliphatic, linear or branched hydrocarbon having from 4 to 18 carbon atoms; R2 is an aliphatic hydrocarbon radical linear or branched having 2 to 26 carbon atoms; x is a integer with an average value of 0.5 to 1.5 and more preferably is 1, e and is an integer that has a value of at least 15 and more preferably of at least twenty.

Preferably, the surfactant of the formula I has at least 10 carbon atoms in the terminal epoxy unit [CH 2 CH (OH) R 2]. Surfactants of formula I suitable, according to the present invention, are non-surfactants Poly-Tergent® SLF-18B ionic Olin Corporation, as described, for example, in WO-94/22800, published October 13, 1994 by Olin Corporation

Terminal (protected oxyalkylated alcohols) with ether groups

Preferred surfactants for use in the Present invention include poly (oxyalkylated alcohols) terminal protected with ether groups that have 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 saturated hydrocarbon radicals unsaturated, aliphatic or aromatic having 1 to 30 atoms of carbon; R 3 is H, or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 30, where when x is 2 or greater R 3 can be the same or different and k and j are integers that they have an average value of 1 to 12, and more preferably 1 to 5.

R 1 and R 2 are preferably radicals linear or branched, saturated or unsaturated hydrocarbons, aliphatic or aromatic having 6 to 22 carbon atoms, 8 to 18 carbon atoms being the most preferred. For R3 lo more preferred is H or a chain aliphatic hydrocarbon radical linear that has 1 to 2 carbon atoms. Preferably, x is an integer that has an average value of 1 to 20, plus preferably from 6 to 15.

As described above, when in preferred embodiments x is greater than 2, R 3 can be the same or different That is, R3 may vary between any of the alkyleneoxy units as described above. By example, if x is 3, R3 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and your order can vary between (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Evidently number three is chosen by way of example only and the variation can be much greater with a higher integer value of x and includes, for example, multiple units (EO) and a much smaller number of units (PO).

Especially preferred surfactants such as described above include those that have a point of low cloudiness of less than 20ºC. These surfactants of Low cloud point can be used together with a high cloud point surfactant, as described in detail later, to achieve greater cleaning advantages of grease.

Alcohol type surfactants poly (oxyalkylated) terminally protected with ether groups most preferred are those where k is 1 and j is 1 so that Surfactants have the formula:

R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2

where R 1, R 2 and R 3 are as defined above and x is an integer with an average value of 1 to 30, preferably 1 to 20 and even more preferably from 6 to 18. The most preferred surfactants are those where R 1 and R 2 are from 9 to 14, R 3 is H which ethyleneoxy form and x is 6 to fifteen.

Alcohol type surfactants poly (oxyalkylated) terminally protected with ether groups they comprise three general components, especially an alcohol linear or branched, an alkylene oxide and a protection Alkyl ether terminal. The terminal alkyl protection and the alcohol act as the oil-soluble hydrophobic fraction of the molecule while the alkylene oxide group acts as the Water soluble hydrophilic fraction of the molecule.

These surfactants have an improvement significant stain removal characteristics and films and greasy dirt removal when used together with high cloud point surfactants compared with conventional surfactants.

Generally speaking, type surfactants poly (oxyalkylene) alcohol with unit protected ends  ether can be obtained by reacting an aliphatic alcohol with a epoxide to form an ether, which then reacts with a base to form a second epoxide. The second epoxy after it is reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Method Examples to prepare the alcohol type surfactants poly (oxyalkylated) terminally protected with ether group se described below:

Preparation of a C 12/14 alkyl glycidyl ether

A C 12/14 fatty alcohol is mixed (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol, marketed by Aldrich) in a three round bottom flask 500 ml mouths equipped with a condenser, argon inlet, addition funnel, magnetic stirrer and temperature probe internal The mixture is heated to 60 ° C. Is added drop by drop epichlorohydrin (47.70 g, 0.515 mol, marketed by Aldrich) of so that the temperature is maintained between 60 and 65 ° C. After stir another hour at 60 ° C, the mixture is cooled to temperature ambient. The mixture is treated with a solution of sodium hydroxide 50% (61.80 g, 0.773 moles, 50%) by stirring mechanically. One time After the addition is complete, the mixture is heated to 90 ° C for 1.5 h, cooled and filtered with ethanol. The filtrate is separated and the phase organic is washed with water (100 ml), dried over MgSO4, dried filter and concentrate. Oil distillation a 100-120 ° C (0.1 mm Hg) providing the ether Glycidyl as an oil.

Preparation of the C 12/14 alkyl alcohol surfactant C_ {9/11} terminally protected with ether groups

Neodol® 91-8 (20.60 g, 0.0393 moles of ethoxylated alcohol sold by Shell Chemical Co) and tin (IV) chloride (0.58 g, 2.23 mmol) in a flask of round bottom of three 250 ml mouths equipped with a condenser, an argon inlet, an addition funnel, a magnetic stirrer and An internal temperature probe. The mixture is heated to 60 ° C, temperature at which the alkyl ether is added dropwise C 12/14 glycidyl (11.00 g, 0.0393 mol) for 15 min. After stirring for 18 h at 60 ° C, the mixture is cooled to room temperature and dissolves in an equal part of dichloromethane The solution is passed through a gel layer of 1.54 cm (1 inch) silica eluting with dichloromethane. He filtrate is concentrated by rotary evaporation and then Distill in a Kugelrohr oven (100ºC, 0.5 mm Hg) to obtain the surfactant as an oil.

Non-ionic fatty alcohol surfactant ethoxylated / propoxylated

Fatty alcohols C 6 -C 18 ethoxylates and fatty alcohols C6 {C} {C18} mixed ethoxylated / propoxylated are surfactants suitable for use in the present invention, especially if they are soluble in water. Preferably the ethoxylated fatty alcohols are fatty alcohols C 10 -C 18 ethoxylated with a degree of ethoxylation from 3 to 50 and most preferably these are the C 12 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the alcohols mixed ethoxylated / propoxylated fatty acids have a chain length alkyl of 10 to 18 carbon atoms, a degree of ethoxylation of 3 at 30 and a degree of propoxylation from 1 to 10.

Non-ionic condensates EO / PO with propylene glycol

Rust Condensation Products ethylene with a hydrophobic base formed by the condensation of oxide of propylene with propylene glycol are suitable for use in the present invention The hydrophobic fraction of these compounds preferably it has a molecular weight of 1500 to 1800 and is insoluble in water. Examples of compounds of this type include some of Pluronic? commercial surfactants, marketed by BASF.

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

Rust Condensation Products ethylene with the product resulting from the reaction between the oxide of Propylene and ethylenediamine are suitable for use in the present invention The hydrophobic rest of these products consists in the reaction product of ethylenediamine and excess oxide of propylene, and generally has a molecular weight of 2,000 to 3,000. Examples of this type of non-ionic surfactant include some Tetronic ™ commercial compounds, marketed by BASF

Mixed non-ionic surfactant system

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

The expression "cloud point", in This report is a well known property of nonionic surfactants which consists in the surfactant being it becomes less soluble when the temperature rises, being called the temperature at which the appearance of a second phase is observable "cloud point" (see Encyclopedia of Chemical Technology by Kirk Othmer, 3rd ed. vol. 22, p. 360-379).

Herein, a surfactant does not Ionic "low cloud point" is defined as a ingredient of the nonionic surfactant system that has a point cloudiness of less than 30 ° C, preferably less than 20 ° C and most preferably less than 10 ° C. The surfactants do not Typical low cloud point ionics include alkoxylated nonionic surfactants, especially ethoxylates primary alcohol derivatives, and inverse block polymers of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). Also, said non-ionic surfactants of Low cloudiness include, for example, alcohol ethoxylated-propoxylated (e.g., Poly-Tergent® SLF18 from Olin Corporation), poly (oxyalkoxylated alcohol) terminally protected with epoxy groups (e.g., the series of non-ionic surfactants Poly-Tergent® SLF18B from Olin Corporation, such as described for example in WO-94/22800, published on October 13, 1994 by Olin Corporation) and surfactants of poly (oxyalkylated) alcohol type with ends protected with ether groups.

Nonionic surfactants can optionally contain propylene oxide in an amount of up to 15% by weight. Other preferred nonionic surfactants may prepare by the processes described in US 4,223,163, issued September 16, 1980 Builloty.

The non-ionic surfactants of additionally clouding comprise a compound polyoxyethylene-polyoxypropylene block polymer. The polymeric polyoxyethylene-polyoxypropylene block compounds  include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as an initiator compound that Reacts with hydrogen. Certain surfactant compounds of block polymer called PLURONIC®, REVERSED PLURONIC® and TETRONIC® from BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable to add to the compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. These types of surfactants are typically useful in the present invention as non-ionic surfactants of low cloud point.

Herein, a surfactant of non-ionic "high cloud point" is defined as a ingredient of the nonionic surfactant system that has a point cloudiness greater than 40 ° C, preferably greater than 50 ° C and more preferably higher than 60 ° C. Preferably the system nonionic surfactant comprises an ethoxylated derivative surfactant of the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol, on average. These surfactants non-ionic high cloud point include, for example, Tergitol 15S9 (marketed by Union Carbide), Rhodasurf TMD 8.5 (marketed by Rhone Poulenc) and Neodol 91-8 (marketed by Shell).

It is also preferred for the purposes of present invention that the nonionic surfactant of point of high cloudiness also have a balance hydrophilic-lipophilic ("HLB"; see Kirk Othmer cited above) within the range of 9 to 15, preferably from 11 to 15. These materials include, for example, Tergitol 15S9 (marketed by Union Carbide), Rhodasurf TMD 8.5 (marketed by Rhone Poulenc) and Neodol 91-8 (marketed by Shell).

Another preferred non-ionic high cloud point surfactant is derived from a linear or preferably branched or secondary chain fatty alcohol containing from 6 to 20 carbon atoms (C 6 -C 20 alcohol), including secondary alcohols and primary branched chain alcohols. Preferably, the high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9 / 11 or C11 / 15 branched alcohol ethoxylates, condensed with an average of 6 to 15 moles, preferably 6 to 12 moles and most preferably 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably, the tension
Ethoxylated non-ionic active thus derived has a narrow distribution of ethoxylate groups with respect to the average.

In a preferred embodiment the tablet of detergent comprising this mixed surfactant system also comprises an amount of water soluble salt to provide a conductivity in deionized water measured at 25ºC higher than 3 milli Siemens / cm, preferably greater than 4 milli Siemens / cm and with maximum preference greater than 4.5 milli Siemens / cm.

In another preferred embodiment the system mixed surfactant dissolves in water with a hardness of 1,246 mmol / l in any dishwasher with adequate cold water inlet to provide a solution with a surface tension of less 4 dynes / cm2 at less than 45 ° C, preferably at less than 40 ° C and most preferably at less than 35 ° C.

In another preferred embodiment the surfactants high cloud point and low cloud point from the mixed surfactant system are separated so that or the high cloud point surfactant or surfactant of low cloud point is present in a first matrix and the another is present in a second matrix. For the purpose of the present invention, the first matrix may be a matrix in form of particles and the second matrix can be a second matrix in particle shape A surfactant can be applied to the component in particulate form by any suitable method known, preferably the surfactant is sprayed onto the component in particle shape In a preferred aspect, the first matrix is the compressed part and the second matrix is the uncompressed part, of the detergent tablet of the present invention. Preferably the low cloud point surfactant is present in the compressed part and the point surfactant of high cloudiness is present in the uncompressed part of the detergent tablet of the present invention.

Anionic surfactant

Virtually any anionic surfactant useful for detersive purposes is appropriate. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium such as monoethanolamine salts, diethanolamine and triethanolamine) of the anionic surfactants of sulfate, sulphonate, carboxylate and sarcosinate type. The ones are preferred sulfate type anionic surfactants.

Other anionic surfactants include the isethionates such as acyl isethionates, N-acyl Taurates, fatty acid amides of methyl tauride, alkyl succinates and sulphosuccinates, sulphosuccinate monoesters (en special saturated C 12 -C 18 monoesters and unsaturated), sulphosuccinate diesters (especially diesters C 6 -C 14 saturated and unsaturated) and N-acyl sarcosinates. Also suitable are resin acids and hydrogenated resin acids, such as the rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from the oil of tallow.

Sulfate-type anionic surfactant

Sulfate-type anionic surfactants Suitable for use in the present invention include the linear and branched primary and secondary alkyl sulfates, alkylethoxysulfates, oleoyl glycerol fatty sulfates, alkylphenol  ethylene oxide ether sulfate, the alkyl C_ {5} -C_ {17} acyl-N- (C 1 -C 4) and -N- (C 1 -C 2 hydroxyalkyl) glucaminsulfates, and alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (non-ionic compounds not sulfated are described herein).

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

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

An especially preferred aspect of the invention uses mixtures of the alkyl sulfate surfactants  and preferred alkylethoxysulfate type. These mixtures have been described in PCT WO-93/18124.

Sulfonate type anionic surfactant

Anionic sulphonate surfactants suitable for use in the present invention include salts C 5 -C 20 alkyl benzenesulfonates linear, alkyl ester sulphonates, alkanes C 6 -C 22 primary sulfonates or secondary, the C 6 -C 24 olefin sulphonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, acyl glycerol fatty sulfonates, oleyl glycerol fatty sulphonates and any mixture thereof.

Anionic Carboxylate Surfactant

Anionic carboxylate surfactants suitable include alkylethoxy type surfactants carboxylate, alkylpolyethoxy polycarboxylate type and soaps ("alkylcarboxyls"), especially certain secondary soaps described herein.

Suitable alkylethoxy carboxylates include those with the formula RO (CH 2 CH 2 O) x CH 2 COO - M + where R is a C 6 alkyl group } at C18, x is from 0 to 10 and the distribution of ethoxylates is such that, by weight, the amount of material where x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO- (CHR 1 -CHR 2 -O) -R 3 where R is a C 6 to C 18 alkyl group , x is 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R 3 is selected from the group consisting of hydrogen,
substituted or unsubstituted hydrocarbons having between 1 and 8 carbon atoms and mixtures thereof.

Suitable soap surfactants include secondary soap type surfactants that contain a carboxyl unit attached to a secondary carbon. The Preferred secondary soap surfactants for use in the The present invention are water soluble elements selected from the group consisting of the water soluble salts of the acid 2-methyl-1-undecanoic, acid 2-ethyl-1-decanoic, acid 2-propyl-1-nonanoic,  acid 2-butyl-1-octanoic and acid 2-pentyl-1-heptanoic. Certain soaps can also be included as suppressants of suds.

Alkali metal sarcosinate type surfactant

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

Amphoteric surfactant

Amphoteric surfactants suitable for your Use in the present invention include surfactants of the type amine oxide and alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds that have the formula R 3 (OR 4) x N 0 (R 5) 2  wherein R 3 is selected from an alkyl, hydroxyalkyl group, acylamidopropoyl and alkylphenyl, or mixtures thereof, which it contains from 8 to 26 carbon atoms; R 4 is an alkylene group or hydroxyalkylene containing from 2 to 3 carbon atoms, or mixtures thereof; x is 0 to 5, preferably 0 to 3; Y each R 5 is an alkyl or hydroxyalkyl group containing 1 to 3, or a poly (ethylene oxide) group containing 1 to 3 groups ethylene oxide. Alkyl are preferred C 10 -C 18 methylamine dioxide and the C 10-18 alkylamido dioxide methylamine

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

Hybrid ion surfactant

Hybrid ion surfactants can also be incorporated into the detergent compositions herein invention. These surfactants can be widely described as derivatives of secondary and tertiary amines, derivatives of amines secondary and tertiary heterocyclic or derivatives of compounds of quaternary ammonium, quaternary phosphonium or tertiary sulfonium. The betaine and sultaine type surfactants are ionic surfactants Illustrative hybrid for use in the present invention.

Suitable betaines are the compounds that they have the formula R (R ') 2 N + R 2 COO -, in where R is a C 6 -C 18 hydrocarbyl group, each R1 is typically alkyl C 1 -C 3, and R 2 is a hydrocarbyl group C_ {1} -C_ {5}. Preferred betaines are C12-18 dimethyl ammonium hexanoate and acylamidopropane (or ethane) dimethyl (or diethyl) C 10-18 betaines. The complex surfactants of betaine type are also suitable for use herein invention.

Cationic surfactants

Cationic ester type surfactants used in this invention are preferably compounds water dispersible having surfactant properties that they comprise at least one ester linkage (ie -COO-) and at least one group with cationic charge. Other cationic surfactants of the type suitable esters, including ester surfactants of choline, have been, for example, described in US-4228042, US-4239660 and US-4260529.

Suitable cationic surfactants include quaternary ammonium surfactants selected from mono-N-alkyl type surfactants or C 6 -C 16 alkenyl ammonium, preferably N-alkyl or alkenyl C_ {6} -C_ {10} ammonium where the N positions remaining are substituted by methyl, hydroxyethyl or hydroxypropyl.

Enzymes

Enzymes are very detergent components preferred. If present, said enzymes are selected from group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylase, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanases, tanasas, pentosanasas, malanasas, β-glucanases, arabinosidases, hyaluronidases, Chondroitinases, lacases or mixtures thereof.

Preferred enzymes include protease, amylase, lipase, peroxidase, cutinase and / or cellulase together with one or more enzymes of degradation of the plant cell wall.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and an activity greater than 50 CEVU (cellulose viscosity unit). Suitable cellulases are described in US-4,435,307, Barbesgoard et al., J61078384 and WO96 / 02653 which describe fungal cellulases obtained from Humicola insolens, Trichoderma, Thielavia and Sporotrichum , respectively. EP-739 982 describes cellulases isolated from novel bacillus types. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832 and WO95 / 26398.

Examples of these cellulases are cellulases produced by a Humicola insolens strain ( Humicola grisea var. Thermoidea ), in particular the Humicola DSM 1800 strain. Other suitable cellulases are Humicola insolens cellulases having a molecular weight of 50KDa, a point isoelectric of 5.5 and contain 415 amino acids and an endoglucanase of - 43kD derived from Humicola insolens , DSM 1800, which has cellulase activity; A preferred endoglucanase component has the amino acid sequence described in PCT application WO-91/17243. Other cellulases that are also suitable are Trichoderma longibrachiatum EGIII cellulases described in WO94 / 21801, published September 29, 1994 by Genencor. Especially suitable cellulases are cellulases that have color care benefits. Examples of cellulases of this type are the cellulases described in EP-91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO91 / 17244 and WO91 / 21801. Other suitable cellulases with tissue protection and / or cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

Said cellulases are normally incorporated in the detergent composition at a level of 0.0001% to 2% enzyme active by weight of the detergent composition.

Peroxidase enzymes are used together with oxygen sources, e.g. ex. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used to "whiten the solution ", that is, to avoid transferring to others substrates in the dye or pigment wash solution removed of the substrates during washing operations. Enzymes peroxidase are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro-peroxidase and bromo-peroxidase. Detergent compositions containing peroxidase are described, for example, in PCT WO-89/099813, WO89 / 09813 and in EP-91202882.6, filed on November 6, 1991, and EP-96870013.8, filed on February 20 1996. The enzyme lacasa is also suitable.

Preferred promoters are fentiacin and substituted phenoxyasin, acid 10-Phenothiazinepropionic acid (PPT), acid 10-ethylphenothiazin-4-carboxylic (EPC), 10-phenoxazinpropionic acid (POP) and 10-methylphenoxazine (described in WO-94/12621) and substituted syringates (alkyl C3-C5 substituted syringates) and phenols. He sodium percarbonate or perborate are sources of peroxide of Preferred hydrogen

Said cellulases and / or peroxidases are normally incorporated in the detergent composition at a level of 0.0001% to 2% of active enzyme by weight of the detergent composition.

Other preferred enzymes that can be included in the detergent composition of the present invention include lipases. Suitable lipase enzymes for use in detergents include those obtained by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in GB-1,372,034. Suitable lipases include those that have a positive immunological cross-reaction with the lipase antibody, produced by the Pseudomonas fluorescent IAM 1057 microorganism. This lipase is marketed by Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the registered name Lipasa P "Amano", mentioned below as "Amano-P". Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases, p. ex. Chromobacter viscosum var . NRRLB 3673 lipolyticum from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA and Disoynth Co., the Netherlands, and lipases of Pseudomonas gladioli . Especially suitable lipases are lipases such as M1 Lipase® Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo) which have proven to be very effective when used in conjunction with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP-258 068, WO-92/05249 and WO-95/22615, of Novo Nordisk, and in WO-94/03578, WO-95/35381 and WO-96/00292, of Unilever

Cutinases are also suitable [EC 3.1.1.50] which can be considered as a special type of lipase, namely lipases that do not require an interface activation. The Addition of cutinases to detergent compositions has been described e.g. ex. in applications WO-A-88/09367 (Genencor); WO-90/09446 (Plant Genetic System) and WO-94/14963 and WO-94/14964 (Unilever).

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

Suitable proteases are the subtilisins that are obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protease is obtained from a strain of Bacillus having a maximum activity in the pH range of 8-12, developed and marketed as Esperase® by Novo Industries A / S of Denmark, then "Novo". The preparation of this enzyme and analogous enzymes is described in GB-1,243,784, de Novo. Other suitable proteases include Alcalase®, Durazym® and Savinase® from Novo and Maxatase®, Maxacal®, Properase® and Maxapem® (Maxacal obtained by protein engineering) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in application EP-87 303761.8, filed on April 28, 1987 (in particular pages 17, 24 and 98), and referred to as "Protease B" herein. , and in application EP-199,404, Venegas, published on October 29, 1986, referring to a serine modified bacterial proteolytic enzyme referred to herein as "Protease A". The so-called "Protease C", which is a variant of a Bacillus serine protease in which a lysine replaces an arginine at position 27, a tyrosine replaces a valine at position 104, a serine is suitable replaces an asparagine at position 123 and an alanine replaces a threonine at position 274. Protease C is described in application EP-90915958: 4, which corresponds to WO-91/06637, published May 16, 1991. This patent also includes genetically modified variants, especially protease C.

A preferred protease referred to as "protease D" is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by replacing a different amino acid with a plurality of amino acid residues in a position in said carbonyl hydrolase equivalent to the +76 position, preferably also together with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222 , +260, +265, and / or +274 according to the subtilisin numbering of Bacillus amyloliquefaciens , as described in WO95 / 10591 and in the patent application of C. Ghoshy col., "Bleaching Compositions Comprising Protease Enzymes" US- 5,677,272.

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

See also a high pH protease from Bacillus sp . NCIMB 40338 described in WO-93/18140 A, granted to Novo. Enzymatic detergents comprising protease, one or more additional enzymes and a reversible protease inhibitor are described in WO-92/03529 A, de Novo. If desired, a protease having less adsorption and greater hydrolysis is available as described in WO-95/07791, granted to Procter & Gamble. A Recombinant trypsin-like protease for detergents suitable in the present invention is described in WO-94/25583, granted to Novo. Other suitable proteases are described in EP-516 200, granted to Unilever.

Other preferred protease enzymes include protease enzymes that are a carbonylhydrolase variant having an amino acid sequence that is not found in nature, which is derived by substituting a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of amino acid residues substituted in the precursor enzyme correspond to the +210 position together with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222 , where the numbered positions correspond to the natural subtilisin of Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as subtilisin Bacillus lentus ). Preferred enzymes of this type include those that have changes in positions +210, +76, +103, +104, +156 and +166.

Proteolytic enzymes are incorporated into the detergent compositions of the present invention at a level of 0.0001% to 2%, preferably 0.001% to 0.2% and more preferably from 0.005% to 0.1%, of pure enzyme by weight of the composition.

Amylases (? And / or?) May be included to remove carbohydrate stains. In WO94 / 02597, published on February 3, 1994 by Novo Nordisk A / S, cleaning compositions incorporating mutant amylases are described. See also application WO95 / 10603, published on April 20, 1995 by Novo Nordisk A / S. Other amylases known for use in the cleaning compositions include both α-amylases and β-amylases. Α-Amylases are known in the art and include those described in US Patents 5,003,257, EP-252,666, WO / 91/00353, FR 2,676,456, EP-285,123, EP-525,610, EP-368,341 and GB-1,296,839 (Novo). Other suitable amylases are stability enhancing amylases described in WO94 / 18314, published on August 18, 1994 and in WO96 / 05295, published on February 22, 1996 by Genencor and amylase variants that have additional modifications in the immediate precursor marketed by Novo Nordisk A / S, described in WO-95/10603 and published in April 1995. The amylases described in EP-277 216, WO95 / 26397 and WO96 / 23873 (all of them of
Novo Nordisk).

Examples of products from Commercial α-amylases are Purafect Ox Am® of Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all of them marketed by Novo Nordisk A / S, Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized by having a specific higher activity in the minus 25% to the specific activity of Termamyl® at a range of temperature of 25ºC to 55ºC and with a pH value in the range of 8 to 10, measured by the activity test of Phadebas® α-amylase. They are adequate variants of the above enzymes, described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes with better properties of activity level and with a combination of thermostability and a higher level of activity are described in WO95 / 35382.

Preferred amylase enzymes include the described in WO95 / 26397 and WO96 / 23873.

Amylolytic enzymes are incorporated into the detergent compositions of the present invention at a level of 0.0001% to 2%, preferably 0.00018% to 0.06% and more preferably from 0.00024% to 0.048%, of pure enzyme by weight of the composition. In an especially preferred embodiment, the detergent tablets of the present invention comprise enzymes amylase, especially those described in WO95 / 26397 and WO96 / 23873, along with a complementary amylase.

The term "complementary" means the addition of one or more amylases suitable for detergency purposes. Examples of complementary amylases (α and / or β) are described later. In WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S, cleaning compositions containing amylases are described mutants Other amylases known for use in compositions cleaners include both α-amylases and β-amylases. The α-amylases are known in the art and they include those described in US Patents 5,003,257; EP-252,666; WO / 91/00353; FR 2,676,456; EP-285,123; EP-525,610; EP-368,341 and GB-1,296,839 (Novo). Other suitable amylases are the improved stability amylases described in WO94 / 18314 and WO96 / 05295, Genencor, and variants of amylase with further modification in the immediate precursor marketed by Novo Nordisk A / S, described in WO-95/10603. Amylases are also suitable described in EP-277 216 (Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all of them marketed by Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity exceeds at least 25% of the activity specific to Termamyl® at a temperature between 25ºC and 55ºC and at a pH between 8 and 10, measured by the Phadebas® activity activity test α-amylase Variants are suitable of the above enzymes, described in WO96 / 23873 (Novo Nordisk) .Other amylolytic enzymes with improved properties with regarding the level of activity and the combination of thermostability and a higher level of activity are described in the application WO95 / 35382. Preferred complementary amylases herein invention are the amylases sold under the registered trademark Purafect Ox Am® described in the applications WO-94/18314, WO96 / 05295 sold by Genencor; Termamyl®, Fungamyl®, Ban® and Duramyl®, all commercialized by Novo Nordisk A / S, and Maxamyl® by Gist-Brocades.

Said complementary amylase is generally incorporated into the detergent composition of the present invention a a level of 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048%, of pure enzyme by weight of the composition. Preferably a weight ratio of pure enzyme between the specific amylase and the complementary amylase is between 9: 1 and 1: 9, more preferably between 4: 1 and 1: 4, and most preferably between 2: 1 and 1: 2.

The enzymes mentioned above may be of any suitable origin such as plant, animal, bacterial, fungal or yeast. The origin can also be mesophilic or Extremophile (psychrophilic, psychotropic, thermophilic, barophile, alkalophilic, acidophilic, halophilic, etc.). Shapes can be used purified or unpurified of these enzymes. Also included by definition the mutants of native enzymes. Mutants can be obtained, e.g. e.g., by protein engineering and / or genetic or chemical and / or physical modifications of native enzymes. A common practice is also the expression of the enzyme through host microorganisms in which the genetic material responsible of the enzyme production has been cloned.

Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% enzyme active by weight of the detergent composition. Enzymes can be added as separate single ingredients (pellets, granules, stabilized liquids, etc., which contain an enzyme) or as mixtures of two or more enzymes (eg cogranulates).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers that are described in the co-dependent European patent application 92870018.6, filed on January 31, 1992. Examples of these Enzyme oxidation scavengers are tetraethylene polyamines ethoxylated.

A range of enzymatic materials and means for incorporation into synthetic detergent compositions are also described in WO-9307263 A and WO-9307260 A, granted to Genencor International, WO-8908694 A, granted to Novo, and US-3,553,139 , granted on January 5, 1971 to McCarty et al. Enzymes are also described in US 4,101,457, granted to Place et al. on July 18, 1978, and in US 4,507,219, granted to Hughes on March 26, 1985. Enzymatic materials useful for liquid detergent formulations and their incorporation into these formulations are described in US 4,261,868, granted to Hora et al. on April 14, 1981. Enzymes for use in detergents can be stabilized by different techniques. Enzyme stabilization techniques are described and illustrated in US-3,600,319, issued August 17, 1971 to Gedge et al., EP-199,405 and EP-200,586, issued October 29, 1986 to Venegas. Enzyme stabilization systems are also described, for example, in US 3,519,570. A Bacillus sp . AC13 providing proteases, xylanases and cellulases, is described in WO-9401532 A, granted to Novo.

Bleaching agent

A very preferred component of the composition of Detergent components is a bleaching agent. The agents Suitable bleaching agents include bleaching agents that release chlorine and oxygen

In a preferred aspect, the oxygen-releasing bleaching agent contains a source of hydrogen peroxide and an organic peroxyacid bleaching precursor compound. The production of organic peroxyacid is produced by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include perhydrated inorganic bleaches. In a preferred alternative aspect, a previously formed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a source of hydrogen peroxide and organic peroxyacid precursor together with a previously formed organic peroxyacid are also contemplated.

Inorganic Perhydrated Bleaches

The detergent component compositions preferably include a source of hydrogen peroxide as an oxygen releasing bleach. The peroxide sources of Suitable hydrogen include perhydrated salts inorganic

Inorganic perhydrated salts are normally incorporated in the form of sodium salt at a level of 1% at 40% by weight, more preferably from 2% to 30% by weight and with maximum preference of 5% to 25% by weight, of the composition.

Examples of inorganic perhydrated salts include perborate salts, percarbonate, perfosphate, persulfate and persilicate Inorganic perhydrated salts are usually the alkali metal salts. Inorganic perhydrated salt can be included as the crystalline solid without additional protection. For certain perhydrated salts, however, the embodiments preferred of these granulated compositions use a form coated with the material that provides better stability during storage for perhydrated salt in the product granulated.

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

Alkali metal percarbonates, especially sodium percarbonate, they are preferred perhydrates for inclusion in the compositions according to the invention. Sodium percarbonate is an addition compound that has a formula corresponding to 2Na2CO3 .3H2 {O2} and It is marketed as a crystalline solid. The percarbonate of sodium, being a hydrogen peroxide addition compound, tends to dissolve to release hydrogen peroxide quite quickly, which can increase the tendency for them to occur high concentrations of bleach in a timely manner. He percarbonate most preferably incorporated into these compositions in a coated form that provides a Product stability.

A suitable coating material that provides stability within the product comprises a mixed salt of water soluble alkali metal sulfate and carbonate. These coatings along with the coating processes have been previously described in GB-1,466,799, granted to Interox on March 9, 1977. The weight ratio between the Coating material of mixed salt and percarbonate is in the range of 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt  it is made of sodium sulfate and sodium carbonate with the general formula Na_ {SO} {4} .n.Na_ {CO2} where n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other suitable coating material that provides stability within the product, includes silicate sodium in a SiO2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied at a level of 2% to 10%, (usually 3% 5%) of SiO 2 by weight of the inorganic perhydrated salt. He Magnesium silicate can also be included in the coating. Coatings containing silicate and borate or acid salts Boric or other inorganic elements are also suitable.

They can also be used advantageously in the present invention other coatings containing waxes, Oils and fatty soaps.

Potassium peroximonopersulfate is another salt inorganic perhydrate useful in the compositions of the present invention

Peroxyacid bleach precursor

The peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Usually peroxyacid bleach precursors can be represented how

one

where L is a leaving group and X is virtually any functionality, so that by Perhydrolysis the structure of the peroxyacid produced is

2

Bleach Precursor Compounds peroxyacid are preferably incorporated at a level of 0.5% to 20% by weight, more preferably from 1% to 10% by weight and with maximum preference of 1.5% to 5% by weight of the compositions.

Bleach Precursor Compounds Suitable peroxyacids typically contain one or more groups N-acyl or O-acyl, being able to Precursors be selected from a wide range of classes. The Suitable types include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Material examples useful within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, GB-A-864798, GB-A-1147871, GB-A-2143231 and EP-A-0170386.

Outgoing groups

The outgoing group, hereinafter group L, must be reactive enough for the perhydrolysis reaction occurs within the optimal timeframe (e.g., a cycle of washed). However, if L is too reactive, this activator it will be difficult to stabilize to use in a composition of Whitening.

Preferred L groups are selected from the group consisting of:

3

       \ vskip1.000000 \ baselineskip
    

4

       \ vskip1.000000 \ baselineskip
    

5

6

       \ vskip1.000000 \ baselineskip
    

7

and mixtures thereof, where R1 is an alkyl, aryl or alkylaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3, R 5 is a alkenyl chain containing 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R 1, R 3 and R 4 It can be replaced by virtually any functional group including, for example, alkyl, hydroxy, alkoxy, halogen groups, amine, nitrosyl, amide and ammonium or alkylammonium

Preferred solubilizing groups are -SO 3 <+> - M +, -CO 2 - M +, -SO4 {+} - M +, -N + (R 3) 4 X - and O <- N (R 3) 3 and most preferably -SO 3 <+> - + M + and -CO 2 - M + where R 3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the activator of the bleach. Preferably, M is an alkali metal cation, ammonium or substituted ammonium being the most preferred sodium and potassium, and X is a halide, hydroxide, methylsulfate or anion acetate.

       \ vskip1.000000 \ baselineskip
    

Perbenzoic acid precursor

Perbenzoic acid precursor compounds They provide perbenzoic acid by perhydrolysis.

Perbenzoic acid precursor compounds Suitable O-acylates include benzoyl substituted and unsubstituted oxybenzenesulfonates, including by example benzoyl oxybenzenesulfonate:

8

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

9

Ac = COCH3; Bz = Benzoyl

Perbenzoic acid precursor compounds imide type include N-benzoyl succinimide, tetrabenzoyl ethylenediamine and ureas substituted with N-Benzoyl Perbenzoic acid precursors of Suitable imidazole type include N-benzoyl imidazole and N-benzoyl benzimidazole and other precursors of perbenzoic acid containing the N-acyl group Useful include N-benzoyl pyrrolidone, dibenzoyl Taurine and pyroglutamic benzoyl acid.

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

10

Phthalic anhydride is another precursor compound of suitable perbenzoic acid in the present invention:

eleven

Perbenzoic acid precursors of type Suitable N-acylated lactam have the formula:

12

where n is from 0 to 8, preferably from 0 to 2 and R 6 is a group benzoyl.

       \ vskip1.000000 \ baselineskip
    

Precursors derived from perbenzoic acid

Precursors derived from perbenzoic acid they provide perbenzoic acids substituted by perhydrolysis.

Precursors derived from perbenzoic acid Suitable substituted include any of the precursors of the perbenzoic acid described herein where the group benzoyl is substituted by virtually any group functional not positively charged (i.e. non-cationic) including, for example, alkyl, hydroxy, alkoxy, halogen groups, amine, nitrosyl and amide.

A preferred class of precursor compounds of the substituted perbenzoic acid are the compounds with substitution Amide of the following general formula:

13

wherein R 1 is an aryl group or alkylaryl with 1 to 14 carbon atoms, R2 is a group arylene or alkylarylene containing from 1 to 14 carbon atoms and R 5 is H or an alkyl, aryl, or alkylaryl group containing from 1 to 10 carbon atoms and L can be virtually any outgoing group. R1 preferably contains from 6 to 12 atoms carbon R2 preferably contains from 4 to 8 atoms of carbon. R1 can be aryl, substituted aryl or alkylaryl which contains branching, substitution or both and may come from synthetic sources or natural sources including, for example, fat of tallow Similar structural variations are allowed to R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups or compounds Typical organic R 5 is preferably H or methyl. R1 and R 5 must not contain more than 18 carbon atoms in total. The bleach activating compounds with amide substitution of this type are described in EP-A-0170386.

Precursors of cationic peroxyacid

The peroxyacid precursor compounds cationic produce cationic peroxyacids by perhydrolysis.

Typically, peroxyacid precursors cationic are formed by replacing the peroxyacid part of a suitable peroxyacid precursor compound with a functional group positively charged such as an ammonium or alkylammonium group, preferably an ethylammonium or methylammonium group. Precursors of cationic peroxyacid are typically present in salt-shaped compositions with a suitable anion as, by example, a halide ion or a methylsulfate ion.

The peroxyacid precursor compound that is going to being cationically substituted can be a precursor compound of perbenzoic acid or a substituted derivative thereof, as has been described above herein. So alternatively, the peroxyacid precursor compound may be a alkyl percarboxylic acid precursor compound or a precursor of alkyl peroxyacid with amide substitution as described in continuation.

Precursors of cationic peroxyacid se They are described in US Pat. Nos. 4,904,406; US 4,751,015; US 4,988,451; US 4,397,757; US 5,269,962; US 5,127,852; US 5,093,022; 5,106,528; GB-1,382,594; EP-475,512, EP-458,396 and EP284,292; and in JP 87-318.332.

The cationic peroxyacid precursors Suitable include any of the alkyl or benzoyl Oxybenzenesulfonates with ammonium or alkylammonium substitution, N-acylated caprolactams and benzoyl peroxides with monobenzoyltetraacetyl glucose.

A cationically benzoyl oxybenzenesulfonate Preferred substituted is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzenesulfonate:

       \ vskip1.000000 \ baselineskip
    

14

       \ vskip1.000000 \ baselineskip
    

A cationically alkyl oxybenzenesulfonate Preferred substituted has the formula:

       \ vskip1.000000 \ baselineskip
    

fifteen

       \ vskip1.000000 \ baselineskip
    

The cationic peroxyacid precursors of the class of preferred N-acylated caprolactam include trialkyl ammonium methylene benzoyl caprolactam, Especially trimethyl ammonium methylene benzoyl caprolactam:

       \ vskip1.000000 \ baselineskip
    

16

       \ newpage
    

Other cationic peroxyacid precursors of the class of preferred N-acylated caprolactam include trialkyl ammonium methylene alkyl caprolactams:

17

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

Another cationic peroxyacid precursor preferred is carbonate chloride 2- (N, N, N-trimethyl ammonium) ethyl 4-Sulfophenyl Sodium

Alkyl Acid Bleach Precursors percarboxylic

Acid bleach precursors alkyl percarboxylic form percarboxylic acids by perhydrolysis Preferred precursors of this type provide peracetic acid by perhydrolysis.

The alkylpercarboxylic precursor compounds Preferred imide type include the N-, N, N 1 N 1 tetra acetylated alkylenediamines where the alkylene group contains 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 atoms of carbon. Tetraacetyl ethylenediamine (TAED) is especially preferred.

Other precursors of alkyl acid preferred percarboxylic include 3,5,5-tri-methyl sodium hexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), acetoxybenzenesulfonate sodium (ABS) and penta acetyl glucose.

Precursors of the alkyl peroxyacid with amide substitution

The alkyl precursor compounds peroxides with amide substitution are also suitable, including those of the following general formula:

18

where R 1 is a group alkyl with from 1 to 14 carbon atoms, R2 is a group alkylene containing 1 to 14 carbon atoms and R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can Be virtually any outgoing group. R1 preferably It contains 6 to 12 carbon atoms. R2 preferably It contains 4 to 8 carbon atoms. R1 may be alkyl of linear or branched chain containing branching, substitution or both and that can be derived from synthetic sources or sources natural including, for example, tallow fat. For R2 they are allowed similar structural variations. Substitution can include alkyl, halogen, nitrogen, sulfur and other groups typical substituents or organic compounds. R 5 is preferably H or methyl. R 1 and R 5 should not contain more of 18 carbon atoms in total. The activating compounds of Amide replacement bleach of this type are described in EP-A-0170386.

Benzoxazine-type organic peroxyacid precursors

Precursor compounds are also suitable. of the benzoxazine type, as described for example, in EP-A-332,294 and EP-A-482,807, especially those that have the formula:

       \ vskip1.000000 \ baselineskip
    

19

including benzoxacins replaced from kind

twenty

where R 1 is H, alkyl, alkylaryl, aryl, arylalkyl, and wherein R 2, R 3, R 4, and R 5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR 6 (where R 6 is H or a alkyl group) and functions carbonyl

An especially preferred type precursor Benzoxacin is:

twenty-one

Organic peroxyacid previously formed

The bleaching system with organic peroxyacid may contain, additionally or alternatively, a compound organic peroxyacid bleach precursor, a peroxyacid previously formed organic, typically at a level of 0.5% at 25% by weight, more preferably from 1% to 10% by weight, of the composition.

A preferred class of peroxyacid compounds organic are the amide substitution compounds of the following General Formula:

22

where R 1 is a group alkyl, aryl or alkylaryl of 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms and R 5 is H or an alkyl, aryl or alkylaryl containing from 1 to 10 carbon atoms. R1 preferably it contains 6 to 12 carbon atoms. R2 preferably it contains 4 to 8 carbon atoms. R1 can be straight or branched chain alkyl, substituted aryl or alkylaryl containing branching, substitution or both and may come from synthetic sources or natural sources including by example, sebum fat. Similar structural variations are allowed for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups Typical or organic compounds. R 5 is preferably H or methyl. R1 and R5 must not contain more than 18 atoms of carbon in total. Organic peroxyacid compounds with Amide substitution of this type is described in EP-A-0170386.

Other organic peroxyacids include diacilperoxides and tetra acylperoxides, especially acid diperoxidedecanedioic acid, diperoxytetradecanedioic acid and acid diperoxyhexadecanedioic. Dibenzoyl peroxide is a peroxy acid organic preferred in the present invention. Mono acids perazelaic and diperazelaic, monoperbrasilic acids and diperbrasilic acid N-Phthalolaminoperoxicaproproic are also suitable in the present invention.

Means to control the speed of release

A means of controlling the release rate of the bleaching agent, especially of oxygen releasing bleach, to the wash solution.

A means of controlling the bleach release speed to control the Release of peroxide type to wash solution. This medium could, for example, include controlling the release of any inorganic perhydrated salt, which acts as a source of peroxide of hydrogen, to the wash solution.

The appropriate controlled release means they may include confining the bleach in the compressed part or in The uncompressed part. If more than one part is present, no compressed, the bleach can be confined to the non part compressed first and / or second and / or optional.

Another mechanism to control the speed of bleach release can be to coat the bleach with a coating designed to provide controlled release. The coating can therefore, for example, comprise a water-soluble material or have sufficient thickness so that the dissolution kinetics of the thick coating provide the controlled release speed.

The coating material can be applied using various methods. Any coating material is typically present in a weight ratio between the Coating material and bleach from 1:99 to 1: 2, preferably from 1:49 to 1: 9.

The right coating materials include triglycerides (eg partially vegetable oil hydrogenated, soybean oil, cottonseed oil), monoglycerides or diglycerides, microcrystalline waxes, gelatin, Cellulose, fatty acids and any mixture thereof.

Other suitable coating materials may comprise metal sulfates, silicates and carbonates alkaline and alkaline earth, including calcium carbonate and Silicas

A preferred coating material, especially for a source of perhydrated salt bleaching inorganic comprises sodium silicate in a ratio SiO2: Na2O from 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2,4: 1, and / or sodium metasilicate, preferably applied at a level 2% to 10%, (usually 3% to 5%) of SiO 2 by weight of the inorganic perhydrated salt. Magnesium silicate is also It can include in the coating.

Any salt coating material inorganic can be combined with organic binder materials to provide salt compound coatings inorganic / organic binder. The appropriate binders include ethoxylated C 10 -C 20 alcohols containing 5-100 moles of ethylene oxide per  mole of alcohol and more preferably the alcohols C_ {15} -C_ {20} primary ethoxylates containing 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and the polyethylene glycols (PEG) with an average molecular weight of 600 to 5 x 10 6 preferably 1000 to 400,000 and with maximum 1000 to 10,000 preference are examples of these materials polymeric The copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid and maleic anhydride that constitutes at least 20 moles percent of the polymer are other examples of polymeric materials useful as agents binders These polymeric materials can be used as such or together with solvents such as water, propylene glycol and aforementioned alcohols C_ {10} -C_ {20} ethoxylates containing 5-100 moles of ethylene oxide per mole. Others Examples of binders include monoglycerol ethers and C 10 -C 20 diglycerol and also acids C 10 -C 20 fatty.

Cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, and homopolymeric or copolymeric polycarboxylic acids or their salts are other examples of binders suitable for use in the present invention

A method to apply the material of coating includes the agglomeration. The agglomeration processes Preferred include the use of any of the materials organic binders described above herein memory. Any agglomerator / mixer can be used conventional including, but not limited to, those of type tray, rotating drum and vertical mixer. Can be applied also cast compositions cast by pouring or spraying on a moving bed of agent bleaching

Other means to provide release required control include mechanical means to modify the physical characteristics of the bleach and control its solubility and release speed Appropriate protocols could include compression, mechanical injection, manual injection and adjustment of the solubility of the bleaching compound by selecting particle size of any component in the form of particles

Although the choice of particle size will depend on the composition of the particulate component and of the desire to achieve the desired controlled release kinetics, it is desirable that the particle size be greater than 500 micrometers, preferably having a particle diameter average 800 to 1200 micrometers.

Additional protocols to provide the controlled release means include the right choice of any other component of the detergent composition matrix so that when the composition is incorporated into the solution of washing, the ionic strength of the environment allows the kinetics of controlled release required.

       \ newpage
    

Metal containing bleach catalyst

The compositions described herein memory containing bleach as a detergent component may additionally contain as preferred component a metal containing bleach catalyst. Preferably the metal containing bleach catalyst is a catalyst of bleach containing transition metal, more preferably a bleach catalyst containing manganese or cobalt.

A suitable type of bleach catalyst it is a catalyst comprising a heavy metal cation of Catalytic activity of the bleach defined, such as cations of copper, iron, an auxiliary metal cation that has an activity Catalytic of the reduced or zero bleach, such as cations of zinc or aluminum, and a sequestrant that has constants of stability defined for catalytic metal cations and auxiliary, especially ethylenediaminetetraacetic acid, acid ethylenediaminetetra (methylene phosphonic) and water soluble salts thereof. Such catalysts are described in the patent. 4,430,243.

The types of bleach catalyst Preferred include the manganese-based complexes described in US 5,246,621 and US 5,244,594. Preferred examples of these catalysts include Mn IV 2 (u-O) 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 2) 4) 2, Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 - (ClO 4) 2, Mn III Mn IV 4 (uO) 1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4) 3,  and mixtures thereof. Others are described in the application EP-. 549,272. Other ligands suitable for use herein invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

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

Other type of bleach catalyst, such as the one described in US-5,114,606, is a complex of water soluble manganese (III) and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof.

US 5,114,611 describes a bleach catalyst comprising a metal complex of transition, including Mn, Co, Fe, or Cu, with a non-ligand (macro) -cyclic. These ligands have the formula:

2. 3

wherein R 1, R 2, R 3 and R4 can each be selected from H, groups alkyl and aryl substituted so that each R 1 -N = C-R 2 and R 3 -C = N-R 4 form a ring of five or six elements. Said ring may also be replaced. B is a bridge group selected from O, S. CR 5 R 6, NR 7 and C = O, wherein R 5, R 6 and R 7 can each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridacin, pyrimidine, pyrazine rings, imidazole, pyrazole and triazole. Optionally said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand. 2,2'-bispyridylamine. The catalysts of Preferred bleach include complexes of Co, Cu, Mn, Fe with bispyridylmethane and bispyridyl amine. The most catalysts preferred include Co (2,2'-bispyridylamine) Cl2, di (isothiocyanate) bispyridylamino-cobalt  (II), perchlorate of trisdipyridylamino-cobalt (II), Co (2,2-bispyridylamine) 2 O 2 ClO 4, copper bis- (2,2'-bispyridylamine) perchlorate (II), perchlorate of tris (di-2-pyridylamine) of iron (II) and mixtures thereof. Preferred examples include Mn binuclear complexes with ligands tetra-N-dentate and bi-N-toothed, including N 4 Mn III (u-O) 2 Mn IV N 4) + and [Bipi 2 Mn III (u-O) 2 Mn IV bipi 2] - (ClO 4) 3.

Although complex structures manganese bleach-catalysts have not been elucidated, it can be speculated that they comprise chelates or others hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the cation manganese. Similarly, the oxidation state of the cation Manganese during the catalytic process is not known with certainty, and it can be the state of Valencia (+ II), (+ III), (+ IV) or (+ V). Due to the possible six binding points of the cation ligand manganese, it can be reasonably speculated that they may exist multinuclear and / or "cage" type structures in the middle aqueous bleaching. Regardless of the form of the type of actually binding existing active Mn, this acts in a way apparently catalytic to provide greater ability to bleaching in persistent spots such as tea, ketchup, Coffee, wine, juice and the like.

Other bleach catalysts are described, for example, in European patent application EP-408,131 (cobalt complex catalysts), European patent application with publication No. EP-384,503 and EP-306,089 (metalloporphyrin catalysts), US -4,728,455 (manganese / multidentate ligand catalyst), US-4,711,748
and European patent application EP-224,952, (manganese absorbed in aluminosilicate catalyst), US-4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), US-4,626,373 (manganese catalyst /
ligand), US-4,119,557 (ferric complex catalyst), DE-2,054,019 (cobalt chelating catalyst), CA-866,191 (salts containing transition metal), US-4,430,243 (manganese cation chelators and non-catalytic metal cations) and US-4,728,455 (manganese gluconate catalysts).

Other preferred examples include catalysts of cobalt (III) that have the formula:

Co [(NH 3) n M 'm B' b T 't Q_q q P] Y_ {y}

where the cobalt is in the oxidation state +3; n is an integer from 0 to 5 (preferably 4 or 5; most preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably  1 or 2; most preferably 1); B 'represents a ligand bided b is an integer from 0 to 2; T 'represents a ligand tridentado; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P it is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; And it is one or more properly selected counter-anions present in a number and, where and is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a anion with charge -1), to obtain a salt with balanced charges, Preferred Y values are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof; and where also at least one of the coordination sites linked to cobalt is labile in conditions of use of the dishwasher and coordination sites remaining stabilize the cobalt in the washing conditions of the dishwasher so that the potential for cobalt reduction (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) versus a hydrogen electrode normal.

Cobalt catalysts of this type Preferred have the formula:

[Co (NH 3) n (M ') m] Y_ {y}

where n is an integer of 3 to 5 (preferably 4 or 5; most preferably 5); M 'is a labile coordination rest, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is higher that 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6; e Y is a properly selected counter-anion that is present in a number y, which is an integer from 1 to 3 (preferably from 2 to 3; most preferably 2 when Y is an anion with charge -1), for get a salt with load balanced

Cobalt catalysts of this type Preferred useful in the present invention are chloride salts of cobalt pentaamine that have the formula [Co (NH 3) 5 Cl] Y y, and especially [Co (NH 3) 5 Cl] Cl 2.

More preferred are the compositions of the present invention using bleach catalysts cobalt (III) that have the formula:

[Co (NH 3) n (M) m (B) b] T_ {y}

where the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more cobalt coordinated ligands per site; m is 0, 1 or 2 (preferably 1); B is a cobalt coordinated ligand by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more counter-anions properly selected present in a number and, being and a integer to obtain a salt with balanced load (preferably and is 1 to 3; most preferably 2 when T it is an anion with charge -1); and where also said catalyst has a basic hydrolysis rate constant of less than 0.23 M <-1> s <-1> (25 ° C).

Preferred T values are selected from group consisting of chloride, iodide, I 3 -, formate, nitrate, nitrite, sulfate, sulphite, citrate, acetate, carbonate, bromide, PF 6 -, BF 4 -, B (Ph) 4 -, phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T can be protonated if there is more than one group T anionic, p. e.g., HPO4-2, HCO3-, H_ {2} PO_ {4} -, etc. In addition, T can be selected from the group which consists of non-traditional inorganic anions such as anionic surfactants (e.g., alkylbenzene sulphonates (LAS) linear, alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and / or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).

The M remains include, but not in form limiting, for example, F <->, SO_4 <2>, NCS <->, SCN -, S 2 O 3 - 2, NH 3, PO 4 3-, and carboxylates (which are preferably mono-carboxylates, although the rest may be present more than one carboxylate if cobalt binding is performed by only one carboxylate per residue, in which case the other carboxylate in the remainder M may be protonated or in its form of Salt). Optionally, M can be protonated if there is more than one group anionic in M (e.g., HPO 4 2-, HCO 3 -), H 2 PO 4 - -, HOC (O) CH 2 C (O) O-, etc.) The M residues Preferred are C 1 -C 30 carboxylic acids substituted and unsubstituted that have the formula:

RC (O) O-

where R preferably is select from the group consisting of hydrogen and C 1 -C 30 (preferably alkyl C 1 -C 18) unsubstituted and substituted, aryl C 6 -C 30 (preferably C 6 -C 18) unsubstituted and substituted, and C3-C30 heteroaryl (preferably C 5 -C 18) unsubstituted and substituted, in where the substituents are selected from the group consisting of -NR '3, -NR' 4 +, -C (O) OR ', -OR', -C (O) NR '2, where R' is selected from the group consisting of hydrogen and C 1 -C 6 moieties. Accordingly, said substituted R includes the moieties - (CH 2) n OH and - (CH 2) n NR '4 +, where n is a number integer from 1 to 16, preferably from 2 to 10 and most preferably from 2 to 5.

The most preferred M are carboxylic acids that they have the previous formula, where R is selected from the group that consists of hydrogen, methyl, ethyl, propyl, alkyl C4 -C12 linear or branched and benzyl. He Most preferred R is methyl. The M carboxylic acid moieties Preferred include those of formic, benzoic, octanoic acids, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethyl-hexanoic, naphthenoic, oleic, palmitic, triflic, tartaric, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

Residues B include carbonate, dicarboxylates and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid and alpha and beta amino acids (e.g. eg, glycine, alanine, beta-alanine, phenylalanine)

The cobalt bleach catalysts useful in the present invention are known and are described, for example, together with their basic hydrolysis rates in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg Bioinorg Mech ., (1983), 2, pages 1-94. For example, Table 1 on page 17 provides basic hydrolysis rates (referred to therein as k_ {OH)) for cobalt pentaamine catalysts complexed with oxalate (k_ {OH} = 2.5 x 10 ^ {-4 M <-1> s <-1> (25 [deg.] C.)), NCS <-> (k_H = 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 in the present invention are cobalt pentaamine acetate salts having the formula [Co (NH 3) 5 OAc] T y, wherein OAc represents an acetate moiety and especially cobalt pentaamine chloride-acetate, [Co (NH 3) 5 OAc] Cl 2 as well as [Co (NH 3) 5 OAc] (OAc) 2 ; [Co (NH 3) 5 OAc] (PF 6) 2; [Co (NH 3) 5 OAc] (SO 4); [Co (NH 3) 5 OAc] (BF 4) 2 and [Co (NH 3) 5 OAc] (NO 3) 2 ( herein "PAC").

These cobalt catalysts are readily prepared by known methods such as those described, for example, in the previous Tobe article and references cited therein, in US 4,810,410, granted to Diakun et al. on March 7, 1989, J. Chem. Ed . (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, WL Jolly (Prentice-Hall; 1970), p. 461-3; Inorg Chem ., 18 , 1497-1502 (1979); Inorg Chem ., 21 , 2881-2885 (1982); Inorg Chem ., 18 , 2023-2025 (1979); Inorg Synthesis, 173-176 (1960); and Journal of Physical Chemistry , 56 , 22-25 (1952); as well as the illustrative examples provided below.

Cobalt catalysts suitable for your incorporation into the detergent tablets of the present invention can be produced according to the synthetic routes described in US 5,559,261, US 5,581,005 and 5,597,936.

These catalysts can be processed together with adjuvant materials to reduce the impact of color if desired for the aesthetics of the product, or be included in Enzyme-containing particles as illustrated below, or the compositions can be manufactured to contain "specks" of catalyst.

Organic polymeric compound

Organic polymeric compounds can be added as preferred components of detergent tablets according to the invention. The expression polymeric compound organic basically means any polymeric compound organic that is usually found in the compositions detergents that have dispersant properties, anti-redeposition, to release dirt or other detergency properties.

The organic polymeric compound typically is incorporated into the detergent composition of the invention at a level from 0.1% to 30%, preferably from 0.5% to 15%, more preferably from 1% to 10%, by weight of the composition.

Examples of organic polymeric compounds include homopolymeric organic polycarboxylic acids or water soluble copolymers, modified polycarboxylates or its salts wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two atoms of carbon. Polymers of the latter type are described in GB-A-1,596,756. Examples of these salts are molecular weight polyacrylates 2000-10000 and its copolymers with other units suitable monomers including acrylic, fumaric acids, maleic, itaconic, aconitic, mesaconic, citraconic and methylene modified malonic or its salts, maleic anhydride, acrylamide, alkylene, vinyl methyl ether, styrene and any mixture of same. Acrylic acid and anhydride copolymers are preferred maleic having a molecular weight of 20,000 to 100,000.

Polymers that contain acrylic acid preferred commercial with a molecular weight of less than 15,000 include those distributed with the registered trademark Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH and those distributed with The trademark Acusol 45N, 480N, 460N by Rohm and Haas.

Copolymers that contain acrylic acid Preferred include those containing as units monomeric: a) from 90% to 10%, preferably from 80% to 20%, by weight of acrylic acid or its salts and b) from 10% to 90%, preferably of 20% to 80%, by weight of a substituted acrylic monomer or its salts that have the general formula - [CR2 -CR_ {1} (CO-O-R3)] -  wherein at least one of the substituents R 1, R 2 or R 3, preferably R 1 or R 2, is an alkyl group or hydroxy alkyl of 1 to 4 carbons, R 1 or R 2 may be a hydrogen and R 3 may be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer where R1 is methyl, R2 is hydrogen (i.e. a monomer of methacrylic acid). The most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acid acrylic and 40% to 20% by weight methacrylic acid.

The polyamine and polyamine compounds modified are useful in the present invention, including those aspartic acid derivatives such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Other optional polymers can be polyvinyl alcohols and acetates both modified and unmodified, cellulose and modified celluloses, polyoxyethylenes, polyoxypropylenes and copolymers thereof, both modified as unmodified, ethylene terephthalate esters or propylene glycol or mixtures thereof with units polyoxyalkylene.

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

Agents to release dirt

Polymeric dirt release agents suitable include those agents to release dirt that they have: (a) one or more non-ionic hydrophilic components that basically they consist of (i) polyoxyethylene segments with a degree of polymerization of at least 2, (ii) segments of oxypropylene or polyoxypropylene with a polymerization degree of 2 to 10, wherein said hydrophilic segment does not cover any unit of Oxypropylene unless attached to adjacent moieties in each of the ends by ether type links or (iii) a mixture of oxyalkylene units comprising oxyethylene and 1 to 30 oxypropylene units, preferably comprising said at least 25% hydrophilic segments of oxyethylene units and more preferably, especially for those components that have from 20 to 30 units of oxypropylene, at least 50% of units of oxyethylene; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, in which if said hydrophobic components also comprise terephthalate of oxyethylene, the ratio between oxyethylene terephthalate units and C3 oxyalkylene terephthalate units is 2: 1 or less,  (ii) C4-C6 alkylene segments or of C4-C6 oxyalkylene or mixtures of the same, (iii) polyvinyl ester segments, preferably poly (vinyl acetate) that have a degree of polymerization  of at least 2, or (iv) alkyl substituents C 1 -C 4 ether or hydroxyalkyl C 4 ether or mixtures thereof, wherein said substituents are present in the form of alkyl derivatives C 1 -C 4 cellulose ether or hydroxyalkyl C4 cellulose ether or mixtures thereof or a combination of (a) and (b).

Typically, polyoxyethylene segments of (a) (i) will have a degree of polymerization of 200, although the degree can be higher, preferably from 3 to 150, more preferably from 6 to 100. The hydrophobic segments of Suitable C4-C6 oxyalkylene include, although not limited to, terminal protections of agents to release polymeric dirt like MO 3 S (CH 2) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as described in US-4,721,580, issued to Gosselink on January 26, 1988.

Polymeric dirt release agents useful in the present invention also include derivatives cellulosics such as hydroxy ether cellulosic polymers, blocks copolymers of ethylene terephthalate or propylene terephthalate with poly (ethylene oxide) or polypropylene terephthalate oxide, and Similar. These agents are marketed and include cellulose hydroxyethers such as METHOCEL (Dow). The agents to release cellulosic dirt from use herein invention also include those agents selected from the group consisting of C 1 -C 4 alkylcellulose C4 hydroxyalkylcellulose; see patent US 4,000,093, granted to Nicol et al. on 28 of December 1976

Agents to release dirt characterized by hydrophobic segments of polyvinyl ester include polyvinyl ester graft copolymers, e.g. eg C 1 -C 6 vinyl ester, preferably poly (vinyl acetate) grafted onto main chains of poly (alkylene oxide), such as main chains of poly (ethylene oxide). See application EP-0 219 048, published on April 22, 1987 by Kud et al.

Another agent to release adequate dirt is a copolymer that has random blocks of terephthalate of ethylene and poly (ethylene oxide) terephthalate (PEO). The weight molecular of this agent to release polymeric dirt is in the range of 25,000 to 55,000. Watch US 3,959,230, granted to Hays on May 25, 1976, and US Patent 3,893,929 issued to Basadur on July 8, 1975.

Another agent to release polymer dirt suitable is a polyester with repetitive terephthalate units of ethylene containing 10-15% by weight units of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol with an average molecular weight of 300-5,000.

Another agent to release polymer dirt suitable is a sulfonated product of an ester oligomer practically linear comprising an ester main chain oligomeric repetitive units of terephthaloyl and oxyalkyleneoxy and terminal moieties covalently linked to the chain principal. These agents to release dirt are described in detail in US-4,968,451, granted to J.J. Scheibel and E.P. Gosselink on November 6, 1990. Other agents for release the appropriate polymeric dirt include polyesters of US-4,711,730 patent terephthalate, granted to Gosselink et al. on December 8, 1987, the esters anionic oligomers with patent protected ends US-4,721,580, issued to Gosselink on January 26 of 1998, and the oligomeric polyester block compounds of the US Patent 4,702,857, issued to Gosselink on 27 October 1987. Other agents to release dirt Polymers also include agents to release dirt of US-4,877,896, granted to Maldonado and cabbage. on October 31, 1989, which describes esters of anionic terephthalate with protected ends, especially with sulfoarolyl

Another agent to release dirt is a oligomer with repetitive terephthaloyl units, units of sulfoisoterephthaloyl, oxyenyloxy units and oxy-1,2-propylene. The units repetitive form the oligomer's main chain and preferably they are finished with modified protected ends of isethionate. An agent to release dirt particularly Preferred of this type comprises a sulfoisophthaloyl unit, terephthaloyl units, oxyethylene oxy units and units of oxy-1,2-propylene in a ratio of 1.7 to 1.8 and two units with terminal protection 2- (2-hydroxyethoxy) -ethanesulfonate of sodium.

Heavy metal ion sequestrant

The detergent tablet of the invention preferably contains as an optional component a sequestrant of heavy metal ions. Heavy metal ion sequestrant means herein which components act kidnapping (chelating) heavy metal ions. These components they may also have the ability to chelate calcium and magnesium but preferably show selectivity to bond metal ions heavy such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and with maximum preference from 0.5% to 5%, by weight of the composition.

Heavy metal ion sequestrants, which they are acidic and have for example acid functionalities phosphonic or carboxylic acid, may be present in its form acidic or as a complex / salt with a suitable counterpart such as an alkali or an alkali metal ion, ammonium ion, or ammonium substituted or any mixture thereof. Preferably the salts / complexes are soluble in water. The molar relationship between said counter-cation and the heavy metal ion sequestrant is preferably at least 1: 1.

Heavy metal ion sequestrants suitable for use in the present invention include phosphonates organic such as aminoalkylene poly (alkylene phosphonates), ethane 1-hydroxy alkali metal diphosphonates and nitrile-trimethylene phosphonates. Between The above types are preferred diethylenetriamine penta (methylene phosphonate), ethylene diamino tri (methylene phosphonate), hexamethylene diamino tetra (methylene phosphonate) and hydroxyethyl 1,1 diphosphonate

Other heavy metal ion sequestrants suitable for use in the present invention include acid nitrilotriacetic and polyaminocarboxylic acids such as ethylenediamine tetraacetic acid, the acid ethylenetriamine pentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, acid 2-hydroxypropylene diamine disuccinic or any salt thereof.

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

Crystal growth inhibitor component

The detergent tablet preferably contains a crystalline growth inhibitor component, preferably an organodiphosphonic acid component, preferably incorporated at a level of 0.01% to 5%, more preferably from 0.1% to 2%, by weight of the compositions.

The term "organodiphosphonic acid" means herein an organodiphosphonic acid that does not It contains nitrogen as part of its chemical structure. This definition therefore excludes organoaminophosphonates that, without However, they can be included in the compositions of the invention as heavy metal ion sequestrant components.

The organodiphosphonic acid is preferably a C 1 -C 4 diphosphonic acid, plus preferably a C2 diphosphonic acid, such as acid ethylenediphosphonic acid, or more preferably ethane acid 1-hydroxy-1,1-diphosphonic (HEDP) and may be present partially or totally ionized, especially in the form of salt or complex.

Water soluble sulfate salt

The detergent tablet optionally contains a water soluble sulfate salt. If present, sulfate salt Water soluble is at a level of 0.1% to 40%, more preferably from 1% to 30% and most preferably from 5% to 25%, by weight of the composition.

The water soluble sulfate salt can be virtually any sulfate salt with any countercation. The Preferred salts are selected from alkali metal sulfates and alkaline earth metals, especially sodium sulfate.

Alkali metal silicate

According to an embodiment of the present invention, an alkali metal silicate is a preferred component of the detergent tablet In other embodiments of the present invention the presence of an alkali metal silicate is optional. A preferred alkali metal silicate is silicate sodium having a SiO2: Na2O ratio of 1.8 to 3.0, preferably from 1.8 to 2.4 and most preferably 2.0. He sodium silicate is preferably present at a level of less 20%, preferably 1% to 15% and most preferably 3% at 12% by weight of SiO2. The alkali metal silicate can be in the form of anhydrous salt or hydrated salt.

A silicate of alkali metal as a component of an alkalinity system.

The alkalinity system too preferably contains sodium metasilicate, present at a level of at least 0.4% SiO2 by weight. Sodium metasilicate has a nominal SiO2 ratio: Na2O of 1.0. The relationship of weight between said sodium silicate and said sodium metasilicate, measured as SiO2, it is preferably 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1 and most preferably from 10: 1 to 5: 2.

Colorant

The term "dye", herein memory means any substance that absorbs lengths of specific wave in the visible light spectrum. These dyes when they are added to a detergent composition they have the effect of changing the visible color and, consequently, the appearance of the detergent composition The dyes can be, for example, dyes or pigments Preferably the dyes are stable in the composition to which they are incorporated. Therefore, in a high pH composition, the dye is preferably stable in alkaline medium and in a pH composition under the dye is preferably stable in acidic medium.

The compressed part and / or the uncompressed part may contain a dye, a mixture of dyes, particles colored or a mixture of colored particles so that the compressed part and the uncompressed part look different visual. Preferably one of the compressed or uncompressed parts It comprises a dye.

When the uncompressed part comprises two or more compositions of active detergent components, preferably at least one of the first, second compositions and / or later comprises a dye. When the first, the second and / or subsequent compositions comprise a dye, it is preferred that the dyes have a different visual appearance.

When the coating layer is present, This preferably comprises a dye. When the part compressed and the coating layer comprise a dye, it prefers dyes to provide a visual effect different.

Examples of suitable dyes include reactive dyes, direct dyes and azo dyes. The Preferred dyes include phthalocyanine dyes, dyes anthraquinone, quinoline dyes, monoazo, disazo and poliazo. The most preferred dyes include anthraquinone, quinoline and monoazo. Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name), all of them marketed by Clariant UK, HEXACOLQUINOLINE YELLOW (name commercial) and HEXACOL BRILLIANT BLUE (trade name), both marketed by Pointings, RU, ULTRA MARINE BLUE (name commercial), marketed by Holliday, or LEVAFIX TURQUOISE BLUE EBA (trade name), marketed by Bayer, USA.

The dye can be incorporated into the parts compressed and / or uncompressed by any suitable method. Suitable methods include mixing all components. active or selected detergents with a dye in a drum or spray all detergent components active or selected with the dye in a drum Rotary

The dye when present as component of the compressed part, is present at a level of 0.001% to 1.5%, preferably 0.01% to 1.0% and with maximum Preference from 0.1% to 0.3%. When present as a component of the uncompressed part, the dye is generally present at a 0.001% to 0.1% level, more preferably from 0.005% to 0.05% and with highest preference of 0.007% to 0.02%. When present as component of the coating layer, the dye is present at a level of 0.01% to 0.5%, more preferably 0.02% to 0.1% and with highest preference of 0.03% to 0.06%.

Corrosion inhibitor compound

The detergent tablets of the present invention suitable for use in washing methods in dishwasher may contain corrosion inhibitors preferably selected from silver coating agents organic, in particular paraffin, corrosion inhibitors that contain nitrogen and compounds of Mn (II), in particular Mn (II) salts of organic ligands.

Organic silver coating agents se described in PCT WO94 / 16047 and in the codependent application EP-A-690122. The compounds corrosion inhibitors containing nitrogen are described in the codependent request EP-A-634,478. The compounds of Mn (II) for use in corrosion inhibition is described in the codependent application EP-A-672 749.

The organic silver coating agent it can be incorporated at a level of 0.05% to 10%, preferably of 0.1% to 5%, by weight of the total composition.

The functional role of the coating agent of silver is to form "during use" a coating layer protector on any component of silver tableware included in the wash load to which the Compositions of the invention. Therefore, the agent of Silver coating should have a high binding affinity to solid silver surfaces, particularly when present as a component of the aqueous wash and bleach solution with which the solid silver surfaces will be treated.

Organic Silver Coating Agents Suitable in the present invention include fatty acid esters of monohydroxylated or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.

The fatty acid part of the fatty ester can obtained from monocarboxylic acids or polycarboxylics having 1 to 40 atoms of carbon in the hydrocarbon chain. Suitable examples of acids monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acid  acetic acid, propionic acid, butyric acid, isobutyric acid, acid valeric, lactic acid, glycolic acid and acid β, β'-dihydroxyisobutyric. Examples of Suitable polycarboxylic acids include: acid n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

The fatty alcohol radical in the fatty ester it can be represented by monohydric alcohols or polyhydroxylates having 1 to 40 carbon atoms in the hydrocarbon chain Examples of suitable fatty alcohols include behenyl, arachidyl, cocoyl, oleyl alcohols and lauryl, ethylene glycol, glycerol, ethanol, isopropanol, alcohol vinyl, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid group and / or fatty alcohol of the fatty ester adjuvant material has 1 to 24 carbon atoms in the alkyl chain.

The preferred fatty acid esters in the Present invention are esters of ethylene glycol, glycerol and sorbitan where the fatty acid part of the ester normally comprises a selected type of behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

Glycerol esters are also very preferred. These are the monoesters, diesters or tri esters of Glycerol and fatty acids as defined above.

Specific examples of fatty alcohol esters of use in the present invention include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate and tallow propionate. Fatty acid esters useful in the present invention include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, monostearate of ethylene glycol, sorbitan esters. Sorbitan esters Suitable include sorbitan monostearate, sorbitan palmitate,  sorbitan monolaurate, sorbitan monomiristate, monobehenate sorbitan, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, dioleate sorbitan and also mono-esters and mixed di-esters of seboalkyl sorbitan

Glycerol monostearate, monooleate from glycerol, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are preferred glycerol esters in The present invention.

Organic Silver Coating Agents include triglycerides, monoglycerides or diglycerides and derivatives totally or partially hydrogenated thereof and any mixture thereof. Suitable sources of fatty acid esters They include vegetable oils and fish oils and animal fats. Suitable vegetable oils include soybean oil, the cotton oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grape oil, palm oil and oil corn.

Waxes, including microcrystalline waxes, they are suitable organic silver coating agents in the present invention Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise from 12 to 70 carbon atoms Type oil waxes are preferred paraffin and microcrystalline that are composed of compounds long chain saturated hydrocarbons.

Alginates and gelatin are agents of Organic silver coating in the present invention.

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

Other silver coating agents Organic include certain polymeric materials.

Polyvinylpyrrolidones with a molecular weight average of 12,000 to 700,000, polyethylene glycols (PEG) with a average molecular weight of 600 to 10,000, the N-oxide polymers of polyamine, the copolymers of N-vinyl pyrrolidone and N-vinylimidazole, and cellulose derivatives such such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, they are Examples of these polymeric materials.

Certain perfume materials, especially those that have a high surface persistence metallic, they are also useful as silver coating agents organic in the present invention.

Polymeric dirt release agents can also be used as silver coating agents organic

An organic silver coating agent preferred is a paraffin oil, typically a hydrocarbon predominantly branched aliphatic that has a number of atoms carbon in the range of 20 to 50; where the oils of Preferred paraffin are selected from types C_ {25-45} predominantly branched with a ratio between cyclic and non-cyclic hydrocarbons from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A paraffin oil that meets these characteristics and that has a relationship between hydrocarbons 32:68 cyclic and non-cyclic is marketed by Wintershall, Salzbergen, Germany, with the registered name WINOG 70.

Corrosion inhibitor compounds containing nitrogen

The corrosion inhibitor compounds that Suitable nitrogen-containing include imidazole and derivatives of same as benzimidazole, 2-heptadecyl imidazole and those derived from imidazole described in the Czech patent 139,279 and in GB-A-1,137,741, which also describes a method for the preparation of compounds of imidazole

Also suitable as inhibitor compounds of corrosion containing nitrogen are pyrazole compounds and its derivatives, especially those where pyrazole is substituted in any of positions 1, 3, 4 or 5 by substituents R 1, R 3, R 4 and R 5 where R 1 is any of H, CH 2 OH, CONH 3, or COCH 3, R 3 and R 5 are either alkyl or hydroxyl C 1 -C 20, and R 4 is any of H, NH2 or NO2.

Other corrosion inhibitor compounds that Suitable nitrogen containing include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, steroyl stearamide, cyanuric acid, aminotriazole, aminotetrazol e indazole

Also suitable are compounds that contain nitrogen such as amines, especially distearylamine  and ammonium compounds such as ammonium chloride, bromide ammonium, ammonium sulfate or diammonium hydrogen citrate.

Corrosion inhibitor compounds of Mn (II)

Detergent tablets may contain a Mn (II) corrosion inhibitor compound. The compound of Mn (II) is preferably incorporated at a level of 0.005% at 5% by weight, more preferably from 0.01% to 1% and with maximum preference of 0.02% to 0.4% by weight of the compositions. Preferably, the Mn (II) compound is incorporated into a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably 1 ppm to 20 ppm, by weight of Mn (II) ions in any bleaching solution.

The compound of Mn (II) can be a salt inorganic in anhydrous form or in any hydrated form. The Suitable salts include manganese sulfate, carbonate manganese, manganese phosphate, manganese nitrate, acetate manganese and manganese chloride. The compound of Mn (II) it can be a salt or a complex of an organic fatty acid such as manganese acetate or manganese stearate.

The compound of Mn (II) can be a salt or a complex of an organic ligand. In a preferred aspect, the Organic ligand is a heavy metal ion sequestrant. In Another preferred aspect, the organic ligand is an inhibitor of crystal growth

Other corrosion inhibitor compounds

Other corrosion inhibitor compounds Additional suitable include mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionephthol, thionalide and thioantranol. Too C 10 -C 20 fatty acids are suitable saturated or unsaturated, or its salts, especially triestearate of aluminum. Fatty hydroxy acids C 12 -C 20, or its salts, are also adequate. Phosphonated octa-decans and others Antioxidants such as butylhydroxytoluene (BHT) are also adequate.

The copolymers of butadiene and maleic acid, especially those supplied with reference number 07787 by PolySciences Inc, are especially useful as compounds corrosion inhibitors

Hydrocarbon oils

Another preferred active detergent component for use in the present invention is a hydrocarbon oil, so typical a predominantly long chain aliphatic hydrocarbon which has a number of carbon atoms in the range of 20 to fifty; Preferred hydrocarbons are saturated and / or branched; preferred hydrocarbon oil selected from types C_ {25-45} predominantly branched with a ratio between cyclic and non-cyclic hydrocarbons from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin A A paraffin oil that meets the characteristics described above and that has a relationship between 32:68 cyclic and non-cyclic hydrocarbons is marketed by Wintershall, Salzbergen, Germany, with the registered name WINOG 70.

Water soluble bismuth compound

The detergent tablets of the present invention suitable for use in washing methods in dishwashers may contain a soluble bismuth compound in water, preferably present in an amount of 0.005% to 20%, more preferably from 0.01% to 5% and most preferably from 0.1% to 1%, by weight of the compositions.

The water soluble bismuth compound can be virtually any salt or bismuth complex with virtually any inorganic or organic contraanion. The Preferred inorganic bismuth salts are selected from trihalides of bismuth, bismuth nitrate and bismuth phosphate. Acetate and Bismuth citrate are preferred salts with a counter-anion organic.

Enzyme stabilizer system

Compositions containing enzymes Preferred in the present invention may comprise from 0.001% to 10%, preferably 0.005% to 8% and most preferably 0.01% to 6%, by weight of an enzyme stabilizer system. He enzyme stabilization system can be any system stabilizer that is compatible with the detersive enzyme. Sayings enzyme stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorinated bleach removers and mixtures of the same. Such stabilizer systems may comprise also reversible enzyme inhibitors, such as inhibitors of reversible proteases.

Dispersing compound of calcareous soap

The detergent component compositions they may contain a dispersing compound of calcareous soap, preferably present at a level of 0.1% to 40% by weight, more preferably from 1% to 20% by weight and most preferably from 2% to 10% by weight of the compositions.

A limestone soap dispersant is a material which prevents the precipitation of alkali metal, ammonium salts or fatty acid amine by calcium or magnesium ions. Preferred limestone soap dispersant compounds are described in PCT WO93 / 08877.

Soap suppressor system

The detergent tablets of the present invention, when formulated for use in compositions of washing in washing machine, preferably comprise a suppressor system of the soaps present at a level of 0.01% to 15%, preferably from 0.05% to 10% and most preferably from 0.1% to 5%, by weight of the composition.

Soap suppressor systems suitable for use in the present invention may comprise virtually any known antifoam compound, including, for example, silicone antifoam compounds or 2-alkyl and alkanol defoamer compounds. Suppressor systems of soaps and compounds Preferred defoamers are described in PCT WO93 / 08876 and in EP-A-705 324.

Polymeric agents transfer inhibitors dyes

The detergent tablets of the present invention may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5%, by weight of polymeric agents that inhibit dye transfer

Polymeric agents inhibiting the dye transfer are preferably selected from polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

Optical brightener

Detergent tablets suitable for use in laundry methods such as those described herein memory also optionally contain 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful in The present invention includes those having the formula structural:

24

where R_ {1} is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is select from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; and M is a salt forming cation such like sodium or potassium.

When in the previous formula R_ {1} is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', - bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triacin-2-yl) amino] -2,2'-stilbendisulfonic acid  and the disodium salt. This particular polishing species is marketed under the brand name Tinopal UNPA-GX by Ciba-Geigy Corporation. Tinopal UNPA-GX is the hydrophilic optical brightener preferred useful in detergent compositions herein invention. When in the above formula R 1 is aniline, R 2 is N-2-hydroxyethyl-N-2-methylamino  and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triacin-2-yl) amino] 2,2'-stilbendisulfonic acid,  disodium salt This particular brightener is marketed under the name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the previous formula R_ {1} is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6-morfilino-s-triacin-2-yl) amino] 2,2'-stilbendisulfonic acid, sodium salt This particular type of brightener is marketed. with the trade name Tinopal AMS-GX by Ciba Geigy Corporation

Clay softener system

Detergent tablets suitable for use in laundry methods may contain a softener system of clay comprising a clay mineral compound and optionally a clay flocculating agent.

The mineral clay compound is preferably a smectite clay compound. Clays smectite type are described in the patents US 3,862,058, US 3,948,790, US 3,954,632 and US 4,062,647. In the European patents EP-A-299,575 and EP-A-313,146 on behalf of Procter and Gamble Company described clay flocculating agents suitable organic polymers.

Softening agents of cationic tissues

Softening agents can also be incorporated from cationic tissues to compositions according to the present invention that are suitable for use in methods of laundry Softening agents of cationic tissues Suitable include tertiary amines or long double chain amides not soluble in water as described in the patents GB-A-1 514 276 and EP-B-0 011 340.

The cationic tissue softening agents are typically incorporate at total levels of 0.5% to 15% by weight, normally from 1% to 5% by weight.

Other optional ingredients

Other optional ingredients suitable for your Inclusion in the compositions of the invention include perfumes and loading salts, with sodium sulfate being a loading salt preferred.

pH of the compositions

The detergent tablets of the present invention preferably are not formulated to have a pH unduly high, preferably so that they have a measured pH as a 1% solution in distilled water from 8.0 to 12.5, plus preferably from 9.0 to 11.8 and most preferably from 9.5 to 11.5

In another aspect of the present invention the compressed and uncompressed parts are formulated to deliver different pHs.

       \ newpage
    

Dishwasher washing method

Any suitable method is contemplated for Machine wash or cleaning stained tableware. A Preferred method for dishwashing comprises the treatment of selected stained earthenware items, glassware, silverware, metalware, cutlery and mixtures thereof with an aqueous liquid where it has dissolved or dispensed an effective amount of a detergent tablet according to the invention. For an effective amount of the pill Detergent is understood from 8 g to 60 g of dissolved product or dispersed in a wash solution with a volume of 3 to 10 liters, which are the typical product dosages and volumes of wash solution commonly used in conventional dishwashing methods Preferably detergent tablets have 15 g to 40 g in weight, more preferably from 20 g to 35 g by weight.

       \ vskip1.000000 \ baselineskip
    

Laundry method

The washing methods in the washing machine of the present invention typically comprise treating dirty clothes with an aqueous wash solution in a clothes washer that has dissolved or dispensed therein an effective amount of a composition of detergent tablet for washing in washing machine clothes according to the invention. An effective amount of detergent tablet composition means from 40 g to 300 g of product dissolved or dispersed in a wash solution with a volume from 5 to 65 liters, such as product doses and typical wash solution volumes commonly used in Conventional washing methods for clothes washer.

In an aspect of preferred use in the method of Washing a dispensing device is used. The device Dispenser is loaded with detergent product and used to Introduce the product directly into the drum of the washing machine before the wash cycle begins. Your capacity should be such that it can contain enough detergent product like the one It is normally used in the washing method.

Once the clothes washer has been loaded with clothes, the dispensing device that contains the product Detergent is placed inside the drum. At the beginning of the cycle of Washing of the clothes washer introduces water into the drum and the Drum rotates periodically. The design of the dispensing device It should be in a way that allows product confinement dry detergent but then allow the release of this product during the wash cycle in response to your custom agitation that the drum rotates and also as a result of its contact with the wash water

To allow product release detergent during washing, the device may have a series of openings through which the product can pass. From alternatively, the device may be made of a material that is liquid permeable but impervious to solid product and that allows the release of the dissolved product. Preferably, the detergent product will be released quickly at the beginning of the wash cycle, thus providing high concentrations transient product premises in the washing machine drum in this washing cycle stage

Preferred dispensing devices are reusable and are designed so that the integrity of the container both in the dry state and during the cycle washing

Alternatively, the dispensing device It can be a flexible container such as a bag or sachet. The bag can have a fibrous structure coated with a material waterproof protector to preserve the contents, such as It is described in EP-0018678. Alternatively it can be formed by an insoluble synthetic polymeric material in water provided with an edge or seal seal designed to break into an aqueous medium, as described in the applications EP- 0011500, EP-0011501, EP-0011502 and EP-0011968. A suitable form of breakable closure Water comprises a water soluble adhesive disposed and sealed  along an edge of a bag formed by a film water impermeable polymer such as polyethylene or Polypropylene.

       \ vskip1.000000 \ baselineskip
    

Examples Abbreviations used in the Examples

In detergent compositions, the abbreviated identifications of the components have the following meanings:

STPP

: Sodium Tripolyphosphate

Citrate

: Trisodium citrate dihydrate

Baking soda

: Sodium hydrogen carbonate

Citric acid

: Anhydrous citric acid

Carbonate

: Anhydrous sodium carbonate

Silicate

: Amorphous sodium silicate (ratio SiO2: Na2O = 1.6-3.2)

Metasilicate

: Sodium Metasilicate (SiO2 ratio: Na2O = 1.0)

PB1

: Anhydrous sodium perborate monohydrate

PB4

: Sodium perborate tetrahydrate of formula nominal NaBO_2 .3H2 {2} O.H2 {O2}

TAED

: Tetraacetyl ethylenediamine

HEDP

: Acid ethane-1-hydroxy-1,1-diphosphonic

DETPMP

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

PAAC

: Cobalt Pentaaminoacetate Salt (III)

Paraffin

: Paraffin oil marketed under the name Winog 70 by Wintershall.

Protease

: Proteolytic Enzyme

Amylase

: Amylolytic enzyme.

BTA

: Benzotriazole

PA30

: Polyacrylic acid of average molecular weight of approximately 4,500

pH

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

       \ vskip1.000000 \ baselineskip
    

Example 1

A multilayer detergent tablet according to the present invention can be prepared as follows: A detergent composition of Example 2, formulation A, is prepared and passed to a conventional rotary press. The press includes a punch shaped so that an indentation is formed on one of the surfaces of the tablet. A gel matrix formulation is then prepared as described in Example 2, formulation A. The appropriate amount of non-aqueous solvent is introduced into a mixer and shear is applied to the solvent at a moderate speed (2,500-5,000 rpm). A suitable amount of gelling agent is gradually added to the solvent under shear conditions until the mixture is homogeneous. The shear rate of the mixture is gradually increased to a high shear condition of about 10,000 rpm. The temperature of the mixture is increased to a temperature of 48 ° C to 55 ° C. The shearing is then interrupted and the mixture is allowed to cool to a temperature of 30 ° C to 32 ° C. Using the low shear mixer, the remaining ingredients in the form of solids are added to the mixture. The final mixture is then introduced into the indentation of the compressed tablet body and allowed to stand until the gel has hardened or no longer
It is fluid.

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

(Table goes to page next)

       \ newpage
    

Example 2

Detergent tablets according to the present Invention can be formulated as follows:

25

27

The levels are expressed as% by weight of the cap.

Example 3

The following tablet compositions of bilayer detergent M and N were prepared in accordance with the present invention. A first layer is prepared by compressing a composition particulate detergent in a tablet press conventional suitable for preparing detergent tablets. The second layer is prepared by pouring a detergent composition granulated on top of the first compressed and compressed layer of new. The first and second layers can be exchanged. The levels are expressed as% by weight of the layer.

28

Claims (2)

1. A washing detergent in the form of a multilayer tablet having a compressed part with a density from 1.3 g / cm 3 to 1.9 g / cm 3, wherein each layer of the tablet comprises a detergent composition, wherein at least one detergent composition is compressed and dissolved in a dishwasher in less than 3 minutes (using a Bosch dishwasher according to DIN 44990; normal program at 65 ° C; water hardness of 18ºH), and where the tablet comprises a non-detergent layer tablet comprising detergent components that are negatively affected by compression pressure and selected of enzyme, corrosion inhibitor and perfume. 2. A washing detergent according to the claim 1, wherein at least one detergent composition is Dissolve in a dishwasher in less than 2 minutes.