ES2199904T3 - DETERGENT TABLET - Google Patents

Abstract

A multi-stage laundry detergent tablet, comprising: a) a first phase that is in the form of a shaped body having at least one mold on its surface; and b) a second phase that is in the form of a compressed body, adhesively contained within said mold, in which the composition of the tablet comprises one or more detergent active ingredients that are predominantly concentrated in the second phase, and in the that the second phase additionally comprises a binding agent, and the first and second phases are in a weight ratio of at least 6: 1, and the tablet is such that the differential dissolution of the phases takes place during use.

Description

Detergent tablet

Technical field

The present invention relates to tablets of multi-phase laundry detergent.

Background

Compositions of Detergents in the form of tablets. It is understood that the compositions of detergents in the form of tablets contain several advantages with with respect to particulate detergent compositions, such as ease of dosing, handling, transport and storage.

Detergent tablets are prepared in the manner more current by previously mixing the components of a detergent composition and forming the components previously mixed detergent to the form of a tablet using any  suitable equipment, preferably a press for compression of tablets Tablets are typically formed by compression of the components of the detergent composition so that the produced tablets are robust enough to be able to withstand handling and transport without substantial damage. In addition to being robust, tablets should also be dissolved fast enough so that the detergent components be released into the wash water as soon as possible by beginning of the wash cycle.

However, there is a dichotomy in the sense that, as the compression pressure increases, the dissolution rate of the tablets is slower. Thus, The present invention seeks to find a balance between the robustness of the tablet and dissolution of the tablet.

The solutions to this problem, as seen in the prior art, have included compressing the tablet with a low compression pressure However, tablets made from this way, although they have a relative dissolution rate fast, they tend to fall apart, being damaged and unacceptable for the consumer Other solutions have included preparing tablets using a relatively high compression pressure, so to achieve the required level of robustness, and compress an auxiliary of the solution, such as an effervescent agent.

Multi-phase detergent tablets described in the prior art are prepared by compressing a first composition in a tablet press, to form a First substantially flat layer. Then it is supplied to the tablet press an additional detergent composition over the top of the first layer. This second composition is then compressed to form another second layer substantially flat. In this way, the first layer is subjected generally more than one compression, since it also compresses during compression of the second composition. Typically, the first and second compression forces are of Same order of magnitude. The applicant has found that when This is the case, because the compression force must be enough to bind the first and second compositions, the force used in both first and second compression stages must be in the range of about 4,000 to about 20,000 Kg (assuming a cross section of the tablet of about 10 cm 2). A consequence of this is a slower dissolution rate of the tablet. Other tablets of multiple phases, which show a differential solution, are they prepare so that the second layer is compressed to a force smaller than the first layer. However, although the dissolution rate of the second layer, the second layer is soft compared to the first layer and therefore it is vulnerable to damage caused by manipulation and transport.

The patent EP-B-0.055.100 describes a block for washbasin formed by the combination of a shaped body of Slow dissolution with a tablet. The sink block is designed to be placed in a toilet cistern, and it dissolve over a period of days, preferably weeks. How means to slow the dissolution rate of the block to washbasin, the patent shows the mixture of one or more agents of solubility control. Examples of such control agents of the solubility are paradichlorobenzene, waxes, fatty acids of long chain and its alcohols and their esters, and fatty alkylamides. Detergent tablets for use in laundry or in the Automatic dishwasher should be substantially dissolved in a cycle of the washing machine or dishwasher, that is, from 15 to 120 minutes

Summary of the invention

According to a first aspect of the invention, Provides a multi-stage detergent tablet for use in a laundry washing machine, and understanding the tablet:

a) a first phase in the form of a body shaped, which has at least one mold on its surface; Y

b) a second phase in the form of a body adhesive content within said mold, in which the tablet composition comprises one or more active ingredients detergents, which are predominantly concentrated in the second phase, and in which the second phase additionally comprises a binding agent, and in which the first and second phases are in a weight ratio of at least 6: 1, and the tablet is such that differential dissolution of the phases occurs during use.

In preferred embodiments, the first phase is a compressed shaped body, prepared at a pressure of applied compression of at least 40 Kg / cm2, preferably at minus 250 kg / cm 2, more preferably at least 350 kg / cm 2 (3.43 kN / cm2), even more preferably at least from 400 Kg / cm2 up to about 2000 Kg / cm2, and especially from about 600 Kg / cm2 to approximately 1,200 kg / cm2 (the compression pressure in this invention is the applied force divided by the area of the cross section of the tablet in a plane transverse to the applied force - actually, the cross-sectional area of the rotary pressure die). It is also preferred that the particulate solid of the second phase (whose terminology is intended to include the possibility of multiple "second" phases, sometimes referred to in this invention as "phases optional later ") is compressed in said mold at a pressure of compression applied less than that applied to the first phase and preferably at a compression pressure less than approximately 350 kg / cm2, preferably in the range of  approximately 40 kg / cm2 up to approximately 300 Kg / cm2, and more preferably from about 70 Kg / cm2 up to about 270 Kg / cm2, with preference in this invention such tablets from the point of view of provide optimum integrity and resistance characteristics to the tablet (measures, for example, by the Child Bite test Strength CBS), and dissolution characteristics of the product. The tablets of the invention preferably have a CBS of at least 6 Kg, preferably greater than about 8 Kg, more preferably greater than about 10 kg, especially greater that approximately 12 Kg, and more especially greater than approximately 14 Kg, the CBS being measured by the Specification Test of the US Commission Product Safety at Consumer. Also, the compression pressures applied to the first and second phases will generally be in a relationship of at less about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1.

Thus, according to a preferred aspect of the invention, the tablet comprises:

a) a first phase in the form of a body compressed forming having at least one mold; preparing the body shaped at a compression pressure of at least about 350 Kg / cm2; Y

b) a second phase in the form of a solid in particles, compressed within said mold, the second being compressed phase at a pressure less than about 350 Kg / cm2.

The second phase is in the form of a body compressed or shaped adhesive content, for example by physical or chemical adhesion, within at least one mold of the first body. It is essential that the first and second phases are in a relatively high weight ratio to each other, at least about 6: 1, preferably at least about 10: 1; also that the tablet composition contains one or more detergent active ingredients (for example enzymes, bleaching, bleaching agent activators, catalysts bleaching agents, surfactants, chelating agents, etc.), which are predominantly concentrated in the second phase, by example, at least 50%, preferably at least 60%, especially about 80% by weight of the active ingredient (based on weight total active ingredient in the tablet) is in the second tablet phase. Again, such compositions are optimal for the characteristics of resistance, dissolution, cleaning and pH regulation of the tablet, providing, for example, tablet compositions capable of dissolving in the liquor of washing, to supply at least 50%, preferably at least 60%, and more preferably at least 80% by weight of the ingredient detergent active to the wash liquor within 10, 5, 4 or even 3  minutes from the beginning of the washing process.

Thus, according to another preferred aspect of the invention, the tablet comprises:

a) a first phase in the form of a body shaped that has at least one mold in it; Y

b) a second phase in the form of a solid in particles, compressed within said mold, and in which the tablet comprises at least one detergent active ingredient and is formulates so that at least 50%, preferably at least 60%, more preferably at least 80% by weight of the active ingredient detergent is supplied to the wash within the first 10 minutes, preferably within the first 5 minutes, and more preferably within the first 3 minutes of the process of washed.

An additional benefit of the invention is the ability to achieve differential dissolution of the phases, of so that one phase of the tablet will dissolve significantly before another phase, and can even be dissolved in a way essentially complete before the other phase has dissolved. This is particularly valuable for the differential supply of detergent active ingredients.

Thus, according to another preferred aspect of the invention, the tablet comprises:

a) a first phase in the form of a body shaped that has at least one mold in it; Y

b) a second phase in the form of a body tablet, adhesively contained within said mold, in the that the composition comprises one or more active ingredients detergents that are predominantly concentrated in the second phase, and in which the second phase additionally comprises a agent to undo the tablet.

Suitably, the active ingredient (s) Detergents are selected from enzymes, bleaching agents, bleach activators, bleach catalysts, surfactants, chelating agents, growth inhibitors of crystals, and mixtures thereof, with particular preference being given to Enzymatic active ingredients to enhance the performance of  cleaning during the earliest cold water stage of the wash or cleaning operation Therefore, they are preferred considerably for use in this invention the ingredients active enzymatic detergents, and especially enzymes and mixtures of enzymes comprising one or more enzymes that have a increased or optimal activity in the temperature range of 25 ° C at 55 ° C, and at a pH value in the range of 8 to 10 (for example, Natalase)

Thus, according to yet another aspect Preferred of the invention, the tablet comprises:

a) a first phase in the form of a body shaped that has at least one mold in it; Y

b) a second phase in the form of a body compressed, adhesively contained within said mold, and in the that the second phase additionally comprises an enzyme.

Detailed description of the invention

It is an object of the present invention provide a detergent tablet that is not only robust enough to withstand handling and transport, but also at least a significant portion of it dissolves quickly in the wash water, providing a quick supply of the active ingredient Detergent. It is preferred that at least one phase of the tablet be dissolve in the wash water within the first ten minutes, preferably five minutes, more preferably four minutes of the washing cycle of an automatic dishwasher or a Automatic washing-machine. Preferably, the washing machine is a Automatic dishwasher or an automatic washing machine. The time in the that the multi-phase tablet or one of its phases or a Detergent active component dissolves is determined according with DIN 44990 using a dishwasher available in the Bosch brand in the normal washing program at 65ºC with a hardness of 18ºH water, using a minimum of six replicas or a number enough to ensure reproducibility.

The multi-stage detergent tablet of the The present invention comprises a first phase, a second and optionally later phases. The first phase is in the form of a shaped body of detergent composition, comprising one or more detergent components as described below. The Preferred detergent components include a builder detergency, a bleaching agent, enzymes and surfactant. The components of the detergent composition are mixed together, by example, mixing the dry components or spraying the liquid components Then the components conform to a first phase using any suitable equipment but preferably by compression, for example, in a press for tablets Alternatively, the first phase can be prepared by extrusion, casting, etc. The first phase can take a variety of geometric shapes, such as spheres, cubes, etc., but the preferred embodiments have a generally symmetrical shape with respect to an axis, with a cross section generally Round, square or rectangular.

The first phase is prepared so that you understand at least one mold on the surface of the shaped body. Mold or molds may also vary in size and shape, and in their location, orientation and topology in relation to the first phase. For example, the mold or molds can generally have circular, square or oval cross sections; they can form an internally closed cavity or a recess on the surface of the shaped body, or they can extend between regions not connected from the body surface (for example, surfaces facing axially opposite) to form one or more topological "holes" in the shaped body; and you can arrange axially or otherwise symmetrically in relation to the first phase or can be arranged asymmetrically. In a preferred embodiment, the mold is created using a press specially designed for tablets in which the surface of the punch that comes into contact with the detergent composition is shaped so that when in contact and press the detergent composition, press a mold or multiple molds in The first phase of the multi-phase detergent tablet. Preferably, the mold will have a concave surface towards inside, or generally concave, to provide adhesion improved to the second phase. Alternatively, the mold can be create compressing a preformed body of composition of detergent arranged annularly around a die cutter central, thereby forming a shaped body that has a mold in the form of a cavity that extends axially between opposite surfaces of the body.

The tablets of the invention also include a or more additional phases, prepared from a composition or compositions comprising one or more detergent components such as They are described later. At least one phase (named in this invention as a second phase) preferably takes the form of a particulate solid (whose expression encompasses powders, granules, agglomerates, and other particulate solids, including mixtures of the same with liquid binders, meltable solids, sprays, etc.) compressed in / with one or more molds of the first phase of the detergent tablet, so that the own Second phase takes the form of a shaped body. Phases Additional optional include one or more compositions in form of a separate layer or layers. Detergent components Preferred include detergency builders, dyes, binders, surfactants, tablet undoing agents, and enzymes, in particular amylase enzymes and proteases. In other preferred aspect of the present invention, the second phase, and optionally the subsequent phases comprise an agent for undo the tablet that can be selected from an agent disintegrant or effervescent agent. Disintegrating agents Suitable include agents that swell upon contact with water or that facilitate the entry and / or exit of water through channel formation in the detergent tablet. In this invention  any suitable disintegrating or effervescent agent is provided for use in laundry or dishwasher applications. The agent Suitable disintegrant includes starches (such as starches natural, modified, and pregelatinized, for example derived from corn, rice and potato starch), derived from starch such as U-Sperse (trade name), Primojel (trade name) and Explotab (trade name); celluloses, microcrystalline celluloses, and cellulose derivatives, such as Arbocel (trade name) and Vivapur (trade name),  both available from Rettenmaier, Nymcel (trade name), available in Metsa-serla, Avicel (name commercial), Lattice NT (trade name) and Hanfloc (name commercial), alginates, acetate trihydrate, burkeite, carbonate monohydrate of formula Na 2 CO 3 .H 2 O, hydrated STPP with a phase I content of at least about 40%, carboxymethyl cellulose (CMC), CMC type polymers, sodium acetate, aluminum oxide. Suitable effervescent agents may be those that produce a gas in contact with water. The agents Suitable effervescent can be species that give off oxygen, nitrogen dioxide or carbon dioxide. Examples of agents Preferred effervescent can be selected from the group that consists of perborate, percarbonate, carbonate, bicarbonate, in combination with carboxylic acid or other acids such as acid citric, sulfamic, malic or maleic.

The components of the detergent composition are mix together, for example by mixing the dry components, and mixing or spraying liquid components. The components of the second phase, and optionally later phases, are fed then in the mold and are retained in the mold provided by the first phase.

The preferred embodiment of the present invention It comprises two phases: a first phase and a second phase. The first phase will normally comprise a mold, and the second phase It will normally consist of a single active detergent composition. Without  However, the first phase is expected to comprise more than one mold, and the second phase can be prepared from more than one active detergent composition. In addition, it is also expected that the second phase can comprise more than one active composition detergent contained within a mold. It is also expected that various detergent active compositions are contained in molds  separated. In this way, components can be separated potentially sensitive detergents chemical, in order to avoid any loss in the benefits of behavior caused by components that react together and that they become potentially inactive or run out.

In the present invention, the first phases, second and / or optionally subsequent phases, may comprise a binder. The binder is selected from the group consisting in organic polymers, for example polyethylene- and / or polypropylene glycols, especially those of 4,000 molecular weight, 6,000 and 9,000; paraffins; polyvinyl pyrolindone (PVP), especially PVP of molecular weight 90,000; polyacrylates; sugars and sugar derivatives; starch and starch derivatives, by example hydroxypropyl methylcellulose (HPMC) and carboxymethyl cellulose (CMC); and inorganic polymers, such as hexametaphosphate. The binder is valuable for both the integrity of the tablet and to help achieve differential dissolution of the phases First and second as described below.

In a preferred aspect of the present invention, the first phase weighs more than 3 g, preferably more than 4 g, more preferably more than 5 g. More preferably, the first phase weighs from 10 g to 30 g, even more preferably from 15 g to 25 g, and most preferred, from 18 g to 24 g. The second phase, and the phases optionally later, weigh less than 4 g. Plus preferably, the second phase and / or the phases optionally later weigh between 0.1 g and 3.5 g, preferably between 1 g and 3.5 g, most preferred from 1.3 g to 2.5 g.

In another embodiment of the present invention, places a barrier layer, which comprises a layer composition barrier, between the first and second phases and / or phases optionally later, or in fact between the second and optionally phases later. The composition of the barrier layer comprises at least one binder selected from the group described previously. The advantage of the presence of a barrier layer is prevent or reduce the migration of components from one phase to the another, for example from the first phase to the second phase and / or optionally later phases, and vice versa.

The components of the second phase and the phases optionally later they are preferably compressed to a relatively low compression pressure, relative to the compression pressure normally used to prepare tablets. From Thus, an advantage of the present invention is that, due to The low compression pressure used, can be incorporated into the detergent tablet heat sensitive detergent components, to pressure or chemically sensitive, without suffering loss consistent of benefits usually found when incorporate such components in the tablets. Alternatively, the second phase or phases can be compressed at the same pressure of compression or at higher pressure than the first phase, in order to achieve the differential dissolution of the phases as described further down.

An additional advantage of the present invention is Improved protection of the second phase against the damage caused, for example, by handling and transport. How has it described above, detergent tablets of multiple phases in which the second layer is compressed to a smaller compression pressure than the first layer. However, although improves the speed of dissolution, the second layer of these tablets become vulnerable to damage, tending to crumble or to form chips on contact. The phase or phases slightly tablets of the detergent tablets of the present invention are they protect, however, within the mold provided by the First phase of the detergent tablet.

Yet another advantage of the present invention is the ability to prepare a multi detergent tablet phases in which a phase can be designed to dissolve, of preferably significantly, before the other phase. In the In the present invention, it is preferred that the second phase and the (s) optionally subsequent phase (s) are dissolve (n) before the first phase. According to the intervals Preferred weights described above, it is preferable that the first phase dissolves in 5 to 20 minutes, more preferably of 10 to 15 minutes, and the second phase and / or the phases optionally later dissolve in less than 5 minutes, more preferably in less than 4.5 minutes, most preferred, in less 4 minutes Alternatively, the second phase can be dissolved. after the first phase or the other phases, for example, when you want it to provide cleaning or rinse benefits towards the end of the washing operation. The time in which the first, the second and / or the optionally subsequent phases are Dissolve is independent of each other. Thus, in the present Invention the differential dissolution of the phases is achieved. A particular benefit of being able to achieve dissolution differential of the multi-phase detergent tablet is that a component that is inactive can be separated in a different phase chemically by the presence of another component. In this case, the component that is inactive is preferably placed in the second phase or in the optionally subsequent phases.

Yet another advantage of the present invention is Improved adhesion between the phases of the multi tablet phases It is believed that improved adhesion is achieved by reducing the second phase exposure compared to tablets multiple phases known in the art, resulting in tablets of the present invention that are less susceptible to fracture along the line of contact between the phases.

Process

The multi-phase detergent tablets are prepare using any tablet training equipment suitable, for example, Courtoy R253. Preferably, the tablets they are prepared by compression in a tablet press capable of Prepare a tablet comprising a mold. In one embodiment particularly preferred of the present invention, the first phase is prepared using a press to make tablets especially designed, following the procedure described below. The punch or punches of this tablet press is modified or modify so that the surface of the punch that enters contact with the detergent composition have a surface convex

A first composition of detergent in the tablet press die, and the punch it is lowered to come into contact and then compress the detergent composition to form a first phase. The first detergent composition is compressed using an applied pressure of generally at least 250 Kg / cm2, preferably between 350 kg / cm2 and 2,000 kg / cm2, more preferably 500 Kg / cm2 at 1,500 Kg / cm2, most preferred, 600 Kg / cm2 at 1,200 kg / cm2. Then the punch rises, exposing the First phase containing a mold. Then one is supplied second detergent composition in the mold, and the (s) optionally later (s). Then one second goes down Once the specially designed tablet press punch, to slightly compress the second detergent composition and the optionally posterior (s), to form the second phase and the phase (s) optionally later (s). In another embodiment of the present invention, in which a phase is optionally present subsequent, the optionally subsequent phase is prepared in a optionally subsequent compression stage substantially similar to the second compression stage described above. The second detergent composition and optionally (s) subsequent (s) are compressed at a pressure preferably of 350 Kg / cm2, more preferably from 40 Kg / cm2 to 300 Kg / cm2, most preferred, from 70 Kg / cm2 to 270 Kg / cm2. After compression of the second detergent composition, the punch is raised a second time and the detergent tablet Multiple phases are ejected from the tablet press.

Detergent components

The first and second phases and / or the phases optionally rear multi detergent tablet phases described in this invention are prepared by compression of a or more compositions comprising detergent active components. Suitably, the compositions used in any of these phases they can include a diversity of different components of detergent, including detergency builder compounds, surfactants, enzymes, bleaching agents, sources of alkalinity, dyes, perfumes, dispersants of limestone soaps, organic polymeric compounds, including polymeric agents dye transfer inhibitors, inhibitors of crystal growth, ion sequestering agents of heavy metals, metal ion salts, stabilizers enzymes, corrosion inhibitors, soap suppressants, solvents, fabric softening agents, brighteners Optics and hydrotropic agents.

The highly preferred detergent components of the first phase include a compound improving the detergency or detergency builder, a surfactant, an enzyme and a bleaching agent. Detergent components Highly preferred second phase include a compound detergency builder or detergency builder, enzymes, crystal growth inhibitors, and agents for undo the tablet and / or binders.

Detergency builder compound

The tablets of the present invention contain preferably a detergency builder compound, present typically at a level of 1% to 80% by weight, preferably 10% at 70% by weight, most preferred, from 20% to 60% by weight of the composition, of active components of detergents.

Water soluble detergency builder compound

The detergency builder compounds suitable, water soluble, include polycarboxylates water-soluble monomers, or their acid forms, acids homo- or co-polymeric polycarboxylic acids or their salts, in which the polycarboxylic acid 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 preceding compounds.

The carboxylate detergency builder or polycarboxylate can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred by Cost reasons and benefits.

Appropriate carboxylates containing a carboxy group include water soluble salts of lactic acid, glycolic acid and its derivatives of ethers. Polycarboxylates which contain two carboxy groups include soluble salts in succinic acid water, malonic acid, acid (ethylenedioxy) -diacetic, maleic acid, acid diglycolic, 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 succinates such as the carboxymethyloxysuccinates described in the British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732, and the aminosuccinates described in Dutch patent application 7205873, and the materials of oxypolycarboxylates such as 2-oxa-1,1,3-propane-tricarboxylates which are described in British Patent No. 1,387,447.

Polycarboxylates containing four groups carboxy include the oxidisuccinates described in the patent British No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane-tetracarboxylates and 1,1,2,3-propane-tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulphosuccinate derivatives described in British patents No. 1,398,421 and 1,398,422 and in US Pat. No. 3,936,448, and the sulphonated pyrolyzed citrates described in the patent British No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene-pentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and derivatives of phthalic acid described in British Patent No. 1,425,343.

Among the above, polycarboxylates Preferred are hydroxy carboxylates which contain up to three carboxy groups per molecule, more particularly citrates.

The progenitor acids of chelating agents type monomeric or oligomeric polycarboxylates or mixtures thereof with its salts, eg citric acid or mixtures of a citrate and acid citrus, are also considered as useful improver components of detergency.

The improvers of the borate type detergency, as well as the enhancers of the detergency containing borate-forming materials, which they can produce a borate in the storage conditions of the detergent or washing, but not preferred in conditions wash at less than 50 ° C, especially at less than 40 ° C.

Examples of type detergency builders carbonates are metal carbonates alkaline earth and alkaline, including carbonate and sesqui-sodium carbonate and mixtures with ultrafine calcium carbonate, as described in the application for German Patent No. 2,321,001, published on November 15, 1973

Detergent builder compounds very Preferred for use in the present invention are those water soluble phosphate detergency builders. Specific examples of phosphate builders water soluble, are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, pyrophosphates of sodium and potassium and ammonium, sodium and potassium orthophosphates, sodium polymeta / phosphates, in which the degree of polymerization It is worth between 6 and 21, and salts of phytic acid.

Specific examples of improvers of 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, polymeta / sodium phosphates, in which the degree of polymerization is worth between 6 and 21, and salts of phytic acid.

Partially soluble detergency builder compound or insoluble

The tablets of the present invention can contain a detergency builder compound partially soluble or insoluble. The detergency builder compounds partially soluble and insoluble are particularly appropriate for use in tablets prepared for use in cleaning methods of clothes by mechanical washing. Examples of improvers of partially water soluble detergency include silicates crystalline laminates as described, for example, in the EP-A-0164514, DE-A-3417649 and DE-A-3742043. The ones are preferred crystalline stratified sodium silicates of formula general

NaMSi_ {x} O_ {2 + 1} \ cdot and H2O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystal layered sodium silicates of this type preferably have a two-dimensional "sheet" structure, such as denominated stratified structure-δ, as described in patents EP 0 164514 and EP 0 293640. Methods for the preparation of crystalline layered silicates of this type are described in 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.

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

The stratified sodium silicate material crystalline is preferably present in compositions of granular detergents as an intimate particulate material mixing with an ionizable, water soluble solid material, such as It is described in PCT Patent Application No. WO 92/18594.

The ionizable solid material, soluble in water, is select between organic acids, salts of organic acids and inorganic and mixtures thereof, citric acid being preferred.

Examples of widely water insoluble detergency builders include sodium alumino silicates. Suitable alumino-silicates include alumino-silicate zeolites having the unit cell formula Na_ {[(AlO2) z (SiO2) y}] \ xd2H2O in which z and y are at least 6; the molar ratio of z a y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The alumino-silicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in associated form.

The alumino-silicate zeolites they can be materials present in nature, but preferably they are obtained by synthesis. materials alumino-silicate type ion exchangers synthetic crystals are available under the designations of Zeolite A, Zeolita B, Zeolita P, Zeolita X, Zeolita HS, and their mixtures

A preferred method of synthesizing zeolites alumino-silicates is what has been described by Schoeman et al. (Published in Zeolite (1994) 14 (2), 110-116), in which the authors describe a method to prepare alumino-silicate zeolites colloidal Zeolite particles colloidal alumino-silicates should be preferably such that no more than 5% of the particles have a size larger than 1 µm in diameter and not more than one 5% of particles have a size smaller than 0.05 µm of diameter. Preferably, the zeolite type particles alumino-silicates have an average size of particles, in diameter, between 0.01 µm and 1 µm, more preferably between 0.05 µm and 0.9 µm, most preferred between 0.1 µm and 0.6 µm.

Zeolite A has the formula

Na 12 [(AlO 2) 12 (SiO 2) 12] \ cdot xH_ {2} O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na_ {86} [(AlO_2) _86} (SiO_2) _ {106}] \ cdot276 H2 } Or . The zeolite MAP, as described in EP-B-384.070, is a preferred zeolite detergency builder in the present invention.

Zeolites type Preferred alumino-silicates are zeolites colloidal alumino-silicates. When they are used as one of the components of a detergent composition, the colloidal alumino-silicate zeolites, especially the colloidal Zeolite A, provide the enhancers of the detergency improved performance, in terms of Provide improved stain removal. Also they have been  observed improved performance for the improver of the detergency, in terms of tissue crusting reduced and improved whiteness maintenance tissues, whose problems are believed to be associated with detergent compositions with detergency builders inadequate

A surprising finding is that mixed compositions of zeolite type detergents alumino-silicates, comprising colloidal Zeolite A and Zeolite and colloidal provide equal benefits of sequestration of calcium ions compared to that of a equal weight of a commercially available Zeolite A. Other surprising finding is that mixed detergent compositions type alumino-mixed silicate zeolites, described previously, they provide improved performance for the sequestration of magnesium ions compared to that of a equal weight of a commercially available Zeolite A.

Surfactant

Surfactants are active components of detergents, preferred in the compositions described herein invention. Appropriate surfactants are selected. between anionic, cationic, non-ampholytic surfactants not ionic and ionic hybrids and mixtures thereof. The products for automatic dishwashing machines should present some low foaming properties and therefore the foaming of the surfactant system for use in washing methods of tableware should be suppressed, or more preferably they should have low foaming properties, typically nonionic Soaps caused by surfactant systems used in methods of cleaning clothes by mechanical washing they need to delete at the same extent that is necessary for the dishwashing The surfactant is present typically at a level of 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of the composition of detergent active components.

A typical list of anionic, non-ionic classes, ampholytic and ionic hybrids, and species of these agents surfactants, is presented in US Pat. 3,929,678, granted to Laughlin and Heuring on December 30, 1975. A list of appropriate cationic surfactants is presented in the U.S. Patent 4,259,217, issued to Murphy on March 31, 1981. A list of surfactants that are included typically in detergent compositions for automatic washing of tableware is presented for example in the patent EP-A-0414549 and in applications of PCT patents No. WO93 / 08876 and WO 93/08874.

Nonionic Surfactant

Essentially, it can be included in the tablet detergent any nonionic surfactant useful for detersive purposes. Preferred, non-limiting classes of Useful nonionic surfactants are listed at continuation.

Ethoxylated alcohol nonionic surfactant

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

Compound type surfactant alkyl-alkoxylated capped at the ends

An appropriate surfactant, compound type alkyl-alkoxylated capped at the ends, consists of poly (oxyalkylated) alcohols topped with epoxy, which are 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

wherein R1 is an aliphatic, linear or branched hydrocarbon radical, having from 4 to 18 carbon atoms; R2 is an aliphatic, linear or branched hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of 0.5 to 1.5, more preferably 1; e y is an integer having a value of at least 15, more preferably at least 20.

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

Poly (oxyalkylated) alcohols topped with ethers

Preferred surfactants for use in The present invention includes poly (oxyalkylated) alcohols topped with ethers, which have the formula:

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

wherein R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms; R 3 is H, or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 30, in which, when x is 2 or greater, the R 3 can be the same or different and k and j are integers that have an average value from 1 to 12, and more preferably from 1 to 5.

R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with 8 to 18 carbon atoms being most preferred carbon. H or a linear hydrocarbon radical with 1 to 2 carbon atoms is most preferred for R3 . Preferably, x is an integer having an average value of 1 to 20, more preferably 6 to 15.

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As described above, when, in the preferred embodiments, and x is greater than 2, the R 3 may be the same or different. This means that R 3 can vary between any of the alkylene-oxy units described above. For example, if x is 3, R 3 may be selected to form ethylene-oxy (EO) or propylene-oxy (PO) and may vary in the order of (EO) (PO) (EO); (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the whole number three has been chosen by way of example only and the variation can be much wider with a larger integer value for x, and includes, for example, multiple units (EO) and a much smaller number of units (PO).

Particularly preferred surfactants, such as those described above, include those with a low cloud point of less than 20 ° C. These agents surfactants that have a low cloud point can be then used in conjunction with a surfactant with a high cloud point, as described below with detail, to obtain superior cleaning benefits from fat

The most preferred poly (oxyalkylated) alcohol surfactants capped with more preferred ethers are those in which k is 1 and j is 1, such that the surfactants have the formula:

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

wherein R 1 , R 2 and R 3 are as defined above and x is an integer with an average value of 1 to 30, preferably 1 to 20, and even more preferably from 6 to 18. The most preferred are the surfactants in which R 1 and R 2 range from 9 to 14, R 3 is H forming ethylene-oxy, and x is between 6 and 15.

Alcohol-like surfactants poly (oxyalkylated) terminated with ethers comprise three general components, namely a linear or branched alcohol, a alkylene oxide and an end cap with an alkyl ether. The end cap with an alkyl ether and alcohol serve as a hydrophobic, oil soluble portion of the molecule, while the alkylene oxide group forms the portion Hydrophilic, water soluble, molecule.

These surfactants exhibit improvements significant in the characteristics of motorcycle formation and films and grease stain removal, when used in conjunction with surfactants that have a high point of cloudiness, in relation to those of surfactants conventional.

Generally speaking, the agents type surfactants poly (oxyalkylene) -alcohols topped with ethers can be produced by reacting an aliphatic alcohol with an epoxide to form an ether, which is then reacted with  a base to form a second epoxide. The second epoxide is then reacts with an alkoxylated alcohol to form the new compounds of the present invention. Examples of methods for prepare the alcohol-like surfactants poly (oxyalkylated) capped with ethers, are described as continuation:

Alkyl Preparation C 12/14-glycidyl ethers

A C 12/14 fatty alcohol (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol, available in Aldrich) combine inside a round bottom flask with three mouths that have a capacity of 500 mL, equipped with a condenser, an input for argon, a funnel for additions, a magnetic stirrer and an internal temperature probe. Mix it is heated to 60 ° C. Epichlorohydrin (47.70 g, is added dropwise) 0.515 mol, available in Aldrich) so that the temperature between 60 and 65 ° C. After having stirred for a additional hour at 60 ° C, the mixture is cooled to the temperature environment. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) while being shaking mechanically After the In addition, the mixture is heated at 90 ° C for 1.5 h, cooled, and Filter with the help of ethanol. The filtered material is separated and The organic phase is washed with water (100 mL), dried over MgSO4, filtered and concentrated. Oil distillation a 100-120 ° C (13.33 Pa) provides glycidyl ether in the form of an oil.

Preparation of an alcohol-type surfactant topped with a C 12/14 alkyl-C 9/11 ether

Neodol® 91-8 (20.60 g, 0.0393 mol, ethoxylated alcohol available from Shell Chemical Co.) and chloride of tin (IV) (0.58 g, 2.23 mmol) are combined within a round bottom flask with three mouths that has a capacity of 250 mL, coupled with a condenser, an input for argon, a funnel for additions, a magnetic stirrer and a probe internal temperature The mixture is heated to 60 ° C, at which time an alkyl is added dropwise over the course of 15 min C 12/14 -glycidyl ether (11.00 g, 0.0393 mol). After stirring for 18 h at 60 ° C, the mixture is cooled to room temperature and dissolves in an equal portion of dichloromethane The solution is passed through a pad of 25.4 mm silica gel while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then it is separated by drag in an oven with a tube of balls (Kugelrohr) (at 100 ° C, 66.66 Pa) to provide the agent surfactant in the form of an oil.

Nonionic fatty alcohol type surfactant ethoxylated / propoxylated

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

Non-ionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of oxide of propylene with propylene glycol, are suitable for use in the present invention The hydrophobic portion of these compounds has preferably a molecular weight of 1,500 to 1,800 and exhibits insolubility in water. Examples of compounds of this type include certain of Pluronic® surfactants commercially available, which are sold by BASF.

Non ionic EO condensation products with oxide adducts of propylene and ethylenediamine

The condensation products of ethylene oxide with the product that results from the reaction of propylene oxide and ethylenediamine, are suitable for use herein invention. The hydrophobic residue of these products consists of the reaction product of ethylenediamine and propylene oxide in excess, and generally has a molecular weight of 2,500 to 3,000. Examples of this type of non-ionic surfactant include certain of the commercially available Tetronic® compounds, which They are sold by BASF.

Mixed non-ionic surfactants system

In a preferred embodiment of the present invention, the detergent tablet comprises an agent system mixed nonionic surfactants, comprising at least one agent non-ionic surfactant with a low cloud point and at less a nonionic surfactant with a high point of cloudiness

The term "cloud point", as used in the present invention, is a well-known property of non-ionic surfactants, which is the result that the surfactant becomes less soluble as the temperature increases. The temperature at which the appearance of a second phase is observable is cited as the "cloud point" (see Encyclopedia of Chemical Technology , Kirk Othmer, 3rd edition, volume 22, pages 360-379).

As used in the present invention, an agent non-ionic surfactant with a "low cloud point" It is defined as an ingredient of an agent system non-ionic surfactants, with a cloud point of less than 30 ° C, preferably less than 20 ° C, and most preferably of less than 10 ° C. Typical non-ionic surfactants, with low cloud point, include surfactants nonionic alkoxylates, especially ethoxylated compounds that are derived from a primary alcohol, and inverse block polymers of poly (propylene oxide) / poly (ethylene oxide) / poly (oxide of propylene) (PO / EO / PO). Also, said surfactants do not Ionic with low cloud point include, for example, a ethoxylated-propoxylated alcohol (e.g., the Poly-Tergent® SLF 18 of Olin Corporation), poly (oxyalkylated) alcohols topped with epoxides (e.g., the Poly-Tergent® non-ionic compound series SLF 18B of Olin Corporation, as described, for example, in the Patent application WO 94/22800, published October 13, 1994 by Olin Corporation), and alcohol surfactants poly (oxyalkylated) topped with ethers.

Nonionic surfactants can optionally contain propylene oxide in an amount up to 15% by weight. Other preferred nonionic surfactants are can prepare by the procedures described in the U.S. Patent 4,223,163, issued September 16, 1980, Builloty.

Nonionic surfactants with low cloud point further comprise a compound Polymer block of poly (ethylene oxide) and poly (oxide of propylene) Polymeric block poly (oxide) compounds ethylene) and poly (propylene oxide) include those that are based in ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as an initiator compound with reactive hydrogen. Some of the block polymeric surfactant compounds that are designated as PLURONIC®, REVERSED PLURONIC®, and TETRONIC® sold by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactants are typically useful in the present invention as nonionic surfactants with low cloud point.

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

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It is also preferred for the purposes of the present invention that the nonionic surfactant with a high cloud point also has an equilibrium index hydrophilic-lipophilic ("HLB"; see the work of Kirk Othmer cited above) within the range of 9 to 15, preferably 11 to 15. Such materials include, by example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred non-ionic surfactant with a high cloud point is derived from an alcohol straight chain or preferably branched chain fatty or secondary fatty alcohol, containing 6 to 20 carbon atoms (C 6 -C 20 alcohol), including alcohols secondary and branched chain primary alcohols. Preferably, non-ionic surfactants with a high cloud point are ethoxylated compounds of alcohols branched or secondary, more preferably compounds ethoxylates of branched or secondary alcohols, more preferably ethoxylated compounds of branched alcohols C9 / C11 or C11 / C15 mixed, which have 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 nonionic surfactant ethoxylated, which has been obtained, has a narrow distribution of ethoxylated compounds in relation to the average value.

Anionic surfactant

Essentially any of the anionic surfactants that are useful for detersive purposes. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as salts of mono-, di- and tri-ethanolamine) of the surfactants anionic sulfates, sulphonates, carboxylates and sarcosinates anionic Anionic surfactants are preferred sulfates

Other anionic surfactants include isethionates, such as acyl isethionates, N-acyl-taurates, acid amides fatty acids of tauride, alkylsuccinates and sulfo-succinates, monoesters of sulfo-succinates (especially monoesters C 12 -C 18 saturated and unsaturated), sulfo-succinate diesters (especially C 6 -C 14 saturated and unsaturated diesters),  N-acyl-sarcosinates. They are suitable also resins acids and hydrogenated resin acids such as rosin, hydrogenated rosin, as well as acids resins and hydrogenated resin acids present in, or derivatives of tallow oil.

Sulfate type anionic surfactant (s)

Anionic surfactants type sulfates, suitable for use in the present invention, include linear and branched alkyl sulfates, primary and secondary, alkylethoxysulfates, fatty alkyl sulfates of oleyl glycerol, the ether sulfates of alkylphenol and ethylene oxide, acyl C 5 -C 17 -N- (alkyl C 1 -C 4) and -N- (hydroxyalkyl C 1 -C 2) - glucaminesulfates and alkyl polysaccharide sulfates, such as alkyl polyglucoside sulfates (Describing in this invention non-sulphated compounds not ionic).

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

Type surfactants alkylethoxysulfates are preferably selected from the group consisting of C 10 -C 8 alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the type surfactant alkylethoxysulfate is an alkyl sulfate C 11 -C 18, preferably a C 11 -C 15 alkylsulfate, which has been ethoxylated with 0.5 to 7, preferably with 1 to 5 moles of oxide of ethylene per molecule.

A particularly preferred aspect of the invention employs mixtures of surfactants type preferred alkyl sulfates and alkylethoxysulfates. Such mixtures have described in PCT patent application No. WO 93/18124.

Sulfonate-type anionic surfactant

Anionic surfactants type sulphonate, suitable for use in the present invention, include salts of linear alkylbenzenesulfonates C 5 -C 20, alkyl estersulfonates, primary or secondary alkane sulphonates C 6 -C 22, olefin sulphonates C 6 -C 24, polycarboxylic acids sulphonates, alkyl glycerolsulfonates, acyl glycerolsulfonates fatty, fatty oleyl glycerolsulfonates, and any of their mixtures

Anionic carboxylate surfactant

Anionic surfactants type Appropriate carboxylates include surfactants type alkylethoxycarboxylates, type surfactants alkylpolyethoxy polycarboxylates and soaps ("alkyl carboxyls"), especially certain secondary soaps as described in the present invention.

Suitable alkylethoxycarboxylates include those having the formula RO (CH 2 CH 2 O) x CH 2 COO - M +, wherein R is a C_ alkyl group {6} to C_ {18}, x takes values between 0 and 10, and the distribution of ethoxylated groups is such that, in terms of weight, the amount of material in which x is 0 is less than 20% and M is a cation Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO- (CHR 1 -CHR 2 -O) -R 3 in which R is a C 6 -C 18 alkyl group , x is 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, a methyl acid radical, a succinic acid radical, a hydroxy succinic acid radical and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, a substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Appropriate surfactants based on soaps include soap-based surfactants children that contain a carboxyl unit connected to a secondary carbon Preferred surfactants based on secondary soaps suitable for use in the present invention are water soluble members, selected from the group that consists of water soluble salts of acid 2-methyl-1-undecanoic, acid 2-ethyl-1-decanoic, 2-propyl-1- nonanoic acid, acid 2-butyl-1-octanoic and acid 2-pentyl-1-heptanoic. Certain soaps can also be included as suppressors of suds.

Sarcosinate type metal surfactant (s) alkaline (s)

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON (R 1) CH 2 COOM, wherein R is a linear C 15 -C 17 alkyl or alkenyl group or branched, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactant

Appropriate amphoteric surfactants for use in the present invention include agents surfactants based on amine oxides and acids alkyl anfocarboxylic.

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

An appropriate example of an acid alkylanedicarboxylic is Miranol ™ C2M Conc., manufactured by Miranol, Inc. Dayton, NJ.

Hybrid ion surfactant

Agents can also be incorporated hybrid ionic surfactants in detergent compositions In this invention. These surfactants can be described. broadly as derivatives of secondary and tertiary amines,  derivatives of secondary and tertiary heterocyclic amines, or derivatives of quaternary ammonium compounds, phosphonium quaternary or tertiary sulfonium. Type surfactants betaines and sultains are hybrid ionic surfactants exemplifiers for use in the present invention.

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

Cationic Surfactants

The cationic ester type surfactants of this invention are preferably dispersible compounds in water, which have surfactant properties, and which comprise the less an ester type link (i.e. -COO-) and at least one group cationically charged. Other cationic surfactants type  appropriate esters, including type surfactants choline esters have been described for example in the patents of USA Nos. 4,228,042, 4,239,660 and 4,260,529.

Appropriate cationic surfactants include quaternary ammonium surfactants, selected from type surfactants mono-N-alkyl or mono-N-alkenylammonium C 6 -C 16 -, preferably C_ {6} -C_ {10} -, in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl.

Enzymes

Enzymes are preferred detersive components. of the first phase and, more particularly, of the second and / or phases following optional. Where said enzymes present are select from a group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases,  phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanasas, tannasas, pentosanasas, malanasas, β-glucanases, arabinosidases, hyaluronidase, Chondroitinase, laccasa or mixtures thereof.

Preferred enzymes include protease, Amylase, lipase, peroxidase, cutinase and / or cellulase in conjunction with one or more enzymes that degrade the cell walls of plants.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, these will have an optimum pH value between 5 and 12 and an activity above 50 CEVU ( Cellulose Viscosity Unit = units of cellulose viscosity). Appropriate cellulases are described in US Pat. 4,435,307, of Barbesgoard et al., Patent J61078384 and patent application WO96 / 02653, which describe fungal cellulases produced respectively from Humicola Insolens , Trichoderma , Thielavia and Sporotrichum . EP 739,982 describes cellulases isolated from new Bacillus species. Appropriate cellulases are also described in GB-A 2,075,028, GB-A-2,095,275; DE-OS 2,247,832 and patent application WO 95/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola Insolens ( Humicola grisea var. Thermoidea ), particularly Humicola strain DSM 1800. Other suitable cellulases are cellulases that originate from Humicola insolens , which have a molecular weight of 50 KDa, an isoelectric point of 5.5 and contain 415 amino acids; and a sim43 kD endoglucanase, derived from Humicola insolens , DSM 1800, which exhibits cellulase activity; A preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243. Suitable cellulases are also EGIII cellulases from Trichoderma longibrachiatum , which are described in patent application WO 94/21801, of Genencor, published on September 29, 1994. Especially suitable cellulases are cellulases that have color care benefits. Examples of such cellulases are the cellulases described in EP-A-495257, filed on November 6, 1991 (by Novo). Carezyme and Celluzyme (from Novo Nordisk A / S) are especially useful. See also patent applications WO 91/17244 and WO 91/21801. Other cellulases suitable for obtaining tissue care and / or cleaning properties are described in patent applications WO 96/34092, WO 96/17994 and WO 95/24471.

Said cellulases are normally incorporated into the detergent composition at levels of 0.0001% to 2% of the active enzyme by weight of the detergent composition.

Peroxidases enzymes are used in combination with oxygen sources, eg a percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used for "bleaching in solution", that is, to prevent transfer of dyes or pigments that have been removed since the substrates during washing operations towards others substrates in the wash solution. The peroxidases enzymes are known in the art and include, for example, peroxidase of horseradish, ligninase and a halo-peroxidase such as chloro- and bromine peroxidase. Detergent compositions that they contain peroxidases are described, for example, in applications of PCT international patents WO 89/099813, WO 89/09813 and in the EP-A-540780, filed on 6 November 1991, and patent application WO 97/30143, filed on February 20, 1996. The laccasa enzyme

Preferred intensifiers are the Phenothiazines and substituted phenoxazines, acid 10-phenothiazine-propionic (PPT), acid 10-ethyl-phenothiazine-4-carboxylic  (EPC), acid 10-phenoxazine-propionic (POP) and 10-methyl-phenoxazine (described in the  patent application WO 94/12621) and substituted syringates (C 3 -C 5 substituted alkylcarbonates) and phenols Percarbonate and sodium perborate are sources Preferred hydrogen peroxide.

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

Other preferred enzymes, which 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 Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1,372,034. Appropriate lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the Pseudomonas fluorescent IAM 1057 microorganism. This lipase is available from Amano Pharmaceutical Co., Nagoya, Japan, under the trade name Lipase P "Amano ", then cited as" Amano-P ". Other suitable commercial lipases include Amano-CES, lipases produced by Chromobacter viscosum , eg Chromobacter viscosum var. NRRLB 3673 lipolyticum from Toyo Jozo Co., Tagata, Japan; lipases produced by Chromobacter viscosum , from US Biochemical Corp. USA. and from Disoynth Co., the Netherlands; and lipases produced by Pseudomonas gladioli . Especially suitable lipases are lipases such as M1 Lipase® and Lipomax® (from 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 patents EP 258.068, and patent applications WO 92/05249 and WO95 / 22615, of Novo Nordisk, and in patent applications WO 94/03578, WO 95/35381 and WO 96/00292 , from Unilever.

Cutinases are also appropriate [EC 3.1.1.50], which can be considered as a special kind of lipase, namely lipases that do not require any activation interfacial. The addition of cutinases to detergent compositions described eg in patent applications WO-A-88/09367 (of Genencor); WO 90/09446 (from Plant Genetic System) and WO 94/14963 as well as WO 94/14964 (from Unilever).

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

Appropriate proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). An appropriate protease is obtained from a strain of Bacillus , which has maximum activity over the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter cited as "Novo." The preparation of this enzyme and analogous enzymes is described in British patent GB 1,243,784 to Novo. Other suitable proteases include the ALCALASE®, DURAZYM® and SAVINASE® de Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal engineered by protein engineering) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in EP-A-251,446, filed on April 28, 1987 (particularly on pages 17, 24 and 98), and which is referred to as in the present invention "Protease B", and in European Patent Application 199,404, of Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, which is referred to in the present invention "Protease A". It is appropriate what is called "Protease C" in the present invention, which is a variant of an alkaline serine protease produced by Bacillus , in which lysine has replaced arginine at position 27, tyrosine has replaced valine at position 104, the serine has replaced asparagine in position 123, and the alanine has replaced threonine at position 274. Protease C is described in EP 90915958: 4 corresponding to patent application WO 97 / 06637, published May 16, 1991. Also included in the present invention are genetically modified variants, particularly Protease C.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant that has an amino acid sequence that is not found in nature, which is derived from a carbonyl hydrolase precursor, substituting a different amino acid by a plurality of amino acid residues at a position of said carbonyl hydrolase that is equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions that are equivalent to those selected from the group that consists 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 produced by Bacillus amyloliquefaciens , as described in patent application WO 95/10591 and in the patent application of C. Ghosh et al., Bleaching Compositions Comprising Protease Enzymes , with U.S. Serial Number 08 / 322,677, filed October 13, 1994 (U.S. 6066611).

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

See also a protease with a high pH value produced by Bacillus sp. NCIMB 40338, described in patent application WO 93/18140 A, de Novo. Enzymatic detergents comprising a protease, one or more other types of enzymes, and a reversible protease inhibitor are described in patent application WO 92/03529 A, de Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in patent application WO 95/07791 of Procter & Gamble. A protease of the recombinant trypsin type for detergents, which is appropriate in the present invention, is described in patent application WO 94/25583, de Novo. Other suitable proteases are described in EP 516.200, of Unilever.

Other preferred protease enzymes include protease enzymes that are a variant of carbonyl hydrolase, with an amino acid sequence that is not found in nature, which is obtained by replacing a plurality of amino acid residues of a carbonyl hydrolase precursor with different amino acids, wherein said plurality of amino acid residues replaced 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, in which the numbered positions correspond to a subtilisin that appears in nature from Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those that have changes in the +210, +76, +103, +104, +156 and +166 positions.

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

Amylases (α and / or β) can be include for the removal of spots based on hydrates of carbon. Patent application WO 94/02597, by Novo Nordisk A / S, published on February 3, 1994, describes compositions of cleaning that incorporate mutant amylases. See also the Patent application WO 95/10603, by Novo Nordisk A / S, published on April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β-amylases. The α-amylases are known in the art and include those described in US Pat. nº 5,003,257; and patents EP 252,666; WO patent application 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and the British Patent Specification No. 1,296,839 (de Novo). Other Appropriate amylases are amylases with increased stability, described in patent application 94/18314, published on August 18, 1994, and in patent application WO 96/05295, of Genencor, published on February 22, 1996, and variants of Amylases that have an additional modification in the parent immediate, available in Novo Nordisk A / S, described in the Patent application WO 95/10603, published April 1995. The amylases described in EP patents are also suitable 277.216, patent applications WO 95/26397 and WO 96/23873 (all them from Novo Nordisk).

Examples of products from Commercial α-amylases are Purafect Ox Am®, from Genencor, and Termamyl®, Ban®, Fungamyl® and Duramyl®, Natalase®, all available in Novo Nordisk A / S, Denmark. Patent application WO 95/26397 describes other amylases appropriate: α-amylases characterized by have a specific activity that is at least 25% greater than the specific activity of Termamyl® in a temperature range from 25 ° C to 55 ° C, and at a pH value in the range of 8 to 10, measured by the Phadebas® activity analysis system of α-amylases. Variants are appropriate of the above enzymes, which are described in the application for WO 96/23873 (from Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the level of activity and to the combination of thermostability and a higher level of activity, are described in patent application WO 95/35382.

Preferred amylase enzymes include those that are described in patent application WO 95/26397 and in the application to it associated WO 96/23873, by Novo Nordisk.

Amylolytic enzymes are incorporated into the detergent compositions of the present invention on one level from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.

In a particularly preferred embodiment, the detergent tablets of the present invention comprise Amylase enzymes, particularly those described in the patent application WO 95/26397 and in the associated application WO 96/23873, by Novo Nordisk, in combination with an amylase complementary.

"Complementary" means the addition of one or more appropriate amylases for detersive purposes. Examples of complementary amylases (α and / or β) are described below. Patent applications WO 94/02597 and WO 95/10603, by Novo Nordisk A / S, describes compositions of cleaning that incorporate mutant amylases. Other amylases Known for use in cleaning compositions include both α- as β-amylases. The α-amylases are known in the art and include those described in US Pat. nº 5,003,257; in patents EP 252,666; WO patent application 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the British Patent Specification No. 1,296,839 (de Novo). Other Suitable amylases are amylases with increased stability, described in patent applications WO 94/18314 and WO 96/05295,  of Genencor, and variants of amylases that have a modification additional in the immediate parent, available at Novo Nordisk A / S, described in patent application WO 95/10603. They are also suitable are the amylases described in EP 277,216 (from Novo Nordisk). Examples of products from Commercial α-amylases are Purafect Ox Am®  from Genencor, and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available at Novo Nordisk A / S Denmark. Patent application WO 95/26397 describes other amylases appropriate: α-amylases characterized by have a specific activity that is at least 25% greater than the specific activity of Termamyl® in a temperature range from 25 ° C to 55 ° C and at a pH value in the range of 8 to 10, measured by the Phadebas® analysis system of the α-amylases activity. The variants of the above enzymes, described in the application for WO 96/23873 (from Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the level of activity and to the combination of thermostability and a higher level of activity, are described in patent application WO 95/35382. Amylases Preferred complementary to the present invention are the Amylases sold under the trade name Purafect Ox Am®, described in patent applications WO 94/18314, WO 96/05295, of Genencor; Termamyl®, Fungamyl®, Ban®, Natalase® and Duramyl®, all available in Novo Nordisk A / S; and Maxamyl®, from Gist-Brocades.

Said complementary amylase is incorporated by general in detergent compositions herein invention at a level of 0.0001% to 2%, preferably 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme, per composition weight. Preferably, a weight ratio of pure enzyme, from a specific amylase to amylase complementary, which is between 9: 1 and 1: 9, more preferably between 4: 1 and 1: 4, and most preferably between 2: 1 and 1: 2.

The enzymes mentioned above may be of any appropriate origin, such as a plant, animal origin, Bacterial, fungal and yeast. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these may be used. enzymes Also included are, by definition, enzyme mutants native Mutants can be obtained eg by treatment of protein and / or genetic engineering, as well as modifications chemical and / or physical enzymes native. It is also practical current enzyme expression through organisms hosts, in which the genetic material has been cloned responsible for the enzyme.

Such enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% enzyme active by weight of the detergent composition. Enzymes are they can add as separate individual ingredients (pills, granules, stabilized liquids, etc., containing a enzyme) or as mixtures of two or more enzymes (e.g. co-granules).

       \ newpage
    

Other appropriate detergent ingredients, which can be added are enzyme oxidation scrubbers, which are described in the European patent application associated with EP-A-0553607, filed on 31 January 1992. Examples of such oxidation scrubbers of Enzymes are ethoxylated tetraethylene polyamines.

A range of enzyme materials and media for incorporation into synthetic detergent compositions are also described in patent applications WO 9307263 A and WO 93/07260 A, filed by Genencor International, WO 8908694 A, filed by Novo, and the patent from the USA 3,553,139, granted on January 5, 1971 to McCarty et al. Enzymes are further described in US Pat. 4,101,457, of Place et al., Granted on July 18, 1978, and 4,507,219 of Hughes, granted on March 26, 1985. Useful enzyme materials for liquid detergent formulations, and their incorporation in said formulations, are described in US Pat. 4,261,868, granted on April 14, 1981 to Hora et al. Enzymes suitable for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in US Pat. 3,600,319, issued on August 17, 1971 to Gedge et al., And patents EP 199,405 and EP 200,586 published on October 29, 1986, of Venegas. Enzyme stabilization systems are also described, for example, in US Pat. 3,519,570. A useful strain of Bacillus, sp . AC13, which provides proteases, xylanases and cellulases, is described in patent application WO 9401532 A, filed by Novo.

Bleaching agent

A highly preferred component of the Detergent component composition is an agent of Whitening. Suitable bleaching agents include bleaching that releases chlorine and oxygen.

In a preferred aspect, the oxygen-releasing bleaching agent contains a source of hydrogen peroxide and an organic peroxyacid-type bleaching precursor compound. The production of the organic peroxyacid is carried out by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaching agents. In an alternative preferred aspect, a previously formed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a previously formed organic peroxyacid are also considered.

Bleaching agents type inorganic perhydrates

The detergent component compositions preferably include a source of hydrogen peroxide, such as bleaching agent that releases oxygen. Peroxide sources appropriate hydrogen include perhydrate salts inorganic

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

Examples of salts of inorganic perhydrates include perborate salts, percarbonates, perfosphates, persulfates and persilicates. Inorganic perhydrate salts they are usually alkali metal salts. Salt inorganic perhydrate can be included in the form of a solid crystalline without any additional protection. However, for certain salts of perhydrates, the preferred executions of said granular compositions use a coated form of the material, which provides better storage stability for salt of perhydrate in the granular product.

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

The alkali metal percarbonates, particularly sodium percarbonate, they are perhydrates preferred for inclusion in the compositions according to the invention. Sodium percarbonate is a reaction compound by addition that has a formula corresponding to 2Na_ {2} CO_ {3} \ cdot3H_ {2} O2, and is available commercially in the form of a crystalline solid. Percarbonate of sodium, which is a reaction compound by peroxide addition of hydrogen, tends in its solution to release peroxide from hydrogen quite quickly, which can increase the tendency for high localized agent concentrations to arise of bleaching. The percarbonate is most preferably incorporated into said compositions in a coated form that provides a Product stability.

An appropriate coating material that provides stability to the product comprises a mixed salt of a water-soluble alkali metal carbonate. Said coatings, together with coating procedures, have been described previously in patent GB-1,466,799, issued to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to the percarbonate is located in the range from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9 and most preferably from 1:49 to 1:19. Preferably, the mixed salt is a mixture of sodium sulfate and sodium carbonate having the general formula Na2SO4 .n.Na2CO3, where n is 0.1 to 3, preferably n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

Other appropriate coating material, which provides product stability, includes sodium silicate with a SiO2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied at a level of 2% to 10% (usually of 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. I know It can also include magnesium silicate in the coating. They are also suitable are coatings containing salts silicates and borates, or boric acids or other compounds inorganic

Other coatings containing waxes, oils and / or fatty soaps can also be used advantageously within The present invention.

Potassium peroximonopersulfate is another salt inorganic perhydrate presenting utility in the compositions of the present invention.

Peroxyacid bleaching agent precursor

Precursors of bleaching agents type peroxy acid are the compounds that react with peroxide of hydrogen in a perhydrolysis reaction to produce a peroxyacid Generally, bleaching agent precursors peroxyacid type can be represented as

\uelm{C}{\uelm{\dpara}{O}}

-LX-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

-L

in which L is a leaving group and X is essentially any functionality, such that, when performing a perhydrolysis, the structure of the peroxy acid produced is

\uelm{C}{\uelm{\dpara}{O}}

-OOHX-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

-OOH

Bleaching agent precursor compounds peroxyacid type are preferably incorporated at a level of 0.5% at 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.

Bleaching agent precursor compounds appropriate peroxyacid type typically contain one or more groups N- or O-acyl, whose precursors can be Select from a wide range of classes. The appropriate classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of appropriate materials included in these classes are described in the patent GB-A-1586789. Appropriate esters are described in the patents GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups

The leaving group, hereafter referred to as group L , must be reactive enough for the perhydrolysis reaction to occur within the optimal time frame (eg a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in the bleaching composition.

Preferred L groups are selected from the group consisting of:

3

\delm{N}{\delm{\para}{\delm{R ^{5} }{\delm{\para}{Y}}}}

--

\uelm{C}{\uelm{\dpara}{O}}

--R^{1},

\hskip2cm

4

,

\hskip2cm

--

\delm{N}{\delm{\para}{R ^{3} }}

--

\uelm{C}{\uelm{\dpara}{O}}

--

\delm{C}{\delm{\para}{Y}}

H--R^{4},-

 \ delm {N} {\ delm {\ para} {\ delm {R ^ {5}} {\ delm {\ para} {Y}}}} 

-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--R1,

 \ hskip2cm 

4

,

 \ hskip2cm 

-

 \ delm {N} {\ delm {\ para} {R3}} 

-

 \ uelm {C} {\ uelm {\ dpara} {O}} 

-

 \ delm {C} {\ delm {\ para} {Y}} 

H-R 4,

       \ newpage
    

\uelm{C}{\uelm{\para}{R ^{3} }}

--CH=CH_{2},

\hskip8cm

--O-- CH=

\uelm{C}{\uelm{\para}{Y}}

--CH=CH_{2}-O - CH =

 \ uelm {C} {\ uelm {\ para} {R3}} 

--CH = CH2,

 \ hskip8cm 

--O-- CH =

 \ uelm {C} {\ uelm {\ para} {Y}} 

--CH = CH2

\uelm{C}{\uelm{\dpara}{O}}

--R^{1},

\hskip2cm

6

-OR--

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--R1,

 \ hskip2cm 

6

\uelm{C}{\uelm{\para}{R ^{3} }}

=CHR^{4},

\hskip1cm

y

\hskip8cm

--

\delm{N}{\delm{\para}{R ^{3} }}

--

\melm{\delm{\dpara}{O}}{S}{\uelm{\dpara}{O}}

--

\uelm{C}{\uelm{\para}{Y}}

H--R^{4}-OR--

 \ uelm {C} {\ uelm {\ para} {R3}} 

= CHR 4,

 \ hskip1cm 

Y

 \ hskip8cm 

-

 \ delm {N} {\ delm {\ para} {R3}} 

-

 \ melm {\ delm {\ dpara} {O}} {S} {\ uelm {\ dpara} {O}} 

-

 \ uelm {C} {\ uelm {\ para} {Y}} 

H-R 4

and mixtures thereof, wherein R 1 is an alkyl, aryl or alkylaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , R 5 is an alkenyl chain containing from 1 to 8 carbon atoms, and Y is H or a solubilizing group. Any of the groups R 1 , R 3 and R 4 may be essentially substituted with any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl, amido and ammonium groups or alkylammonium.

Preferred solubilizing groups are -SO 3 <+> - M +, -CO 2 - M +, -SO 4 - M + , -N + (R 3) 4 X - and O <--N (R 3) 3, and most preferably -SO 3 <2> - M <+> and -CO2 <+> - M <+>, in which R <3> is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds they provide perbenzoic acid when performing perhydrolysis.

Perbenzoic acid precursor compounds Appropriate O-acylates include the benzoyl oxybenzene sulfonates substituted and unsubstituted, including, for example, a benzoyl oxybenzene sulfonate:

8

The products of benzoylation of sorbitol, glucose, and all saccharides with benzoylation agents, including, for example:

9

       \ newpage
    

Ac = COCH 3; Bz = benzoyl.

Perbenzoic acid precursor compounds of the type of imides, include N-benzoyl succinimide, tetrabenzoyl ethylenediamine, and ureas N-benzoyl-substituted. The appropriate perbenzoic acid precursor compounds of the type imidazole include N-benzoyl-imidazole and N-benzoyl-benzimidazole, and others perbenzoic acid precursor compounds useful with groups N-acyl include N-benzoyl-pyrrolidone, dibenzoyl-taurine and acid benzoyl pyroglutamic.

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

10

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

eleven

Perbenzoic acid precursor compounds Appropriate type N-acylated lactams have the formula:

12

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

Precursor compounds of perbenzoic acid derivatives

The acid derivative precursor compounds perbenzoic provide substituted perbenzoic acids to Perform perhydrolysis.

Acid derivatives precursor compounds Appropriate substituted perbenzoic include any of the perbenzoic acid precursor compounds than in this invention are described, in which the benzoyl group is substituted essentially with any functional group not positively charged (i.e. non-cationic) which includes, for example, alkyl groups, hydroxy, alkoxy, halogen, amino, nitrosyl and amido.

\delm{C}{\delm{\dpara}{O}}

--

\delm{N}{\delm{\para}{R ^{5} }}

--R^{2}--

\delm{C}{\delm{\dpara}{O}}

--L

\hskip2cm

o

\hskip2cm

R^{1}--

\delm{N}{\delm{\para}{R ^{5} }}

--

\delm{C}{\delm{\dpara}{O}}

-- R^{2}--

\delm{C}{\delm{\dpara}{O}}

--LR 1 -

 \ delm {C} {\ delm {\ dpara} {O}} 

-

 \ delm {N} {\ delm {\ para} {R5}} 

--R 2 -

 \ delm {C} {\ delm {\ dpara} {O}} 

--L

 \ hskip2cm 

or

 \ hskip2cm 

R 1 -

 \ delm {N} {\ delm {\ para} {R5}} 

-

 \ delm {C} {\ delm {\ dpara} {O}} 

- R2 -

 \ delm {C} {\ delm {\ dpara} {O}} 

--L

A preferred class of precursor compounds of substituted perbenzoic acids are the compounds amido-substituted, of the following formulas general:

wherein R 1 is an aryl or alkylaryl group having 1 to 14 carbon atoms, R 2 is an arylene or alkylarylene group containing 1 to 14 carbon atoms, and R 5 } is H or an alkyl, aryl or alkylaryl group containing from 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylaryl containing a branching, a substitution, or both, and may have origin in any synthetic sources or natural sources including, for example, tallow fat. Similar structural variations are permissible for permissible for R2 . The substitution may include alkyl, aryl, halogen, nitrogen, sulfur groups 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. Amido-substituted bleach activating compounds of this type are described in EP-A-0170386.

Precursor compounds of cationic peroxyacids

Peroxyacid precursor compounds cationics produce cationic peroxyacids when performing a perhydrolysis

Typically, the precursor compounds of cationic peroxyacids are formed by replacing the part of peroxyacid of a peroxy acid precursor compound suitable for a positively charged functional group, such as an ammonium group or alkylammonium, preferably an ethyl group or methyl ammonium The precursor compounds of cationic peroxyacids are typically present in the compositions as a salt with an appropriate anion, such as by example a halide ion or a methylsulfate ion.

The peroxyacid precursor compound to be being cationically substituted in this way can be a compound perbenzoic acid precursor, or a substituted derivative thereof, as described earlier in this text. Alternatively, the peroxyacid precursor compound may be a compound precursor of alkylpercarboxylic acid or a precursor compound of amido-substituted alkylperoxy acid, as described in continuation.

The cationic peroxyacid precursor compounds are described in US Pat. 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; and in RU patent 1,382,594; and in patents EP 475,512; 458,396 and 284,292; and in JP 87-318.332.

Precursor compounds of cationic peroxyacids Suitable include any of the alkyl compounds or benzoyl oxybenzene sulfonates Ammonium or alkylammonium substitutes, N-acylated caprolactams and monobenzoyl-tetraacetyl- glucose-benzoyl peroxides.

A benzoyl oxybenzene sulfonate cationically substituted substituted is the derivative 4- (trimethyl-ammonium) -methyl benzoyl-oxybenzene sulfonate:

14

An alkyloxybenzene sulfonate Cationically preferred substituted has the formula:

fifteen

Precursor compounds of cationic peroxyacids from the class of preferred N-acylated caprolactams include the trialkyl-ammonium-methylene-benzoyl-caprolactams,  particularly the trimethyl-ammonium-methylene-benzoyl-caprolactam:

16

Other peroxyacid precursor compounds cationics of the class of preferred N-acylated caprolactams, include the trialkyl-ammonium-methylene-alkyl-caprolactams:

17

in which n is 0 to 12, particularly 1 to 5.

Other cationic peroxyacid precursor compound preferred is chloride 2- (N, N, N-trimethyl-ammonium) -ethyl-4-sulfo-phenyl-carbonate of sodium.

Acid bleaching agents precursor compounds alkylpercarboxylic

Bleaching agent precursor compounds type alkylpercarboxylic acids form percarboxylic acids at Perform perhydrolysis. The precursor compounds of this Preferred types provide peracetic acid when performing a perhydrolysis

Preferred acid type precursor compounds alkylpercarboxylic type imides include alkylenediamines tetraacetylated in N, N, N 1, N 1 in which the group alkylene contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms Particularly preferred is the tetraacetyl ethylenediamine (TAED).

Other acid precursor compounds Preferred alkylpercarboxylic include 3,5,5-trimethylhexanoyloxybenzene sulfonate sodium (iso-NOBS), nonanoyloxybenzene sulphonate sodium (NOBS), sodium acetoxybenzene sulphonate (ABS) and penta-acetyl glucose.

Alkylperoxyacid precursor compounds amido-substituted

The alkylperoxyacid precursor compounds amido-substituted are also appropriate, including those with the following general formulas

\delm{C}{\delm{\dpara}{O}}

--

\delm{N}{\delm{\para}{R ^{5} }}

--R^{2}--

\delm{C}{\delm{\dpara}{O}}

--L

\hskip2cm

o

\hskip2cm

R^{1}--

\delm{N}{\delm{\para}{R ^{5} }}

--

\delm{C}{\delm{\dpara}{O}}

-- R^{2}--

\delm{C}{\delm{\dpara}{O}}

--LR 1 -

 \ delm {C} {\ delm {\ dpara} {O}} 

-

 \ delm {N} {\ delm {\ para} {R5}} 

--R 2 -

 \ delm {C} {\ delm {\ dpara} {O}} 

--L

 \ hskip2cm 

or

 \ hskip2cm 

R 1 -

 \ delm {N} {\ delm {\ para} {R5}} 

-

 \ delm {C} {\ delm {\ dpara} {O}} 

- R2 -

 \ delm {C} {\ delm {\ dpara} {O}} 

--L

wherein R 1 is an alkyl group containing from 1 to 14 carbon atoms, R 2 is an alkylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be a straight or branched chain alkyl group, which contains a branching, a substitution or both, and may have its origin in any of the synthetic sources or natural sources, including, for example, tallow fat . Similar structural variations are permissible for R2 . The substitution may include alkyl, 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. Amido group substituted bleaching agent activating compounds of this type are described in EP-A-0170386.

Organic peroxyacid precursors of the benzoxazine type

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

19

including substituted benzoxazines from kind

twenty

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

An especially preferred precursor compound The type of benzoxazine is:

twenty-one

Organic peroxyacid previously formed

The bleaching system with a peroxyacid Organic may contain in addition to, or as an alternative to, a peroxyacid bleaching agent precursor compound organic, a previously formed organic peroxyacid, typically at  a level of 0.5% to 25% by weight, more preferably 1% to 10% in composition weight.

A preferred class of peroxyacid compounds Organic are the amido-substituted compounds, of The following general formulas:

\delm{C}{\delm{\dpara}{O}}

--

\delm{N}{\delm{\para}{R ^{5} }}

--R^{2}--

\delm{C}{\delm{\dpara}{O}}

-- OOH

\hskip2cm

o

\hskip2cm

R^{1}--

\delm{N}{\delm{\para}{R ^{5} }}

--

\delm{C}{\delm{\dpara}{O}}

-- R^{2}--

\delm{C}{\delm{\dpara}{O}}

--OOHR 1 -

 \ delm {C} {\ delm {\ dpara} {O}} 

-

 \ delm {N} {\ delm {\ para} {R5}} 

--R 2 -

 \ delm {C} {\ delm {\ dpara} {O}} 

- OOH

 \ hskip2cm 

or

 \ hskip2cm 

R 1 -

 \ delm {N} {\ delm {\ para} {R5}} 

-

 \ delm {C} {\ delm {\ dpara} {O}} 

- R2 -

 \ delm {C} {\ delm {\ dpara} {O}} 

--OOH

wherein R 1 is an alkyl, aryl or alkylaryl group having 1 to 14 carbon atoms, R 2 is an alkylene, arylene and alkylarylene group containing 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl or alkylaryl group 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 may be a straight or branched chain alkyl group, aryl or alkylaryl group substituted with a branching, a substitution or both, and may be derived from synthetic sources or natural sources including, for example, tallow fat. Similar structural variations are permissible for R2 . The substitution may include alkyl, aryl, halogen, nitrogen, sulfur groups 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. Amido-substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxidedecanedioic acid, acid diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. The dibenzoyl peroxide is a preferred organic peroxyacid in the present invention They are also suitable in the present invention mono- and di-perazelaic acids, acid mono-and di-perbrasilic acid N-phthaloylaminoperoxicaproproic.

Controlled release-media speed

Means can be provided to control the release rate of a bleaching agent, particularly of an oxygen bleaching agent, to the solution of washed.

The means to control the speed of release of a bleaching agent can provide a controlled release of chemical species of peroxides to the washing solution Such means could include, for example, control the release of any inorganic perhydrate salt, which acts as a source of hydrogen peroxide, to the solution washing

Another mechanism to control the speed of bleaching agent release may consist of coating the bleaching agent with a coating designed to provide controlled release. The coating may comprise, by an example, a little water soluble material, or it can be a coating thick enough for conditions dissolution kinetics of the thick coating provide the controlled release speed.

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

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

Other appropriate coating materials they can comprise sulfates, silicates and carbonates of metals alkaline and alkaline earth, including carbonate of calcium and silicas.

A preferred coating material, particularly for a source of salt bleaching agent of inorganic perhydrate, comprises a sodium silicate with a SiO2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably of 1.8: 1 to 2.4: 1 and / or sodium metasilicate, preferably applied at a level of 2% to 10% (usually 3% to 5%) of SiO2 per weight of inorganic perhydrate salt. It can be included in the also coating a magnesium silicate.

Any coating material based on inorganic salts can be combined with binder materials organic to provide composite coatings based on a inorganic salt and an organic binding agent. Agents Suitable binders include the ethoxylated compounds of C 10 -C 20 alcohols, containing from 5 to 100 moles of ethylene oxide per mole of alcohol and more preferably the ethoxylated compounds of primary alcohols C 15 -C 20 containing 20 to 100 moles of ethylene oxide per mole of alcohol.

Other preferred binding agents include certain polymeric materials. Poly (vinyl pyrrolidones) with an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to
5 x 10 6, preferably 1,000 to 400,000, most preferably 1,000 to 10,000, are examples of such polymeric materials.

Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, constituting maleic anhydride at least 20 moles percent of polymer, are additional examples of polymeric materials that They are useful as binding agents. These polymeric materials they can be used as such or in combination with solvents such such as water, propylene glycol and ethoxylated compounds of alcohols C 10 -C 20 mentioned above, the which contain 5 to 100 moles of ethylene oxide per mole. Additional examples of binding agents include mono- and di-glycerol C 10 -C 20 ethers and also the C 10 -C 20 fatty acids.

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

A method to apply the material of Coating involves an agglomeration. The agglomeration processes Preferred include the use of any one of the materials organic binders that have been described in this invention previously. Any conventional device can be used agglomerator / mixer including, but not limited to, types of tray mixers, rotary and vertical drums. Molten coating compositions can be applied also pouring or atomizing them by projection on a bed in motion of bleaching agent.

Other means to provide release controlled required include mechanical means to alter the physical characteristics of the bleaching agent in order to control its solubility and its release rate. The appropriate protocols could include compression, injection mechanical, manual injection and compound solubility adjustment bleaching by particle size selection of any component in the form of particles.

Although the choice of particle size will depend so much on the composition of the component in the form of particles, as of the desire to satisfy the kinetic conditions controlled release that are desired, it is desirable that the size of  particles are 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 appropriate choice of any other component of the composition matrix of detergent, so that when the composition is introduced into the washing solution, the ionic strength environment there provided makes it possible for the conditions to be achieved controlled release kinetics that are required.

Metal bleaching catalyst

The compositions described herein, which contain a bleaching agent as a component of the detergent can additionally contain, as a preferred component, a catalyst of bleaching containing metal (s). Preferably, the metal containing bleaching catalyst is a catalyst of bleaching containing a transition metal, more preferably a bleaching catalyst containing manganese or cobalt.

An appropriate type of bleaching catalyst is a catalyst comprising a heavy metal cation with a catalytic activity of defined bleaching, such as cations of copper, iron, an auxiliary metal cation that has little or no catalytic activity of bleaching, such as cations of zinc or aluminum, and a sequestering agent that has constants of stability defined for catalytic metal cations and auxiliary, particularly ethylenediaminetetraacetic acid, the ethylenediaminetetramethylene phosphonic acid and its water soluble salts. Such catalysts are described in the U.S. Patent 4,430,243.

Preferred types of bleach catalysts include the manganese-based complexes described in the U.S. Patent 5,246,621 and in US Pat. 5,244,594. Preferred examples of these catalysts include

Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triaza-cyclononane) 2 - (PF 6) 2,

Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triaza-cyclononane)  2 - (ClO 4) 2,

Mn IV 4 (u-O) 6 (1,4,7-triaza-cyclononane) 4 - (ClO 4) 2,

Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triaza-cyclononane)  2 - (ClO 4) 3,

and their mixtures. Other types are described in the European Patent Application Publication No. 549,272. Others ligands suitable for use in the present invention include 1,5,9-trimethyl-1,5,9-triaza-cyclododecane, 2-methyl-1,4,7-triaza-cyclononane,   2-methyl-1,4,7-triaza-cyclononane, 1,2,4,7-tetramethyl-1,4,7-triaza-cyclononane, and their mixtures.

The bleaching catalysts useful in compositions of the present invention can be selected also as appropriate for the present invention. For examples of appropriate bleaching catalysts, see the patent for USA 4,246,612 and US Pat. 5,227,084. See also the U.S. Patent 5,194,416 teaching mononuclear complexes of manganese (IV), such as Mn (1,4,7-trimethyl-1,4,7-triaza-cyclononane) (OCH 3) 3 - (PF 6).

Still, another type of bleaching catalyst, As described in US Patent 5,114,606, it is a complex Water soluble manganese (III) and / or (IV), with a ligand which is a non-carboxylate polyhydroxy compound, which has at least three consecutive C-OH groups. The Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleaching catalyst comprising a metal complex of transition, including Mn, Ce, Fe or Cu, with a non-ligand (macro) cyclic. These ligands are of the formula:

\uelm{C}{\uelm{\para}{R ^{2} }}

--B--

\uelm{C}{\uelm{\para}{R ^{3} }}

=N--R^{4}R1 - N =

 \ uelm {C} {\ uelm {\ para} {R2}} 

--B--

 \ uelm {C} {\ uelm {\ para} {R3}} 

= N-R 4

wherein R 1 , R 2 , R 3 and R 4 can be selected in each case from H, substituted alkyl and aryl groups, such that each R 1 -N = CR 2 and R 3 -C = NR 4 form a five or six member ring. Said ring may additionally be substituted. B is a bridge forming group selected from O, S, CR 5 R 6, NR 7 and C = O, in which each of the R 5 , R 6 } and {7} R may be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the 2,2'-bis-pyridylamine ligand. Preferred bleaching catalysts include complexes of Co, Cu, Mn, Fe, -bis-pyridylmethane- and -bis-pyridylamine. Highly preferred catalysts include Co (2,2'-bis-pyridylamine) Cl 2, di (isothiocyanate) bis-pyridylamine-cobalt (II), tris-dipyridylamine-cobalt (II) -perchlorate, Co (2,2- bis-pyridylamine) 2 O 2 ClO 4, bis- (2,2'-bis-pyridylamine)-copper (II) -perchlorate, tris (di-2-pyridyl-amine)-iron ( II) -perchlorate and mixtures thereof.

Preferred examples include complexes Mn binuclear with ligands tetra-N-dentate and bi-N-dentate, including

N 4 Mn III (u-O) 2 Mn IV N 4) + and [Bipy_2 Mn III (u-O) 2 Mn IV bipy 2] - (CIO 4) 3

Although the structures of the manganese complexes that catalyze bleaching here invention, it can be speculated that they comprise chelates or other hydrated coordination complexes, resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Similarly, the oxidation state of the cation manganese during the catalytic process is not known with certainty, and may be the state of Valencia (+ II), (+ III), (+ IV) or (+ V). Because of the six points of binding to the manganese cation that they are possible for ligands, you can reasonably speculate with which there may be multi-nuclear species and / or "cage" structures in aqueous bleaching media. Whatever the form of the active ligand species with Mn that really exists, acts in a seemingly catalytic way to provide bleaching performance on stains persistent, such as tea, ketchup, coffee, wine, juices and Similar.

Other bleaching catalysts are described, for example, in the European patent application with the number of publication 408,131 (complex cobalt catalysts), in European patent applications with publication numbers 384,503 and 306,089 (catalysts of metallo-porphyrins), US Pat. 4,728,455 (manganese catalyst and a multidentate ligand), the patent of USA 4,711,748 and the European patent application with the number of publication 224.952 (catalyst with absorbed manganese on an alumino-silicate), US Pat. 4,601,845  (alumino-silicate support with manganese and zinc or a magnesium salt), US Pat. 4,626,373 (catalyst of manganese and a ligand), US Pat. 4,119,557 (catalyst with a ferric complex), German patent specification 2,054,019 (catalyst with a cobalt chelating agent), patent Canadian 866,191 (salts containing transition metals) U.S. Patent 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and US Pat. 4,728,455 (gluconate-manganese catalysts).

Other preferred examples include the cobalt (III) catalysts having the formula

Co [(NH_3) n M '{} m} B' {} b {T} {} t} Q_ {q} P_ {p}] Y_ {y}

in which the cobalt is in the oxidation state +3; n is an integer from 0 to 5 (preferably 4 or 5; most preferably 5); M ' represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; most preferably 1); B ' represents a bidentate ligand; b is an integer from 0 to 2; T ' represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected opposite sign anions, present in a number and , in which y is an integer from 1 to 3 (preferably from 2 to 3; most preferably 2, when Y is an anion with charge -1 ), to obtain a balanced salt in terms of the charges, the preferred Y groups are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof; and in that at least one of the cobalt-linked coordination sites is labile in the conditions of use in automatic dishwashing machines and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the potential for reduction for cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) compared to a normal normal hydrogen electrode.

Cobalt catalysts of this type Preferred have the formula:

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

wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M ' is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) their combinations; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6; and Y is an appropriately selected opposite sign anion, present in a number y , which is an integer from 1 to 3 (preferably from 2 to 3; most preferably 2, when Y is an anion with charge -1), for get a balanced salt in terms of loads.

The preferred cobalt catalyst of this type, useful in the present invention, salts of cobalt-pentaamine-chloride which they have the formula [Co (NH 3) 5 Cl] Y_ and especially [Co (NH 3) 5 Cl] Cl 2.

The compositions of the present invention using bleach catalysts with cobalt (III), which have the formula:

[Co (NH 3) n (M) m (B) b] T y

in which the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligand (s) coordinated with cobalt by one 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 is = 0, then m + n is = 6, and when b is = 1 then it is m = 0 and n is = 4; and T is one or more appropriately selected opposite sign anions, which are present in a number and , in which y is an integer, to obtain a balanced salt in terms of the charges (preferably and is 1 to 3; most preferably 2 when T is an anion with charge -1); and in that said catalyst also has a basic hydrolysis rate constant of less than 0.23 M -1 s -1 (at 25 ° C).

Preferred T anions are selected from the 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 more than one anionic group exists in T , eg HPO_ {4} 2-, HCO_ {3} - {,} {2} PO_ {4} ^ {- }, etc. In addition, T can be selected from the group consisting of non-traditional inorganic anions, such as anionic surfactants (eg, linear alkylbenzene sulphonates (LAS), alkyl sulfates (AS), alkylethoxy sulfonates (AES), etc. ) and / or anionic polymers (for example, polyacrylates, polymethacrylates, etc.).

The moieties M include, but are not limited to, for example, F <->, SO_4-2-, NCS <->, SCN <->, S2 {O3} 2-, NH 3, PO 4 3-, and carboxylates (which are preferably monocarboxylates, but more than one carboxylate may be present in the remainder as long as the cobalt binding is performed only by one carboxylate per residue, in which case the other carboxylate existing in the remainder M may be protonated or in its salt form). Optionally, M may be protonated if there is more than one anionic group in M (e.g., HPO_ {4} 2-, HCO_ {3} - {,} {2} PO_ {4} ^ { -}, HOC (O) CH 2 C (O) O-, etc.). Preferred M moieties are substituted and unsubstituted C 1 -C 30 carboxylic acids, with the formulas:

RC (O) O-

\hbox{-(CH _{2} ) _{n} }

NR'_{4}^{+}, en que n es un número entero de 1 a 16, preferentemente de 2 a 10, y lo más preferentemente de 2 a 5.wherein R is preferably selected from the group consisting of hydrogen and C 1 -C 30 alkyl group (preferably C 1 -C 18) unsubstituted and substituted, C 6 -aryl group - C 30 (preferably C 6 -C 18) unsubstituted and substituted, and C 3 -C 30 heteroaryl group (preferably C 5 -C 18) unsubstituted and substituted, wherein the substituents are selected from the group consisting of NR '3, -NR' 4 +, -C (O) OR ', -OR', -C (O) NR ' 2, wherein R ' is selected from the group consisting of hydrogen and C 1 -C 6 moieties. Such substituted Rs therefore include the moieties - (CH2) n OH and

 \ hbox {- (CH2) n 

NR '4 +, in which n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.

The most preferred M are carboxylic acids with the above formula, wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, linear or branched C 4 -C 12 alkyl, and benzyl. The most preferred R is methyl. Preferred M moieties of preferred carboxylic acids include those of formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethyl-hexanoic, naphthenoic, oleic, palmitic, triflate, tartrate acids, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic acid.

The B moieties include carbonate, dicarboxylates and carboxylates of higher order (eg oxalate, malonate, malate, succinate, maleate), picolinic acid, and alpha and beta-amino acids (eg, glycine, alanine, beta-alanine , phenylalanine).

\hbox{[Co(NH _{3} ) _{5} }

OAc](SO_{4}); [Co(NH_{3})_{5}OAc](BF_{4})_{2}; y [Co(NH_{3})_{5}OAc](NO_{3})_{2} (que en esta invención se denomina "PAC").Cobalt bleaching catalysts are known that are useful in the present invention, which are described, for example, in conjunction with their basic hydrolysis rates, in ML Tobe, Base Hydrolysis of Transition-Metal Complexes , Adv. Inorg Bioinorg Mech , (1983), 2, pages 1-94. For example, Table 1, on page 17, presents the rates of basic hydrolysis (which are designated there as k_ {OH}) for catalysts of the cobalt-pentaamine type that have complexed with oxalate (k_ {OH} = 2 , 5 x 10 -4 M-1 s -1 (at 25 ° C)), NCS - (k OH = 5.0 x 10-4 M ^ {-1 s -1 (at 25 ° C)), formate (k OH = 5.8 x 10 -4 M -1 s -1 (at 25 ° C)) and acetate (k OH = 9.6 x 10 -4 M -1 -s -1 (at 25 ° C)). The most preferred cobalt catalyst, which is useful in the present invention, is cobalt-pentaamine-acetate salts having the formula [Co (NH 3) 5 OAc] T y, in which OAc represents an acetate moiety, and especially cobalt-pentaamine-acetate-chloride, [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 (NH3) 5 

OAc] (SO4); [Co (NH 3) 5 OAc] (BF 4) 2; and [Co (NH 3) 5 OAc] (NO 3) 2 (which in this invention is called "PAC").

These cobalt catalysts are readily prepared by known methods, as taught for example in the Tobe article noted in this invention above and the references cited therein, in US Pat. 4,810,410 issued to Diakun et al., On March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1,043-45; The Synthesis and Characterization of Inorganic Compounds , WL Jolly (Prentice-Hall; 1970), pages 461-3; Inorg Chem. , 18 , 1,497-1,502 (1979); Inorg Chem. 21 , 2,881-2,885 (1982); Inorg Chem. , 18 , 2.023-2.025 (1979); Inorg Synthesis, 173-176 (1960); and Journal of Physical Chemistry , 56 , 22-25 (1952); as well as the synthesis examples presented below in this report.

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

These catalysts can be treated together with attached materials in a way that reduces the impact on the color, if desired for aesthetic reasons of product, or can be included in particles containing enzymes as exemplified below, or the compositions are they can manufacture so that they contain "particles" of catalyst.

Organic polymeric compound

Organic polymeric compounds can be added as preferred components of detergent tablets, of according to the invention. By the expression "polymer compound organic "means essentially any compound organic polymer currently found in compositions of detergents having dispersing agents against the redeposition, agents for dirt release, or other detergency properties.

The organic polymeric compound is incorporated typically in detergent compositions at a level of 0.1 to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.

Examples of organic polymeric compounds include homo- or polycarboxylic organic acids water soluble copolymers, 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 carbon Polymers of the latter type are described in the GB-A-1,596,756. Examples of said salts are polyacrylates with a molecular weight of 2,000-10,000 and their copolymers with any other appropriate monomer unit, including those of acids Acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, modified citraconic and methylenemalonic or its salts, anhydride maleic, acrylamide, alkylene, vinyl methyl ether, styrene and any of its mixtures. Preferred are Copolymers of acrylic acid and maleic anhydride with a weight molecular from 20,000 to 100,000.

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

Preferred acrylic acid copolymers include those containing as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight of acrylic acid or its salts, and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts, having the general formula [CR 2 -CR 1 (CO-O-R 3)] - in which at least one of the R 1 , R 2 or R 3 substituents, preferably R 1 or R 2 is an alkyl or hydroxy-alkyl group of 1 to 4 carbon atoms, R 1 or R 2 it can be hydrogen and R3 can be hydrogen or an alkali metal salt. Most preferred is a substituted acrylic monomer, in which R 1 is methyl, R 2 is hydrogen (ie a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3,500 and contains from 60% to 80% by weight of acrylic acid and from 40% to 20% by weight of methacrylic acid.

The polyamine and polyamine compounds modified are useful in the present invention, including those that are derived from aspartic acid, such as those described in EP-A-305,282, EP-A-305,283 and EP-A-351,629.

Other optional polymers can be polyvinyl alcohols and polyvinyl acetates both modified and unmodified, cellulosic materials and modified cellulosics, poly (oxyethylenes), poly (oxypropylenes) and their copolymers, both modified as unmodified, ethylene terephthalate esters or propylene glycol or mixtures thereof with poly (oxyalkylene) units.

Appropriate examples are described in the patents from the USA Nos. 5,591,703, 5,597,789 and 4,490,271.

Agents for dirt removal

The polymeric agents appropriate for the dirt removal include those agents for the dirt removal that have: (a) one or more components non-ionic hydrophilic consisting essentially of (i) segments of poly (ethylene oxide) with a degree of polymerization of at minus 2, or (ii) segments of oxypropylene or poly (oxide of propylene) with a polymerization degree of 2 to 10, in which said hydrophilic segment does not cover any oxypropylene unit a unless it is attached to adjacent remains in each end by ether type links, or (iii) a mixture of units of oxyalkylene comprising oxyethylene units and 1 to 30 oxypropylene units, said hydrophilic segments comprising at least 25% oxyethylene units and more preferably, in special for components that have 20 to 30 units of oxypropylene, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, in which, if said hydrophobic components also comprise terephthalate of oxyethylene, the ratio of oxyethylene terephthalate units to C3 oxyalkylene terephthalate units is 2: 1 or less; (ii) C4-C6 alkylene segments or of C4-C6 oxyalkylene, or mixtures thereof, (iii) segments of a polyvinyl ester, preferably of poly (vinyl acetate), with a degree of polymerization of at least 2, or (iv) alkyl substituents C 1 -C 4 -ether or hydroxyalkyl C4-ether or mixtures thereof, wherein said substituents are present in the form of alkyl derivatives C 1 -C 4 -ether- or hydroxy-C4-alkyl-cellulose  or their mixtures, or a combination of (a) and (b).

Typically, the poly (ethylene oxide) segments of (a) (i) will have a polymerization degree of from 200, although higher levels may be used, preferably from 3 to 150, more preferably from 6 to 100. The segments Suitable C4-C6 oxy-alkylene hydrophobes, include, but are not limited to, finials at the ends of polymeric agents for dirt removal, such as MO3S (CH2) ) n OCH2CH2O-, in which M is sodium and n is an integer of 4-6, as described in US Pat. 4,721,580, issued on January 26, 1988 to Gosselink.

Polymeric agents for the elimination of dirt that are useful in this invention also include cellulosic derivatives such as polymers hydroxyether cellulosics, block copolymers of ethylene terephthalate or propylene terephthalate with terephthalate of poly (ethylene oxide) or poly (propylene oxide) terephthalate and the like Such agents are commercially available and include cellulose hydroxy ethers, such as METHOCEL (from Dow) Cellulosic agents for dirt removal, intended for use in the present invention, also include which are selected from the group consisting of alkyl C 1 -C 4 - and hydroxy-alkyl C4 -cellulose; see US Pat. 4,000,093, issued on December 28, 1976 to Nicol, and collaborators

Dirt removal agents characterized by hydrophobic segments of polyvinyl esters include graft copolymers of polyvinyl esters, e.g., C 1 -C 6 vinyl esters, preferably
poly (vinyl acetate) grafted onto poly (alkylene oxide) main chains, such as poly (ethylene oxide) main chains. See European patent application 0 219 048, published on April 22, 1987 by Kud et al.

Another appropriate agent for the elimination of dirt is a copolymer that you have random blocks of terephthalate of ethylene and poly (ethylene oxide) terephthalate (PEO). The molecular weight of this polymeric agent for the elimination of dirt is within the range of 25,000 to 55,000. See U.S. Patent 3,959,230 issued to Hays on May 25 of 1976 and US Patent 3,893,929 issued to Basadur on 8 July 1975

Another polymeric agent suitable for dirt removal is a polyester with repeated units of ethylene terephthalate containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of terephthalate units of poly (ethylene oxide), which are derived from a poly (oxyethylene) -glycol with a molecular weight 300-5,000 average.

Another polymeric agent suitable for dirt removal is a sulfonated product of an oligomer of substantially linear ester that is composed of a chain main of oligomeric ester based on repetitive units of terephthaloyl and oxyalkyleneoxy and attached terminal moieties covalently to the main chain. These agents for the dirt removal are fully described in the patent  from the USA No. 4,968,451, issued on November 6, 1990 to J.J. Scheibel and E.P. Gosselink Other appropriate polymeric agents for dirt removal include polyesters US Patent Terephthalates 4,711,730, issued on 8 December 1987 to Gosselink and collaborators, the esters oligomers capped with anionic ends of the patent of USA 4,721,580, issued on January 26, 1988 to Gosselink, and the oligomeric block polyester compound of the patent from the USA 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric agents for dirt removal also include agents for the removal of dirt from U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., Which describes terephthalate esters anionic, terminated at the ends especially with sulfo-aroyl.

Another agent for dirt removal is an oligomer with repetitive units based on units of terephthaloyl, sulfoisoterephthaloyl units, units of oxyethylene oxy and oxy-1,2-propyloxy. Repeated units form the oligomer's main chain and They are preferably finished with top ends of modified isethionates. An agent for the elimination of dirt of this type, which is particularly preferred, comprises one unit of sulfoisophthaloyl, 5 units of terephthaloyl, oxyethylene units, and oxy-1,2-propyleneoxy in a ratio from 1.7 to 1.8 and two end units at the ends based on 2- (2-hydroxyethoxy) -ethane sulphonate  of sodium.

Heavy metal ion sequestrant

The tablets of the invention contain preferably, as an optional component, a sequestrant of heavy metal ions. For the concept of "kidnapper of heavy metal ions "is understood in the present invention the components that act by sequestering (chelating) the ions of heavy metals These components may also have capacity for chelation of calcium and magnesium, but preferably manifest a selectivity for the association of metal ions heavy, such as iron, manganese and copper.

Heavy metal ion sequestrants 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, having for example functionalities of phosphonic acids or carboxylic acids, may be present either in its acid form or as a complex or as a salt with a appropriate cation counterion, such as an alkali metal ion or alkaline earth, ammonium, substituted ammonium, or Any of your mixtures. Preferably, any of the salts  or of the complexes are soluble in water. The molar relationship of said cation counterion to the heavy metal ion sequestrant is preferably at least 1: 1.

Heavy metal ion sequestrants suitable for use in the present invention include phosphonates organic, such as amino-alkylene-poly (alkylene phosphonates), ethane-1-hydroxy diphosphonates of alkali metals and nitrile-trimethylene phosphonates. Between species previous chemicals are preferred diethylenetriamine-penta- (methylene phosphonate),  ethylenediamine-tri- (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) e hydroxy-ethylene-1,1-diphosphonate.

Another heavy metal ion sequestrant suitable for use in the present invention includes acid nitrile-triacetic acid polyaminocarboxylic acid such as acid ethylenediamine tetraacetic acid ethylenetriamine-pentaacetic acid ethylenediamine disuccinic acid ethylenediamine diglutaric acid 2-hydroxy-propylenediamine-disuccinic,  or any of its salts.

       \ newpage
    

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

Crystal growth inhibitor component

Detergent tablets contain preferably a growth inhibitor component of the crystals, preferably an acid component diphosphonic organ, preferably incorporated into a 0.01% to 5% level, more preferably 0.1% to 2% by weight of The compositions.

By organ-diphosphonic acid it understood in the present invention an acid diphosphonic organ that does not contain nitrogen as Part of its chemical structure. This definition excludes, so both, organophosphonates, which however can be include in the compositions of the invention as components heavy metal ion sequestrants.

Organ diphosphonic acid is preferably a diphosphonic acid C 1 -C 4, more preferably an acid C2 diphosphonic, such as ethylenediphosphonic acid, or the most preferably acid ethane-1-hydroxy-1,1-diphosphonic (HEDP) and may be present partially or totally ionized, particularly as a salt or complex.

Water soluble sulfate salt

The detergent tablet optionally contains a water soluble sulfate salt. When present, salt Water soluble sulfate is at a level of 0.1% to 40%, plus preferably from 1% to 30%, most preferably from 5% to 25% in Weight of the compositions.

The water soluble sulfate salt can be essentially any sulfate salt with any cation counterion. Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.

Alkali metal silicate

An alkali metal silicate is a component Preferred tablet of the present invention. A silicate of Preferred alkali metal is a sodium silicate with a ratio SiO2: Na2O from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0. Sodium silicate is present preferably at a level of less than 20%, preferably 1% at 15%, most preferably from 3% to 12% by weight of SiO2. The alkali metal silicate may be in the form of the anhydrous salt or  of a hydrated salt.

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

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

Colorant

The term "dye", as used in the present invention means any substance that absorbs light at specific wavelengths of the visible light spectrum. Such dyes, when added to a detergent composition,  they have the effect of changing the visible color and therefore the appearance of the detergent composition. The dyes can be, for example, either dyes or pigments. Preferably, the dyes are stable in the composition in which they are to be incorporated. Thus, in a composition with a high pH value the dye is preferably stable against alkalis, and in a composition with a low pH value, the dye is preferably stable against acids.

The first and / or second phases and / or phases Additional options may contain a dye, a mixture of dyes, colored particles or a mixture of particles colored, so that the various phases have different visual aspects Preferably, any one of the phases First or second comprises a dye. When both the first as the second and / or subsequent phases comprise a dye, it is preferred that the dyes have a different appearance visual.

Examples of suitable dyes include dyes reagents, direct dyes and azo dyes. The preferred dyes include phthalocyanine dyes, anthraquinone dyes, dyes quinoline, monoazoic, disazoic and polyazoic dyes. Dyes more preferred include anthraquinone, quinoline and dyes monoazoic Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE  (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name), all of them available at Clariant U.K. HEXACOL QUINOLINE YELLOW (name commercial) and HEXACOL BRILLIANT BLUE (trade name), both available at Pointings, R.U., ULTRA MARINE BLUE (name commercial), available on Holliday or LEVAFIX TURQUISE BLUE EBA (trade name), available in Bayer, USA.

The dye can be incorporated into the phases by Any appropriate method. Appropriate methods include mixing the all or the detergent components selected with a dye inside a drum, or pulverize all or the detergent components selected with the dye within A rotating drum

The dye, when present as one of the components of the first phase, is present at a level of 0.001% to 1.5%, preferably 0.01% to 1.0%, the most preferably from 0.1% to 0.3%. When present as a component of the second phase and / or optional additional phases, the dye it is generally present at a level of 0.001% to 0.1%, plus preferably from 0.005% to 0.05%, most preferably from 0.007% at 0.02%.

Hydrocarbon oils

Another component of the preferred detergent for your Use in the present invention is a hydrocarbon oil, typically of aliphatic hydrocarbons, predominantly of long chain, with a number of carbon atoms in the range of 20 to 50; the preferred hydrocarbons are saturated and / or branched; a preferred hydrocarbon oil selected from C 25 -C 45 chemical species predominantly branched, with a hydrocarbon ratio cyclic to non-cyclic hydrocarbons from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A preferred hydrocarbon is a paraffin. An oil of paraffin that satisfies the characteristics that have been noted, with a ratio of cyclic hydrocarbons to 32:68 non-cyclic hydrocarbons, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Enzyme stabilizer system

Preferred compositions containing Enzymes in the present invention may comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6% by weight of an enzyme stabilizer system. The system enzyme stabilizer can be any stabilizer system that is compatible with the detersive enzyme. Such systems stabilizers can comprise a calcium ion, boric acid, propylene glycol, a short chain carboxylic acid, an acid boronic, chlorine bleach scrubbers and mixtures thereof. Sayings stabilizer systems may also comprise inhibitors reversible enzymes, such as reversible inhibitors of proteases

Limestone soap dispersant compound

The tablets of the present invention can contain a dispersing compound of limestone soap, present preferably at a level of 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably 2% to 10% by weight of the compositions.

A limestone soap dispersant is a material that prevents precipitation of metal fatty acid salts alkaline, ammonium or amine, by calcium ions or magnesium. Dispersed compounds of preferred limestone soaps are described in PCT application No. WO93 / 08877.

Soap suppressor system

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

Suppressive systems of suitable soaps for use in this invention can essentially comprise any known antifoam compound, including, by example, silicone antifoaming compounds, compounds Type 2-alkyl and alkanol defoamers. The suppressor systems of preferred soaps, and antifoam compounds, are described in PCT application No. WO 93/08876 and in the patent EP-A-705,324.

Polymeric agents transfer inhibitors dyes

The detergent tablets in this invention they can also comprise from 0.01% to 10%, preferably 0.05% at 0.5% by weight of polymeric agents that inhibit dye transfer

Polymeric agents inhibiting the dye transfer are preferably selected from poly (N-oxide amine) polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, or their combinations.

Optical brightener

Detergent tablets suitable for use in laundry washing methods as described in the present invention, may also optionally contain from 0.005% up to 5% by weight of certain types of optical brighteners hydrophilic

Hydrophilic optical brighteners useful in This invention includes those with the structural formula:

24

in which R_ {1} is selected between groups anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is select between groups N-2-bis-hydroxyethyl,   N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; and M is a cation that forms salts, 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 salt acid disodium 4,4'-bis [(4-anilino-6- (N-2-bis-hydroexyethyl) -s-triazine-2-yl)  amino] -2,2'-stilbendisulfonic acid. This particular polishing species is sold commercially under the trade name Tinopal-UNPA-GX, from Ciba-Geigy Corporation. Tinopal-UNTA-GX is the brightener preferred hydrophilic optic useful in detergent compositions of the present invention.

When in the previous 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-hydroexyethyl-N-methylamino) -s-triazine-2-yl)  amino] -2,2'-stilbendisulfonic acid. This particular polishing species is sold commercially under the trade name Tinopal 5BM-GX, from 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-triazine-2-yl)  amino] -2,2'-stilbendisulfonic acid. This particular polishing species is sold commercially under the trade name Tinopal AMS-GX, from Ciba-Geigy Corporation.

Softener Clays System

Detergent tablets suitable for use in cleaning methods in laundries can contain a system of softening clays, comprising a clay mineral compound and, optionally, a clay flocculating agent.

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

Cationic fabric softening agents

They can also be incorporated into the compositions cationic fabric softening agents, according to the present invention, which are suitable for use in methods of laundry washing. Cationic fabric softening agents Suitable include tertiary amines insoluble in water or materials two chain long amide type, as described in the patents GB-A-1,514,276 and EP-B-0.011.340.

Cationic fabric softening agents se typically incorporated in total levels ranging from 0.5% to 15% by weight, usually from 1% to 5% by weight.

Other optional ingredients

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

pH of the compositions

The detergent tablets of the present invention are preferably not formulated so that they have a unduly high pH value, 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, most preferably from 9.5 to 11.5

Washing method for laundry

The machine wash methods of the present invention comprise treating the stained laundry with a solution aqueous wash in a washing machine that has dissolved or dispersed an effective amount of one tablet of the detergent composition  for machine washing according to the invention. By a effective amount of the detergent composition tablet is means from 40 g to 300 g of dissolved or dispersed product in a volume washing solution of 5 to 65 liters, as they are typical product doses and commonly used volumes in conventional machine wash methods.

In a preferred aspect of use, a dispensing device in the washing method. The device Dispenser is loaded with detergent product and used to Introduce the product directly into the machine drum washing machine before the start of the wash cycle. His ability in volume should be such that it could contain enough product detergent like the one normally used in the method of washed.

Once the washing machine has been loaded with the casting, the dispensing device containing the detergent product inside the drum. When the cycle begins washing the washing machine, water is introduced into the drum and the Drum rotates periodically. The design of the dispensing device It should be such that it allows to contain the dry detergent product but then allow the release of this product during the wash cycle in response to agitation as the drum broken and also as a result of its contact with the water of washed.

To allow product release detergent during washing, the device must have a number of holes through which the product can pass. Alternatively, the device may be made of a material. that is permeable to the liquid product but impervious to the product solid, which allows the release of the dissolved product. Preferably, the detergent product will be rapidly released to the beginning of the wash cycle providing high concentrations of product promptly located on the machine drum washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designated in such a way that the integrity of the container is kept both in its dry state and during the wash cycle

Alternatively, the dispensing device It can be a flexible container, such as a bag or sack. The bag can be of fibrous construction coated with a material waterproof protector, so that it retains the contents, as described in the patent application European published with No. 0018678. Alternatively, it can be done of a water insoluble polymeric material provided with an edge sealed or closed designed to break in aqueous medium, as described in European patent applications published with Nos. 0011500, 0011501, 0011502 and 0011968. A convenient way to water-impermeable closure comprises a water soluble adhesive arranged along and sealing an edge of the sack made of a water-impermeable polymeric film, such as polyethylene or Polypropylene.

Multi-phase tablets can be Prepare as follows. The active detergent composition of the Phase 1 is prepared by mixing the granular and liquid components, and then it is passed to a rotary press die cutter conventional. The press includes a punch with a conformation suitable to form the mold. The cross section of the die cutter is approximately 30x38 mm. The composition is submitted then at a compression force of 940 kg / cm2, and then the punch is raised, exposing the first phase of the tablet that It contains the mold on its upper surface. Active composition of phase 2 detergent is prepared similarly, and made pass to the die cutter. The active particle composition is then subjected to a compression force of 170 kg / cm2, the punch is raised, and the multi-phase tablet is ejected from The press to make tablets.

Claims (21)

1. A multi-stage detergent tablet for laundry, which includes: a) a first phase that is in the form of a shaped body that has at least one mold on its surface; Y b) a second phase that is in the form of a compressed body, adhesively contained within said mold, in which the composition of the tablet comprises one or more detergent active ingredients that are concentrated predominantly in the second phase, and in which the second phase additionally comprises a binding agent, and the first and second phases are in a weight ratio of at least 6: 1, and the tablet is such that differential dissolution takes place of the phases during use. 2. A multi-stage detergent tablet according to claim 1, wherein the second phase is compressed at a pressure of less than 350 kg / cm2. 3. A multi-stage detergent tablet according to claim 1 or claim 2, wherein the first phase is a shaped and compressed body, prepared at a pressure of compression of at least 40 kg / cm2, preferably at least 350 Kg / cm2. 4. A multi-stage detergent tablet according to any one of the preceding claims, wherein the second phase dissolves faster than the first phase. 5. A multi-stage detergent tablet according to any one of claims 1 to 3, wherein the Second phase dissolves after the first phase. 6. One multi-stage detergent tablet according to any one of the preceding claims, wherein one or more of the detergent active ingredients are selected between enzymes, bleaching agents, bleaching activators, bleaching catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof. 7. A multi-phase detergent tablet according to any one of claims 1 to 5, wherein one or more of the detergent active ingredients are selected from detergency builders, dyes, surfactants, enzymes and  perfumes 8. One multi-stage detergent tablet according to any one of the preceding claims, wherein the binding agent is selected from a group consisting of sugars and derivatives of sugars, starch and derivatives of starch, inorganic and organic polymers. 9. A multi-phase detergent tablet according to any one of the preceding claims, wherein the binding agent is selected from a group consisting of organic polymers, and is preferably a polyethylene glycol, more preferably with a molecular weight of 4,000, 6,000 or 9,000. 10. A multi-stage detergent tablet according to any one of the preceding claims, which additionally comprises a barrier phase between the first and the Second phases 11. A multi-stage detergent tablet according to claim 10, wherein the barrier layer comprises a binder applied in liquid form. 12. One multi-stage detergent tablet according to any one of the preceding claims, wherein The mold has a concave surface inwards. 13. A multi-stage detergent tablet according to any one of the preceding claims, wherein the first and second phases are in a weight ratio of at minus 10: 1. 14. One multi-stage detergent tablet according to any one of the preceding claims, wherein the times at which the first and second phases dissolve They are independent of each other. 15. A machine wash method on a machine washing machine, which comprises loading a washing machine with one or more multi-phase detergent tablets according to the claim 1. 16. A method according to claim 15, in the that the multi-phase detergent tablet dissolves or disintegrates in less than 15 minutes in the washing machine. 17. A method according to claim 15 or claim 16, wherein the second phase dissolves further Quickly than the first phase.

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18. A method according to any one of the claims 15 to 17, wherein the second phase is dissolved in An automatic washing machine in 5 minutes. 19. A method according to claim 15 or claim 16, wherein the second phase dissolves after The first phase. 20. A method according to claim 15 or claim 16, wherein at least 50%, preferably at least 60%, more preferably at least 80% by weight of the ingredient detergent active is released in the wash in 10 minutes, preferably in 5 minutes, and more preferably in 3 minutes 21. A method according to any one of the claims 15 to 20, wherein the tablets have a any of the additional features cited in the claims 2, 3 and 6 to 13.