RU2203934C2 - Multiphase detergent pellet and process of washing in dish washing machine - Google Patents

Abstract

FIELD: detergent for dish washing machine and method of its use. SUBSTANCE: proposed multiphase detergent pellet includes: a) first phase in the form of shaped body that has at least one mold and b) second phase in the form of pressed body contained due to adhesion in above-mentioned mold. Composition of pellet includes one or more agents with activity of detergent which are predominantly concentrated in second phase and second phase additional has binder. Formed body of first phase is produced under pressing pressure of about 350.0 kg/sq cm, second phase is pressed under pressure less than 350.0 kg/sq cm. EFFECT: excellent solubility and washing characteristics together with proper integrity and strength of pellets. 6 cl

Description

FIELD OF THE INVENTION
The present invention relates to multiphase detergent tablets.

Prior art
The prior art compositions of detergents in the form of tablets. It is understood that tablet detergent compositions have several advantages over particulate detergent compositions, such as ease of dispensing, handling, transportation, and storage.

 Detergent tablets are most often prepared by pre-mixing the components of the detergent composition and molding the pre-mixed detergent components into a tablet using suitable equipment, preferably a tablet press. Tablets are usually formed by compressing the components of the detergent composition such that the resulting tablets become strong enough to withstand handling and transportation without apparent damage. In addition to the strength property, tablets should also dissolve quickly enough so that the components of the detergent pass into the washing water as quickly as possible at the start of the wash cycle.

 However, the duality is that as the compression force increases, the dissolution rate of the tablets decreases. In the present invention, therefore, strive to find a balance between strength and dissolution of the tablets. As follows from the prior art, a solution to this problem involves compressing tablets at low pressure. However, tablets made in this way, although they have a relatively high dissolution rate, tend to crumble, which leads to damage and is unacceptable to the consumer. Other solutions include producing tablets using relatively high compression pressure in order to achieve the desired level of strength, and the inclusion of an auxiliary agent such as an effervescent agent.

The multiphase detergent tablets described previously are prepared by compressing the first composition in a tablet press to form a substantially flat first layer. The additive detergent composition is then fed to the tablet press on top of the first layer. This second composition is then pressed to form a second substantially flat layer. Thus, the first layer is usually subjected to more than one compression, since it is also compressed by pressing the second composition. Typically, the first and second pressing forces are of the same order of magnitude. The applicant has found that in cases where this is the case, since the pressing force must be sufficient to bind the first and second composition together, the force applied in both the first and second stages of compression should be in the range from about 4000 to about 20,000 kg (assuming that the tablet cross section is approximately 10 cm ² ). The consequence of this is a lower dissolution rate of the tablet. Other multiphase detergent tablets exhibiting a differential solubility property are prepared in such a way that the second layer is pressed at a lower force than the first layer. However, although the dissolution rate of the second layer is improved, the second layer is soft compared to the first and, therefore, is susceptible to damage during handling and transportation.

 EP-I-0055100 describes a toilet briquette formed by combining a slowly dissolving formed body with a tablet. The briquette for the toilet is intended to be placed in the tank of the toilet and dissolves over a period of days, preferably a week. As a means of slowing the dissolution rate of a toilet briquette, the patent proposes the mixing of one or more solubility control agents. Examples of such solubility control agents are para-dichlorobenzene, waxes, long chain fatty acids, as well as alcohols and their esters and fatty alkyl amides. Detergent tablets used in washing or automatic dishwashing should essentially dissolve within one wash or automatic dishwashing cycle, i.e. for 15 to 120 minutes.

SUMMARY OF THE INVENTION
According to a first object of the invention, there is provided a multiphase detergent tablet for use in a washing machine, the tablet comprising:
a) a first phase in the form of a shaped body having at least one mold in it, and
b) a second phase in the form of solid particles compressed in said mold.

In preferred embodiments, the first phase is a compressed shaped body obtained with an applied compression pressure of at least about 40 kg / cm ² , preferably at least about 250 kg / cm ² , more preferably at least about 350 kg / cm ² (3.43 kN / cm ² ), even more preferably at least from about 400 to about 2000 and especially from about 600 to about 1200 kg / cm ² (here, the compression pressure is the applied force divided into the cross section of the tablet in a plane perpendicular to the force applied - in fact, the cross section of the matrix of the rotary press). It is also preferred that the solid particles of the second phase (this term is intended to include the possibility of a plurality of “second” phases, sometimes referred to herein as “optional subsequent phases”) are compressed in said mold at an applied compression pressure lower than that applied to the first phase and preferably at a compression pressure of less than about 350 kg / cm ² , preferably in the range of from about 40 to about 300 kg / cm ^2, and more preferably from about 70 to about 270 kg / cm ² , and such tablets are preferred here from the point of view of ensuring optimum tablet integrity and strength (measured, for example, using the Child Bite Strength test [CBS]) and the dissolution characteristics of the product. The tablets of the present invention preferably have a CBS of at least about 6 kg, preferably more than about 8 kg, more preferably more than about 10 kg, especially more than about 12 kg, and more importantly more than about 14 kg, when measuring CBS according to US Consumer Product Safety Commission testing specifications. The pressing pressure applied to the first and second phases should also typically be in a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1 .

Thus, in accordance with a further object of the present invention, there is provided a multiphase detergent tablet for use in a washing machine, a tablet comprising:
a) a first phase in the form of a compressed shaped body having at least one mold, the formed shell being prepared at a pressing pressure of at least about 350 kg / cm ² , and
b) a second phase in the form of solid particles compressed in said mold, the second phase being pressed at a pressure of less than about 350 kg / cm ² .

 In other preferred embodiments, the second phase is in a compressed form or in the form of a shell formed by adhesion, for example physical or chemical adhesion, in at least one mold of the first shell. It is also preferred that the first and second phases are in a relatively high weight ratio to one another, for example at least 6: 1, preferably at least about 10: 1, it is also preferred that the tablet composition contains one or more agents with the activity of detergents (e.g. enzymes, bleaches, bleaching activators, bleaching catalysts, surfactants, chelating agents, etc.), which are mainly concentrated in the second phase, for example, in the second phase ahoditsya, at least about 50%, preferably at least about 60%, especially about 80% by weight of a detergent active agents (based on total weight of active agents in the detergent tablet). Also, such compositions are optimal with respect to characteristics such as tablet strength, solubility, cleaning properties and pH maintenance, giving, for example, tablet compositions the ability to dissolve in a washing liquid such that at least 50%, preferably at least , 60% and more preferably at least 80% by weight of an agent with detergent activity is delivered over a period of time within 10, 5, 4 or even 3 minutes from the start of the washing process.

Thus, in accordance with another object of the invention, there is provided a multiphase detergent tablet for use in a washing machine, the tablet comprising:
a) a first phase in the form of a shaped body having at least one mold in it, and
b) a second phase in the form of solid particles compressed in said mold, and wherein the tablet comprises at least one agent with detergent activity and is formulated so that at least 50%, preferably at least 60% more preferably, at least 80% by weight of the agent with the detergent activity is delivered for washing within a period of time within the first 10 minutes, preferably within the first 5 minutes, and more preferably within the first 3 minutes of the washing process.

 An additional advantage of the invention is the ability to achieve differential phase solubility so that one phase of the tablet must dissolve much faster than the other phase and can even essentially completely dissolve before the dissolution of the other phase. This is especially valuable for the differential delivery of agents with detergent activity.

Thus, in accordance with another objective of the invention, there is provided a multiphase detergent tablet, comprising:
a) a first phase in the form of a shaped body having at least one mold in it, and
b) a second phase in the form of a compressed mold contained by adhesion in said mold, and wherein the tablet composition comprises one or more detergent-active agents that are concentrated predominantly in the second phase, and where the second phase further comprises a disintegrating agent.

In accordance with a further object of the present invention, there is provided a multiphase detergent tablet, comprising:
a) a first phase in the form of a shaped body having at least one mold in it, and
b) a second phase in the form of a compressed form contained by adhesion in said mold, wherein the tablet composition comprises one or more detergent-active agents that are concentrated predominantly in the second phase, and where the second phase further comprises a binder.

It is suitable if one or more agents with detergent activity are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof, and agents with enzyme activity are particularly preferred for improving washing cleanliness during a very short initial wash step or cleaning procedure in cold water. Therefore, for use here, enzymes with detergent activity and especially enzymes and enzyme mixtures comprising one or more enzymes having an increased or optimal activity in the temperature range from 25 to 55 ^{° C.} and at a pH in the range from 8 to 10 ( e.g. natalase).

Thus, in accordance with another objective of the invention, a multiphase detergent tablet is provided, comprising:
a) a first phase in the form of a shaped body having at least one mold in it, and
b) a second phase in the form of a compressed mold contained by adhesion in said mold, and wherein the second phase further comprises an enzyme.

DETAILED DESCRIPTION OF THE INVENTION
The aim of the present invention is to provide a tablet of detergent, which is not only strong enough to withstand handling and transportation, but also at least a significant portion of which quickly dissolves in water for washing, providing fast delivery of agent with detergent activity facilities. Preferably, at least one phase of the tablet is dissolved in the washing water within the first ten minutes, preferably five minutes, more preferably four minutes, of the washing cycle of an automatic dishwasher or washing machine. Preferably, the washing machine is either an automatic dishwasher or a washing machine. The time during which the multiphase tablet or its phase or component with detergent activity dissolves is determined in accordance with DIN 44990 using a dishwasher sold by Bosch with a normal washing program at 65 ^o C with water hardness at 18 ^o N, applying at least six repeated determinations or a sufficient number of them to guarantee reproducibility.

 The multiphase detergent tablet of the present invention includes a first phase, a second and optionally subsequent phases. The first phase is in the form of a formed body of a detergent composition comprising one or more detergent components, as described below. Preferred detergent components include a detergent component, bleach, enzymes, and a surfactant. The components of the detergent composition are mixed together, for example, by admixing the dry components or by injecting the liquid components. The components are then molded, creating the first phase, using any suitable equipment, but preferably by compression, for example, in a tablet press. In the opposite embodiment, the first phase can be obtained by pressing, casting, etc. The first phase may have various geometric shapes, such as spherical, cubic, etc., but preferred embodiments typically have a shape symmetrical in axes, usually with a round, square or rectangular cross section.

 The first phase is prepared so that it includes at least one mold in the surface of the formed body. The mold or molds can also vary in size and shape and their localization, orientation and topology with respect to the first phase. For example, the mold or molds can usually be round, square or oval in cross section; they can form an internally closed cavity or recess in the surface of the shaped body or they can stretch between unrelated areas of the surface of the body (for example, the outer layers of surfaces located on opposite axes), forming one or more topological “holes” in the shaped body, and they can be located symmetrically along the axes or other landmarks with respect to the first phase, or they can be located asymmetrically. In a preferred embodiment, the mold is created using a specially designed tablet press in which the surface of the punch that contacts the detergent composition is shaped so that when it contacts and presses the detergent composition, it compresses the mold or multiple molds in the first phase of a multiphase detergent tablet. Preferably, the mold should have a cavity or a normal concave surface inside to provide improved adhesion to the second phase. Alternatively, a mold can be created by compressing a preformed mold of a detergent composition disposed in a ring around a central matrix, thereby forming a shaped body having a mold in the form of a cavity that extends axially between opposing surfaces of the body.

The tablets of the invention also include one or more additional phases derived from a composition or compositions that include one or more detergent components, as described below. At least one phase (referred to here as the second phase) is preferably in the form of solid particles (this term encompasses powders, granules, agglomerates and other solid particles, including mixtures thereof with liquid binders, melting solid components, nebulizers, etc.) pressed into / inside one or more molds of the first phase of the detergent tablet in such a way that the second phase itself is in the form of a compressed form. Optional additional phases include one or more compositions in the form of a separate layer or layers. Preferred detergent components include detergent components, colorants, binders, surfactants, disintegrants and enzymes, in particular amylase and protease enzymes. In another preferred embodiment of the present invention, the second and optional subsequent phases include a disintegrant, which may be selected from either a disintegrating agent or an effervescent agent. Suitable disintegrating agents include agents that swell upon contact with water or accelerate the influx and / or outflow of water by forming channels in a detergent tablet. Any known disintegrant or effervescent agent suitable for use in washing or dishwashing is considered to be used here. Suitable disintegrating agents include starches (such as natural, modified and pregelatinized starches, for example, derivatives of corn, rice and potato starch), starch derivatives such as U-Sperse (trademark), Primojel (trademark) and Explotab (trademark ), cellulose, microcrystalline cellulose and cellulose derivatives such as Arbocel (trademark) and Vivapur (trademark), both supplied by Rettenmaier, Nymcel (trademark), supplied by Metsa-serla, Avicel (trademark), Lattice Nt (trademark ) and Hanfloc (trademark), alginates, three-water acetate, a carbonate containing one water molecule, burkeite of the formula Na ₂ CO ₃ • H ₂ O, hydrated STTP with a first phase content of at least about 40%, carboxymethyl cellulose (CMC), CMC based polymers, sodium acetate, alumina. Suitable effervescent agents may be oxygen, nitrogen dioxide, or carbon dioxide-giving materials. Examples of preferred effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with carboxylic or other acids, such as citric, sulfamic, malic or maleic acid.

 The components of the detergent composition are mixed together, for example, by mixing dry components or injecting liquid components. Then the components of the second and optional subsequent phases are loaded there and left in the mold provided by the first phase.

 A preferred embodiment of the present invention includes two phases: first and second phases. The first phase should usually include one mold, and the second phase should usually consist of one active detergent composition. However, it is contemplated that the first phase may include more than one mold, and the second phase may be obtained from more than one active detergent composition. Moreover, it is also envisaged that the second phase may include more than one active composition of detergents contained in one mold. It is also contemplated that several active detergent compositions are contained in separate molds. In this way, potentially chemically sensitive detergent components can be separated in order to avoid any loss in performance caused by the interaction of the components with each other and the potential for their inactivation or depletion.

 In a preferred embodiment of the present invention, the first, second and / or optional subsequent phases may include a binder. The binder, if present, is selected from the group consisting of organic polymers, for example polyethylene and / or polypropylene glycol, especially with a molecular weight of 4000, 6000 and 9000, paraffins, polyvinylpyrrolidone (PVP), especially PVP with a molecular weight of 90,000, polyacrylates, sugars and derivatives of sugars, starch and derivatives of starch, for example hydroxypropyl methyl cellulose (HPMC) and carboxymethyl cellulose (CMC), and inorganic polymers such as hexametaphosphate. A binder is valuable both for tablet integrity and for helping to achieve differential solubility of the first and second phases, as described below.

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

 In another embodiment of the present invention, between the first and second phase and / or optional subsequent phases, or indeed between the second phase and optional subsequent phases, is a barrier layer comprising a barrier layer composition. The composition of the barrier layer includes at least one binder selected from the group described above. The advantages of having a barrier layer are to prevent or reduce the transition of components from one phase to another, for example from the first phase to the second and / or optional subsequent phases and vice versa.

 The components of the second and optional subsequent phases are preferably compressed at a very low compression force with respect to the compression force commonly used to make tablets. Thus, an advantage of the present invention is that, due to the low force of a single pressing, the chemically sensitive detergent components can be included in the detergent tablet without the consequent loss of effectiveness that is usually encountered when incorporating such components into tablets. Alternatively, the second phase or phases may be compressed at the same or greater pressing force than the first phase in order to achieve differential phase solubility, as described below.

 An additional advantage of the present invention is the improved protection of the second phase from damage caused, for example, by handling or transportation. As described above, multiphase detergent tablets were prepared when the second layer was compressed at a lower pressing force than the first layer. However, although dissolution rate is improved, the second layer of such tablets becomes susceptible to damage, with a tendency to spill and crack upon contact. The slightly compressed phase (s) of the detergent tablets of the present invention, however, are protected by being placed in the mold provided by the first phase of the detergent tablet.

 Another advantage of the present invention is the possibility of obtaining a multiphase detergent tablet, in which one phase can be designed to dissolve preferably much earlier than the other phase. In the present invention, it is preferred that the second and optional subsequent (s) phase (s) are dissolved before the first phase. According to the preferred weighing ranges described above, it is preferred that the first phase dissolves within 5 to 20 minutes, preferably 10 to 15 minutes, and the second and / or optional subsequent phases dissolve in less than 5 minutes, more preferably in less than 4.5 minutes, most preferably less than 4 minutes. Alternatively, the second phase may dissolve after the first or other phases, for example, when it is desired to create advantages in washing or rinsing at the end of the washing procedure. The time during which the first, second and / or optional subsequent phase is dissolved does not depend on one another. Thus, in a particularly preferred embodiment of the present invention, differential phase solubility is achieved. A particular advantage of a detergent tablet capable of achieving differential dissolution is that a component that is chemically inactive as a result of the presence of another component can be separated by incorporation into another phase. In this case, the component that is inactivated is preferably located in the second and optional subsequent phase (s).

 Another advantage of the present invention is improved adhesion between the phases of the multiphase tablet. It is believed that improved adhesion is achieved by reducing the effect on the second phase compared to multiphase tablets known to the science, which leads to the tablets of the present invention being less susceptible to breaking along the contact line between the phases.

Process
Multiphase detergent tablets are prepared using any suitable tabletting equipment, such as Courtoy R253. Preferably, the tablets are prepared by compression in a tablet press capable of producing a tablet including a mold. In a particularly preferred embodiment of the present invention, the first phase is prepared using a specially designed tablet press, following the procedure described below. The punch (s) of such a tablet press is modified so that the surface of the punch that contacts the detergent composition has a convex shape.

The first detergent composition is delivered to the matrix of the tablet press and the punch is lowered for contact, then the detergent composition is compressed to form the first phase. The first detergent composition is compressed using the applied pressure, usually at least about 250 kg / cm ² , preferably between about 350 and about 2000 kg / cm ² , more preferably from about 500 to about 1,500 kg / cm ² , most preferably from about 600 to about 1200 kg / cm ² . Then the punch is lifted, while the first phase containing the mold is visible. Then a second and optional subsequent detergent composition (s) are placed in the mold. Then, for the second time, a punch of a specially designed tablet press is lowered to easily compress the second and optional subsequent detergent composition (s) to form the second and optional subsequent phase (s). In another embodiment of the present invention, when an optional subsequent phase is present, an optional subsequent phase is prepared in an optional subsequent compression step substantially similar to the second compression step described above. The second and optional subsequent composition (s) are compressed at a pressure of preferably less than about 350 kg / cm ² , more preferably from about 40 to about 300 kg / cm ² , most preferably from about 70 to about 270 kg / cm ² . After compressing the second detergent composition, the punch is raised a second time and the multiphase detergent tablet is removed from the tablet press.

Detergent Components
The first and second and / or optional subsequent phases of the multiphase detergent tablet described herein are prepared by compressing one or more compositions comprising the active components of the detergent. It is suitable if the compositions used in any of these phases may contain many different detergent components, including detergent components, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfumes, calcium soap disintegrants, organic polymer components, including agents, inhibiting the transfer of polymer dyes, crystal growth inhibitors, heavy metal ion traps, metal ion salts, enzyme stabilizers, corrosion inhibitors, inhibitors foams, solvents, fabric softeners, optical gloss enhancers and hydrotropes.

 The most preferred first phase detergent components are a detergent component, a surfactant, an enzyme, and a bleaching agent. The most preferred second phase detergent components are a detergent component, enzymes, crystal growth inhibitors, and disintegrating agents and / or binding agents.

Washing component
The tablets of the present invention preferably contain a detergent component, typically present in an amount of from 1 to 80% by weight, preferably from 10 to 70% by weight, most preferably from 20 to 60% by weight of the composition of the active detergent components.

Water Soluble Detergent
Suitable water-soluble detergent components include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymer polycarboxylic acids or their salts, in which the polycarboxylic acid contains at least two carboxyl radicals separated from each other by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates and mixtures of any of the above components.

 The carboxylate or polycarboxylate detergent component may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred because of their cost and effectiveness.

 Suitable carboxylates containing one carboxyl group include water-soluble salts of lactic acid, glycolic acid and their ester derivatives. Polycarboxylates containing two carboxylic groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetylacetic acid, maleic acid, diglycolic acid, tartaric acid and fumaric acid, as well as carboxylic esters and sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups include, but are not limited to, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as carboxymethyloxy succinates described in UK patent 1379241, lactoxysuccinates described in UK patent 1389732 and Dutch aminosuccinates disclosed 7205873, and hydroxypolycarboxylate materials, such as 2-oxa-1,1,3-propanetricarboxylates, as described in British Patent 1,387,447.

 Polycarboxylates containing four carboxyl groups include the oxide disuccinates disclosed in British Patent 1261829, 1,1,2,2-ethantetracarboxylates, 1,1,3,3-propantetracarboxylates and 1,1,2,3-propantetracarboxylates. Polycarboxylates containing sulfosubstituents include sulfosuccinate derivatives disclosed in UK patents 1398421, 1398422 and US patent 3936448, and sulfonated pyrolyzed citrates described in UK patent 1439000.

 Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2 , 5-tetrahydrofurant tetracarboxylates, 1,2,3,4,5,6-hexanehexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include derivatives of mellitic acid, pyromellitic acid and phthalic acid disclosed in UK patent 1425343.

 Among the above, preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups per molecule, more specifically citrates.

 Parent acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example citric acid or citrate / citric acid mixtures, are also considered useful detergent components.

Borate detergent components, as well as detergent components containing borate-giving materials that can produce borate during storage of the detergent or under washing conditions, can also be used, but are not preferred under washing conditions at less than 50 ^{° C.} , especially at less than 40 ^o C.

 Examples of carbonate detergent components are alkaline earth and alkali metal carbonates, including sodium carbonate and a double salt of acidic and medium sodium carbonate and mixtures thereof with ultrafine calcium carbonate, as disclosed in German Patent Application 2321001, published November 15, 1973.

 The most preferred detergent components of the present invention are water-soluble phosphate detergent components. Specific examples of water-soluble phosphate detergent components are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, in which the degree of polymerization ranges from 6 to 21, and phytic acid salt.

 Specific examples of water-soluble phosphate detergent components are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, in which the degree of polymerization ranges from 6 to 21, and phytic acid salt.

Partially soluble or insoluble detergent component
The tablets of the present invention may contain a partially soluble or insoluble detergent component. Partially soluble and insoluble detergent components are particularly suitable for tablets made for washing. Examples of partially water-soluble detergent components include layered crystalline silicates, as described, for example, in patents EP-A-0164514, DE-A-3417649 and DE-A-3742043. Layered crystalline sodium silicates of the general formula are preferred.
NaMSi _x O _{2x + 1} • yH ₂ O
where M represents sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Layered crystalline sodium silicates of this type preferably have two spatial "sheet" structures, such as the so-called structure of the δ-layer, as described in patent EP 0164514 and EP 0293640. Methods for producing layered crystalline silicates of this type are disclosed in patents DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the general formula presented above represents a value of 2, 3 or 4, and is preferably 2.

The most preferred component of the layered crystalline sodium silicates is of the formula δ-Na ₂ Si ₂ O ₅ , known as NaSKS-6 (trademark) sold by Hoechst AG. The material of the layered crystalline sodium silicates is preferably present in the particulate detergent granular compositions in a homogeneous mixture with a solid, water-soluble ionizing material, as described in PCT patent application WO 92/18594. The solid, water-soluble, ionizable material is selected from organic acids, salts of organic and inorganic acids, and mixtures thereof, with citric acid being preferred.

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

 Aluminosilicate zeolites can be natural materials, but are preferably synthetic derivatives. Synthetic crystalline aluminosilicate ion exchange materials are available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.

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

Zeolite A has the formula
Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] • H ₂ O
where x is from 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] • 276H ₂ O). Zeolite MAP, as disclosed in patent EP-B384070 is here a preferred zeolite detergent component.

 Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. When used as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide increased washing efficiency in terms of improved paint removal. Increased washing efficiency is also observed in terms of reducing rust contamination of the fabric and improving the maintenance of whiteness of the fabric; problems that are believed to be associated with unsuccessful detergent properties of detergent compositions.

 An unexpected property was that mixed aluminosilicate zeolite detergent compositions, including colloidal zeolite A and colloidal zeolite Y, provide equal removal of calcium ions relative to the same weight of commercially available zeolite A. Another unexpected property was that mixed aluminosilicate zeolite compositions the detergents described above provide improved removal of magnesium ions relative to the same weight of commercially available zeolite A.

Surface-active substance
Surfactants are preferred active detergent components of the compositions described herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof. Products for an automatic dishwashing machine should have low foaming and, therefore, the foaming of the surfactant system when used in such dishwashing methods should be suppressed or, more preferably, they have a low foaming, typically characteristic of nonionic surfactants substances. Foaming caused by surfactant systems when used in washing methods does not need to be suppressed to the extent necessary for washing dishes. The surfactant is usually present at a level of from 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 the active detergent components.

 A typical list of anionic, nonionic, ampholytic and zwitterionic classes and types of these surfactants is given in US Pat. March 1981, a list of surfactants commonly included in detergent compositions for automatic dishwashing is given, for example, in patent EP-A-0414549 and PCT applications WO 93/08876 and WO 93/08874.

Nonionic Surfactant
As such, any nonionic surfactants intended for washing may be included in a detergent tablet. Preferred, non-limiting classes of applicable non-ionic surfactants are listed below.

Nonionic Ethoxylated Alcohol Surfactant
Alkyl ethoxylated condensation products of aliphatic alcohols with from 1 to 25 mol of ethylene oxide are suitable for use here. The alkyl chain of an aliphatic alcohol can be either linear or branched, primary or secondary, and usually contains from 6 to 22 carbon atoms. Especially preferred are condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms, from 2 to 10 mol of ethylene oxide per 1 mol of alcohol.

Alkylalkoxylated Captive Surfactant
A suitable cap-alkylated alkoxylate surfactant is epoxy-capped poly (oxyalkylated) alcohols of the formula
R ₁ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ₂ ] (I)
where R ₁ represents a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R ₂ represents a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably 1; y is an integer having a value of at least 15, more preferably at least 20.

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

Poly (oxyalkylated) ether alcohols
Preferred surfactants for use herein include ether-capped poly (oxyalkylated) alcohols represented by the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²
where R ¹ and R ² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R ³ represents hydrogen or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having an average of 1 to 30, wherein when x is 2 or more, R ³ may be the same or different, and k and j are integers having an average of 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 from 6 to 22 carbon atoms, most preferably from 8 to 18 carbon atoms. H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms is most preferred for R ³ . Preferably, x is an integer having an average of from 1 to 20, more preferably from 6 to 15.

As described above, when in preferred embodiments, x is greater than 2, R ³ may be the same or different. It is understood that R ³ may vary between any alkyleneoxy units as described above. For example, if x is 3, R ³ may be selected from ethyleneoxy (EO) or propyleneoxy (PO) and the order may vary as (EO) (PO) (EO); (EO) (EO) (RO); (EO) (EO) (EO); (RO) (EO) (RO); (RO) (RO) (EO) and (RO) (RO) (RO). Of course, the integer here is chosen only as an example, and with a higher integer for x variations can be much larger and they include, for example, many (EO) units and a much smaller number (PO) units.

As described above, particularly preferred surfactants include those having a low cloud point, less than 20 ^° C. These low cloud point surfactants can then be used in combination with high cloud point surfactants, as described in detail described below for the great benefits of fat removal.

The most preferred ether-capped poly (oxyalkylated) alcohol surfactants are those in which k is 1 and j is 1, so these surfactants are of the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²
where R ¹ , R ² and R ³ have the meanings given above, and x is an integer having an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18. Most preferred are surfactants in which R ¹ and R ² range from 9 to 14, R ³ is H, forming ethyleneoxy, and x is in the range from 6 to 15.

 Ether-capped poly (oxyalkylated) alcohol surfactants include three common components, namely a linear or branched alcohol, ethylene oxide, and an alkyl ether-capped end. The end escaped by alkyl ether and alcohol serve as hydrophobic, oil soluble parts of the molecule, while the ethylene oxide group forms the hydrophilic, water soluble part of the molecule.

 These surfactants exhibit significantly improved stain and film removal properties as well as grease contaminants when used in combination with high cloud point surfactants compared to conventional surfactants.

 Generally speaking, ether-capped poly (oxyalkylene) alcohol surfactants of the present invention can be prepared by reacting an aliphatic alcohol with an epoxide to form an ester, which then reacts with a base to form a secondary epoxide. The secondary epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Examples of methods for producing ether-capped poly (oxyalkylated) alcohol surfactants are described below.

Obtaining C _12/14 glycidylalkyl ether
C _12/14 fatty alcohol (100.00 g, 0.515 mol) and tin chloride (IV) (0.58 g, 2.23 mmol sold by Aldrich) are mixed in a 500 ml three-necked round bottom flask equipped with a condenser inlet Argon intake, an additional funnel, a magnetic stirrer and a device for measuring internal temperature. The mixture was heated to 60 ^° C. Epichlorohydrin (47.70 g, 0.515 mol sold by Aldrich) was added dropwise so as to maintain a temperature between 60 ^° C. and 65 ^° C. After stirring for an additional hour at 60 ^{° C., the} mixture was cooled to room temperature. temperature. The mixture is then treated with a 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) with mechanical stirring. After complete addition, the mixture is heated to 90 ^{° C.} for 1.5 hours, cooled and filtered with ethanol. The filtrate was separated and the organic phase was washed with water (100 ml), dried over MgSO ₄ , filtered and concentrated. Distillation of the oil at 100-120 ^o C (0.1 mm Hg) gives glycidic ether in the form of oil.

Obtaining C _12/14 alkyl-C _9/11 ether-capped alcohol surfactant
Neodol ^® 91-8 (20,6 g, 0.0393 mol ethoxylated alcohol sold by Shell Chemical Co.) and tin chloride (IV) (0,58 g, 2.23 mmol) were combined in a 250 mL three-necked round bottom flask, equipped with a condenser, an input for the arrival of argon, an additional funnel, a magnetic stirrer and a device for measuring internal temperature. The mixture was heated to a temperature of 60 ^{° C.} , at which C _12/14 glycidylalkyl ether (1.00 g, 0.0393 mol) was added dropwise over 15 minutes. After stirring for 18 hours at 60 ^{° C., the} mixture was cooled to room temperature and dissolved in an equal portion of dichloromethane. The solution was passed through a 1-inch (2.5 cm) pad of silica gel, eluting with dichloromethane. The filtrate was concentrated using a rotary evaporator and then stirred in a ball furnace (100 ^{° C.} , 0.5 mm Hg) to obtain a surfactant in the form of an oil.

Nonionic Ethoxylated / Propoxylated Aliphatic Alcohol Surfactant
Fatty ethoxylated C ₆ -C ₁₈ alcohols and mixed fatty C ₆ -C ₁₈ ethoxylated / propoxylated alcohols are suitable surfactants used here, especially when water soluble. Preferably, the fatty ethoxylated alcohols are C ₁₀ -C ₁₈ ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 50, most preferred are those C ₁₀ -C ₁₈ ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. It is preferable that the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain containing from 10 to 18 carbon atoms, an ethoxylation degree of 3 to 30, and a propoxylation degree of 1 to 10.

Non-ionic EO / PO condensates with propylene glycol
Condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol are suitable for use here. The hydrophobic portion of these components preferably has a molecular weight of from 1500 to 1800 and is insoluble in water. Examples of compounds of this type include certain commercially available Pluronic ^™ surfactants sold by BASF.

Non-ionic condensation products of EO with propylene oxide / ethylene diamine additives
Condensation products of ethylene oxide with a product obtained by the reaction of propylene oxide and ethylene diamine are suitable for use here. The hydrophobic portion of these products consists of the reaction product of ethylene diamine with an excess of propylene oxide and usually has a molecular weight of 2500 to 3000. Examples of non-ionic surfactants of this type include certain commercially available Tetronic ^™ components sold by BASF.

Mixed system of nonionic surfactants
In a preferred embodiment of the present invention, the detergent tablet comprises a mixed system of nonionic surfactants comprising at least one nonionic surfactant with a low cloud point and at least one nonionic surfactant with a high cloud point.

The "cloud point" in the sense used here is a well-known property of nonionic surfactants, which is characterized by the fact that the surfactant becomes less soluble with increasing temperature, the temperature at which the appearance of the second phase is observed, is called the "cloud point" (see Kirk Othmer's Encyclopedia of Chemical Technology, 3 ^rd Ed. Vol. 22, pp. 360-379).

As used herein, a “low cloud point” nonionic surfactant is defined as an ingredient in a nonionic surfactant system having a cloud point of less than 30 ^{° C.} , preferably less than 20 ^{° C.} and most preferably less than 10 ^° C. low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyox polymers ethylene / polyoxypropylene (PO / EO / PO) reverse to order of blocks. Also such non-ionic low cloud point surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent ^® SLF18), epoxy-capped poly (oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent ^® SLF18B series nonionic substances, as described, for example, in patent WO 94/22800, published on October 13, 1994 by Olin Corporation) and ether-capped poly (oxyalkylated) alcohol surfactants.

 Non-ionic surfactants may optionally contain propylene oxide in an amount up to 15% by weight. Other preferred non-ionic surfactants can be obtained using the processes described in US patent 4223163, published by Builloty September 16, 1980, incorporated herein by reference.

Non-ionic surfactants with a low cloud point further include a polymer compound of polyoxyethylene, polyoxypropylene blocks. Polymeric compounds of the 'blocks of polyoxyethylene, polyoxypropylene include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane and ethylene diamine as the initiator of the reactive hydrogen compound. Some of the block polymeric surfactant compounds designated by BASF-Wyandotte Corp. Wyandotte, Michigan as PLURONIC ^® , REVERSED PLURONIC ^® and TETRONIC ^® are suitable for ADD (detergent for an automatic dishwasher) compositions of the invention. Preferred examples include REVERSED PLURONIC ^® 25R2 and TETRONIC ^® 702. Such surfactants are typically used herein as nonionic surfactants with low cloud point.

As used herein, a "high cloud point" non-ionic surfactant is defined as an ingredient in a non-ionic surfactant system having a cloud point higher than 40 ^° C, preferably higher than 50 ^° C and more preferably higher than 60 ^° C. Preferably so that the non-ionic surfactant system includes an ethoxylated surfactant resulting from the reaction of a monohydric alcohol or alkyl phenol containing from 8 to 20 carbon atoms, from 6 to 15 mol of ethylene oxide per 1 mol of alcohol or alkyl phenol on average. Such high cloud point non-ionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by Shell).

 For the purposes of the present invention, it is also preferred that the non-ionic surfactant with a high cloud point further has a hydrophilic-lipophilic balance (HLB; see Kirk Othmer above) in the range of 9 to 15, preferably 11 to 15. Such materials include, for 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 a derivative of a linear or preferably branched alcohol or a fatty secondary alcohol containing from 6 to 20 carbon atoms (C ₆ -C ₂₀ alcohol), including secondary alcohols and branched primary alcohols . It is preferred that the non-ionic surfactants with a high cloud point are branched or secondary ethoxylate alcohol esters, more preferably 6 to 9 mol of ethylene oxide per 1 mol of alcohol. Preferably, the ethoxylated surfactant thus obtained has a compact distribution of the degree of ethoxylation relative to the average.

Anionic Surfactant
As detergents, essentially any anionic surfactants are suitable. These may include salts (including, for example, sodium, potassium, ammonium salts and substituted ammonium salts such as mono-, di- and triethanolamine salts) of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

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

Anionic Sulfate Surfactant
Suitable anionic sulfate surfactants for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, oleoyl glycerides sulfates, alkyl phenol ethylene oxide esters, C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) and -N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfates and sulfates of alkyl polysaccharides, such as alkyl polyglucoside sulfates (non-ionic non-sulfated compounds described herein).

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

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

 In a particularly preferred embodiment of the invention, mixtures of preferred alkyl sulfate and alkyl ethoxysulfate surfactants are used. Such mixtures are disclosed in PCT patent application WO 93/18124.

Anionic Sulfonate Surfactant
Suitable anionic sulfonate surfactants for use here include sulfonic acid ester salts of C ₅ -C ₂₀ linear alkylbenzene, alkyl sulfonate esters, C ₆ -C ₂₂ primary or secondary alkanesulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, sulfonic acid esters and alkyl glyceride, sulphonic acid esters of a fatty acyl glyceride, sulphonic acid esters of oleoyl glyceride and any mixtures thereof.

Anionic Carboxylate Surfactant
Suitable anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"), especially certain secondary soaps, as described herein.

Suitable alkyl ethoxycarboxylates include those with the formula RO (CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ in which R is a C ₆ -C ₁₈ alkyl group, x is from 0 to 10, and the distribution of ethoxylate is such that in terms of weight, the amount of material in which x is 0 is less than 20%, and M represents a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula RO- (CHR ₁ —CHR ₂ —O) —R ₃ in which R represents a C ₆ -C ₁₈ alkyl group, x is from 1 to 25, R ₁ and R ₂ are selected from the group consisting of hydrogen, formic acid radical, succinic acid radical, hydroxy succinic acid radical and mixtures thereof, and R _{3 is} selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms , and mixtures thereof.

 Suitable soap surfactants include secondary soap surfactants that contain a carboxy unit linked to a secondary carbon atom. Preferred secondary soap surfactants used herein are water soluble, which are selected from the group consisting of water soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as foam inhibitors.

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

Amphoteric surfactant
Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

где R³ выбирают из алкильной, гидроксиалкильной, ациламидопропоильной и алкилфенильной группы и их смесей, содержащих от 8 до 26 атомов углерода; R⁴ представляет собой аликиленовую или гидроксиалкиленовую группу, содержащую от 2 до 3 атомов углерода или их смеси; х составляет от 0 до 5, предпочтительно от 0 до 3, и каждый R⁵ представляет собой алкильную или гидроксиалкильную группу, содержащую от 1 до 3, или полиэтиленоксидную группу, содержащую от 1 до 3 групп окиси этилена. Предпочтительными являются окись C₁₀-C₁₈ алкилдиметиламина и окись C₁₀-C₁₈ ациламидоалкилдиметиламина.Suitable amino oxides include those compounds of the formula

where R ³ selected from alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl groups and mixtures thereof containing from 8 to 26 carbon atoms; R ⁴ represents an alikylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 5, preferably from 0 to 3, and each R ⁵ represents an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxide and C ₁₀ -C ₁₈ acylamidoalkyl dimethylamine oxide.

 A suitable example of alkylamphodicarboxylic acid is Miranol (TM) C2M Cone., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant
Zwitterionic surfactants may also be included in the detergent compositions used herein. These surfactants can be generally described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or a tertiary sulfonium compound. Examples of zwitterionic surfactants used herein are betaine and sultaine.

Suitable betaines are those compounds which have the formula R (R ¹ ) ₂ N ⁺ R ² COO ^- , where R represents a C ₆ -C ₁₈ hydrocarbyl group, each R ^{1 is} usually C ₁ -C ₃ alkyl and R ² represents C ₁ -C ₅ hydrocarbyl group. Preferred betaines are C ₁₂ -C ₁₈ dimethylammoniohexanoates and C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use here.

Cationic Surfactants
The cationic ester surfactants used in the present invention are preferably a water-dispersible compound having the properties of a surfactant, comprising at least one ether (i.e., -COO-) bond and at least one positively charged group. Other suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

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

Enzymes
Enzymes are preferred components of the detergents of the first phase and in particular the second and / or optional subsequent phases. When available, these enzymes are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, lignin tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, or from mixtures thereof.

 Preferred enzymes include protease, amylase, lipase, peroxidase, cutinase and / or cellulase in combination with one or more enzymes that destroy the wall of the plant cell.

 Cellulases useful in the present invention include both bacterial and fungal cellulase. Preferably, they have an optimum pH between 5 and 12 and an activity above 50 CEVU (cellulose viscosity units). Suitable cellulases are disclosed in US Pat. EP 739982 describes cellulases isolated from new species of Bacillus. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275; DE-OS-2247832 and WO 95/26398.

 Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. Thermoidea), and in particular a strain of Humicola DSM 1800. Other suitable cellulases are cellulases derived from Humicola insolens, having a molecular weight of 50 kDa, an isoelectric point of 5.5 and containing 5.5 isoelectric point 415 amino acids, as well as 43 kDa endoglucanase from Humicola insolens, DSM 1800, exhibiting cellulase activity; the preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO 91/17243. Suitable cellulases are also EGIII cellulases from Trichoderma longibrachiatum, described in patent WO 94/21801, Genencor, published September 29, 1994. Cellulases having the advantage of preserving color are particularly suitable cellulases. Examples of such cellulases are cellulases described in European Patent Application 91202879.2, filed November 6, 1991 (Novo). Particularly suitable are Carezyme and Celluzyme (Novo Nordisk A / S). See also patents WO 91/17244 and WO 91/21801. Other cellulases suitable from the point of view of preserving the fabric and / or washing properties are described in patents WO 96/34092, WO 96/17994 and WO 95/24471.

 These cellulases are usually included in the detergent composition in an amount of from 0.0001 to 2% of the active enzyme by weight of the detergent composition.

 Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used to “bleach the solution”, i.e. to prevent the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chloro and bromo peroxidase. Detergent compositions containing peroxidase are disclosed, for example, in PCT International Application WO 89/099813, WO 89/09813 and European Patent Application EP 91202882.6, registered on November 6, 1991, and EP 96870013.8, registered on February 20, 1996. Laccase enzyme is also suitable.

 Preferred enhancers are substituted phenyazine and phenoxazine, 10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP), and 10-methylphenoxazine (described in WO 94/12621), substituted or esters of lilacic acid (C3-C5 substituted alkyl syringates) and phenols. Preferred sources of hydrogen peroxide are percarbonate or sodium perborate.

 These cellulases and / or peroxidases are usually included in the detergent composition in an amount of from 0.0001 to 2% of the active enzyme by weight of the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes used for washing include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1372034. Suitable lipases include those that exhibit a positive immunological cross-reaction with anti-lipase antibody produced byasoresorescent IAM 1057. This lipase can be obtained from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Amano-CES, lipases from Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673 from Touo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as Ml Lipase ^R and Lipomax ^R (Gist-Brocades) and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also useful are the lipolytic enzymes described in patents EP 258068, WO 92/05249 and WO 95/22615 owned by Novo Nordisk, and in patents WO 94/03578, WO 95/35381 and WO 96/00292 owned by Unilever.

 Cutinases (EC 3.1.1.50), which can be considered as a type of lipase, namely lipase, for which interphase activation is not required, are also suitable. The addition of cutinases to detergent compositions has been described, for example, in patents WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System); WO 94/14963 and WO 94/14964 (Unilever).

 Lipases and / or cutinases are usually included in the detergent composition in an amount of from 0.0001 to 2% of the active enzyme by weight of the detergent composition.

и МАХАРЕМ (сконструированный белок Maxacal) от Gist-Brocades. Протеолитические ферменты также охватывают модифицированные бактериальные сериновые протеазы, такие как те, что описаны в Европейской патентной заявке, серийный номер 87 303761.8, зарегистрированной 28 апреля 1987 г. (особенно страницы 17, 24 и 98), и которые здесь называют как "протеаза В", и описанные в Европейской патентной заявке 199404, Venegas, опубликованной 29 октября 1986 г., которые относятся к модифицированному бактериальному сериновому протеолитическому ферменту, который здесь называют "протеаза А". Пригодным является то, что здесь называют "протеаза С", которая является вариантом щелочной сериновой протеазы из Bacillus, в которой аргинин в положении 27 заменен на лизин, валин в положении 104 заменен на тирозин, аспарагин в положении 123 заменен на серин и треонин в положении 274 заменен на аланин. Протеаза С описана в патенте ЕР 90915958:4, соответствующем патенту WO 91/06637, опубликованному 16 мая 1991 г. Сюда включены также генетически модифицированные варианты, в особенности протеазы С.Suitable proteases are subtilisins, which are obtained from specific strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease obtained from a strain of Bacillus having maximum activity in the pH range of 8-12, developed and sold by Novo Industries A / S, Denmark (hereinafter "Novo") as a ESPERASE ^®. The preparation of this enzyme and similar enzymes is described in GB 1243784, Novo. Other suitable proteases include

and MACHAREM (engineered Maxacal protein) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in the European patent application, serial number 87 303761.8, registered April 28, 1987 (especially pages 17, 24 and 98), and which are here referred to as "protease B" and described in European Patent Application 199404, Venegas, published October 29, 1986, which relate to a modified bacterial serine proteolytic enzyme, which is here called "protease A". Suitable is what is called “protease C”, which is a variant of the alkaline serine protease from Bacillus, in which the arginine at position 27 is replaced by lysine, the valine at position 104 is replaced by tyrosine, the asparagine at position 123 is replaced by serine and threonine at position 274 replaced by alanine. Protease C is described in patent EP 90915958: 4, corresponding to patent WO 91/06637, published May 16, 1991. Genetically modified variants are also included, especially protease C.

 A preferred protease, referred to as “protease D”, is a variant of a carbonyl hydrolase having an amino acid sequence not found in nature that is obtained from a carbonyl hydrolase precursor by replacing a particular amino acid with a plurality of amino acid residues at the position of said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more positions of amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, + 156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274, according to the numbering of subtilisin Bacillus amyloliquefaciens, as described in patent WO 95/10615 and in patent application C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes", having serial US 08/322677, registered October 13, 1994

Suitable for the present invention are also proteases described in patent applications EP 251446 and WO 91/06637, protease BLAP ^®, as described in patent WO 91/02792 and their variants described in patent WO 95/23221.

 See also protease for high pH values from Bacillus sp. NCIMB 40338 described in patent WO 93/18140 A, owned by Novo. Enzymatic detergents containing a protease and one or more other enzymes, as well as a reversible protease inhibitor, are described in patent WO 92/03529 A, owned by Novo. When desired, a protease is available having reduced absorption and increased hydrolytic activity, as described in WO 95/07791, owned by Procter & Gamble. A recombinant trypsin-like protease for detergents suitable here is described in patent WO 94/25583, owned by Novo. Other suitable proteases are described in patent EP 516200, owned by Unilever.

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

 Proteolytic enzymes are included in the detergent compositions of the present invention in an amount of from 0.0001 to 2%, preferably from 0.001 to 0.2%, more preferably from 0.005 to 0.1% of the pure enzyme by weight of the composition.

 Amylases (α and / or β) can be included to remove stains with a hydrocarbon base. Patent WO 94/02597, owned by Novo Nordisk A / S, published February 3, 1994, describes detergent compositions comprising mutant amylases. See also patent WO 95/10603, owned by Novo Nordisk A / S, published April 20, 1995. Other amylases known in the use of detergent compositions include both α and β amylases. α-amylases are known in the art and include those disclosed in US Pat. No. 5,003,257, EP 252666, WO 91/00353; FR 2,676,456; EP 285123; EP 525610; EP 368341 and British Patent Specification 1296839 (Novo). Other suitable amylases are the amylases with increased stability described in patent WO 94/18314, published August 18, 1994, and patent WO 96/05295, owned by Genencor, published February 22, 1996, and variants of amylase containing an additional modification in direct the precursor available from Novo Nordisk A / S disclosed in WO 95/10603 published in April 1995. Amylases described in EP 277216, WO 95/26397 and WO 96/23873 (all owned by Novo Nordisk are also suitable) )

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

 Preferred amylase enzymes include those described in patent W0 95/26397 and in the parallel patent application Novo Nordisk PCT / DK96 / 00056.

 Amylolytic enzymes are included in the detergent compositions of the present invention in an amount of from 0.0001 to 2%, preferably from 0.00018 to 0.06%, more preferably from 0.00024 to 0.048% of the pure enzyme by weight of the composition.

 In a particularly preferred embodiment, the washing tablets of the present invention include amylase enzymes, especially those described in patent WO 95/26397 and in the parallel patent application Novo Nordisk PCT / DK96 / 00056 in combination with additional amylase.

все от Novo Nordisk A/S, а также Maxamyl^® от Gist-Brocades.The term "additional" means the addition of one or more amylases used for washing. Examples of additional amylases (α and / or β) are described below. Patents WO 94/02597 and WO 95/10603, owned by Novo Nordisk A / S, describe detergent compositions comprising mutant amylases. Other amylases known to be used in detergent compositions include both α and β amylases. α-amylases are known in the art and include those disclosed in US Pat. No. 5,003,257, EP 252666, WO 91/00353; FR 2,676,456; EP 285123; EP 525610; EP 368341 and British Patent Specification 1296839 (Novo). Other suitable amylases are the amylases with increased stability described in patents WO 94/18314 and WO 96/05295, owned by Genencor, and amylase variants containing an additional modification in the immediate precursor that can be obtained from Novo Nordisk A / S, disclosed in WO. 95/10603. Amylases described in patent EP 277216, owned by Novo Nordisk, are also suitable. Examples of commercially available α-amylase products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, all from Novo Nordisk A / S, Denmark. Other suitable amylases are described in patent WO 95/26397: α-amylases characterized by a specific activity of at least 25% higher than the specific activity of Termamyl ^® in the temperature range from 25 to 55 ^{° C.} and pH values in the range from 8 to 10 measured by analysis of the activity of α-amylase Phadebas ^® . Suitable are variants of the above enzymes described in patent WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties in relation to the level of activity and the combination of thermal stability with a higher level of activity are described in patent WO 95/35382. Preferred additional amylases for the present invention are amylases sold under the brand name Purafect Ox Am ^R described in patents WO 94/18314, WO 96/05295 sold by Genencor;

everything from Novo Nordisk A / S, as well as Maxamyl ^® from Gist-Brocades.

 These additional amylases are usually included in the detergent compositions of the present invention in an amount of from 0.0001 to 2%, preferably from 0.00018 to 0.06%, more preferably from 0.00024 to 0.048% of the pure enzyme by weight of the composition. Preferably, the weight ratio of the pure specific amylase enzyme to the additional amylase is from 9: 1 to 1: 9, more preferably from 4: 1 to 1: 4, and even more preferably from 2: 1 to 1: 2.

 The enzymes mentioned above may be of any suitable origin, of plant, animal, bacterial, fungal or yeast origin. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotropic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified and untreated forms of these enzymes may be used. Mutants of natural enzymes are also included by definition. Mutants can be obtained, for example, by protein and / or genetic engineering, chemical and / or physical modifications of natural enzymes. The usual way is also the expression of the enzyme in the host organism, in which the genetic material responsible for the formation of the enzyme has been cloned.

 These enzymes are usually included in the detergent composition in an amount of from 0.0001 to 2% of the active enzyme by weight of the detergent composition. Enzymes can also be added as individual simple ingredients (granules, grains, stabilized liquids, etc. containing one enzyme) or mixtures of two or more enzymes (for example, joint granules).

 Other suitable detergent ingredients that can be added are enzyme oxidation traps, which are described in parallel European Patent Application 92870018.6, filed January 31, 1992. Examples of such enzyme oxidation traps are polyamine ethoxylated tetraethylene.

 The nomenclature of enzyme materials and methods for incorporating them into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A by Genencor International, WO 8908694 A by Novo, and US Pat. No. 3,553,139 dated January 5, 1971 by McCarty et al. Enzymes are also disclosed in US Pat. No. 4,101,457 of July 18, 1978, owned by Place et al., And in US Pat. No. 4,507,219 of March 26, 1985, owned by Hughes. Enzymatic materials suitable for liquid detergent compositions and methods for incorporating them into such compositions are disclosed in US Pat. No. 4,261,868 dated April 14, 1981, owned by Nora et al. Enzymes for use in detergents can be stabilized in various ways. Methods for stabilizing enzymes are disclosed and illustrated in US Pat. No. 3,600,319 of August 17, 1971, owned by Gedge et al., EP 199405 and EP 200586 of October 29, 1986, owned by Venegas. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. A useful species of Bacillus, AC13 producing proteases, xylanases and cellulases, is described in Novo patent WO 9401532 A.

 Whitening agent.

 The most preferred component of the detergent composition is a whitening agent. Suitable whitening agents include chlorine and oxygen bleaching agents.

 In one preferred embodiment, the oxygen bleaching agent comprises a source of hydrogen peroxide and a precursor compound of an organic peroxyacid bleach. Organic peroxyacid production occurs due to an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In the opposite preferred embodiment, a preformed organic peroxy acid is directly included in the composition. Compositions are also provided comprising mixtures of a source of hydrogen peroxide and an organic peroxy acid precursor in combination with a preformed organic peroxy acid.

Inorganic Perhydrate Bleach
The composition of the detergent components preferably includes a source of hydrogen peroxide as an oxygen bleaching agent. Suitable sources of hydrogen peroxide include inorganic perhydrate salts.

 Inorganic perhydrate salts typically include in the form of a sodium salt in an amount of from 1 to 40% by weight, more preferably from 2 to 30% by weight and most preferably from 5 to 25% by weight of the composition.

 Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. Inorganic perhydrate salts are usually alkali metal salts. The inorganic perhydrate salt may be included as a crystalline solid without additional protection. For some perhydrate salts, however, in preferred embodiments of such granular compositions, a coated material form is used which provides better storage stability of the perhydrate salt in the granular product.

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

Preferred perhydrates for inclusion in the compositions according to the invention are alkali metal percarbonates, in particular sodium percarbonate. Sodium percarbonate is an additional compound having the formula corresponding to 2Na ₂ CO ₃ • 2H ₂ O ₂ and is commercially available as a crystalline solid. Sodium percarbonate, being an additional compound to hydrogen peroxide, has a tendency to release hydrogen peroxide quite quickly during dissolution, which can increase the tendency to local increase in high concentration of bleach. Most preferably, the inclusion of percarbonate in such compositions in a coated form that provides stability in the product.

Suitable coating materials to ensure product stability include a mixed salt of water-soluble sulfate and alkali metal carbonate. Such coatings, together with coating methods, were previously described in GB-1466799, awarded to Interox on March 9, 1977. The weight ratio of the mixed salt of the coating material and percarbonate ranges from 1: 200 to 1: 4, more preferably from 1:99 to 1 : 9 and most preferably from 1: 49 to 1: 9. It is preferable that in the mixed salt of sodium sulfate and sodium carbonate with the general formula Na ₂ SO ₄ • n • Na ₂ CO ₃ , where n is from 0.1 to 3, n ranged from 0.3 to 1.0, and most preferably, n ranged from 0.2 to 0.5.

Another suitable coating material that provides stability in the product includes sodium silicate at a ratio of SiO ₂ : Na ₂ O from 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied in an amount of from 2 to 10% (usually 3 to 5%) by weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating. Coatings containing silicate and borate salts, boric acids or other inorganic compounds are also suitable.

 Other coatings containing waxes, oils, fatty soaps can also be advantageously applied in the present invention.

 Another useful inorganic perhydrate salt useful in the compositions used is potassium peroxymonopersulfate.

где L представляет собой уходящую группу, а Х является по существу любой функциональной группой, такой, что структура образуемой при пергидролизе пероксикислоты представляет собой

Соединения - предшественники пероксикислотного отбеливателя - предпочтительно включают в количестве от 0,5 до 20% по весу, более предпочтительно от 1 до 10% по весу и наиболее предпочтительно от 1,5 до 5% от веса композиции.Peroxyacid bleach precursor
Precursors of peroxyacid bleach are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form peroxyacid. Typically, peroxyacid bleach precursors can be presented as

where L represents a leaving group, and X is essentially any functional group, such that the structure formed during the perhydrolysis of peroxyacids is

The peroxyacid bleach precursor compounds preferably include in an amount of from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, and most preferably from 1.5 to 5% by weight of the composition.

 Suitable compounds - precursors of peroxyacid bleach - usually contain one or more N - or O-acyl groups, while the precursors can be selected from a wide range of classes of substances. Suitable classes include anhydrides, esters, amides, lactams, and acylated derivatives of imidazoles and oximes. Examples of suitable materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1143231 and EP-A-0170386.

Outgoing groups
The leaving group, hereinafter referred to as the L group, must be substantially reactive in order for the perhydrolysis reaction to take place within the optimal time frame (for example, in the washing cycle). However, if L is excessively reactive, then this activator will be difficult to stabilize for use in the whitening composition.

и их смесей, где R¹ представляет собой алкильную, арильную или алкарильную группу, содержащую от 1 до 14 атомов углерода, R³ представляет собой алкильную цепь, содержащую от 1 до 8 атомов углерода, R⁴ представляет собой Н или R³, R⁵ представляет собой алкенильную цепь, содержащую от 1 до 8 атомов углерода, и Y представляет собой Н или солюбилизирующую группу. Любой из R¹, R³ и R⁴ может быть замещен по существу любой функциональной группой, включая, например, алкильную, гидроксильную, алкоксильную, галогеновую, аминную, нитрозильную, амидную и аммонийную или алкиламмонийную группы.Preferred L groups are selected from the group consisting of:

and mixtures thereof, where R ¹ represents an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R ³ represents an alkyl chain containing from 1 to 8 carbon atoms, R ⁴ represents H or R ³ , R ⁵ represents an alkenyl chain containing from 1 to 8 carbon atoms, and Y represents H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted by essentially any functional group, including, for example, alkyl, hydroxyl, alkoxyl, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

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

Prebenzoic Acid Precursor
Compounds - precursors of superbenzoic acid - give superbenzoic acid during perhydrolysis.

Пригодны также продукты бензоилирования сорбитола, глюкозы и всех сахаридов бензоилирующим агентом, включая, например:

Ac = COCH₃; Bz = бензоил.Suitable O-acylated prebenzoic acid precursors include substituted and unsubstituted benzoyloxybenzene sulfonates, including, for example, hydroxybenzene sulfonate:

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

Ac = COCH ₃ ; Bz = benzoyl.

 Imide-type prebenzoic acid precursor compounds include N-benzoylsuccinimide, tetrabenzylethylenediamine and N-benzoyl substituted ureas. Suitable imidazole type prebenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl group-containing prebenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurin and benzoylpyroglutamic acid.

Другим пригодным здесь соединением - предшественником надбензойной кислоты - является фталевый ангидрид:

Подходящие N-ацетилированные лактамовые предшественники надбензойной кислоты имеют формулу:

где n равно от 0 до 8, предпочтительно от 0 до 2, и R⁶ представляет собой бензоильную группу.Other prebenzoic acid precursors include benzoyldiacyl peroxides, benzoyl tetraacyl peroxides, and a compound having the formula:

Another suitable compound here, the precursor of perbenzoic acid, is phthalic anhydride:

Suitable N-acetylated lactam prebenzoic acid precursors have the formula:

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

Precursors of derivatives of superbenzoic acid
Precursors of derivatives of superbenzoic acid provide substituted superbenzoic acids for perhydrolysis. Suitable substituted prebenzoic acid derivative precursors include any of the superbenzoic precursors disclosed herein in which the benzoyl group is substituted by essentially any uncharged positive (i.e., non-cationic) functional group, including, for example, alkyl, hydroxyl, alkoxyl, halogen, amine, nitrosyl and amide groups.

где R¹ представляет собой арильную или алкарильную группу, содержащую от 1 до 14 атомов углерода, R² представляет собой ариленовую или алкариленовую группу, содержащую от 1 до 14 атомов углерода, R⁵ представляет собой Н или алкильную, арильную или алкарильную группу, содержащую от 1 до 10 атомов углерода, и L может быть по существу любой уходящей группой. R¹ предпочтительно содержит от 6 до 12 атомов углерода, R² предпочтительно содержит от 4 до 8 атомов углерода. R¹ может быть арилом, замещенным арилом или алкарилом, содержащим разветвление, замещение или оба и может происходить либо из синтетических, либо природных источников, например твердого жира. Аналогичные структурные вариации допустимы для R². Замещение может включать алкильную, арильную, галогенную, азотную, серную и другие типичные заместительные группы или органические соединения. R⁵ предпочтительно является Н или метилом. R¹ и R⁵ в сумме не должны содержать более 18 атомов углерода. Амидозамещенные соединения активатора отбеливателя этого типа описаны в патенте ЕР-А-0170386.A preferred class of substituted prebenzoic acid precursor compounds are amide substituted compounds of the following general formula:

where R ¹ represents an aryl or alkaryl group containing from 1 to 14 carbon atoms, R ² represents an arylene or alkarylene group containing from 1 to 14 carbon atoms, R ⁵ represents H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms, and L may be essentially any leaving group. R ¹ preferably contains from 6 to 12 carbon atoms, R ² preferably contains from 4 to 8 carbon atoms. R ¹ may be aryl substituted with aryl or alkaryl containing branching, substitution, or both, and may be from either synthetic or natural sources, for example, solid fat. Similar structural variations are acceptable for R ² . Substitution may include alkyl, aryl, halogen, nitrogen, sulfur, and other typical substituent groups or organic compounds. R ^{5 is} preferably H or methyl. R ¹ and R ⁵ in total should not contain more than 18 carbon atoms. Amide substituted compounds of this type of bleach activator are described in patent EP-A-0170386.

Precursors of Cationic Peroxy Acids
Compounds - precursors of cationic peroxyacids - give cationic peroxyacids during perhydrolysis.

 Typically, cationic peroxy acid precursors are formed by replacing the peroxy acid portion of a suitable compound, a peroxy acid precursor, with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Precursors of cationic peroxyacids are usually present in salt formulations with a suitable anion, such as, for example, a halogen ion or methyl sulfate ion.

 The peroxyacid precursor compound, which is subjected to cationic substitution, can be a precursor of a perbenzoic acid or a substituted derivative thereof, as described hereinabove. In the opposite embodiment, the peroxy acid precursor compound may be an alkyl percarboxylic acid precursor compound or a substituted alkyl peroxy acid amide precursor, as described hereinafter.

 Precursors of cationic peroxyacids are described in US Pat. Nos. 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5127852; 5093022; 5,106,528; U.K. patents 1382594; EP 475512, 458396 and 284292 and in JP 87-318332.

 Suitable precursors of cationic peroxyacids include any of the ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyl tetraacetyl glucosobenzoyl peroxides.

Предпочтительный катионно-замещенный сульфонат имеет формулу:

Предпочтительные предшественники катионных пероксикислот класса N-ацилированного капролактама включают триалкиламмонийметиленбензоилкапролактамы, в особенности триметиламмонийметиленбензоилкапролактам:

Другие предпочтительные предшественники катионных пероксикислот класса N-ацилированного капролактама включают триалкиламмонийметиленалкилкапролактамы:

где n равняется от 0 до 12, в особенности от 1 до 5.A preferred cationically substituted benzoyloxybenzenesulfonate is 4- (trimethylammonium) methyl derivative of benzoyloxybenzenesulfonate:

A preferred cationically substituted sulfonate has the formula:

Preferred precursors of cationic peroxyacids of the N-acylated caprolactam class include trialkylammoniummethylenebenzoylcaprolactam, in particular trimethylammoniummethylenebenzoylcaprolactam:

Other preferred precursors of cationic peroxyacids of the N-acylated caprolactam class include trialkylammoniummethylenealkylcaprolactams:

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

Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids upon perhydrolysis. Preferred precursors of this type give peracetic acid upon perhydrolysis.

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

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

где R¹ представляет собой алкильную группу с от 1 до 14 атомами углерода, R² представляет собой алкиленовую группу, содержащую от 1 до 14 атомов углерода, R⁵ представляет собой Н или алкильную группу, содержащую от 1 до 10 атомов углерода, и L может быть по существу любой уходящей группой. R¹ предпочтительно содержит от 6 до 12 атомов углерода. R² предпочтительно содержит от 4 до 8 атомов углерода. R¹ может быть алкилом с линейной или разветвленной цепью, содержащей разветвление, замещение или то и другое, и может происходить либо из синтетических, либо природных источников, включая, например, твердый жир. Аналогичные структурные вариации допустимы для R². Замещение может включать алкильную, галогенную, азотную, серную и другие типичные заместительные группы или органические соединения. R⁵ предпочтительно является Н или метилом. R¹ и R⁵ в сумме не должны содержать более 18 атомов углерода. Амидозамещенные соединения активатора отбеливателя этого типа описаны в патенте ЕР-А-0170386.Amide substituted alkyl peroxy acid precursors
Amide substituted compounds, precursors of alkyl peroxy acids, are also suitable, including those having the following general formula:

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

включая замещенные бензоксазины типа

где R₁ представляет собой Н, алкил, алкарил, арил, арилалкил и где R₂, R₃ R₄ и R₅ могут быть одинаковыми или различными заместителями, выбираемыми из Н, галогеновой, алкильной, алкиленовой, арильной, гидроксильной, алкоксильной, амино, алкиламино, COOR₆ (где R₆ является Н или алкильной группой) и карбонильной функций.Benzoxazine Organic Peroxy Acid Precursors
Also suitable are benzoxazine-type precursor compounds as disclosed, for example, in EP-A-332294 and EP-A-482807, in particular those having the formula:

including substituted benzoxazines of the type

where R ₁ represents H, alkyl, alkaryl, aryl, arylalkyl and where R ₂ , R ₃ R ₄ and R ₅ may be the same or different substituents selected from H, halogen, alkyl, alkylene, aryl, hydroxyl, alkoxy, amino , alkylamino, COOR ₆ (where R ₆ is H or an alkyl group) and carbonyl functions.

Предварительно образованная органическая пероксикислота
Система отбеливания органической пероксикислотой может содержать в дополнение к или, в противоположном варианте, вместо соединения - предшественника органического пероксикислотного отбеливателя, - предварительно образованную органическую пероксикислоту, обычно в количестве от 0,5 до 25% по весу, более предпочтительно от 1 до 10% от веса композиции.A particularly preferred precursor of the benzoxazine type is:

Preformed Organic Peroxy Acid
The organic peroxy acid bleaching system may contain, in addition to or, in the opposite embodiment, instead of the precursor organic peroxyacid bleach compound, a preformed organic peroxy acid, typically in an amount of 0.5 to 25% by weight, more preferably 1 to 10% by weight weight of the composition.

где R¹ представляет собой алкильную, арильную или алкарильную группу, содержащую от 1 до 14 атомов углерода, R² представляет собой алкиленовую, ариленовую или алкариленовую группу, содержащую от 1 до 14 атомов углерода, R⁵ представляет собой Н или алкильную, арильную или алкарильную группу, содержащую от 1 до 10 атомов углерода. R¹ предпочтительно содержит от 6 до 12 атомов углерода. R² предпочтительно содержит от 4 до 8 атомов углерода. R¹ может быть алкилом с линейной или разветвленной цепью, замещенным арилом или алкиларилом, содержащим разветвление, замещение или то и другое, и может происходить либо из синтетических, либо природных источников, включая, например, твердый жир. Аналогичные структурные вариации допустимы для R². Замещение может включать алкильную, арильную, галогенную, азотную, серную и другие типичные заместительные группы или органические соединения. R⁵ предпочтительно является Н или метилом. R¹ и R⁵ в сумме не должны содержать более 18 атомов углерода. Амидозамещенные органические пероксикислотные соединения этого типа описаны в патенте ЕР-А-0170386.A preferred class of organic peroxyacid compounds are amide substituted compounds of the following general formula:

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

 Other organic peroxyacids include tetraacylperoxides, in particular diperoxydecandicarboxylic acid, diperoxydecane dicarboxylic acid and diperoxytetradecandicarboxylic acid. Dibenzoyl peroxide is the preferred organic peroxy acid here. Mono- and diperazelaic acid, mono- and di-brassilic acid and N-phthaloylaminoperoxy-caproic acid are also suitable here.

Release rate controls
Means may be provided to control the rate of release of the bleaching agent, in particular oxygen bleach, into the washing solution.

 Means for controlling the rate of release of bleach can be provided for the controlled release of peroxides into the washing solution. Such agents could, for example, include controlling the release of any inorganic perhydrate salt acting as a source of hydrogen peroxide into the cleaning solution.

 Another mechanism for controlling the rate of release of bleach may consist in coating the bleach with a shell designed to provide controlled release. The coating may thus, for example, include a poorly water-soluble material, or be of sufficient thickness so that the dissolution kinetics of the thick coating provides a controlled release rate.

 The coating material can be applied using various methods. Any coating material is usually present at a weight ratio of coating material to bleach of from 1:99 to 1: 2, preferably from 1:49 to 1: 9.

 Suitable coating materials include triglycerides (for example, partially) hydrogenated vegetable oil, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and mixtures thereof.

Other suitable coating materials may include sulfates, silicates and carbonates of alkali and alkaline earth metals, including carbonate and calcium silicates. A preferred coating material, in particular for a bleach source based on an inorganic perhydrate salt, comprises sodium silicate with a ratio of SiO ₂ : Na ₂ O from 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2.4 : 1, and / or methacil sodium, preferably applied in an amount of from 2 to 10% (usually 3 to 5%) of SiO _{2 based} on the weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating.

Any inorganic salt based coating materials may be combined with organic binders to form composite inorganic salt / organic binder coatings. Suitable binders include ethoxylate esters of C ₁₀ -C ₂₀ alcohol containing from 5-100 mol of ethylene oxide per 1 mol of alcohol and more preferably ethoxylate esters of C ₁₅ -C _{20 of} primary alcohol containing from 20-100 mol of ethylene oxide per 1 mol of alcohol.

Other preferred binders include certain polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 • 10 ⁶ , preferably from 1000 to 400,000, most preferably from 1000 to 10,000. Other examples of polymeric materials suitable as binding agents are copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride being at least 20 mol% of the polymer. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the aforementioned ethoxylate esters of C ₁₀ -C ₂₀ alcohol containing from 5-100 mol of ethylene oxide per 1 mol. Other examples of binders include mono- and diglycerol C ₁₀ -C ₂₀ esters, as well as C ₁₀ -C ₂₀ fatty acids.

 Other examples of binders suitable for use herein are cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, as well as homo- or copolymer polycarboxylic acids or their salts.

 One method of applying a coating material involves agglomeration. A preferred agglomeration process includes the use of any of the organic binders described herein above. Any conventional agglomerator / mixer may be used, including, but not limited to, an apparatus such as a vat, rotary drum and vertical mixer. The molten coating compositions can also be applied either by pouring or by droplet spraying onto a moving layer of a whitening agent.

 Other methods for providing the desired controlled release include mechanical means of changing the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compression, mechanical injection, manual injection and adjusting the whitening component to the required solubility by selecting the particle size of any granular component.

 Since the choice of particle size should depend both on the composition of the granular component and on the desired kinetics of controlled release, it is desirable that the particle size exceeds 500 micrometers, preferably the average particle diameter is from 800 to 1200 micrometers.

 Additional protocols providing means for controlled release include the appropriate selection of any other base components of the detergent composition, such that when the composition is introduced into the detergent solution, the ionic strength of the medium will achieve the desired release kinetics.

Metal-containing bleach catalyst
The compositions described herein containing bleach as a detergent component may further comprise an additional component containing a metal bleach catalyst. Preferably, the metal-containing bleach catalyst is a bleach catalyst containing a transition metal, more preferably a bleach catalyst containing manganese or cobalt.

 A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation having a specific catalytic activity with respect to a bleach, such as copper, iron cations, an auxiliary metal cation having no or low catalytic activity with respect to a bleach, such as zinc or aluminum cations, and sequestering agent with certain strength constants for catalytic and auxiliary metal cations, in particular ethylenediaminetetraux hydrochloric acid, ethylene diamine tetra (methylene phosphinic acid) and their water-soluble salts. Such catalysts are disclosed in US Pat. No. 4,430,243.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in US Pat. Nos. 5,246,621 and 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (u-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₂ , Mn ^IV ₄ (uO ) ₆ (1,4,7-triazacyclononan) ₄ - (ClO ₄ ) ₂ ,
Mn ^III Mn ^IV ₄ (u-O) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₃ and mixtures thereof. Others are described in published European patent application 549272. Other suitable ligands for use here include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononan, 1,2,4,7-tetramethyl-1,4,7-triazacyclononan and mixtures thereof.

Suitable bleach catalysts in the compositions may also be selected in accordance with the present invention. Examples of brighteners suitable catalysts, see U.S. Patents 4246612 and 5227084. See also United States patent, wherein proposed mononuclear manganese complexes of (IV), such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ - (PF ₆ ).

 Another type of bleach catalyst, as disclosed in US Pat. Preferred ligands include sorbitol, idit, dulsite, mannitol, xylitol, arabitol, adonite, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

где каждый из R¹, R², R³ и R⁴ может быть выбран из Н, замещенной алкильной или арильной групп, так что каждый из R¹-N=C-R² и R³-C=N-R⁴ образует пяти- или шестичленное кольцо. Указанное кольцо может быть дополнительно замещено. В представляет собой мостиковую группу, выбираемую из О, S, CR⁵R⁶, NR⁷ и С= О, где каждый из R⁵, R⁶ и R⁷ может быть Н, алкильной или арильной группой, включая замещенные и незамещенные группы. Предпочтительные лиганды включают пиридиновое, пиридазиновое, пиримидиновое, пиразиновое, имидазольное, пиразольное и триазольное кольца. Указанные кольца необязательно могут быть замещены такими заместителями, как алкил, арил, алкокси, галоид и нитро. Особенно предпочтительным лигандом является 2,2'-биспиридиламин. Предпочтительные катализаторы отбеливателей включают комплексы Со, Сu, Mn, Fe-биспиридилметана и -биспиридиламина. Высоко предпочтительные катализаторы включают Со(2,2'-биспиридиламин)Cl₂, ди(изотиоцианато)биспиридиламин-кобальт(II), трисдипиридиламин-кобальт(II)перхлорат, трис(ди-2-пиридиламин)железо(II)перхлорат и их смеси.US Pat. No. 5,114,611 discloses a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a non- (macro) cyclic ligand. These ligands have the formula:

where each of R ¹ , R ² , R ³ and R ⁴ can be selected from H, substituted alkyl or aryl groups, so that each of R ¹ -N = CR ² and R ³ -C = NR ⁴ forms a five- or six-membered ring. The specified ring may be further substituted. B represents a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C = O, where each of R ⁵ , R ⁶ and R ⁷ may be H, an alkyl or aryl group, including substituted and unsubstituted groups. Preferred ligands include the pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. These rings may optionally be substituted with substituents such as alkyl, aryl, alkoxy, halogen and nitro. A particularly preferred ligand is 2,2'-bispyridylamine. Preferred bleach catalysts include complexes of Co, Cu, Mn, Fe-bispyridylmethane and -bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and their mixtures.

Preferred examples include Mn binuclear complexes with tetra-N-dentate and bi-N-dentate ligands, including N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^III (uO) ₂ Mn ^IV bipy ₂ ] - (ClO ₄ ) ₃ .

 Although the structures of the bleaching catalysts of the magnesium complexes of the present invention have not been explained, it can be assumed that they include chelates or other hydrated coordinate complexes resulting from the interaction of carboxyl and ligand nitrogen atoms with a manganese cation. Similarly, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and valence states (+ II), (+ III), (+ IV) or (+ V) are possible. Due to the six possible points of attachment of manganese to the cation in the ligand, it may be reasonable to assume that multinuclear species and / or “cell-like” structures may be present in the aqueous bleaching medium. Whatever the actual form of the active species of Mn • ligand, it functions obviously in a catalytic manner, providing improved whitening characteristics for stubborn stains such as tea, ketchup, coffee, wine, juice, and the like.

 Other bleach catalysts are described, for example, in European patent application, publication 408131 (catalysts based on cobalt complexes), in European patent applications, publications 384503 and 306089 (metal-porphyrin catalysts), US patent 4728455 (catalyst based on manganese / multidentate ligand ), US Pat. No. 4,711,748 and European Patent Application, Publication 224952 (manganese adsorbed on an aluminosilicate catalyst), US Pat. No. 4,601,845 (aluminosilicate base with manganese and zinc or a magnesium salt), US Pat. No. 4,636,373 (catalysis manganese / ligand torus), US Pat. No. 4,119,557 (iron complex catalyst), German Patent Specification 2,054,019 (cobalt chelate catalyst), Canadian Patent 866,191 (salts containing transition metals), US Pat. No. 4,430,243 (chelating compounds with manganese cations and non-catalytic metal cations) and US Pat. No. 4,728,455 (manganese gluconate catalysts).

Other preferred examples include cobalt (III) based catalysts having the formula:
Co [NH ₃ ) _n M ' _m B' _b T ' _t Q' _q P _p ] Y _y
where the oxidation state of cobalt is +3; n is an integer from 0 to 5 (preferably 4 or 5, most preferably 5); M 'is a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, most preferably 1); B 'is 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 represents a pentadentate ligand; p is 0 or 1; n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counter anions present in an amount equal to y, where y is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when Y is an anion with a charge of -1) to obtain a balanced according to salt charges, preferred Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof, and where at least one of the coordinate sites attached to cobalt is further labile under applicable conditions av aromatic dishwashing, and the remaining coordinate sites stabilize cobalt under automatic dishwashing conditions, so that the reduction potential of the conversion of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) with respect to normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula:
[Co [NH ₃ ) _n (M ') _m ] Y _y
where n is an integer from 3 to 5 (preferably 4 or 5, most preferably 5); M 'is a labile coordinate part, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (with m greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, most preferably 1); m + n = 6; Y is a suitably selected counteranion present in an amount equal to y, which is an integer from 1 to 3 (preferably from 2 to 3, most preferably 2 when Y is an anion with a charge of -1) to obtain a charge balanced salt.

Preferred cobalt catalysts of this type that are suitable here are the pentaamine chloride salts of the formula [Co (NH ₃ ) ₅ Cl] Y _y and especially [Co [NH ₃ ) ₅ Cl] Cl ₂ .

More preferred are the compositions of the present invention, which use cobalt (III) based bleach catalysts having the formula:
[Co (NH ₃ ) _n (M) _m (B) _b ] T _y
where the oxidation state of cobalt is +3; n is 4 or 5 (preferably 5); M represents one or more ligands coordinated with cobalt through one site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated with cobalt through two sites; b is 0 or 1 (preferably 0) and when b = 0, m + n = 6, and when b = 1, then m = 0 and n = 4; T is one or more appropriately selected counter anions present in an amount equal to y, where y is an integer to obtain a charge balanced salt (preferably, y is 1 to 3, most preferably 2 when T is an anion with a charge of -1 ), and where further the specified catalyst has a constant rate of hydrolysis of the base of not less than 0.23 M ^-1 s ^-1 (25 ^o C).

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

M parts include, for example, but are not limited to, F ^- , SO ₄ ^-2 , NCS ^- , SCN ^- , S ₂ O ₃ ^-2 , NH ₃ , PO ₄ ^{3 -} and carboxylates (which are preferably monocarboxylates, however, in this parts, more than one carboxylate may be present if binding to cobalt takes place through only one carboxylate per part, in which case the other carboxylate in the M part may be protonated or may be in its salt form). M may optionally be protonated if there is more than one anionic group in M (for example, HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- , HOC (O) CH ₂ C (O) O-, etc.) Preferred M parts are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids having the formula:
RC (O) O-
where R is preferably selected from the group consisting of hydrogen and C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) unsubstituted and substituted alkyl, C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) unsubstituted and substituted aryl and C ₃ - C ₃₀ (preferably C ₅ -C ₁₈ ) unsubstituted and substituted heteroaryl, in which the substituents are selected from the group consisting of -NR ' ₃ , -NR' ₄ ⁺ , -C (O) OR ', -OR', -C ( O) NR ' ₂ , where R' is selected from the group consisting of hydrogen and C ₁ -C ₆ parts. Such substituted Rs therefore include portions of - (CH ₂ ) _n OH and - (CH ₂ ) _n NR ' ₄ ⁺ , where n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.

Most preferred M are carboxylic acids having the formula above, wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, linear or branched C ₄ -C ₁₂ alkyl and benzyl. Most preferred M is methyl. Preferred M parts — carboxylic acids — include formic, benzoic, caprylic, nonanoic, decanoic, lauric, malonic, maleic, succinic, adipic, phthalic, 2-ethylcaproic, naphthenic, oleic, palmitic, triflate, tartaric, stearic, lemon oil Acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic acid.

 Parts include capronate, di- and higher carboxylates (e.g., oxalate, malonate, malate, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g. glycine, alanine, beta-alanine, phenylalanine).

The cobalt bleach catalysts suitable here are known, having been described together with their base hydrolysis rates, for example, in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech (1983), 2, pages 1-94. For example, table 1 on page 17 shows the rate of hydrolysis of the bases (indicated there as k _OH ) for pentamine cobalt catalysts complexed with oxalate (k _he = 2.5 • 10 ^-4 M ^-1 s ^-1 (25 ^o C)) , NCS ^- (k _o = 5.0 • 10 ^-4 M ^-1 sec ^-1 (25 ^o С)), formate (k _it = 5.8 • 10 ^-4 М ^-1 sec ^-1 (25 ^o С) ) and acetate (k _it = 9.6 • 10 ^-4 M ^-1 sec ^-1 (25 ^o С)). The most preferred cobalt catalysts useful here are cobalt pentamine amine salts of the formula [Co (NH ₃ ) ₅ OAc] T _y , where OAc is the acetate moiety, in particular cobalt acetic pentamine 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 (NH ₃ ) ₅ OAc] (SO ₄ ); [Co (NH ₃ ) ₅ OAc] (BF ₄ ) ₂ and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (here PAC).

 These cobalt catalysts are readily prepared using known methods such as those cited, for example, in Tobe and the references cited herein, in US Pat. No. 4,810,410 to Diakun et al. published March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960), and Journal of Physical Chemistry, 56, 22-25 (1952), as well as in the synthesis examples presented below.

 Cobalt catalysts suitable for inclusion in the detergent tablets of the present invention can be prepared according to the synthetic routes disclosed in US Pat. Nos. 5,559,261, 5,598,005 and 5,597,939, the disclosures of which are incorporated herein by reference.

 These catalysts can be processed in conjunction with additional materials so as to reduce the effect of the dye, if desired in terms of aesthetics of the product, or to include particles containing the enzyme, as shown here in the examples below, or compositions containing catalyst specks can be obtained.

Organic polymer compound
In accordance with the invention, organic polymer compounds can be added as preferred components of the washing tablets. An organic polymer compound is understood to mean essentially any polymer organic compound commonly found in detergent compositions that has dispersant properties, anti-redeposition, anti-dirt, or other detergent properties.

 The organic polymer compound is usually included in the detergent compositions of the invention in an amount of from 0.1 to 30%, preferably from 0.5 to 15%, and most preferably from 1 to 10% by weight of the composition.

 Examples of organic polymeric compounds include water-soluble organic homo- or copolymer polycarboxylic acids, modified polycarboxylates or their salts, in which the polycarboxylic acid includes at least two carboxy radicals separated from each other by no more than two carbon atoms. The polymers of the latter type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates with a molecular weight of 2000-10000 and their copolymers with any other suitable monomer units, including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconite, citraconic and methylene malonic acids or their salts, maleic anhydride, acrylates vinyl methyl ether, styrene and any mixtures thereof. Preferred are copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.

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

Preferred acrylic acid-containing copolymers include those which contain as monomer units: a) from 90 to 10%, preferably from 80 to 20%, by weight of acrylic acid or its salt, and b) from 10 to 90%, mainly from 20 to 80% by weight of the substituted acrylic monomer or its salts having the general formula - [CR ₂ —CR ₁ (CO — O — R _s )] -, where at least one of the substituents R ₁ , R ₂ or R ₃ preferably R ₁ or R ₂ is an alkyl or hydroxyalkyl group with 1-4 carbon atoms, R ₁ or R ₂ may be hydrogen and R ₃ can be hydrogen, or with Strongly alkaline metal. Most preferred is a substituted acrylic monomer in which R ₁ is methyl, R ₂ is hydrogen (i.e., 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.

 Suitable polyamine and modified polyamine compounds, including those that are derivatives of aspartic acid, such as disclosed in patents EP-A-305282, EP-A-305283 and EP-A-351629.

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

 Suitable examples are disclosed in US patents 5591703, 5597789 and 4490271.

Mud Removing Agents
Suitable polymeric dirt removing agents include those removing dirt that have: (a) one or more non-ionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) hydroxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, where the specified hydrophilic segment does not cover any oxypropylene unit, if it is not connected to adjacent parts at each end using an ether bond or, (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophilic segments preferably comprising at least 25% oxyethylene units and more preferably, especially for those components that contain from 20 to 30 oxypropylene units, at least 50% oxyethylene units, or (b) one or more hydrophobic components comprising (i) C ₃ oxyalkylene terephthalate segments, in which, if these hydrophobic components also include oxyethylene terephthalate lat, the ratio of oxyethylene terephthalate units: C ₃ oxyalkylene terephthalate units is 2: 1 or lower, (ii) C ₄ -C ₆ alkylene or C ₄ -C ₆ oxyalkylene segments or mixtures thereof, (iii) poly (vinyl ether) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents or mixtures thereof, said substituents being in the form of a C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof, or a combination of (a) and (b).

Typically, the polyoxyethylene segments (a) (i) should have a polymerization degree of from 200, although higher degrees can be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable C ₄ -C ₆ hydroxyalkylene hydrophobic segments include, but not limited to this, end caps of polymeric dirt-removing agents, such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, where M is sodium and n is an integer from 4-6, as disclosed in US Pat. Gosselink, published January 26, 1988

Suitable polymeric dirt-removing agents herein include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyoxyethylene or polyoxypropylene terephthalate and the like. Such agents are commercially available and include cellulose partial esters such as METHOCEL (Dow). Cellulosic dirt-removing agents used herein also include those selected from the group consisting of C ₁ -C ₆ alkyl and C ₄ hydroxyalkyl celluloses; see U.S. Patent 4000093, owned by Nicol et al., published December 28, 1978

Mud removing agents characterized by poly (vinyl ester) hydrophobic segments include grafted copolymers of poly (vinyl esters), for example C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate), grafted onto polyoxyalkylene bases such as polyoxyethylene bases. See European Patent Application 0219048, owned by Kud et al., Published April 22, 1987.

 Another suitable dirt removing agent is a copolymer of randomly arranged blocks of ethylene terephthalate and polyoxyethylene (PEO) terephthalate. The molecular weight of this polymeric dirt-removing agent is in the range of 25,000 to 55,000. See US Pat. No. 3,959,230, owned by Hays, published May 25, 1976, and US Pat.

 Another suitable polymeric dirt removing agent is a repeating polyester of ethylene terephthalate units that contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units derived from polyoxyethylene glycol with an average molecular weight of 300-5000.

 Another suitable polymeric dirt-removing agent is a sulfonated product of a suitable linear ether oligomer selected from the oligomeric ether base of terephthaloyl and oxyalkyleneoxy repeat units, and end parts covalently attached to the base. These dirt removing agents are fully described in US Pat. No. 4,968,451 to J. J. Scheibel and E.P. Gosselink, published November 6, 1990. Other suitable polymeric dirt-removing agents include terephthalate polyesters of US Pat. 1988, and block polyester oligomeric compounds of US Pat. No. 4,702,857 to Gosselink, published October 27, 1987. Other suitable polymeric dirt-removing agents include also dirt-removing agents of US Pat. No. 4,877,896, Maldonado et al., published October 31, 1989, discloses anionic, especially sulfoaroyl, end-terephthalate esters.

 Another dirt removing agent is an oligomer with repeating units of terephthaloyl units, sulfoisoterephthaloyl units, hydroxyethyleneoxy and hydroxy-1,2-propylene units. Duplicate units form the backbone of the oligomer and preferably end with modified isethionate end caps. A particularly preferred dirt-removing agent of this type includes one sulfoisophthaloyl unit, five terephthaloyl units, hydroxyethyleneoxy and hydroxy-1,2-propylene units in a ratio of 1.7 to 1.8, and two ends capping units of 2- (2-hydroxyethoxy) sodium ethanesulfonate.

Heavy Metal Ion Trap
The tablets of the invention preferably contain, as an optional component, a heavy metal ion trap. A heavy metal ion trap here refers to components that act by binding (chelating) heavy metal ions. These components may also have the ability to chelate calcium and magnesium, but preferably they exhibit selectivity in the binding of heavy metal ions such as iron, manganese and copper.

 Heavy metal ion traps are typically present in an amount of from 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.

 Traps of heavy metal ions that are acidic in nature, possessing, for example, phosphonic acid or carboxylic acid functionality, can be present either in their acid form or in the form of a complex / salt with a suitable anti-cation, such as an alkali or alkaline earth metal ion, ammonium, or a substituted ammonium ion or any mixtures thereof. Preferably, any salts / complexes are water soluble. The molar ratio of said protocation and trap of heavy metal ions is preferably at least 1: 1.

 Suitable heavy metal ion traps for use here include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxydiphosphonates and nitrilotrimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

 Other heavy metal ion traps suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediamine pentaacetic acid, ethylenediamidineduccinic acid, ethylenediamindiglutaric acid, 2-hydroxypropylenediamidine-succinic acid.

 Ethylene diamine-N, N'-di-succinic acid (EDDS) or its salts with an alkali metal, alkaline earth metal, ammonium or substituted ammonium, or mixtures thereof, is particularly preferred. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.

Crystal Growth Inhibitor
The detergent composition preferably contains a crystal growth inhibiting component, preferably an organic diphosphonic acid component, preferably included in an amount of from 0.01 to 5%, more preferably from 0.1 to 2% by weight of the compositions.

 By organic diphosphonic acid is meant organic diphosphonic acid, which does not contain nitrogen as part of its chemical structure. This definition, therefore, excludes organic amino phosphonates, which, however, can be included in the compositions of the invention as components of traps for heavy metal ions.

The organic diphosphonic acid is preferably C ₁ -C ₄ diphosphonic acid, more preferably C ₂ diphosphonic acid such as ethylene diphosphonic acid, or most preferably ethane-1-hydroxy-1,1-diphosphonic acid (HTDP), and it may be present in partially or fully ionized form, especially in the form of a salt or complex.

Water Soluble Sulfuric Acid
A washing tablet optionally contains a water soluble salt of sulfuric acid. If present, the water-soluble salt of sulfuric acid is in an amount of from 0.1 to 40%, more preferably from 1 to 30%, and most preferably from 5 to 25%, by weight of the compositions.

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

Alkali metal silicate
An alkali metal silicate is a preferred component of the tablet of the present invention. A preferred alkali metal silicate is sodium silicate with an SiO ₂ : Na ₂ O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0. Silica is preferably present in an amount of less than 40%, preferably from 1 to 15% and most preferably from 3 to 12%, by weight of SiO ₂ . The alkali metal silicate may be in the form of either an anhydrous salt or in the form of a hydrated salt.

 An alkali metal silicate may also be present as a component of the alkalizing system.

The alkalization system also preferably contains sodium methacilate present in an amount of at least 0.4% SiO ₂ by weight. Sodium metasilicon has a nominal ratio of SiO ₂ : Na ₂ O 1,0. The weight ratio of said sodium silicate to said sodium methacilate, measured by SiO ₂ , is preferably from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, most preferably from 10: 1 to 5: 2.

Dye
The term "dye", as used here, means any substance that absorbs certain wavelengths of light of the visible part of the spectrum. Such dyes, when added to the detergent composition, have the effect of changing the visible color and, consequently, the appearance of the detergent composition. Dyes can be, for example, paints or pigments. Preferably, the dyes are stable in the composition in which they are to be included. Thus, in a high pH composition, the dye is preferably alkali resistant, and in a low pH composition, the dye is preferably acid resistant.

 The first and / or second and / or optionally other phases may contain a dye, a mixture of dyes, colored particles or a mixture of colored particles, so that the various phases differ in appearance. Preferably, either the first or second phases include a dye. When the first and second and / or subsequent phases include a dye, it is preferred that the dyes have a different appearance. Examples of suitable inks include active inks, direct inks, and azo paints. Preferred paints include phthalocyanine paints, anthraquinone paints, quinoline paints, monoazo, diazo and polyazo. More preferred paints include anthraquinone, quinoline and monoazokraski. Preferred paints include SANOLAN E-HRL 180% (trademark), SANOLAN MILLING BLUE (trademark), TURQUOISE ACID BLUE (trademark) and SANOLAN BRILLIANT GREEN (trademark), all sold by Clariant UK, HEXACOL QUINOLINE YELLOW (trademark) and HEXACOL BRILLIANT BLUE (trademark), both sold by Pointings, UK, ULTRA MARINE BLUE (trademark) sold by Holliday, or LEVAFIX TURQUISE BLUE EVA (trademark) sold by Bayer, USA.

 The dye may be incorporated into the phases in any suitable manner. Suitable methods include mixing all or selected detergent components with a colorant in a drum or spraying all or selected detergent components with a colorant in a rotating drum.

 Dye, if present as a component of the first phase, it is in an amount of from 0.001 to 1.5%, preferably from 0.01 to 1.0%, and most preferably from 0.1 to 0.3%. If the dye is present as a component of the second and / or optionally other phases, then it is usually in an amount of from 0.001 to 0.1%, more preferably from 0.005 to 0.05%, and most preferably from 0.007 to 0.02%.

Compound Corrosion Inhibitor
Tablets of the present invention suitable for use in dishwashing methods may contain corrosion inhibitors, preferably selected from organic silver coating agents, in particular paraffin, nitrogen-containing compounds — corrosion inhibitors — and Mn (II) compounds, in particular Mn (II) organic salts ligands.

 Organic silver coating agents are described in PCT publication WO 94/16047 and parallel European application EP-A-690122. Nitrogen-containing compounds - corrosion inhibitors - are disclosed in parallel European application EP-A-634478. Compounds of Mn (II) used to inhibit corrosion are described in parallel European application EP-A-672749.

 Organic silver coating agents may be included in an amount of from 0.05 to 10%, preferably from 0.1 to 5%, of the total weight of the composition.

 The functional role of the silver coating agent is to form a "when applied" protective coating layer on any silver components of a batch of dishes to be washed for washing onto which the compositions of the invention are applied. The silver coating agent, therefore, must have a high affinity for bonding to solid silver surfaces, especially when it is present as a component in an aqueous washing and bleaching solution with which solid silver surfaces are treated.

 Suitable organic silver coating agents include fatty esters of monohydric or polyhydric alcohols containing from 1 to 40 carbon atoms in the hydrocarbon chain. The fatty acid portion of the fatty ester can be obtained from mono- or polycarboxylic acids containing from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, β-glycolic, β-glycolic dihydroxyisobutyric acid. Examples of suitable polycarboxylic fatty acids include n-butyl malonic acid, isolimonic acid, citric acid, maleic acid, malic acid and succinic acid.

 The fatty alcohol radical of the fatty ester can be represented by monohydroxy or polyhydric alcohols containing from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Preferably, the fatty acid and / or alcohol group of the fatty series of the fatty ester additive material contains from 1 to 24 carbon atoms in the alkyl chain.

 Preferred fatty esters here are ethylene glycol, glycerol and sorbitan esters in which the fatty acid portion of the ester typically includes species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

 Glycerol esters are also most preferred. There are mono-, di- and triesters of glycerol and fatty acids, as defined above.

 Specific examples of fatty alcohol esters for use herein include stearyl acetate, palmityldylactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate and thalloyl propionate. Fatty acid esters useful here include xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable esters of sorbitan include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan mono-behenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibegenate, sorbitan dioleate, and mixed diaryloalkyl.

 Preferred glycerol esters are glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobegenate and glycerol distearate.

 Suitable organic silver coating agents include triglycerides, mono- or diglycerides, their fully or partially hydrogenated derivatives, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grape seed oil, palm oil and corn oil.

Organic silver coating agents useful here are waxes, including microcrystalline waxes. Preferred waxes have a melting point in the range of 35 to 110 ^{° C.} and typically include 12 to 70 carbon atoms. Preferred are paraffin oil waxes and microcrystalline type waxes consisting of long chain saturated hydrocarbon components.

 Alginates and gelatin are suitable here as organic silver coating agents.

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

 Other suitable organic silver coating agents include some polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole and cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose.

 Some flavoring agents are also suitable as silver coating organic agents, in particular those that exhibit high substantiality with respect to metal surfaces.

 As an organic silver coating agent, dirt-removing polymeric agents can also be used.

The preferred organic silver coating agent is paraffin oil, usually a predominantly branched aliphatic hydrocarbon containing from 20 to 50 carbon atoms in a chain, a preferred paraffin oil is selected from predominantly branched C _25-45 species with a ratio of cyclic and acyclic hydrocarbons from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A paraffin oil meeting these characteristics and having a cyclic to acyclic hydrocarbon ratio of 32:68 is sold by Wintershall, Salzbergen, Germany, under the trademark WINOG 70.

Compounds - Nitrogen Corrosion Inhibitors
Suitable nitrogen inhibitor compounds include imidazole and its derivatives such as benzimidazole, 2-heptadecylimidazole, and imidazole derivatives as described in Czech Patent 139279 and GB Patent GB-A-1137741, which also disclose a process for the preparation of imidazole compounds.

Suitable compounds, corrosion inhibitors containing nitrogen, are also pyrazole compounds and their derivatives, especially those in which pyrazole is substituted in any of the 1, 3, 4 or 5 positions with R ₁ , R ₃ , R ₄ and R ₅ , where R ₁ represents any substituent from H, CH ₂ OH, CONH ₃ or COCH ₃ , R ₃ and R ₅ represent any substituent from C ₁ -C ₂₀ alkyl or hydroxyl and R ₄ represents any substituent from H, NH ₂ or NO ₂ .

 Other suitable compounds, nitrogen inhibitors, include benzothiazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, moroline, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole , aminotetrazole and indazole.

 Compounds containing nitrogen, such as amines, especially distearylamine, and ammonium compounds, such as ammonium chloride, ammonium bromide, ammonium sulfate or ammonium citrate, are also suitable.

Compounds - Corrosion Inhibitors Containing Mn (II)
Detergent tablets may contain a corrosion inhibitor compound containing Mn (II). A compound containing Mn (II) is preferably included in an amount of from 0.005 to 5% by weight, more preferably from 0.01 to 1%, most preferably from 0.02 to 0.4%, by weight of the compositions. Preferably, the compound containing Mn (II) is included in such an amount as to provide a weight content of Mn (II) ions in any whitening solution of from 0.1 to 250 ppm, more preferably from 0.5 to 50 ppm. most preferably from 1 to 20 ppm, by weight.

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

 Compound Mn (II) may be a salt or complex compound of an organic ligand. In one preferred embodiment, the organic ligand is a crystal growth inhibitor.

Other compounds - corrosion inhibitors
Other suitable additional compounds, corrosion inhibitors, include mercaptans and diols, especially mercaptans containing 4 to 20 carbon atoms, including lauryl mercaptan, thiophenol, thionaphthol, thionalide and thioanthranol. Saturated or unsaturated C ₁₀ -C ₂₀ fatty acids or their salts, especially aluminum tristearate, are also suitable. C ₁₀ -C ₂₀ hydroxylated fatty acids or their salts are also suitable. Phosphonated octadecane and other antioxidants such as beta-hydroxytoliol (BHT) are also suitable.

 It has been found that, as corrosion inhibitor compounds, copolymers of butadiene and maleic acid are especially suitable, especially those sold under the trademark 07787 Polysciences Inc.

Hydrocarbon oils
Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically a long chain predominant aliphatic hydrocarbon having a carbon number in the range of 20 to 50; preferred hydrocarbons are saturated and / or branched; a preferred hydrocarbon oil is selected from C _25-45 branched chain predominant species with a cyclic to non-cyclic hydrocarbon ratio of from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin. A paraffin oil meeting the characteristics described above, having a cyclic hydrocarbon to non-cyclic ratio of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trademark WINOG 70.

Water Soluble Bismuth Compound
Detergent tablets of the present invention that are suitable for dishwashing methods may contain a water-soluble bismuth compound, preferably present in an amount of from 0.005 to 20%, more preferably from 0.01 to 5%, most preferably from 0.1 to 1%, weight of the compositions.

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

Enzyme Stabilizing System
Preferred enzyme compositions used herein may include from 0.001 to 10%, preferably from 0.005 to 8%, more preferably from 0.01 to 6%, by weight of the enzyme stabilizing system. An enzyme stabilizing system can be any stabilizing system that is compatible with a detergent enzyme. Such stabilizing systems may include calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boric acid, chlorine bleaching agents, and mixtures thereof. Such stabilizing systems may also include reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap loosening compound
The tablets of the present invention may contain a lime soap disintegrant compound, preferably present in an amount of from 0.1 to 40% by weight, more preferably from 1 to 20% by weight, most preferably from 2 to 10%, by weight of the compositions.

 A lime soap loosening compound is a material that prevents the precipitation of alkali metal, ammonium or amine salts by the action of calcium or magnesium ions. Preferred lime soap disintegrant compounds are disclosed in PCT Patent Application WO 93/08877.

Anti-foaming system
The detergent tablets of the present invention, when formulated as detergent compositions for machine use, preferably include an anti-foaming system present in an amount of 0.01 to 15%, preferably 0.05 to 10%, most preferably 0.1 to 5% , by weight of the composition.

 Suitable foaming suppressing systems herein may include essentially any known anti-foam compound, for example, silicone anti-foam compounds, 2-alkyl and alkanol anti-foam compounds. Preferred anti-foaming systems and anti-foam compounds are disclosed in PCT Patent Application WO 93/08876 and EP-A-705324.

Polymer agents that inhibit molting
The detergent tablets provided herein may also include from 0.01 to 10%, preferably from 0.05 to 0.5%, by weight of polymer agents that inhibit shedding.

 The moulting inhibitor polymers are preferably selected from polymers of N-oxide polyamine, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polymers of polyvinylpyrrolidone or combinations thereof.

Optical Gloss Amplifier
Detergent tablets suitable for use in laundry washing methods as described herein also optionally contain from 0.005 to 5% by weight of certain types of hydrophilic optical gloss enhancers.

где R₁ выбирают из анилино, N-2-бис-гидроксиэтила и NH-2-гидроксиэтила; R₂ выбирают из N-2-бис-гидроксиэтила, N-2-гидpoкcиэтил-N-мeтилaминo, морфилино, хлоро и амино и М представляет собой образующий соль катион, такой как натрий или калий.Useful hydrophilic optical gloss enhancers for use herein include those that have the formula:

where R ₁ selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R _{2 is} selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro, and amino, and M is a salt forming cation, such as sodium or potassium.

When in the above formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the optical gloss enhancer is 4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid and its disodium salt. These specific types of optical gloss enhancers are sold by Ciba-Geigy Corporation under the brand name Tinopal-UNPA-GX. Tinopal-UNPA-GX is the preferred hydrophilic optical gloss enhancer useful in the detergent compositions provided herein.

When in the above formula, R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the optical brightener is a disodium salt of 4,4'-bis [( 4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid. These specific types of optical gloss enhancers are sold by Ciba-Geigy Corporation under the brand name Tinopal 5BM-GX.

When in the above formula, R ₁ is anilino, R ₂ is morphilino, and M is a cation such as sodium, the optical gloss enhancer is 4,4'-bis [(4-anilino-6-morphilino-s- triazin-2-yl) amino] -2,2'-stilbendisulfonic acid. These specific types of optical gloss enhancers are sold by Ciba-Geigy Corporation under the brand name Tinopal AMS-GX.

Clay softening system
Detergent tablets suitable for use in laundry washing methods may include a clay softener system comprising a mineral clay compound and an optional clay flocculating agent.

 The mineral clay compound is preferably a smectite clay compound. Smectite clays are disclosed in US patents 3862058, 3948790, 3954632 and 4062647. European patents EP-A-299575 and EP-A-313146, owned by Procter and Gamble Company, describe suitable organic polymer flocculating clay agents.

Cationic Fabric Softeners
Cationic fabric softening agents that are suitable for use in laundry washing methods may also be included in the compositions of the present invention. Suitable cationic tissue softening agents include water-insoluble tertiary amines or two long chain amide materials as described in GB-A-1514276 and EP-B-0011340.

 Cationic fabric softening agents typically include in a total amount of 0.5 to 15% by weight, typically 1 to 5% by weight.

Other optional ingredients
Other optional ingredients that are suitable for inclusion in the compositions of the invention include perfumes and filler salts, with sodium sulfate being the preferred filler salt.

pH of the compositions
The detergent tablets of the present invention are preferably so that they do not have an excessively high pH, and it is preferable that they have a pH, measured in their 1% solution in distilled water, from 8.0 to 12.5, more preferably from 9.0 up to 11.8, most preferably from 9.5 to 11.5.

The method of washing dishes
Any suitable methods for machine washing or cleaning contaminated tableware are contemplated.

 A preferred method for washing dishes by machine involves treating contaminated items selected from earthenware, glassware, silverware, metal dishes, knives and combinations thereof, with an aqueous liquid containing an effective amount of a detergent tablet dissolved or dispersed therein in accordance with the invention. By an effective amount of a detergent tablet is meant from 8 to 60 g of a product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are the usual dosages of the product and the volumes of washing solutions commonly used in traditional dishwashing methods. Preferably, the detergent tablets comprise from 15 to 40 g by weight, more preferably from 20 to 35 g by weight.

The method of washing clothes
The methods used for washing in a washing machine typically include treating the soiled laundry with an aqueous washing solution in a washing machine containing an effective amount of a detergent tablet composition of a machine wash detergent dissolved or dispersed therein in accordance with the invention. An effective amount of a detergent tablet composition is understood to mean from 40 to 300 g of a product dissolved or dispersed in a washing solution with a volume of 5 to 65 liters, which are the usual dosages of the product and the volumes of detergent solutions commonly used in traditional washing machines.

 In a preferred embodiment, a dispenser is used in the washing method. The dispenser is filled with a detergent product and used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its capacity should be such as to be able to accommodate a sufficient amount of detergent product, as should normally be used with the washing method.

 As soon as the washing machine is loaded with laundry, the dispenser containing the washing product is placed inside the drum. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The mechanism of the dispenser should be such that it inhibits the spread of the dry detergent product, but then allows this product to be released during the washing cycle in response to mixing during rotation of the drum, as well as as a result of its contact with washing water.

 To permit the release of the detergent product during washing, the device may have a number of openings through which the product can pass. Alternatively, the device may be made of a material that is permeable to liquid but impermeable to a solid product, which should allow the dissolved product to be released. Preferably, the detergent product is quickly released at the beginning of the washing cycle, thereby providing a temporarily existing high concentration of the product in the drum of the washing machine at this stage of the washing cycle.

 Preferred dispensers are reusable devices and are designed so that the integrity of the container is maintained both in a dry state and during the wash cycle.

 Alternatively, the dispensing device may be a flexible container, such as a bag or bag. The bag may be a fibrous structure coated with a waterproof protective material so as to retain the contents as disclosed in published European patent application 0018678. Alternatively, it may be formed from a water-insoluble synthetic polymer material provided with an edge bond or fastener designed to break into aqueous medium, as disclosed in published European patent applications 0011500, 0011501, 0011502 and 0011968. A suitable form of water-destructible stasis The LCD includes a water-soluble adhesive agent placed along the entire line and gluing one edge of the bag formed of a waterproof polymer film, such as polyethylene or polypropylene.

 The table shows examples of the compositions (in parts by weight) of the detergent tablets of the present invention, which is suitable for use in a dishwashing machine, as well as abbreviations of the components are given (see the end of the text).

Compositions of multiphase tablets are prepared as follows. Phase 1 of the active detergent composition is obtained by mixing granular and liquid components and then placing them in a matrix of a standard rotary press. The press includes a punch that has a suitable shape to form a mold. The cross section of the matrix is approximately 30 x 38 mm. Then the composition is subjected to compression with a compression force of 950 kg / cm ² and the punch is lifted, revealing the first phase of the tablet containing a mold on its upper surface. Phase 2 of the active detergent composition is prepared in a similar manner and placed in a matrix. The active composition containing the particles is then compressed with a compression force of 170 kg / cm ² , the punch is lifted and the multiphase tablet is taken out of the tablet press. The resulting tablets are dissolved or destroyed in a washing machine, as described above, within 12 minutes, and the phase 2 tablets dissolve within 5 minutes. The tablets provide excellent dissolution and washing characteristics along with the proper integrity and strength of the tablets.

Claims (6)

1. A multiphase dishwasher detergent tablet containing a binder, characterized in that the tablet comprises a) a first phase in the form of a shaped body having at least one mold; and b) the second phase in the form of a compressed form contained by adhesion in the specified mold, where the tablet composition includes one or more agents with detergent activity, which are concentrated mainly in the second phase, and where the second phase further includes a binder, the formed body of the first phase is obtained at a compression pressure of at least about 350 kg / cm ² and the second phase is pressed at a pressure of less than about 350 kg / cm ² .  2. A multiphase detergent tablet according to claim 1, characterized in that one or more agents with detergent activity are selected from enzymes, bleaches, bleaching activators, bleaching catalysts, surfactants, chelating agents, crystal growth inhibitors, and mixtures thereof.  3. A multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that the binder is selected from the group consisting of sugar and derivatives of sugar, starch and derivatives of starch, inorganic and organic polymers.  4. A multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that it further comprises a barrier phase between the first and second phases.  5. A multiphase detergent tablet according to claim 4, characterized in that the barrier layer comprises a binder applied in liquid form.  6. A method of washing in a dishwasher, comprising loading the dishwasher with one or more multiphase detergent tablets, characterized in that the multiphase detergent tablets according to any one of the preceding paragraphs are used. Priority on points:
07.17.1998 - pp. 1-4;
05/17/1999 - pp. 5-6.

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