ES2280302T3 - DETERGENT PAD. - Google Patents

Abstract

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

Description

Detergent tablet

Technical field

The present invention provides a pill of detergent comprising a compressed part and a part not uncompressed encapsulant.

Background of the invention

Detergent compositions in the form of Pills 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 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 the components of the detergent composition to obtain a pill. However the applicant has discovered that some components of the composition detergent are negatively affected by the pressure of compression applied to form the pads. Previously these components could not be included in a composition of detergent tablet without loss of performance. In some cases the components even suffer a destabilization or inactivation as a result of the compression.

In addition, when compressing the components of the detergent composition these are very close to each other. How consequence of the close proximity of the components, some components can react with each other, being unstable, Inactive or exhausted. A solution to this problem, depending on the state of the technique, it has been to separate the components of the composition detergent that can react with each other when the detergent composition to form the tablet. This separation of the components have been achieved, for example, by 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. The layers of the tablet that are subjected to more than one compression stage suffer a total compression pressure cumulative and potentially superior. It is known that an increase in Press compression pressure reduces dissolution speed of the tablet making this multiple layer may not dissolve satisfactorily during use.

Other methods for performing the separation of detergent components. For example in EP-A 0.224.135 describes a laundry detergent of dishes in a form comprising a water-soluble melt temperate in which a cold water soluble tablet is compressed. The document describes a detergent composition consisting of two part, the first part dissolves in the pre-cleared and the second part dissolves in the main dishwasher wash.

In EP-B-0.055.100 describes a block for the toilet that is formed by combining a shaped body of Slow dissolution and a pill. The toilet block is designed to be placed in a toilet cistern and it dissolves over several days, preferably over weeks As a means to control the dissolution of the block to the toilet, the document describes the mixture of one or more agents solubility regulators. Examples of these regulatory agents of the solubility are paradichlorobenzene, waxes, fatty acids of long chain, alcohols and esters thereof and alkylamides fat The detergent tablets used in washing machines or dishwashers should dissolve practically during a cycle of clothes washer or dishwasher, that is within 30 to 120 minutes

The applicant has discovered that by providing a detergent tablet comprising a compressed part and a non-encapsulating non-compressed part is possible to incorporate into a detergent tablet detergent components formerly considered unacceptable for detergent tablets. In addition, components of the potentially reactive detergent composition.

Another advantage of using a pill of detergent as described herein is an improvement of performance achieved by being able to prepare the detergent tablet so that, if necessary, the compressed part and the part not Compressed have different dissolution rate. This advantage performance is achieved by selectively providing the washing solution active detergent components in different moments

Summary of the invention

According to the present invention a detergent tablet to use in a clothes washer or a dishwasher, the tablet comprising an enzyme and:

(to)

a compressed part comprising an active detergent component; Y

(b)

a uncompressed non-encapsulating part comprising a component active detergent; Y

(C)

a coating layer on the non-encapsulating non-compressed part, wherein the non-encapsulating non-compressed part is fixed or subject to the compressed part

In addition a process is also provided for prepare the detergent tablet described herein memory.

Detailed description of the invention

Therefore, in accordance with the present invention it has been discovered that the active detergent components of a detergent tablet that was previously negative affected by the compression pressure used to form the tablet can now be included in a detergent tablet. Examples of these components include bleaching agents and Enzymes In addition, according to the present invention, it has been discovered that the active detergent components of a tablet of detergent can be separated from each other by having one or more compatible components contained in a compressed part and one or more compatible components contained in an uncompressed part of The pill. Examples of components that can interact between yes and therefore may need to be separated include agents bleaches, bleach activators or catalysts and enzymes; bleaching agents and bleach catalysts or activators; bleaching agents and surfactants; alkalinity sources and enzymes

In addition, it may be advantageous to provide the compressed part and the uncompressed part so that these are dissolve in the wash water with different speed of dissolution. By controlling the dissolution rate of each part in relation to the others and the selection of active detergent components in the respective parts can control its release order to the wash water and can the cleaning capacity of the detergent tablet is improved. By example it is often preferred that enzymes be supplied to the wash before bleaching agent and / or activator of bleach. It may also be preferred that a source of alkalinity be released to the wash water faster than other components of the detergent tablet. It is also contemplated that it can be advantageous to prepare a detergent tablet according to the present invention in which the release of certain components of the tablet is produced delayed with respect to others components.

It is also contemplated that the tablet can comprise a plurality of compressed or uncompressed parts. For example, a plurality of compressed parts may be arranged in layers and / or a plurality of uncompressed parts may be present as different sections of the separate tablet on a compressed part. Therefore, there may be a first part and a second part and optional backs compressed and / or not tablets, wherein each comprises a detergent component active and where at least the first part and the second part can comprise different active detergent components or mixtures of components. This plurality of compressed parts or parts not tablet can be advantageous and allows to produce a pill that have, for example, a first part and a second part and parts optional backs that have different speeds of dissolution. These performance advantages are achieved by supplying selectively active detergent components to the wash water At different times.

The detergent tablets described in the presently they are preferably from 15 g to 100 g by weight, more preferably from 18 g to 80 g by weight, even more preferably from 20 g to 60 g by weight. The detergent tablets described in the present memory suitable for use in dishwasher methods they most preferably have between 20 g and 40 g by weight. The detergent tablets suitable for use in washing methods of fabrics most preferably have between 40 g and 100 g, more preferably between 40 g and 80 g and most preferably between 40 g g and 65 g by weight. The weight ratio between the compressed part and the uncompressed part is generally greater than 0.5: 1, preferably greater than 1: 1, more preferably greater than 2: 1, even more preferably greater than 3: 1 or even 4: 1, with maximum preference at least 5: 1.

The detergent tablets described in the present memory have a resistance to child bite (CBS) which is generally greater than 10 kg, preferably greater than 12 kg and most preferably greater than 14 kg. CBS value is measured in accordance with the test specification of the Commission of American consumer product safety.

Test method of resistance to child bite : According to this method the tablet is placed horizontally between two strips or metal plates. The upper plate and the lower plate are articulated on one side, so that the plates simulate the human jaws. Increasing force is applied downstream to the upper plate, mimicking the closure of the jaws, until the tablet is broken. The CBS of the tablet is a measure of the force, in kilograms, needed to break the tablet.

The detergent tablets described in the present memory generally have a dissolution rate greater than 0.33 g / min, preferably greater than 0.5 g / min, more preferably greater than 1.00 g / min, even more preferably greater than 2.00 g / m and most preferably greater than 2.73 g / min. The dissolution rate is measured using the test method of SOTAX solution. For the purposes of the present invention the Detergent tablet solution is achieved using a SOTAX machine (trade name); AT7 model, marketed by SOTAX

SOTAX Dissolution Test Method : The SOTAX machine consists of a water bath with a lid and a controlled temperature. 7 containers are suspended in the water bath. 7 electric stir rods are suspended from the bottom of the lid, in positions that correspond to the position of the vessels in the water bath. The lid of the water bath also serves as the lid of the containers.

The SOTAX water bath is filled with water and the Temperature control is set to 50 ° C. Below each container is filled with 1 liter of deionized water and stirring set at 26.2 rad / s (250 r / min). The bathroom cover is closed water, letting the deionized water temperature of the Containers balance with that of the water bath for 1 hour.

The pills are weighed, a pill is placed in each container and the lid is closed. The pill is controlled visually until completely dissolved. The time that is recorded is recorded. It takes the tablet to dissolve completely. The speed of tablet dissolution is calculated as the average weight (g) of the tablet dissolved in deionized water per minute.

Compressed part

The compressed part of the detergent tablet it comprises at least one active detergent component but can comprise a mixture of more than one active detergent component, which They are compressed. 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. Active detergent components Suitable are described below. Detergent components Preferred assets include additive compound reinforcing the detergency, surfactant, bleaching agent, activator bleach, bleach catalyst, enzyme and a source of alkalinity.

The one or more active detergent components present in the compressed layer can optionally be prepared together with a vehicle and / or a binder, for example water, polymer (for example PEG) or liquid silicate. Detergent components assets are preferably prepared in the form of particles (it is say, in the form of powder or granulate) and can be prepared by any known method, for example drying methods by conventional spraying, granulation or agglomeration. The one or more particulate active detergent components are then compressed using any suitable equipment to form tablets, blocks, bricks or compressed briquettes; as described below in detail.

Non-encapsulating part not compressed

The non-encapsulating part not compressed (mentioned below as an uncompressed part) includes the less an active detergent component although it may comprise a mixture of more than one active detergent component. The components active detergents suitable for incorporation in part no compressed include components that interact with one or more detergent components present in the compressed part. In in particular, the components of the preferred uncompressed part are those who are negatively affected by the pressure of compression of, for example, a tablet press. Examples of these active detergent components include, but not limiting, surfactant, bleaching agent, activator of bleach, bleach catalyst, enzyme, inhibitor corrosion, perfume and a source of alkalinity. These components are described in more detail below. The one or more components Active detergents can be in any form, for example in particle form (i.e. powder or granulate), gel or liquid. The uncompressed part, in addition to comprising a detergent component active, it can also optionally comprise a component of vehicle. The active detergent component may be present in solid, gel or liquid form before being combined with a vehicle component.

The uncompressed part 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 portion be incorporated into the compressed portion so that the compressed portion and the uncompressed portion are in contact with each other. The uncompressed part can be incorporated into the compressed part in solid or fluid form. When the uncompressed part is in solid form, it is pre-prepared, optionally shaped and then incorporated into the compressed part. The uncompressed part is then fixed to a preformed compressed part, for example, by adhesion or insertion of the uncompressed part into a cooperating surface of the compressed part. Preferably the compressed part comprises a previously prepared depression or mold to which the non-part is incorporated
compressed

The uncompressed part is incorporated preferably to the compressed part in fluid form. The part no compressed is then fixed to the compressed part forming a coating on the uncompressed layer to fix it to the part compressed

Preferably the compressed part comprises a previously prepared depression or mold (hereinafter referred to as "mold") to which the uncompressed part is incorporated. In an alternative embodiment, the surface of the compressed part comprises more than one mold to which the uncompressed part can be incorporated. The one or more molds preferably house at least partially one or more uncompressed parts. The one or more uncompressed parts are then incorporated into the mold and fixed to the compressed part as described.
previously.

The uncompressed part may comprise particles The particles can be prepared by any known method, for example, spray drying, granulation, conventional encapsulation or agglomeration. The particles are fixed to the compressed part forming a coating layer on the uncompressed part.

If the detergent tablet comprises more than an uncompressed part, the first part and the second part and the optional backs not compressed can comprise particles that have an average particle size basically different. The expression average particle size basically different means that the difference between the average size of particles of the first composition and the second composition and / or the subsequent compositions is 5% higher, preferably 10% higher, more preferably 15% higher or even 20% higher, compared to the average particle size Minor.

The average particle size of the components detergent assets in the form of particles used herein Invention is calculated using a series of Tyler sieves. The series consists of different sieves, each with a different mesh size. Samples of a composition of Active detergent components are screened through the series of sieves (typically 5 sieves). The weight of a sample of the composition retained in the sieve versus the size of sieve mesh. The average particle size of the composition is defined as the mesh size through which 50% passes in Sample weight of the composition.

In another embodiment the first composition and the second composition and subsequent optional compositions of active detergent components basically have a density different so that the difference between the density of the first composition and the second composition and / or subsequent compositions is 5% higher, preferably higher in a 10%, more preferably higher by 15% or even higher by 20%, at the lowest density. The density of the composition in the form of particles of the active detergent components can be measured by any known method suitable for measuring density of particulate materials.

Preferably the density of the composition of Active detergent components are measured using a simple funnel and cup device consisting of a conical funnel rigidly molded on a base and provided with a valve fin at its lower end to allow emptying the contents of the funnel in an axially aligned cylindrical cup and placed underneath of the funnel. The funnel has a height of 130 mm and a diameter internal 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 it has a total height of 90 mm, an internal height of 87 mm and a internal diameter of 84 mm. Its nominal volume is 500 ml.

A manual density measurement is performed pouring the composition into the funnel. When the funnel is full, the flap valve is opened and the powder is allowed to flow through the funnel to fill until the cup overflows. The full cup is removed from the frame and excess dust is removed from the cup by passing a element with a straight edge, p. eg a knife, by its edge higher. The full cup is then weighed and the value is doubled obtained for the weight of powder in order to obtain a density apparent in grams / liter. If necessary, the measurements.

Pills are preferred where one or more of uncompressed parts comprise particles and the average size of particles and / or the density of the first part and the second part and optional backs not compressed are basically different and where the first part and the second part and the optional backs not compressed should have different dissolution rate

When the uncompressed part comprises a solidified melt, the melt is prepared by heating a composition comprising a detergent active component and one or more optional vehicle components to a temperature 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 one or more vehicle components can be heated to a temperature above their melting point and then an active detergent component can be added. Suitable vehicle components for the preparation of 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 active detergent components. A preferred non-active carrier component is an organic polymer that is solid at room temperature. Preferably the non-active detergent component is polyethylene glycol (PEG). The compressed portion of the detergent tablet preferably provides a mold for housing the dough
cast.

The fluid uncompressed part may be in a form comprising a dissolved active detergent component or discontinued. The uncompressed fluid part can harden with the course of time to form a solid uncompressed part, semi-solid or very viscous liquid by any of the methods described above. In particular, the fluid part does not Compressed can be hardened by evaporation of a solvent. The solvents suitable for use in the present invention may include any known solvent in which a solution can be dissolved binder. Preferred solvents may be polar or not. polar and may include water, alcohol (for example ethanol, acetone) and alcohol derivatives. In an alternative embodiment it can be used More than one solvent.

The fluid uncompressed part may comprise one or more binders. Any binder that can make the composition becomes solid, semi-solid or very viscous with the Time course is considered suitable for use in the present invention Although without trying to impose any theory, believes that the mechanisms by which the binder causes a non-solid composition becomes solid, semi-solid or very viscous include: chemical reaction (such as chemical crosslinking) or effect interaction between two or more components of the fluid compositions or chemical or physical interaction of the binder with a component of the composition. Preferred binders include a combination of sugar / gelatin, starch, glycerol and organic polymers 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 the For purposes of the present invention, type A jellies can be used or B marketed, for example, by Sigma. Gelatin is preferred Type A because it has greater stability in alkaline conditions than type B. The preferred gelatin also has a consistency between 65 and 300, most preferably between 75 and 100. Preferred organic polymers include polyethylene glycol (PEG) of molecular weight of 500 to 10,000, preferably 750 to 8000 and most preferably from 1000 to 6000, marketed by Hoechst.

If the uncompressed part is an extrudate, the Extruded is prepared by premixing the active detergent components with optional vehicle components to form a paste viscose. The viscous paste is then extruded using any common extrusion equipment such as an extruder single or double screw screw, p. e.g., by APV Baker, Peterborough, United Kingdom. Then the extrudate can be cut to the right size either after releasing the compressed part or before releasing the compressed part of the detergent tablet. The compressed part of the tablet preferably comprises a mold to which the uncompressed part can be incorporated extruded

The uncompressed part is coated with a layer of coating. The coating is used to fix a part not compressed to the compressed part.

The coating layer preferably it comprises a material that becomes solid when put in contact with the compressed part and / or with the uncompressed part in less than preferably 15 minutes, more preferably in less than 10 minutes, even more preferably in less than 5 minutes and with Maximum preference in less than 60 seconds. Preferably the layer Coating is water soluble. Coating layers Preferred comprise materials selected from the group that It consists of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, acetate polyvinyl (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA), polyethylene glycol (PEG) and mixtures thereof. Acids preferred carboxylic or dicarboxylic acids preferably comprise an even number of carbon atoms. Preferably acids carboxylic or dicarboxylic comprise at least 4, more preferably at least 6, even more preferably at least 8, carbon atoms and most preferably from 8 to 13 atoms of carbon. Preferred dicarboxylic acids include acid adipic acid, subic acid, azelaic acid, sub-acidic acid undecanedioic, dodecanedioic acid, tridecanedioic acid and mixtures thereof. Preferred fatty acids are those that they have a carbon chain length from C12 to C22 and with maximum preference from C18 to C22. The coating layer may comprise also preferably a disruptive agent. The layer of coating is generally present at a level of at least 0.05%, preferably at least 0.1%, more preferably at minus 1%, with maximum preference of at least 2% or even at minus 5% of the detergent tablet.

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.

In a preferred embodiment the compressed part and / or the uncompressed part and / or the coating layer comprises additionally a disintegrating agent. The disruptive agent can be a disintegrating or effervescent agent. Disintegrating agents Suitable include agents that swell upon contact with water or that facilitate the influx and / or efflux of water forming channels in compressed and / or uncompressed parts. Any agent disintegrant or effervescent agent suitable for use in laundry or dishwashing applications can be used in the present invention. Disintegrating agents Suitable include starch, starch derivatives, alginates, carboxymethyl cellulose (CMC), CMC based polymers, acetate sodium and aluminum oxide. Suitable effervescent agents are those that produce a gas when in contact with water. The suitable effervescent agents can be types that give off oxygen, nitrogen dioxide or carbon dioxide. Examples of preferred effervescent agents may be selected from the group that It consists of perborate, percarbonate, carbonate, bicarbonate and acids carboxylic acids, such as citric acid or maleic acid.

The inclusion of a disruptive agent in the detergent tablet of the present invention provides a Advantage of transport, storage and handling when increasing the hardness of the detergent tablet without affecting negatively to the cleaning capacity.

Process

According to the present invention also provides a process to prepare a detergent tablet for use in a clothes washer or dishwasher, including pick up an enzyme and: the process comprising the stages of:

to)

compress a detergent component active to form a compressed part;

b)

provide a non-encapsulating part uncompressed comprising an active detergent component to the compressed part; and subsequently

C)

cover at least a part of the part not compressed with a coating layer to fix or hold the uncompressed part to the compressed part.

As described above, the tablet of detergent described herein is made by preparing separately the composition of active detergent components and forming the compressed part and the uncompressed part and then providing or adhering the composition of the uncompressed part to the compressed part.

The compressed part is prepared by obtaining less an active detergent component that is optionally premixed with vehicle components. Any premixes will be made in a suitable mixer; such as tray mixer, drum Swivel, vertical mixer or high shear mixer. Preferably the components in the form of dry particles are mix in a mixer, as described above, and the Liquid components are added to the components in the form of dry particles, for example by spraying the liquid components directly on the components in the form of dry particles. The resulting composition is then formed into one part compressed in a compression stage using any equipment adequate known. Preferably the composition is formed in a compressed part in a tablet press, where the tablet it is prepared by compressing the composition between an upper punch and other lower. In a preferred embodiment of the present invention the composition is incorporated into a perforation cavity of a tablet press and compressed to form a compressed part using a pressure preferably greater than 6.3 KAN / cm2, more preferably greater than 9 KAN / cm2, with maximum preference greater than 14.4 KAN / cm2.

To form a preferred tablet of the invention, wherein the compressed part provides a mold for receive the uncompressed part, the compressed part is prepared using a modified tablet press comprising upper and / or lower punches that are modified. The upper and lower punches of the modified tablet press they are modified so that the compressed part has one or more indentations that form one or more molds where the uncompressed part.

The uncompressed part comprises at least one active detergent component. If the uncompressed part comprises more than one active detergent component, the components are premix using any known mixing equipment suitable. In addition, the uncompressed part can optionally understand a vehicle with which the components are combined active detergents The uncompressed part can be prepared in solid or fluid form. Once the composition is prepared, it is It incorporates the compressed part. The uncompressed part can be incorporate into the compressed part manually or using a nozzle feeder or extruder. When the compressed part It comprises a mold, the uncompressed part is incorporated preferably to the mold by means of an exact feeding equipment, for example a nozzle feeder, such as a feeder weight loss screw marketed by Optima, Germany, or an extruder

When the fluid uncompressed part is in particle form, the process includes the incorporation of a fluid uncompressed part to the compressed part in a stage of pouring and then coating at least one part of the uncompressed part with a coating layer so that the coating layer basically has the effect of adhering the uncompressed part to the compressed part.

It is also planned that the compressed part can be prepared so that it has a plurality of molds. The plurality of molds are then filled with a non part compressed It is also planned that each mold can be filled with a different uncompressed part or, alternatively, that each mold can be filled with a plurality of different parts not compressed

Active detergent components

The compressed part of the detergent tablet described herein is prepared by compressing the composition of active detergent components. A composition suitable can include a variety of different components detergent assets including reinforcing compounds of the detergency, surfactants, enzymes, bleaching agents, sources alkalinity, dyes, perfume, calcareous soap dispersants, organic polymeric compounds including inhibitors of dye transfer, growth inhibitors crystalline, heavy metal ion sequestrants, salts of metal ions, enzyme stabilizers, inhibitors of corrosion, suds suppressors, solvents, softeners of fabrics, optical brighteners and hydrotropes.

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

Detergency builder compound

The detergent tablets of the present invention preferably contain a reinforcing compound of the detergency, which is typically present in an amount from 1% to 80% by weight, preferably from 10% to 70% by weight and with maximum preference of 20% to 60% by weight, of the composition of active detergent components.

Water-soluble detergency additive compound

Strengthening compounds of detergency Suitable water-soluble include monomeric polycarboxylates Water soluble or acidic forms, polycarboxylic acids homopolymers or copolymers or their salts in which 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 polycarboxylates are generally preferred monomeric for reasons of cost and performance.

Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid and the ether derivatives thereof. The polycarboxylates containing two carboxyl 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-1,379,241, the lactoxysuccinates described in GB-1,389,732 and the aminosuccinates described in NL-7205873 and type materials oxypolycarboxylate such as 2-oxa-1,1,3-propane tricarboxylates described in GB-1,387,447.

Polycarboxylates containing four groups carboxy include oxydisuccinates 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 and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexycarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, Mannitol and Xylitol. Aromatic polycarboxylates include acid melitic, pyromellitic acid and phthalic acid derivatives described in GB-1,425,343.

Of the aforementioned, the Preferred polycarboxylates are hydroxycarboxylates that they contain up to three carboxy groups per molecule and more in particular Citrates

They are also considered as additive components useful detergency boosters precursor acids of chelating agents of the monomeric or oligomeric polycarboxylate type or mixtures thereof with their salts, e.g. ex. citric acid or mixtures of citrate / citric acid.

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

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

The additive reinforcing compounds of the Highly preferred detergency for use in the present invention are phosphate-type detergency builders water soluble. Specific examples of reinforcing agents of the Water soluble phosphate type detergency are tripolyphosphates of alkali metals, sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, orthophosphates of sodium and potassium, the sodium polymeta / phosphates whose degree of polymerization is 6 to 21 and the salts of phytic acid.

Specific examples of reinforcing agents of the water soluble phosphate type detergency are tripolyphosphates of alkali metals, sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, orthophosphates of sodium and potassium, the sodium polymeta / phosphates whose degree of polymerization is 6 to 21 and the 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. Additive compounds partially soluble and insoluble detergency builders are particularly suitable for use in tablets prepared for be used in laundry methods. Examples of partially water-soluble detergency builders include crystalline laminar silicates as described by example in EP-A-0164514, DE-A-3417649 and DE-A-3742043. The ones are preferred sodium crystalline laminar silicates 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 structures denominated δ-laminar, as described in EP 0 164514 and EP 0 293640

Methods of preparing laminar silicates crystals of this type are described in the patents 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.

Sodium crystalline laminar silicate plus preferred has the formula δ-Na_ {2} Si_ {2} O_ {5} and 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 intimate mixing with a material Water-soluble ionizable solid as described in PCT WO92 / 18594. He solid water-soluble ionizable material is selected from acids organic, salts of organic and inorganic acids and mixtures of themselves, citric acid being preferred.

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

The aluminosilicate zeolites can be natural although preferably they are obtained by synthesis. The aluminosilicate ion exchange synthetic materials Crystalline are marketed under the names of Zeolita A, Zeolita B, Zeolita P, Zeolita X, Zeolita HS and mixtures thereof.

A preferred method of synthesizing zeolites from aluminosilicate is that described by Schoeman et al. (published in Zeolite [1994] 14 [2], 110-116), in which the author describes a method of preparation of zeolites of colloidal aluminosilicate. The zeolite particles of aluminosilicate should preferably be such that no more 5% of the particles are larger than 1 µm of diameter and not more than 5% of particles are smaller than 0.05 µm in diameter. Preferably the zeolite particles of aluminosilicate have a particle size diameter average of 0.01 µm to 1 µm, more preferably 0.05 µm to 0.9 µm and most preferably 0.1 µm to 0.6 \ mum.

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 the patent EP-B-384.070 is an additive zeolite detergency builder preferred herein invention.

Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. When used as a component of a detergent composition, the zeolites of colloidal aluminosilicate, especially colloidal zeolite A, provides enhanced detergency strengthening capacity in terms of better stain removal. There is also a better detergency booster performance in terms of less tissue inlay and better whiteness preservation tissue, problems believed to be associated with the compositions with poor reinforcing power of detergency.

A surprising finding is that detergent compositions with mixed aluminosilicate zeolite which comprise colloidal zeolite A and colloidal zeolite Y provide the same calcium ion sequestration capacity as an equal amount of commercial zeolite A. Another surprising finding is that mixed detergent compositions with mixed aluminosilicate zeolite described above provide a sequestration capacity of the improved magnesium ion with respect to an equal amount of zeolite A commercial.

Surfactant

Surfactants are detergent components preferred assets of the compositions described herein memory. Suitable surfactants are selected from surfactants anionic, cationic, nonionic, ampholytic and hybrid ion and mixtures thereof. Dishwasher products must be low foaming and therefore the formation of foam of the surfactant system used in the washing methods of crockery or more preferably these should be of little type sparkling, typically non-ionic type. Soaps caused by the surfactant systems used in the methods of laundry do not need to be suppressed at the same level as in The case of dishwashers. The surfactant is typically present at a level of 0.2% to 30% by weight, more preferably of 0.5% to 10% by 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

In the detergent tablet can be included virtually all nonionic surfactants useful for purposes detersives Below are non-limiting classes Preferred of useful nonionic surfactants.

Nonionic surfactant of ethoxylated alcohol type

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

Surfactant of alkyl alkoxylate type with ends protected

A type of alkyl type surfactant Suitable terminal protected alkoxylate are the poly (oxyalkylated alcohols) 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 linear or branched aliphatic 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 that has an average value of 0.5 to 1.5, plus preferably 1; and is an integer that has a value of at at least 15 and more preferably at least twenty.

Preferably, the surfactant of formula I has at least 10 carbon atoms in the epoxy terminal unit [CH 2 CH (OH) R 2]. The surfactants of the formula Suitable I, according to the present invention, are non-surfactants POLY-TERGENT® SLF-18B ionic Olin Corporation, as described, for example, in WO 94/22800, published on 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 of the formula:

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

wherein R 1 and R 2 are aliphatic or aromatic, linear or hydrocarbon radicals branched, saturated or unsaturated having 1 to 30 atoms of carbon; R 3 is H or a linear aliphatic hydrocarbon radical that it has 1 to 4 carbon atoms; x is an integer that has a mean value from 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 have a average value from 1 to 12, and more preferably from 1 to 5.

R 1 and R 2 are preferably aliphatic or aromatic, saturated or unsaturated, straight or branched chain hydrocarbon radicals having 6 to 22 carbon atoms, with 8 to 18 carbon atoms being most preferred carbon. For R3, H or a straight chain aliphatic hydrocarbon radical having 1 to 2 carbon atoms is most preferred. Preferably, x is an integer with an average value of 1 to 20 and more preferably 6 to
fifteen.

As described above, when in preferred embodiments x is greater than 2, R 3 may be the same or different. That is, R3 may vary between any of the alkyleneoxy units, as described above. By For example, if x is 3, R3 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and may vary order 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).

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

Alcohol type surfactants poly (oxyalkylated) with ends protected with ether groups most preferred are those in which 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, x is an integer with a average value from 1 to 30, preferably from 1 to 20 and even more preferably from 6 to 18. The most preferred surfactants are those in which R 1 and R 2 are from 9 to 14, R 3 is a H and x ethyleneoxy forming is 6 to fifteen.

Alcohol type surfactants poly (oxyalkylated) with ends protected with ether groups They comprise three general components: a linear alcohol or branched, an alkylene oxide and a terminal protection of alkyl ether. Terminal protection of alkyl ether and alcohol act as the hydrophobic oil soluble fraction of the molecule while that the alkylene oxide group acts as the hydrophilic fraction, Water soluble molecule.

These surfactants show improvements significant with respect to conventional surfactants in in terms of pretreatment and film formation characteristics and grease stain removal when used in conjunction with high cloudiness surfactants.

In general terms, the type surfactant poly (oxyalkylated) alcohol terminally protected with groups Ether of the present invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether that at It then reacts with a base to form a second epoxide. Then the second epoxide is reacted with an alcohol alkoxylated to form the novel compounds of the present invention. Examples of methods of Preparation of alcohol type surfactants poly (oxyalkylated) protected with ether groups.

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, an argon inlet, an addition funnel, a magnetic stirrer and a probe internal temperature The mixture is heated to 60 ° C. Drop is added dropwise epichlorohydrin (47.70 g, 0.515 mol, marketed by Aldrich) so that the temperature is maintained between 60 and 65 ° C. After stirring another hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a solution of 50% sodium hydroxide (61.80 g, 0.773 mol, 50%) while stirring mechanically. Once the addition is complete, the mixture is heated to 90 ° C for 1.5 h, it is cooled and filtered with ethanol. He The filtrate is separated and the organic phase is washed with water (100 ml), Dry in MgSO4, filter and concentrate. The oil is distilled to 100-120 ° C (13.3 Pa [0.1 mm Hg]) obtaining ether glycidyl in the form of oil.

Preparation of the C 12/14 alkyl alcohol type 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 on a rotary evaporator and then Distill in a Kugelrohr oven (100 ° C, 66.7 Pa [0.5 mm Hg]) to obtain the surfactant in the form of 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 suitable surfactants for use in the present invention, especially if they are water soluble. Preferably the alcohols ethoxylated fatty acids 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 fatty alcohols mixed ethoxylated / propoxylated have an alkyl chain of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 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 has preferably a molecular weight of 1,500 to 1,800 and have insolubility in water. Examples of compounds of this type include some of the commercially available Pluronic ™ surfactants by BASF.

EO non-ionic condensation products with compounds of addition of propylene oxide / ethylenediamine

Rust Condensation Products ethylene with the product resulting from the reaction between oxide Propylene and ethylenediamine are suitable for use herein. invention. The hydrophobic residue of these products consists of the reaction product between ethylenediamine and an excess oxide of propylene and generally has a molecular weight of 2,500 to 3,000. Examples of this type of nonionic surfactants include certain commercial Tetronic ™ 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 nonionic surfactant with low cloud point and at least a nonionic surfactant of high cloud point.

"Cloud point", in the present memory is a well known property of non-surfactants ionic which is the result of the conversion of the surfactant into less soluble as the temperature rises, where the temperature at which a second phase is observed is known as the "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 of cloudiness below 30 ° C, preferably below 20 ° C and most preferably less than 10 ° C. Nonionic Surfactants Typical low cloud point include surfactants nonionic alkoxylates, especially ethoxylates derived from primary alcohols and inverse block polymers of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). Also, said non-ionic cloud point surfactants Low 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 October 13, 1994 by Olin Corporation) and alcohol-type surfactants poly (oxyalkylated) with ends protected with groups ether.

Nonionic surfactants may contain optionally propylene oxide at a level of up to 15% by weight. Other preferred nonionic surfactants can be prepared by the processes described in US 4,223,163, granted to Builloty on September 16, 1980.

Non-ionic low point surfactants cloudiness also comprise a polymeric block compound of polyoxyethylene-polyoxypropylene. The compounds block polymers polyoxyethylene-polyoxypropylene include those based in ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as a hydrogen compound that reacts with the initiator. Some of the polymer-type surfactant compounds called PLURONIC®, REVERSED PLURONIC® and TETRONIC® of BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable for adding to the compositions of the invention. Examples Preferred include REVERSED PLURONIC® 25R2 and TETRONIC® 702. This Type of surfactants are typically useful herein. invention as low ion non-ionic surfactants of cloudiness

Herein, a surfactant does not "high cloud point" ionic is defined as a non-ionic surfactant system that has a cloud point 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 alkyl phenol containing 8 to 20 carbon atoms, with 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol 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 high-point nonionic surfactant of 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).

Other non-ionic high point surfactant of Preferred cloudiness is derived from a fatty alcohol of linear chain or preferably branched chain or an alcohol secondary fat containing 6 to 20 carbon atoms (alcohol C 6 -C 20), including secondary alcohols and branched chain primary alcohols. Preferably, the nonionic surfactants of high cloud point are branched or secondary alcohol ethoxylates, more preferably C9 / 11 or C11 / 15 mixed 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 ethoxylated nonionic surfactant thus derivative has a narrow distribution of ethoxylated groups with Regarding the average.

In a preferred embodiment, the tablet detergent comprising this mixed surfactant system also it comprises an amount of water soluble salt to provide a conductivity in deionized water, measured at 25 ° C, greater 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 automatic dishwasher with cold water inlet suitable to provide a solution with a surface tension from less than 0.4 Pa (4 dynes / cm2) to less than 45 ° C, preferably less than 40 ° C and most preferably 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 cloudiness surfactant or the 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 high point surfactant of 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 surfactants they can include salts (such as sodium, potassium salts, ammonium and substituted ammonium as the monoethanolamine salts, diethanolamine and triethanolamine) of the anionic surfactants of sulfate, sulphonate, carboxylate and sarcosinate type. The sulfate type anionic surfactants are preferred.

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 primary and secondary straight chain alkyl sulfates and branched, alkyl ethoxy sulfates, oleyl fatty sulfates glycerol, ethylene oxide ether alkylphenolsulfates, C 5 -C 17 sulfates acyl-N- (C 1 -C 4 alkyl) and C5-C17 acyl-N- (C 1 -C 2) hydroxyalkyl) glucamine and alkylpolysaccharide sulfates such such as alkyl polyglucoside sulfates (non-ionic compounds sulfates that are described in the present invention).

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

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

In a particularly preferred embodiment of the invention mixtures of surfactants of the type are used Preferred alkyl sulfate and alkyl ethoxy sulfate 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 of C 5 -C 20 alkyl linear benzene sulphonates, alkyl sulphonate esters, alkanes C 6 -C 22 primary or secondary sulfonates, C 6 -C 24 olefin sulfonates, acids sulfonated polycarboxylic acids, alkyl glycerol sulphonates, Acyl glycerol fatty sulphonates, the oleyl glycerol sulfonates fatty and any mixture thereof.

Anionic Carboxylate Surfactant

Anionic carboxylate surfactants Suitable include those of the alkyl ethoxycarboxylate, alkyl type polyethoxypolycarboxylate and soaps ("alkyl carboxyls"), especially certain secondary soaps such as those described in the present memory

Suitable alkyl ethoxy carboxylates include those of formula RO (CH 2 CH 2 O) x CH 2 COO - M +, where R is a C 6 alkyl group at C 18, x is from 0 to 10 and the distribution of ethoxylate is such that the quantity by weight of product when x is 0 is less than 20% and M is a cation Alkyl polyethoxy surfactants Suitable polycarboxylate include those of formula RO- (CHR_ {1} -CHR 2 -O) -R 3}, wherein R is a C 6 to C 18 alkyl group, x is 1 to 25, R_ {1} and R2_ are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, radical hydroxysuccinic acid and mixtures thereof, and R 3 is select from the group consisting of hydrogen, hydrocarbon substituted or unsubstituted containing 1 to 8 carbon atoms and mixtures thereof.

Suitable soap surfactants include secondary soap type surfactants that contain a carboxyl group attached to a secondary carbon. The surfactants of Preferred secondary soap type of use in the present invention are water-soluble components selected from the group consisting of water soluble salts of acids 2-methyl-1-undecanoic, 2-ethyl-1-decanoic, 2-propyl-1-nonanoic, 2-butyl-1-octanoic Y 2-pentyl-1-heptanoic. You can also include certain soaps as suppressants Soaps.

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 methylsarcosinates and the oleyl methylsarcosinates 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 phenyl alkyl, 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 oxide is preferred C 10 -C 18 dimethylamine and the oxide of C 10-18 acylamidoalkyl dimethylamine.

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

Hybrid ion surfactant

In the detergent compositions herein invention hybrid ion surfactants can also be incorporated. These surfactants can be broadly described as derivatives. of secondary and tertiary amines, derivatives of secondary amines and tertiary heterocyclics or derivatives of ammonium compounds quaternary, quaternary phosphonium compounds or compounds of tertiary sulfonium. The surfactants of the betaine and sultaine type are illustrative of the hybrid ion surfactants used in the present invention

Suitable betaines are the compounds that has the formula R (R ') 2 N + R 2 COO -, wherein R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group. Preferred betaines are dimethylammonium C 12-18 hexanoate and acyl C 10-18 amidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants They are also suitable for use in the present invention.

Cationic surfactants

Cationic ester type surfactants used in this invention are preferably compounds water dispersible having surfactant properties and they comprise at least one ester linkage (i.e. -COO-) and at least one group with cationic charge. Other cationic surfactants of the type suitable esters, including ester surfactants of choline, have been described, for example, in patents US 4,228,042, US 4,239,660 and US 4,260,529.

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

Enzymes

In the present invention an enzyme is a Essential element of the detergent tablet. Enzymes are select from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, 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, peroxidases, cutinase and / or cellulase together with one or more cell wall degradation enzymes vegetable.

Cellulases usable in the present invention include bacterial or fungal cellulase. Preferably, it 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 Pat. Nos. 4,435,307, issued to Barbesgoard et al., J61078384 and WO96 / 02653, which describe the fungal cellulases produced from Humicola insolens , Trichoderma, Thielavia and Sporotrichum, respectively. EP-739 982 describes cellulases isolated from a new species of Bacillus. 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 obtained from a strain of Humicola insolens ( Humicola grisea var. Thermoidea ), especially the Humicola DSM 1800 strain. Other suitable cellulases are cellulases from Humicola insolens with a molecular weight of 0.08 ag (50 KDa), an isoelectric point of 5.5 and containing 415 amino acids; and a 0.07 ag endoglucanase (? 43 kD) derived from Humicola insolens , DSM 1800, which exhibits cellulase activity; a preferred endoglucanase component has the amino acid sequence described in PCT WO 91/17243. Also suitable are the EGIII cellulases of Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published on September 29, 1994. Especially suitable cellulases are those that have advantages of color care. 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 into the detergent composition in amounts of 0.0001% to 2% enzyme active by weight of the detergent composition.

Peroxidase enzymes are used together with oxygen sources, for example percarbonate, perborate, persulfate or hydrogen peroxide. These are used for "bleaching in solution ", that is to avoid the transfer of dyes or pigments that have separated from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, by example, horseradish peroxidase, ligninase and haloperoxidase such as chloro-peroxidase and the bromine peroxidase. Detergent compositions that containing peroxidase are described, for example, in PCT WO 89/099813, WO89 / 09813 and EP 540,784. The enzyme lacasa is also suitable.

Preferred improvers are fentiazine 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), the syringates (C3-C5 alkyl substituted syringates) and the substituted phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

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

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group such as, for example, 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 trade name lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases, such as 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® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in combination 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 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

Cutinases are also suitable [EC 3.1.1.50] which can be considered as a special type of lipase, to Know lipases that do not require an interface activation. The Addition of cutinases to detergent compositions has been described, for example, in 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 in amounts of 0.0001% to 2% active enzyme by weight of the composition Detergent.

Suitable proteases are the subtilisins that are obtained from specific strains of B. subtilis and B. licheniformis (subtilisins BPN and BPN '). A suitable protease is obtained from a Bacillus strain that has a maximum activity in the pH range of 8-12 and is developed and marketed as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB-1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® de Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (obtained by protein engineering by Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in EP 251,446 and referred to herein as "protease B", and in EP-199,404, Venegas, published October 29, 1986, which refers to an enzyme modified bacterial proteolytic serine, referred to as "protease A" herein. Is suitable enzyme called "Protease C" herein, which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaces asparagine at position 123 and alanine replaces threonine at position 274. Protease C is described in EP 451.244, corresponding to WO 91/06637, published May 16, 1991. Also included herein. memory 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 carbonylhydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination 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 numbering of subtilisin Bacillus amyloliquefaciens , as described in WO95 / 10591 and in the patent application of C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes" of US- 5,677,272.

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

See also a high pH protease of Bacillus sp. NCIMB 40338 described in WO 93/18140 A, granted to Novo In WO 92/03529 A, granted to Novo, detergents are described enzymes comprising protease, one or more additional enzymes and a reversible protease inhibitor. If desired, there is a protease with reduced adsorption and increased hydrolysis as described in WO 95/07791, granted to Procter & Gamble. In WO 94/25583, granted to Novo, a recombinant protease is described similar to trypsin for detergents suitable according to the present invention. Other suitable proteases are described in EP-516 200, granted to Unilever.

Other preferred protease enzymes include protease enzymes that are a variant of carbonyl hydrolase having an amino acid sequence that does not exist in nature derived by substituting a plurality of amino acid residues of a carbonyl hydrolase precursor with different amino acids, wherein said plurality of amino acid residues substituted in the precursor enzyme correspond to the +210 position in combination 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 (α and / or β) may be included to remove carbohydrate stains. In WO94 / 02597, published on February 3, 1994 by Novo Nordisk A / S, are described cleaning compositions that incorporate mutant amylases. See also WO95 / 10603, published by Novo Nordisk A / S on April 20 from 1995. Other known amylases for use in the compositions cleaners include both α-amylases and β-amylases. The α-amylases are known in the art and include those described in US-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 amylases suitable are amylases with improved stability described in WO94 / 18314, published August 18, 1994, and WO96 / 05295, published on February 22, 1996 by Genencor, and variants of amylase that have an additional modification in the precursor immediately marketed by Novo Nordisk A / S, described in WO 95/10603 and published in April 1995. Also suitable are Amylases described in EP 277 216, WO95 / 26397 and WO96 / 23873 (all 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. In WO95 / 26397, describe other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the activity Termamyl® specific at a temperature range of 25 ° C to 55 ° C and with a pH in the range of 8 to 10, measured by α-amylase activity assay Phadebas®. Enzyme variants are suitable above, described in WO96 / 23873 (Novo Nordisk). Other enzymes amylolytics with better activity level properties and with a combination of thermostability and a higher level of activity is They are described in WO95 / 35382.

Preferred amylase enzymes include the described in WO95 / 26397.

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.

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In an especially preferred embodiment, the detergent tablets of the present invention comprise enzymes amylase, in particular those described in WO95 / 26397, together with a complementary amylase.

"Complementary" means the addition of one or more amylases suitable for detergency purposes. Examples of complementary amylases (α and / or β) are described more ahead. In WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S, are described cleaning compositions containing mutant amylases. Other Amylases known for use in cleaning compositions include both α-amylases and β-amylases. The α-amylases are known in the art and include those described in US-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 amylases suitable are the improved stability amylases described in WO94 / 18314 and WO96 / 05295, Genencor, and the amylase variants with additional modification in the immediate precursor marketed by Novo Nordisk A / S, described in WO 95/10603. Are also suitable the amylases 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. In WO95 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® in a temperature range of 25 ° C to 55 ° C and with a pH 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 improved properties in relation to the level of activity and the combination of thermostability and a higher level of activity are described in WO95 / 35382. Preferred complementary amylases herein invention are amylases marketed under the name Purafect Ox Am® described in WO 94/18314 and WO96 / 05295 and marketed by Genencor; Termamyl®, Fungamyl®, Ban® and Duramyl®, all of them marketed by Novo Nordisk A / S, and Maxamyl® by Gist-Brocades.

Said complementary amylase is incorporated generally to detergent compositions according to the present invention in amounts of 0.0001% to 2%, preferably 0.00018% at 0.06%, more preferably from 0.00024% to 0.048%, of pure enzyme in composition weight. Preferably, the weight ratio between pure enzyme specific amylase and complementary amylase it will be 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 vegetable, animal, Bacterial, fungal or yeast. The origin can also be mesophilic or extremophilic (psychrophile, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic or halophilic). Can be used purified or unpurified forms of these enzymes. I also know they include by definition the native enzyme mutants. Too mutants can be obtained, for example, by protein engineering and / or genetic or chemical and / or physical modifications of enzymes native Common practice is also the expression of the enzyme to through host microorganisms in which it has been cloned the genetic material responsible for the production of the enzyme.

Such enzymes are normally incorporated into the detergent composition in amounts of 0.0001% to 2% enzyme active by weight of the detergent composition. Enzymes can be added as separate ingredients (pellets, granules, liquids stabilized containing an enzyme) or as mixtures of two or more enzymes (for example cogranulates).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in the codependent application EP 553.607. Examples of these enzyme oxidation scavengers are tetraethylene ethoxylated polyamines.

In WO 9307263 A and WO 9307260 A, of Genencor International, WO 8908694 A, of Novo, and US 3,553,139, granted to McCarty et al. On January 5, 1971, different enzymatic materials and means for incorporation in synthetic detergent compositions are also described. Enzymes are also described in US 4,101,457, granted to Place et al. on July 18, 1978, and US 4,507,219, granted to Hughes on March 26, 1985. Useful enzymatic materials for liquid detergent formulations and for incorporation thereof into said 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. In US-3,600,319, granted to Gedge et al. on August 17, 1971, and EP-199,405 and EP-200,586, granted to Venegas on October 29, 1986, techniques for enzyme stabilization are described and illustrated. Enzyme stabilization systems are also described, for example, in US 3,519,570. A useful Bacillus, sp. AC13, which produces proteases, xylanases and cellulases is described in WO 9401532 A de Novo .

Bleaching agent

A very preferred component of the composition of Active detergent components is a bleaching agent. The suitable bleaching agents include bleach releasing Chlorine and oxygen releasing bleach.

In a preferred aspect, the oxygen-releasing bleaching agent contains a source of hydrogen peroxide and a compound of the peroxyacid bleach precursor type. The organic peroxyacid is obtained by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrated bleaches. In an alternative preferred aspect, a previously obtained organic peroxyacid is incorporated directly into the composition. Also included in the invention are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor together with a previously obtained organic peroxyacid.

Inorganic Perhydrated Bleaches

The compositions of detergent components assets preferably include a source of peroxide of hydrogen, as an oxygen-bleaching bleach. The sources of Suitable hydrogen peroxide include inorganic salts perhydrated

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

Examples of perhydrated inorganic salts include salts perborate, percarbonate, perfosphate, persulfate and persilicate Perhydrated inorganic salts are usually those alkali metal salts. Perhydrated inorganic salt can be included as a crystalline solid without any other protection additional. However, in the case of certain salts perhydrated, preferred embodiments of said compositions granules use a coated form of the material that provides better storage stability for perhydrated salt in the granulated product.

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

The alkali metal percarbonates, in Particularly sodium percarbonate, are preferred perhydrates for its inclusion in the compositions of the invention. Percarbonate sodium is an addition compound with a formula that corresponds to 2Na2CO3 .3H2O2 marketed as solid crystalline. Sodium percarbonate, being an addition compound of hydrogen peroxide, during dissolution it tends to release the hydrogen peroxide quite quickly, which can increase the tendency of formation of localized and high concentrations of bleach. Percarbonate in these compositions is incorporated with highest preference in coated form to improve stability within the product

A suitable coating material that provides stability to the product, comprises a mixed salt of a Water-soluble alkanyl metal sulfate and carbonate. This type of coatings along with the coating processes have already been described in GB-1,466,799, granted to Interox on 9 March 1977. The weight ratio between the material of mixed salt and percarbonate coating is in the range from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9 and with maximum preference from 1:49 to 1:19. Preferably, the mixed salt is of sodium sulfate and sodium carbonate, which has the formula general Na2 {SO4 {.} .n.Na_ {2} CO3 {where n is 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 to the product comprises sodium silicate in a SiO 2: Na 2 O ratio of 1.8: 1 to 3.0: 1, preferably of 1.8: 1 to 2.4: 1 and / or sodium metasilicate, preferably applied to a 2% to 10% level (usually 3% to 5%) of SiO2 by weight of inorganic perhydrated salt. Magnesium silicate is also It can include in the coating. The coatings that contain salts of silicate and borate or boric acid or the other products Inorganic 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. Generally peroxyacid bleach precursors can be represented as

one

where L is a leaving group and X is virtually any functionality, so that by perhydrolysis the following structure of peroxyacid:

2

The 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.

The bleach precursor compounds Suitable peroxyacids typically contain one or more groups N-acyl or O-acyl, being able to Select precursors from a wide range of types. The Suitable types include anhydrides, esters, imides, lactam and acylated derivatives of imidazole and oximes. Product Examples useful of these types are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups

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

Preferred L groups are selected from the group consisting of:

3

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4

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5

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6

       \ vskip1.000000 \ baselineskip
    

7

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

Preferred solubilizing groups are -SO 3 <+> - M +, -CO 2 - M +, -SO 4 M -, -N + (R 3) 4 X - and O <-N (R3) 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 favors the solubility of the bleach activator and X is an anion that favors the solubility of the activator of the bleach. Preferably, M is an alkali metal cation, ammonium or substituted ammonium, with sodium and potassium being the most preferred, and X is a halide, hydroxide, methylsulfate or anion acetate.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds They provide perbenzoic acid by perhydrolysis.

Acid precursor type compounds Suitable O-acylated perbenzoic include the unsubstituted benzoyl oxybenzene sulfonates, including for example Benzoyl Oxybenzene Sulfonate:

8

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 of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylenediamine and N-benzoyl ureas replaced. Perbenzoic acid precursors of the imidazole type Suitable include N-benzoyl imidazole and N-benzoyl benzimidazole and other acid precursors perbenzoic containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and pyroglutamic benzoyl acid.

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

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10

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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.

Precursors derived from perbenzoic acid

Precursors derived from perbenzoic acid They provide adequate perbenzoic acids by perhydrolysis.

Precursors derived from perbenzoic acid Suitable substitutes include any of the precursors perbenzoic described herein and in which the benzoyl group is replaced by virtually any group functional not positively charged (i.e. non-cationic) including, for example, alkyl, hydroxy, alkoxy groups, halogen, 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 formulas:

13

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wherein R 1 is an aryl group or alkylaryl with 1 to 14 carbon atoms, R2 is a group arylene or alkarylene containing from 1 to 14 carbon atoms and R 5 is H or an alkyl, aryl or alkylaryl group containing 1 to 10 carbon atoms and L can be virtually any group outgoing. R1 preferably contains from 6 to 12 atoms of carbon. R2 preferably contains from 4 to 8 atoms of carbon. R1 may be aryl, aryl or substituted alkylaryl which it contains branching, substitution or both and that can come from synthetic or natural sources including, for example, fat from tallow. Similar structural variations are allowed for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R 5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. The compounds bleach activators with amide replacement of this type are described in EP-A-0170386.

Precursors of cationic peroxyacid

Peroxyacid Precursor Compounds cationics produce cationic peroxyacids by perhydrolysis.

Typically, peroxyacid precursors cationics are formed by replacing the peroxyacid part of a peroxy acid precursor compound suitable for a functional group positively charged, such as an ammonium or alkyl ammonium group and preferably an ethyl or methyl ammonium group. The precursors of cationic peroxyacid are typically present in the 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 in this way can be a compound precursor of perbenzoic acid or a substituted derivative thereof, as described previously in memory. So alternatively, the peroxyacid precursor compound may be a alkyl percarboxylic acid precursor compound or a precursor of the alkyl amide substituted peroxyacid as described by 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 EP-284,292; and in JP 87-318.332.

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

A cationically benzoyl oxybenzene sulfonate Preferred substituted is the 4- (trimethyl ammonium) methyl derivative of Benzoyl Oxybenzene Sulfonate:

14

A cationically alkyl oxybenzene sulfonate Preferred substituted has the formula:

fifteen

The precursors of cationic peroxyacid Preferred N-acylated caprolactam class includes trialkylammonium methylene benzoyl caprolactams, Especially the trimethylammonium methylene benzoyl caprolactams:

16

Other precursors of cationic peroxyacid Preferred N-acylated caprolactam class include trialkyl ammonium methyl caprolactams:

17

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

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Another precursor of cationic peroxyacid preferred is 2- (N, N, N-trimethyl chloride) ammonium) -ethyl 4-sulfophenyl carbonate sodium

Precursors of the alkyl percarboxylic acid bleach

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

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

Other precursors of alkyl acid Preferred percarboxylic include the 3,5,5-tri-methyl hexanoyloxybenzene sodium sulfonate (iso-NOBS), nonanoyloxybenzene sodium sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and Pentaacetyl glucose.

Precursors of the alkyl peroxyacid with amide substitution

Type compounds are also suitable precursor of the alkyl peroxyacid with amide substitution, including those with the following general formulas:

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 contains preferably from 6 to 12 carbon atoms. R2 contains preferably from 4 to 8 carbon atoms. R1 can be straight or branched chain alkyl containing branching, substitution or both and that may derive from synthetic sources or from natural sources including, for example, tallow fat. Be they allow analogous structural variations for R2. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R 5 It is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. The compounds bleach activators with amide replacement of this type are described in EP-A-0170386.

Benzoxazine-type organic peroxyacid precursors

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

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

Preformed organic peroxyacid

The bleaching system with organic peroxyacid may also contain, or alternatively, a compound organic peroxyacid bleach precursor, a peroxyacid previously obtained 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 type of peroxyacid compounds Organic are the compounds with amide substitution of the formulas General following:

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 contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 can be aryl or alkylaryl substituted straight or branched chain which it contains branching, substitution or both and that can come from synthetic or natural sources including, for example, fat from tallow. Similar structural variations are allowed for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R 5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. The compounds of organic peroxyacid with amide substitution of this type are described in EP-A-0170386.

Other organic peroxyacids include diacil and tetraacylperoxides, especially diperoxidedecanedioic acid, Diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid dibenzoyl peroxide is a preferred organic peroxyacid in the present invention Monoperazelaic acid and diperazelaic acid, the monoperbrasilic acid and diperbrasilic acid and acid N-phthalethylaminoperoxycaproic are also suitable in the present invention.

Means for speed control release

A means is provided to control the release rate of the bleaching agent, in particular a oxygen releasing bleach, in the wash solution.

The means to control the speed of bleach release can provide release Controlled peroxide species in the wash solution. Such means could, for example, include the control of release of any inorganic perhydrated salt, acting as a source of hydrogen peroxide, to the wash solution.

Suitable controlled release media may include confinement of bleach in any of the parts compressed or uncompressed When more than one part is present Uncompressed, the bleach can be confined to a first part and / or a second part and / or other optional uncompressed part.

Another mechanism to control the speed of bleach release can be by coating the bleach with a coating designed to provide the release control. Therefore, the coating can, for example, understand a slightly water-soluble material or be a coating of sufficient thickness so that the kinetics of thick coating solution provide speed controlled release.

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 metal, including calcium carbonate and Silicas

A preferred coating material, especially for a source of salt bleach inorganic perhydrate comprises sodium silica 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 from 2% to 10%, (usually 3% to 5%) of SiO2 by weight of the salt inorganic perhydrate. Magnesium silicate can also be include in the coating.

Any salt coating material inorganic can be combined with organic binder materials to provide salt compound coatings inorganic / organic binder. Suitable binders include ethoxylated C 10 -C 20 alcohols that contain 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 1,000 to 400,000 and with maximum preference of 1,000 to 10,000, are examples of such 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 binding agents. These polymeric materials can be used as such or together with solvents like water, propylene glycol and alcohols C 10 -C 20 ethoxylated above mentioned containing 5-100 moles of oxide ethylene per mole. Other examples of binders include ethers of monoglycerol and diglycerol C 10 -C 20 and also the C 10 -C 20 fatty acids.

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

A method for the application of the material of coating includes the agglomeration. The agglomeration processes Preferred include the use of any of the materials organic binders described above. Can be used any conventional agglomerator / mixer including, but of non-exclusive form, those of tray type, rotating drum and vertical mixer Compositions of molten coating by pouring or spraying on a moving bed of bleaching agent.

Other means to provide release controlled required include mechanical means to alter the physical characteristics of the bleach to control its solubility and release rate. Appropriate protocols could include compression, mechanical injection, manual injection and adjustment of the solubility of the bleaching compound by size selection of particle 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 desired controlled release kinetics, it is desirable that the particle size is greater than 500 micrometers, preferably having an average particle diameter of 800 to 1,200 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 to reach the kinetics of controlled release required.

Metal containing bleach catalyst

The compositions described herein memory containing bleach as active detergent component may additionally contain as preferred component a bleach catalyst that contains a metal. 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 defined bleaching catalytic activity, such as copper cation, iron, an auxiliary metal cation that has little or no catalytic activity, such as zinc or aluminum cation and a sequestrant that has stability constants defined for the catalytic and auxiliary metal cations, in particular acid ethylenediaminetetraacetic acid ethylenediaminetetra (methylene phosphonic) and salts water soluble thereof. Such catalysts are described in the US 4,430,243.

Preferred types of bleach catalysts 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 (uO) 3 (1,4,7-trimethyl-
1,4,7-triazacyclononane) 2 - (PF 6) 2, Mn III 2 (uO) 1 (u-OAc) 2 ( 1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4) 2, Mn IV 4 (uO) 6 (1 , 4,7-triazacyclononane) 4 - (ClO 4) 2, Mn III Mn IV 4 (uO) 1 (u-OAc) _ {2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4) 3 and
mixtures thereof. Others are described in EP-549,272. Other ligands suitable for use in the present 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 properly selected for the present invention. Can be seen examples of suitable bleach catalysts in US 4,246,612 and US 5,227,084. See also US Patent 5,194,416, which describes mononuclear (IV) manganese complexes 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 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 Patent 5,114,611 describes a bleach catalyst comprising a metal complex 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 substituted alkyl and aryl, 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 they can each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrazine, pyrimidine, imidazole, Pirazo and Triazole. Optionally said rings may 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 preferred catalysts 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 of same.

Preferred examples include complexes Mn binuclear 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 the structures of the manganese bleach catalyst complexes of the In the present invention, it has been speculated that these comprise chelates or other hydrated coordination complexes that result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Similarly, it is not known with certain the oxidation state of the manganese cation during catalytic process and can have the state of Valencia (+ II), (+ III), (+ IV) or (+ V). Due to the six possible junction points of the manganese cation ligands, you can speculate reasonably there are multinuclear species and / or structures in "cage" in aqueous bleaching media. Regardless of the form of the type of active Mn ligand really existing, this acts in a seemingly catalytic way to provide better stain bleaching performance persistent such as tea, ketchup, coffee, wine or juice.

Other bleach catalysts are described, for example, in EP-408,131 (cobalt complex catalysts), EP-384,503 and EP-306,089 (metalloporphyrin catalysts), US-4,728,455 (multidented manganese / ligand catalyst), US -4,711,748 and EP-224,952, (manganese catalyst absorbed on aluminosilicate), US-
4,601,845 (aluminosilicate substrate with manganese and zinc or magnesium salt), US 4,626,373 (manganese / ligand catalyst), US 4,119,557 (ferric complex catalyst), DE-2,054,019 (chelating catalyst of cobalt), CA-866.191 (salts containing transition metal), US-4,430,243 (chelators with manganese cations 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} P_ {p}] \ Y_ {y}

where the cobalt is in a oxidation state of +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 charged anion -1), to obtain a salt with a balanced charge, preferably Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and where, in addition, at least one of the coordination sites attached to cobalt is labile in the conditions of use of dishwasher and other coordination sites stabilize cobalt in the conditions of use of dishwasher so that the reduction of the potential of cobalt (III) to cobalt (II) under alkaline conditions it is less than 0.4 volts (preferably less than 0.2 volts) with respect to an electrode of hydrogen 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 and most preferably 5); M 'is a labile coordination rest, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer of 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6; and And it is a selected counter-anion properly present in a number and, which is an integer from 1 to 3 (preferably from 2 to 3; with highest preference 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) with 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, where and is an integer to obtain a salt with balanced load (preferably and is 1 to 3; most preferably 2 when T is an anion with charge -1); and where, in addition, said catalyst has a constant basic hydrolysis rate 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 may be protonated if in T there is more than one anionic group, for example, HPO4-2, HCO3-, H_ {PO} {4} -. In addition, T can be selected from the group that consists of non-traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES)) and / or anionic polymers (e.g., polyacrylates, polymethacrylates).

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 monocarboxylates, although in the rest may be present more than one carboxylate provided that the Cobalt binding is performed only with a carboxylate by remainder, in which case the other carboxylate existing in the remainder M it may be protonated or in its salt form). Optionally, M can be protonated if more than one anionic group exists in M (for example, HPO 4 2-, HCO 3 -, H 2 PO 4 -, HOC (O) CH 2 C (O) O-). The remains M Preferred are C 1 -C 30 carboxylic acids substituted and unsubstituted that have the formula:

RC (O) O-

where R is selected preferably from the group consisting of hydrogen and alkyl C 1 -C 30 (preferably 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 and 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. The R More preferred 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.

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Residues B include carbonate, dicarboxylates and (higher) (eg oxalate, malonate, malate, succinate, maleate), picolinic acid, as well as alpha-amino acids and beta-amino acids (e.g., 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 rate, in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg Bioinorg Mech ., (1983), 2, p. 1-94. For example, table 1 on page 17 shows the rates of basic hydrolysis (referred to herein as k_ {OH}) for cobalt pentaamine catalysts that complex with oxalate [k_ {OH} = 2.5 x 10 <4> M <-1> s <-1> (25 ° 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 the pentaamine and cobalt acetate salts having the formula [Co (NH 3) 5 OAc] T y, wherein OAc represents an acetate moiety and especially cobalt pentamine 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 ("PAC" herein).

These cobalt catalysts are readily prepared by known methods, such as those described for example in the article to be cited above and in the references cited herein, 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 synthesis examples provided below.

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

These catalysts can be processed together with adjuvant materials if you want to reduce the color impact for aesthetic purposes of the product or can be include in particles containing enzyme as illustrated by then, or the compositions can be manufactured in a manner containing "specks" of catalyst.

Organic polymeric compound

Organic polymeric compounds can be added as preferred components of conforming detergent tablets to the invention. By organic polymeric compound is meant virtually any organic polymeric compound that usually found in detergent compositions that have dispersant properties, antiredeposition, to release the dirt or other detergency properties.

In the detergent compositions of the invention organic polymeric compounds are typically incorporated into a 0.1% to 30% level, preferably 0.5% to 15% and with maximum preference from 1% to 10%, by weight of the composition.

Examples of organic polymeric compounds include homopolymeric or copolymeric polycarboxylic acids water-soluble organic, modified polycarboxylates or their 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 last type are described in GB-A-1,596,756. Examples of this type of salts are molecular weight polyacrylates 2,000-10,000 and their copolymers with any other suitable monomer unit including acrylic acid, acid fumaric, maleic acid, itaconic acid, aconitic acid, acid mesaconic, citraconic acid and methylenemalonic acid or its salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixture thereof. The copolymers of Acrylic acid and maleic anhydride having a molecular weight of 20,000 to 100,000.

Polymers that contain acrylic acid Preferred commercials having a molecular weight less than 15,000 include those distributed with the trade name Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH and the distributed under the trade name 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 hydroxyalkyl with 1 to 4 carbon atoms, R 1 or R 2 can be a hydrogen and R 3 can be a hydrogen or a metal salt alkaline. Most preferred is an acrylic monomer substituted in where R 1 is methyl, R 2 is hydrogen (i.e., a monomer of methacrylic acid). The most preferred copolymer of this type It has a molecular weight of 3500 and contains 60% to 80% by weight of Acrylic acid 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 glycol 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, or (ii) segments of oxypropylene or polyoxypropylene with a polymerization degree of 2 to 10, wherein said hydrophilic segment does not cover any unit Oxypropylene unless attached to adjacent debris in each end by ether type links, or (iii) a mixture of units oxyalkylene comprising oxyethylene and 1 to 30 units oxypropylene, said hydrophilic segments comprising preferably at least 25% oxyethylene units and more preferably, especially for these components that have 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, where, if said hydrophobic components also comprise oxyethylene terephthalate, the relationship between oxyethylene terephthalate units and units C3 oxyalkylene terephthalate is 2: 1 or less, (ii) C4-C6 alkylene or oxyalkylene segments C 4 -C 6, or mixtures thereof, (iii) poly (vinyl ester) segments, preferably poly (acetate vinyl), with a polymerization degree of at least 2, or (iv) C 1 -C 4 alkyl ether substituents or C4 hydroxyalkyl ether, or mixtures thereof, wherein said substituents are present in the form of alkyl ether derivatives C 1 -C 4 or C 4 hydroxyalkyl ether cellulose, or mixtures thereof, or a combination of (a) and (b).

Typically, polyoxyethylene segments of (a) (i) will have a polymerization degree of 200, although the degree it may be higher, preferably from 3 to 150, more preferably from 6 to 100. Hydrophobic oxyalkylene segments Suitable C4 {C6} include, but not limiting form, terminal protections of agents to release the 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 oxide terephthalate. Such agents are commercialized and include hydroxyethers of cellulose such as METHOCEL (Dow). Agents to release the cellulosic dirt of use in the present invention also include those selected from the group consisting of alkyl C 1 -C 4 cellulose and C 4 hydroxyalkyl cellulose; see US-4,000,093, granted to Nicol et al. on December 28, 1976.

Agents to release dirt characterized by having hydrophobic segments of poly (vinyl ester) include polyvinyl graft copolymers ester), p. e.g., C 1 -C 6 vinyl esters, preferably the polyvinyl acetate grafted into main chains of poly (alkylene oxide), such as main chains of poly (ethylene oxide). Watch EP-0 219 048, granted on April 22, 1987 to Kud et al.

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

Another agent to release polymer dirt suitable is a polyester with repeated 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 medium molecular weight polyoxyethylene glycol 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 of repeated units of terephthaloyl and oxyalkyleneoxy and terminal residues covalently linked to the main chain. These agents to release dirt are fully described in US 4,968,451, granted to J.J. Scheibel and E.P. Gosselink on November 6, 1990. Other agents to release the Suitable polymeric dirt include polyesters of US-4,711,730 patent terephthalate, granted to Gosselink et al. on December 8, 1987, the oligomeric esters anionic 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 polymeric dirt also include agents to release the dirt from the patent US 4,877,896, granted to Maldonado et al. on 31 of October 1989, which describes anionic terephthalate esters with protected ends, especially with sulfoarolyl.

Another agent to release dirt is a oligomer with repeated units of terephthaloyl units, sulfoisoterephthaloyl units, 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 tablets of the invention preferably they contain as an optional component a sequestrant Heavy metal ion. Per heavy metal ion sequestrant it is understood herein those components that act sequestering (chelating) heavy metal ions. These components they may also have the ability to chelate calcium and magnesium ions, although they are especially selective for metal ions heavy as iron, manganese or copper.

Heavy metal ion sequestrants will they 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 most preferably from 0.5% to 5%, by weight of the compositions

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

Heavy metal ion sequestrants Suitable in the present invention include organic phosphonates such as the amino alkylene poly (alkylene phosphonates), the ethane-1-hydroxy diphosphonates of alkali metals and nitrile-trimethylene phosphonates. The Preferred species among the above are the diethylene triamino penta (methylene phosphonate), the ethylenediamine-tri (methylene phosphonate), the hexamethylene diamine tetra (methylene phosphonate) and the hydroxyethylene-1,1-diphosphonate.

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

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

Crystal growth inhibitor component

Detergent tablets preferably contain 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.

By organodiphosphonic acid is understood in the present memory an organodiphosphonic acid that does not contain nitrogen in its chemical structure. Therefore, this definition excludes organic aminophosphonates, which, without However, they can be included in the compositions of the invention as heavy metal ion sequestrant components.

The organophosphonic acid is preferably a C 1 -C 4 diphosphonic acid, plus preferably a C2 diphosphonic acid such as ethylene acid diphosphonic or most preferably an ethane acid 1-hydroxy-1,1-diphosphonic (HEDP), and may be present partially or totally ionized, especially as salt or complex.

Water Soluble Sulfate Salt

The detergent tablet optionally contains a water-soluble sulfate salt. When the water-soluble sulfate salt is present, is at a level of 0.1% to 40%, more preferably of 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 metal sulfates alkaline and alkaline earth, in particular sodium sulfate.

Alkali metal silicate

According to an embodiment of the present invention, An essential component of the detergent tablet is a silicate alkali metal In other embodiments of the present invention The presence of an alkali metal silicate is optional. A Preferred alkali metal silicate is the sodium silicate which has a SiO2: Na2O ratio of 1.8: 3.0, preferably of 1.8: 2.4 and most preferably 2.0. The sodium silicate is preferably present at a level below 20%, preferably from 1% to 15% and most preferably from 3% to 12%, by weight, of SiO_ {2}. The alkali metal silicate can be in salt form anhydrous or hydrated salt.

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

The alkalinity system also contains preferably a sodium metasilicate, present at a level of at minus 0.4% SiO2 by weight. Sodium metasilicate has a Nominal ratio SiO2: Na2O of 1.0. Weight ratio 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 certain wavelengths of the visible light spectrum. These dyes, when added to a detergent composition, they have the effect of change the visible color and therefore 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 composition with high pH the dye is preferably stable against alkalis and in a pH composition under the dye is preferably stable against acids.

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 have visual aspects different. Preferably or the compressed part or the non-part Compressed comprises a dye.

When the uncompressed part comprises two or more compositions of active detergent components, preferably at least the first or second and / or other Additional compositions comprise a dye. When both the first as the second and / or other additional compositions comprise a dye, it is preferred that the dyes have a different visual aspect.

The coating layer preferably comprises a dye. When the compressed part and the coating layer comprise a dye, it is preferred that the dyes provide a different visual effect.
tea.

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

The dye can be incorporated into the part compressed and / or to the uncompressed part by any method suitable. Suitable methods include mixing all or of selected active detergent components with a dye in a drum or spray all detergent components assets selected with the dye in a rotating drum.

The dye, if present as a component of the compressed part, is in an amount of 0.001% to 1.5%, preferably 0.01% to 1.0% and most preferably 0.1% to 0.3%. If the dye is present as a component of the uncompressed part, is generally in an amount of 0.001% to 0.1%, more preferably from 0.005% to 0.05% and most preferably from 0.007% to 0.02%. If the dye is present as a component of the coating layer, is in an amount of 0.01% to 0.5%, more preferably from 0.02% to 0.1% and most preferably 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 are described in the codependent application EP-A-672 749.

The organic silver coating agent is it can incorporate in an amount 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 protective over any of the silver components of the load wash to which the compositions of the invention are applied. Therefore, the silver coating agent should have high binding affinity to solid silver surfaces, in particular when present as a component of the solution aqueous wash and bleach with which the solid silver surfaces.

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

The fatty acid fraction of the fatty ester is can be obtained from monocarboxylic or polycarboxylic acids which have 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include acid Behenic, stearic acid, oleic acid, palmitic acid, acid myristic, lauric acid, acetic acid, propionic acid, acid butyric acid, isobutyric acid, valeric acid, lactic acid, acid glycolic 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 is can represent by monohydric or polyhydric alcohols that they have 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty acid alcohols include the Behenyl, arachidyl, cocoyl, oleyl and lauryl alcohols, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan

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

Preferred fatty acid esters herein invention are ethylene glycol, glycerol and sorbitan esters in the that the fatty acid fraction of the ester normally comprises a selected species of behenic acid, stearic acid, acid oleic, 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 dilactate, cocoyl isobutyrate, oleyl maleate, Oleil dimaleate and tallow propionate. Acid esters Fatty useful in the present invention include: monopalmitate xylitol, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, esters of sorbitan Suitable sorbitan esters include monostearate sorbitan, sorbitan palmitate, sorbitan monolaurate, sorbitan monomiristate, sorbitan monobehenate, monooleate sorbitan, sorbitan dilaurate, sorbitan distearate, dibehenate sorbitan, sorbitan dioleate and also monoesters and diesters of seboalkyl sorbitan.

Glycerol monostearate, monooleate 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, cottonseed, castor oil, olive oil, oil peanut, safflower oil, sunflower oil, rapeseed oil, Grape oil, palm oil and corn oil.

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

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

Dialkyl oxides are also suitable amine such as C 12 -C 20 methylamine oxide and quaternary dialkylammonium compounds and salts, such as C 12 -C 20 methylammonium halides.

Other silver coating agents Organic include certain polymeric materials. The polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole and cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethylcellulose are examples of this type of materials polymeric

Certain perfume materials, in particularly those that have demonstrated high efficacy in metal surfaces are also useful as agents of Organic silver coating in the present invention.

They can also be used as an agent of organic silver coating agents to release dirt polymeric

An organic silver coating agent preferred is a paraffin oil, typically a hydrocarbon fundamentally branched aliphatic that has a number of atoms carbon in the range of 20 to 50; paraffin oil preferred is mainly selected from fundamentally species branched C 25-45 with a relationship between cyclic hydrocarbons 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 hydrocarbons is marketed by Wintershall, Salzbergen, Germany, with the name WINOG 70.

Corrosion inhibitor compounds containing nitrogen

Corrosion inhibitor compounds that Suitable nitrogen containing include imidazole and derivatives of the themselves, such as benzimidazole, 2-heptadecyl imidazole, and the imidazole derivatives described in the patent CZ-139.279 and in GB-A-1,137,741, which also describes a method for the preparation of compounds of imidazole

They are also suitable as compounds corrosion inhibitors containing nitrogen compounds pyrazole and its derivatives, especially those in which the 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 it 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 they contain nitrogen, like amines, especially the distearylamine and ammonium compounds, such as ammonium, ammonium bromide, ammonium sulfate or hydrogen citrate Demon

Corrosion inhibitor compounds of Mn (II)

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

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

The compound of Mn (II) can be a salt or 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 include mercaptan and diols, especially mercaptan with 4 to 20 carbon atoms, including lauryl mercaptan, thiophenol, thionaphthol, thionalide and thioantranol. Acids are also suitable C 10 -C 20 saturated or unsaturated fatty acids or its salts, especially aluminum triestearate. The C 12 -C 20 fatty hydroxy acids, or their salts, They are also suitable. The phosphonated octadecane and others Antioxidants such as butylhydroxytoluene (BHT) are also adequate.

It has been observed that butadiene copolymers and maleic acid, in particular those supplied with the reference Commercial 07787 by Polysciences Inc, are especially useful as corrosion inhibitor compounds.

Hydrocarbon oils

Another preferred active detergent component for its use in the present invention is a hydrocarbon oil, of typically a predominantly chain aliphatic hydrocarbon long that has a number of carbon atoms in the range of 20 to 50; Preferred hydrocarbons are saturated and / or branched. A Preferred hydrocarbon oil is selected from types C_ {25-45} predominantly branched with a relationship between cyclic hydrocarbons and non-cyclic hydrocarbons of 1:10 to 2: 1, preferably 1: 5 to 1: 1. A hydrocarbon oil Preferred is paraffin. A paraffin oil that meets the characteristics defined above and that has a relationship between cyclic hydrocarbons and non-cyclic hydrocarbons of 32:68 is distributed by Wintershall, Salzbergen, Germany, with the name commercial WINOG 70.

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Water soluble bismuth compound

The detergent tablets of the present invention suitable for use in washing methods in Dishwashers may contain a water-soluble bismuth compound, 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 that has virtually any inorganic or organic contraanion. Salts of preferred inorganic bismuth are selected from trihalides of bismuth, bismuth nitrate and bismuth phosphate. The acetates and Bismuth citrates are the 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 bleaching agent and mixtures thereof. Such stabilizer systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Dispersing compound of calcareous soap

The compositions of detergent components assets may contain a dispersing compound of calcareous soap, preferably present in an amount 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 amine of fatty acids 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 the compositions of machine wash preferably comprise a suppressor system of 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 transfer inhibiting agents of polymeric dyes.

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

Optical brightener

The right detergent tablets for your use in laundry methods as described in the This report also optionally contains 0.005% to 5% in weight of certain types of optical brighteners hydrophilic

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

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'-stilbenedisulfonic acid and the disodium salt. This particular type of brightener is marketed under the registered trademark 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 anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is salt acid disodium 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triacin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This type of brightener in particular is marketed with 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 the acidic sodium salt 4,4'-bis [(4-anilino-6-morfilino-s-triacín-2-yl) amino] -2,2'-stilbenedisulfonic acid. This type of brightener in particular is marketed with the registered trademark Tinopal AMS-GX by Ciba-Geigy Corporation.

Clay softener system

The right detergent tablets for your Use in laundry methods may contain a system clay softener comprising a clay mineral compound and optionally a clay flocculating agent.

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

Cationic fabric softeners

They can also be incorporated into the compositions according to the present cationic softening agents of fabrics suitable for use in laundry methods. The Suitable cationic fabric softening agents include amines tertiary or amides with double long chain insoluble in water as those described in GB-A-1 patents 514 276 and EP-B-0 011 340.

Cationic fabric 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 a preferred loading salt being sulfate of sodium.

pH of the compositions

The detergent tablets of the present invention are preferably formulated so that they do not have a Excessively high pH, preferably having a pH, measured as a 1% solution in distilled water, from 8.0 to 12.5, more 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 part and the uncompressed part are formulated so that have different pH.

Dishwashing method

Any suitable method is contemplated for Machine wash or cleaning stained tableware.

A preferred method for washing in dishwasher includes the treatment of stained items selected crockery, glassware, silver items, items metal, cutlery and mixtures thereof with an aqueous liquid in which an effective amount of one has been dissolved or dispensed detergent tablet according to the invention. For a quantity Effective detergent tablet is understood from 8 g to 60 g of product dissolved or dispersed in a wash solution with a volume of 3 to 10 liters, which are the product dosages typical and usually wash solution volumes used in conventional dishwashing methods. Preferably the detergent tablets have 15 g to 40 g in weight, more preferably from 20 g to 35 g by weight.

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Laundry method

The laundry methods of this invention typically comprise the treatment of clothing stained with an aqueous wash solution in a washing machine in which an effective amount of a composition has been dissolved or dispensed of detergent tablet for washing machine clothes according to the invention. For an effective amount of a tablet composition of detergent means from 40 g to 300 g of the dissolved product or dispersed in a wash solution with a volume of 5 to 65 liters, such as typical product dosages and volumes of wash solution commonly used in Conventional machine washing methods.

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 washing machine is loaded with the clothes, the dispensing device containing the detergent product is Place inside the drum. At the beginning of the wash cycle of the washing machine water is introduced into the drum and the drum rotates periodically The design of the dispensing device should be such that allows the containment of the dry detergent product but that then allow the release of this product during the cycle of washing in response to agitation as the drum rotates and also as a result of its coming into contact with the water of washed.

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

Preferred dispensing devices are reusable and are designed in such a way 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 sack or bag. He bag can have a fibrous structure covered with a waterproof protective material so that it retains the contents, as described in EP-0018678. So alternative may be formed of a synthetic polymeric material insoluble in water provided with a seal on the edge or a closure designed to break into aqueous medium as described in EP-0011500, EP-0011501, EP-0011502 and EP-0011968. Form Suitable fragile closure in water comprises a water-soluble adhesive arranged along and closing an edge of a bag formed by a water-impermeable polymeric film of polyethylene or Polypropylene.

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 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}. 3H 2 O. H 2 O 2

Plurafac

: C 13 -C 15 fatty alcohol mixed ethoxylated / propoxylated with an average degree of ethoxylate- {} \ 3.8 of 3.8 and an average degree of propoxylation of 4,5, marketed under the name {} \ hskip0.13cm Plurafac by BASF

Tergitol

: Non-ionic surfactant marketed with the name Tergitol 15S9 by Union Carbide

SLF18

: Poly (oxyalkylated) alcohol terminally protected with epoxy groups of Example III {} of WO 94/22800 in which 1,2-epoxidedecane has been substituted by 1,2-epoxidecano, {} \ hskip0.13cm marketed under the name Polytergent SLF18D by OLIN

TAED

: Tetraacetyl ethylenediamine

HEDP

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

DETPMP

: Diethyltriamino-penta- (methylene) phosphonate, marketed by Monsanto with the name {} \ hskip0.13cmm Dequest 2060

PAAC

: Cobalt pentaamine acetate salt (III)

BzP

: Benzoyl peroxide

Paraffin

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

Protease

: Proteolytic Enzyme

Amylase

: Amylolytic enzyme.

BTA

: Benzotriazol

PA30

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

480N

: Random copolymer with a 7: 3 ratio of acrylate / methacrylate, molecular weight {} \ hskip0.13cm average 3,500

Sulfate

: Anhydrous sodium sulfate.

PEG 3000

: Polyethylene glycol with a molecular weight of approximately 3000 marketed by {} \ hskip0.13cm Hoechst

PEG 6000

: Polyethylene glycol with a molecular weight of approximately 6000 sold by {} \ hskip0.13cm Hoechst

Sugar

: Domestic Sucrose

Jelly

: Type A jelly, consistency 65, marketed by Sigma

CMC

: Carboxymethylcellulose

Dodecanedioic acid

: C12 dicarboxylic acid

Adipic acid

: C6 dicarboxylic acid

Lauric acid

: C12 monocarboxylic acid

pH

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

In Example 1 all levels are expressed as% by weight of the compressed part, of the uncompressed part or of The coating layer. The total weight (g) of the compressed part, the uncompressed part and the layer of covering.

Example 1

Below are examples of detergent tablets of the present invention suitable for Use in a dishwasher.

The compressed part is prepared by introducing the composition of active detergent components in a cavity of punch of a 12-head swivel pad press modified and compressing the composition at a pressure of 13 KN / cm2. The modified tablet press provides a tablet in which the compressed part has a mold. In the Examples A-F the uncompressed part is in the form of particles The uncompressed part is supplied exactly to the mold of the compressed part using a nozzle feeder. The uncompressed part adheres to the compressed part by coating the uncompressed part with a coating layer that is in contact with the compressed part.

25

26

27

Claims (21)

1. A detergent tablet to use in a clothes washer or dishwasher, the tablet comprising one enzyme and:

(to)

a compressed part comprising a detergent component active;

(b)

a uncompressed non-encapsulating part comprising a component active detergent, and

(C)

a coating layer on the non-encapsulating non-compressed part, where the non-encapsulating non-compressed part is fixed or subject to the compressed part

2. A detergent tablet according to the claim 1, wherein the compressed portion provides a mold previously prepared and the uncompressed part is at least partially contained in the mold. 3. A detergent tablet according to the claim 1 or claim 2, comprising a plurality of compressed parts arranged in layers. 4. A detergent tablet according to any of the preceding claims, comprising a plurality of uncompressed parts and where the compressed part provides a plurality of molds and each uncompressed part is at least partially contained in a mold. 5. A detergent tablet according to any of the preceding claims, wherein the uncompressed part It is in fluid form. 6. A detergent tablet according to any of the preceding claims, wherein the layer of Coating is water soluble. 7. A detergent tablet according to any of the preceding claims, wherein the layer of coating comprises a component selected from the group that It consists of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acids, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), poly (acetic acid) (PLA), polyethylene glycol (PEG) and mixtures of same. 8. A detergent tablet according to any of the preceding claims, wherein the speed of dissolution of the uncompressed part is greater than the speed of dissolution of the compressed part, measured with the test method of SOTAX solution described herein. 9. A detergent tablet according to any of claims 1 to 7, wherein the dissolution rate of the compressed part is greater than the dissolution rate of the uncompressed part, measured with the test method of SOTAX solution described herein. 10. A detergent tablet according to any of the preceding claims, wherein the enzyme is selected from the group consisting of amylases, proteases, cellulases, hemicellulases, peroxidases, lipases, phospholipases and mixtures of same. 11. A detergent tablet according to any of the preceding claims, wherein the component Active detergent of the uncompressed part is selected from surfactant, bleaching agent, bleach activator, bleach catalyst, enzyme, corrosion inhibitor, perfume and a source of alkalinity. 12. A detergent tablet according to any of the preceding claims, wherein the component Active detergent of the uncompressed part is a surfactant. 13. A detergent tablet according to any of the preceding claims, comprising a silicate of alkali metal 14. A detergent tablet according to any of the preceding claims, wherein the weight ratio between the compressed part and the uncompressed part is greater than 0.5: 1, the detergent tablet comprises silicate and the tablet detergent comprises at least 20% by weight of reinforcing compounds of detergency, with respect to detergent components assets. 15. A detergent tablet according to any of the preceding claims, wherein the layer of coating encapsulates the detergent tablet. 16. A detergent tablet according to any of the preceding claims, wherein the tablet of detergent further comprises a disruptive agent that is a disintegrating agent, an effervescent agent or mixtures of same. 17. A detergent tablet according to claim 16, wherein the disruptive agent is selected from the group consisting of starch, starch derivatives, alginate, polymers based on carboxymethyl cellulose (CMC), sodium acetate, aluminum oxide, carbonate, bicarbonate, carboxylic acids and mixtures thereof. 18. A process to prepare a pill of detergent to use in a clothes washer or in a dishwasher, the tablet comprising an enzyme and the process comprising the stages of:

(to)

compress a composition that comprises an active detergent component to form a part compressed

(b)

provide a composition that it comprises an active detergent component to the compressed part for form an uncompressed non-encapsulating part; Y later

(C)

cover at least part of the uncompressed part with a coating layer to fix or fasten the uncompressed part to the compressed part.

19. A process to prepare a pill of detergent to use in a clothes washer or dishwasher, the tablet comprising an enzyme and the process comprising the stages of:

(to)

compress a composition that comprises an active detergent component to form a part tablet that has a mold;

(b)

provide a composition that it comprises an active detergent component to the mold to form a non-encapsulating part not compressed so that the part does not tablet is at least partially contained in the mold, and later

(C)

cover at least part of the uncompressed part with a coating layer to fix or fasten the uncompressed part to the compressed part.

20. A process according to claim 19, in the which compressed part is prepared using a press to modified pads comprising upper punches and / or bottoms that are modified so that the compressed part provide one or more indentations that form the mold. 21. A process according to any of the claims 18 to 20, wherein the tablet has any of the additional features mentioned in the claims 3 to 17.