RU2205869C2 - Multi-phase detergent tablet, method for its obtaining and washing method in washer - Google Patents

Abstract

FIELD: detergent products. SUBSTANCE: the suggested detergent tablet contains a) the first phase as a formed body containing, at least, one form; and b) the second phase as solid particles pressed inside the above- mentioned form, moreover, the formed body of the first phase is obtained at pressing pressure being, at least, about 350 kg/sq. cm, as for the second phase it is pressed at the pressure value being not less than about 350 kg/sq. cm. The present innovation provides excellent characteristics of solubility and purifying properties along with high integrity and strength values of the above mentioned detergent tablets. EFFECT: higher efficiency. 14 cl, 1 tbl

Description

Description Scope of the invention
The present invention relates to multiphase detergent tablets.

State of the art
Tablet detergent compositions are well known. It should be understood that detergent compositions in the form of tablets have several advantages compared to detergent compositions in the form of particles (powders), such as ease of dispensing, ease of handling, during transportation and storage.

 Detergent tablets are most often prepared by pre-mixing the components of the detergent composition and forming the pre-mixed detergent components into tablets using any suitable equipment, preferably a tablet press. Tablets are usually formed by compressing the components of the detergent composition, so that the resulting tablets are strong enough to withstand various manipulations and transportation without significant damage. In addition to being strong tablets, they must also dissolve quickly enough so that the detergent components are released into the wash water as quickly as possible at the beginning of the wash cycle.

 However, the problem is that as the compression force increases, the dissolution rate of the tablets decreases. Therefore, the present invention attempts to find a balance between the strength of tablets and their solubility.

 The solution to this problem, as follows from the prior art, includes compression (pressing) of the tablets at low compression pressures. However, the tablets thus obtained, although they have a relatively fast dissolution rate, tend to crumble, becoming damaged and unacceptable to the consumer. Other solutions include preparing tablets using a relatively high compression pressure to achieve the required degree of strength and introducing a dissolving agent such as a blowing agent.

The multiphase detergent tablets previously described are prepared by compressing the first composition in a tablet press to form a substantially flat first layer. The next detergent composition is then placed in a tablet press over the first layer. This second composition is then pressed to form another substantially flat second layer. Thus, the first layer is usually subjected to more than one compression, since it is also pressed during the pressing of the second composition. Typically, the pressure forces during the first and second compression are of the same order of magnitude. The applicant found that in this case, due to the fact that the pressure force must be sufficient to bind the first and second compositions together, the force applied in both the first and second stages of pressing should be in the range from about 4000 to about 20,000 kg (based on the estimated value of the cross-section of the tablet is about 10 cm ² ). The consequence of this is a lower dissolution rate of the tablets. Other multiphase tablets exhibiting different dissolution rates are prepared in such a way that the second layer is pressed at a lower pressure than the first layer. However, although the dissolution rate of the second layer is increased, the second layer is softer than the first layer and therefore is vulnerable to damage caused by further handling and transportation.

 EP-B-0055100 discloses a toilet unit formed by combining a slowly dissolving shaped body with a tablet. The toilet unit is designed to be placed in a toilet bowl where it dissolves within a few days, preferably weeks. As a means to reduce the dissolution rate of the toilet unit, the patent indicates the addition of one or more dissolution rate controlling agents. Examples of such dissolution rate controlling agents are paradichlorobenzene, waxes, long chain fatty acids and alcohols and their esters and fatty alkyl amides. Detergent tablets used in washing or automatic dishwashers should essentially dissolve in a single cycle of operation of the washing or dishwasher, i.e. for 15 to 120 minutes.

SUMMARY OF THE INVENTION
According to a first aspect of the present invention, there is provided a multiphase detergent tablet for use in a washing machine, the tablet comprising:
a) the first phase in the form of a formed body containing at least one shape; and
b) a second phase in the form of solid particles pressed into this mold.

In preferred embodiments, the first phase is a compressed shaped body obtained using a 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 ) and even more preferably from about 400 to about 2000 and especially from about 600 to about 1200 kg / cm ² (the compression pressure is the applied force divided by the cross-sectional area of the tablet in the plane perpendicular to the applied force - actually cross-sectional area of the punch rotary press). It is also preferred that the solid particles of the second phase (this term includes the possibility of numerous "second" phases, sometimes referred to herein as "optionally subsequent phases") be pressed into said shape at an applied compression pressure that is less 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, such tablets being preferred herein from Points of providing optimum tablet integrity and strength (determined, e.g., via test Child Bite Strength [CBS]) and product dissolution characteristics. 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 especially more than about 14 kg, with CBS measured in accordance with the US Consumer Product Safety Commission Test Specification. In addition, the pressing pressures applied to the first and second phases are usually 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 aspect of the present 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 compressed shaped body in which there is at least one shape, the shaped body being obtained at a compression pressure of at least 350 kg / cm ² ; and
b) the second phase in the form of solid particles pressed into the inside of the specified form, and the second phase is pressed at a pressure of less than about 350 kg / cm ² .

 In other preferred embodiments, the second phase is in the form of a compressed or formed body contained by adhesion, for example, by physical or chemical adhesion, within at least one shape of the first body. It is also preferred that the first and second phases are in a relatively high weight ratio to each other, for example at least about 6: 1, preferably at least about 10: 1; and also that the tablet composition contains one or more of the active detergent substances (for example, enzymes, bleaches, bleaching activators, bleaching catalysts, surfactants, chelating agents, etc.) that are concentrated mainly in the second phase, for example, at least about 50%, preferably at least about 60%, especially about 80% by weight of the active substance (based on the total weight of the active substance in the tablet) is in the second phase of the tablet. Again, such compositions are optimal in terms of tablet strength, solubility, washing properties and pH control characteristics, which provides, for example, tablet compositions capable of dissolving in a washing solution so as to isolate at least 50%, preferably at least 60%, and more preferably at least 80 weight. % of the active substance of the detergent in the washing solution for 10, 5, 4 or even 3 minutes, counting from the beginning of the washing process.

Thus, in accordance with a further aspect of the present invention, there is provided a multiphase detergent tablet for use in a washing machine, the tablet comprising:
a) the first phase in the form of a formed body in which there is at least one shape and
b) a second phase in the form of solid particles, pressed into the inside of the specified form, and the tablet contains at least one detergent active substance and is designed in such a way that at least 50%, preferably at least 60%, more preferably, at least 80 wt.% of the detergent active substance enters the washing solution during the first 10 minutes, preferably during the first 5 minutes, and more preferably during the first 3 minutes of the washing process.

 An additional advantage of the invention is the ability to achieve different dissolution of the phases, so that one phase of the tablet will dissolve much earlier than the other phase and may even dissolve essentially completely before the other phase dissolves. This is especially valuable for various delivery of detergent active substances.

Thus, in accordance with another aspect of the invention, there is provided a multiphase detergent tablet comprising:
a) the first phase in the form of a shaped body in which there is at least one shape; and
b) a second phase in the form of a compressed body contained by adhesion within the specified form, wherein said tablet composition contains one or more detergent active substances, which are mainly concentrated in the second phase, and where the second phase further comprises a destructive agent.

In accordance with a further aspect of the present invention, there is provided a multiphase detergent tablet comprising:
a) the first phase in the form of a shaped body in which there is at least one shape and
b) a second phase in the form of a compressed body contained by adhesion within the specified form, wherein said tablet composition contains one or more detergent active substances, which are mainly concentrated in the second phase, and where the second phase further comprises a binder.

Suitably, one or more detergent active agents is selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors, and mixtures thereof, with enzymatic actives being particularly preferred for improving cleaning properties during the initial stage of operations washing or cleaning (in very cold water). Therefore, enzymatic detergent active substances and especially enzymes and enzyme mixtures containing one or more enzymes having an increased or optimal activity in the temperature range of 25 to 55 ^{° C.} and at pH values in the range of 8 to 10 (for example, Natalase).

Thus, in yet another aspect of the present invention, there is provided a multiphase detergent tablet comprising:
a) the first phase in the form of a shaped body in which there is at least one shape; and
b) a second phase, in the form of a compressed body, contained due to adhesion within the specified form, and the specified second phase further comprises an enzyme.

DETAILED DESCRIPTION OF THE INVENTION
The aim of the present invention is the creation of detergent tablets that are not only strong enough to withstand handling and transportation, but also at least a significant portion of which quickly dissolves in washing water, providing fast delivery of detergent active substances. Preferably, at least one phase of the tablet is dissolved in the wash water for the first ten minutes, preferably five minutes, more preferably four minutes of the wash cycle in an automatic dishwasher or washing machine. Preferably, the washer is either an automatic dishwasher or a washing machine. The time period during which the multiphase tablet dissolves, or its phase, or detergent active component, is determined in accordance with DIN 44990 using a Bosch dishwasher according to the normal program for washing at 65 ^o C with a water hardness of 18 ^o N, using a minimum six repetitions or a sufficient number of them to ensure reproducibility.

 The multiphase detergent tablet of the present invention contains a first phase, a second phase 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 modified additive, bleach, enzymes, and a surfactant. The components of the detergent composition are mixed together, for example, by mixing dry components or by spraying liquid components. The components are then molded into the first phase using any suitable equipment, but preferably by compression, for example in a tablet press. Alternatively, the first phase can be obtained by extrusion, casting, etc. The first phase may have various geometric shapes, such as spheres, cubes, etc., but in preferred embodiments it usually has an axially symmetrical shape, usually with a round, square or rectangular cross section.

 The first phase is obtained in such a way that it contains at least one shape in the surface of the molded body. The shape or forms may also vary in size and shape, in their position and orientation, and in topology with respect to the first phase. For example, the shape or shapes may typically have a circular, square or oval cross section; they can form internally closed cavities or depressions in the surface of the molded body, or they can stretch between unconnected portions of the body surface (for example, axially opposite external surfaces), forming one or more topological “holes” in the molded body; and they can be axially or otherwise symmetrically arranged with respect to the first phase, or they can be asymmetrically arranged. In a preferred embodiment, the mold is created using a specially designed tablet press, in which the punch surface that is in contact with the detergent composition is so shaped that when the detergent composition is contacted and pressed, it compresses the mold or multiple forms into the first phase of the multiphase detergent tablet. Preferably, the mold will have an internally concave curved surface or, as a rule, a concave surface to provide improved adhesion to the second phase. Alternatively, the shape can be created by extruding a preformed body of the detergent composition, located annularly around a central punch, thereby forming a body having a cavity shape axially extending axially between opposing body surfaces.

Tablets of the present invention also include one or more additional phases obtained from a composition or compositions that contain one or more detergent components, as will be described below. At least one phase (hereinafter referred to as the second phase) preferably takes the form of solid particles (this term covers powders, granules, agglomerates and other solid particles, including mixtures thereof with liquid binders, fusible solids, sputtering, etc.), pressed inside one or more forms of the first phase of the detergent tablet so that the second phase itself takes the form of a molded body. The optional following phases include one or more compositions in the form of a separate layer or layers. Preferred detergent components include modified additives, dyes, binders, surfactants, disruptive agents and enzymes, in particular amylase and protease enzymes. In another preferred embodiment of the present invention, the second and optionally subsequent phases comprise a destructive agent, which may be selected from either a disintegrator or a blowing agent. Suitable disintegrating agents include agents that swell upon contact with water or facilitate the inflow and / or outflow of water by forming channels in a detergent tablet. For use, any known disintegrating or foaming agents suitable for use in dishwashers or washing machines are considered. Suitable disintegrating agents include starches (such as natural, modified and pregelatinized starches, for example, derived from corn, rice and potato starches), starch derivatives such as U-Sperse (trademark), Primojel (trademark) and Explotab (trademark brand), cellulose, microcrystalline cellulose and cellulose derivatives such as Arbocel (brand) and Vivapur (brand), which are available from Rettenmaier, Nymcel (brand) from Metsa-sere, Avicel (brand). Lattice NT (trademark) and Hanfloc (trademark), alginates, acetate trihydrate, burkeite, monohydrate carbonate of the formula Na ₂ CO ₃ • H ₂ O, hydrated STPP with a phase I content of at least about 40%, carboxymethyl cellulose (CMC ), CMC-based polymers, sodium acetate, alumina. Suitable blowing agents are those which form a gas upon contact with water. Suitable blowing agents may be oxygen, nitrogen dioxide or carbon dioxide releasing compounds. Examples of preferred blowing agents can 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, mixing dry components and mixing or spraying liquid components. Then the components of the second and optionally subsequent phases are placed and stored inside the mold formed by the first phase.

 A preferred embodiment of the present invention includes two phases: a first and a second phase. The first phase will usually contain one form, and the second phase will usually consist of one detergent active composition. However, it is contemplated that the first phase may contain more than one form, and the second phase may be obtained from more than one detergent active composition. In addition, it is also envisaged that the second phase may contain more than one detergent active composition contained in one form. It is also contemplated that several detergent active compositions are contained in separate forms. In this way, the potentially chemically sensitive detergent components can be separated to avoid any loss of performance caused by the components reacting with each other and potentially becoming inactive or spent.

 In a preferred aspect of the present invention, the first, second and / or optionally subsequent phases may contain a binder. In cases where a binder is present, it is selected from the group consisting of organic polymers, for example, polyethylene and / or polypropylene glycols, 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 sugar derivatives, starch and starch derivatives, for example hydroxypropyl methylcellulose (HPMC) and carboxymethyl cellulose (CMC); and inorganic polymers such as hexametaphosphate. A binder is valuable both for the integrity of the tablet and for helping to achieve different dissolution of the first and second phases, as described below.

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

 In another embodiment of the present invention, the barrier layer containing the composition of the barrier layer is located between the first and second phases and / or optionally subsequent phases, or even between the second and optionally subsequent phases. The composition of the barrier layer contains at least one binder selected from the group indicated above. The advantage of having a barrier layer is that it prevents or reduces the migration of components from one phase to another, for example, from the first phase to the second and / or optionally subsequent phases and vice versa.

 The components of the second and optionally subsequent phases are preferably pressed at very low compressive forces compared to the compressive forces that are commonly used to make tablets. Thus, an advantage of the present invention is that due to the use of low compression force, detergent components that are sensitive to heat, pressure or chemical attack can be included in detergent tablets without the risk of subsequent performance degradation, which usually happens when such components are included in tablets. Alternatively, the second phase or phases can be pressed with the same or greater pressure force as the first phase to achieve different phase solubilities, as described below.

 A further advantage of the present invention is the improved protection of the second phase from damage caused, for example, by manipulations and during transportation. As indicated above, multiphase detergent tablets were prepared in which the second layer was pressed at a lower pressure force than the first layer. However, while increasing the dissolution rate, the second layer of such tablets becomes prone to damage and tends to crumble or break upon contact. However, the weakly compressed phase (s) of the detergent tablets of the present invention are protected within the mold provided by the first phase of the detergent tablets.

 Another advantage of the present invention is the possibility of obtaining a multiphase detergent tablet, in which one phase can be created so as to dissolve preferably much earlier than the other phase. In the present invention, it is preferred that the second and optionally subsequent phase (s) dissolve before the first phase. In accordance with the above preferred weight ratios, it is preferred that the first phase dissolves in 5-20 minutes, more preferably 10-15 minutes, and the second and / or optionally subsequent phases dissolve in less than 5 minutes, more preferably in less than 4, 5 minutes and most preferably in less than 4 minutes. Alternatively, the second phase may dissolve after the first or other phases, for example, if it is desired to provide the benefits of cleaning or rinsing closer to the end of the washing process. The time during which the first, second and / or optionally subsequent phase is dissolved does not depend on each other. Thus, in a particularly preferred aspect of the present invention, various phase dissolution is achieved. A particular advantage of the fact that it is possible to achieve different dissolution of a multiphase detergent tablet is that a component that is chemically inactivated due to the presence of another component can be isolated into another phase. In this case, the component that is inactivated is preferably placed in a second and optionally subsequent phase (s).

 Another advantage of the present invention is an improved adhesion between phases of a multiphase tablet. It is believed that improved adhesion is achieved by reducing the openness of the second phase compared to previously known multiphase tablets, which makes the tablets of the present invention less susceptible to disruption along the contact line between the phases.

Way
Multiphase detergent tablets are prepared using any suitable tabletting equipment, such as Courtoy R253. Preferably, tablets are prepared by compression in a tablet press, in which tablets containing a mold can be obtained. In a particularly preferred embodiment of the present invention, the first phase is obtained using a specially designed tablet press by the method described below. The punch (s) of such a tablet press is modified so that the surface of the punch that is in contact with the detergent composition has a convex surface.

The first detergent composition is placed in the matrix of the tablet press and the punch is lowered to touch, and then the detergent composition is pressed to form the first phase. The first detergent composition is pressed using the applied pressure, usually at least about 250 kg / cm ² , preferably from about 350 to about 2000 kg / cm ² , more preferably from about 500 to about 1500 kg / cm ² , most preferably from about 600 to about 1200 kg / cm ² . Then the punch is lifted, revealing the first phase containing the mold. Then a second and optionally subsequent detergent composition (s) are placed in the mold. Then, the punch of the specially designed tablet press is lowered a second time to easily compress the second and optionally subsequent detergent composition (s) to obtain a second and optionally subsequent phase (s). In another embodiment of the present invention, when an optional subsequent phase is present, an optional subsequent phase is obtained at an optional subsequent pressing step substantially similar to the second pressing step described above. The second and optionally subsequent detergent composition (s) are pressed 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 pressing the second detergent composition, the punch is lifted a second time and the multiphase detergent tablet is removed from the tablet press.

 Detergent components.

 The first and second and / or optionally subsequent phases of the multiphase detergent tablet described above are prepared by compressing one or more compositions containing the active components of the detergent. Suitable compositions used in any of these phases may include a number of different detergent components, including modifying compounds, surfactants, enzymes, bleaches, alkalis, colorants, perfumes, lime soap dispersants, organic polymer compounds, including polymeric inhibiting agents dye transfer, crystal growth inhibitors, binding agents of heavy metal ions, metal ion salts, enzyme stabilizers, corrosion inhibitors, foaming suppressants, astvoriteli, fabric softeners, optical brighteners and hydrotropes.

 Particularly preferred components of the first phase detergent include a modifying compound, a surfactant, an enzyme, and a bleach. Particularly preferred second phase detergent components include a modifying compound, enzymes, crystal growth inhibitors and disruptive agents and / or binders.

Modifying compound
The tablets of the present invention preferably contain a modifying compound, which is usually present in an amount of from 1 to 80 wt.%, Preferably from 10 to 70 wt.% And most preferably from 20 to 60 wt.% Of the weight of the composition of the active detergent components.

Water Soluble Modifying Compounds
Suitable water-soluble modifying compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo- or copolymers of 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 foregoing.

 The carboxylate or polycarboxylate modifying component may be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred in terms of cost and performance.

 Suitable carboxylates containing one carboxy group include water-soluble salts of lactic acid, glycolic acid and their ester derivatives. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, but are not limited to, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as carboxymethyloxy succinates disclosed in UK patent 1379241, lactoxysuccinates disclosed in UK patent 1389732, and Dutch patent 58 and hydroxypolycarboxylate materials, such as 2-oxa-1,13-propane tricarboxylate, disclosed in UK patent 1387447.

 Polycarboxylates containing four carboxy groups include the oxide disuccinates disclosed in British Patent 1261829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfosubstituents include sulfosuccinate derivatives disclosed in UK patent 1398421 and 1398422 and US patent 3936448, and sulfonated pyrolytic citrates disclosed in UK patent 1439000.

 Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclo-pentadienide carboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarb-oxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexa-carboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include derivatives of mellitic acid, polymellitic acid and phthalic acid, disclosed in UK patent 1425343.

 Of the above, preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups in the molecule, more particularly citrates.

 Related modifying components may also be used the related acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example citric acid or citrate / citric acid mixtures.

You can also use borate modifying components, as well as modifying components containing borate-forming materials that can form borate under detergent storage conditions or in washing conditions, but it is preferable not to use them in washing conditions at a temperature of less than 50 ^{o C.} , especially less than 40 ^o C.

 Examples of carbonate modifying components are alkali metal and alkaline earth metal carbonates, including sodium carbonate and sesquicarbonate, and mixtures thereof with ultrathin calcium carbonate, as disclosed in German Patent Application 2321001, published November 15, 1973.

 Particularly preferred modifying compounds for use in the present invention are water soluble phosphate modifying compounds. Specific examples of water-soluble phosphate modifying components are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, polymer sodium / phosphate, in which the degree of polymerization is in the range from 6 to 21, and phytic acid salts.

Partially soluble or insoluble modifying compounds
The tablets of the present invention may contain a partially soluble or insoluble modifying compound. Partially soluble and insoluble modifying compounds are particularly suitable for use in tablets obtained for use in cleaning methods for washing. Examples of partially water-soluble modifying compounds include crystalline layered silicates as disclosed, for example, in EPA-A-0164514, DE-A-3417649 and DE-A-3742043. Crystalline layered silicates of the general formula are preferred.
NaMSi _x O _{2x + 1} • yH ₂ O
where M represents sodium or hydrogen, x represents a number from 1.9 to 4, and y represents a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "sheet" structure, such as the so-called δ-layered structure, as disclosed in EP 0164514 and EP 0293640. Methods for producing crystalline layered silicates of this type are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula is 2, 3 or 4, and preferably 2.

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

 The material of the crystalline layered sodium silicate is preferably present in the granular detergent compositions in the form of particles of a hydrogen mixture with a solid water-soluble ionizable material, as disclosed 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 modifying compounds include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites with a unit cell formula
Na _z [(AlO ₂ ) _z (SiO ₂ ) y] • xH ₂ O,
where z and y represent at least 6, the molar ratio of z to y is from 1.0 to 0.5, ax 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 a crystalline material containing from 10 to 28%, more preferably from 18 to 20%, of water in bound form.

 Aluminosilicate zeolites can be natural materials, but preferably they are synthetically prepared. 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 the synthesis of aluminosilicate zeolites is the method described by Schoeman et al. (published in Zeolite (1994) 14 (2), 110-116), where the author discloses a method for producing colloidal aluminosilicate zeolites. The colloidal particles of aluminosilicate zeolites should preferably be such that no more than 5% of the particles have a diameter of more than 1 μm and no more than 5% of the particles have a diameter of less than 0.05 μm. Preferably, the particles of aluminosilicate zeolites have an average diameter of from 0.01 to 1 μm, more preferably from 0.05 to 0.9 μm, and most preferably from 0.1 to 0.6 μm.

Zeolite A has the formula
Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] • xH ₂ O,
where x takes values 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 EP-B-384070, is a preferred zeolite modifying component.

 Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. If used as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide improved modifying characteristics in terms of providing improved stain removal. Improved modifying characteristics are also manifested in terms of reduced crust formation on tissues and improved preservation of whiteness of tissues; problems that are believed to be related to the poor composition of detergent compositions.

 It was unexpectedly found that a mixed aluminosilicate zeolite detergent composition containing colloidal zeolite A and colloidal zeolite Y provides the same binding characteristics of calcium ions in comparison with the equal weight of commercially available zeolite A.

 Surprisingly, it was also found that the mixed aluminosilicate zeolite detergent compositions described above provide improved magnesium ion binding characteristics compared to equal weight characteristics of commercially available zeolite A.

Surfactants
Surfactants are preferred active detergent components of the compositions disclosed herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof. Compositions for automatic dishwashers should have low foaming, and therefore the foaming of a surfactant system for use in dishwashing methods should be suppressed, or more preferably have low foaming. Foaming caused by the surfactant system used in cleaning methods for washing does not need to be suppressed to the same extent as is necessary when washing dishes. Surfactants are usually present in an amount of from 0.2 to 30 weight. %, more preferably from 0.5 to 10 wt.% and most preferably from 1 to 5 wt.% of the composition of the active detergent components.

 A typical listing of the anionic, nonionic, ampholytic and zwitterionic classes and types of these surfactants is given in US Pat. No. 3,929,678 issued to Lauhlin and Heurng on December 30, 1975. A list of suitable cationic surfactants is given in US Pat. No. 4,259,217 to Murphy on March 31, 1981. A list of surfactants commonly included in detergent compositions for automatic dishwashers is provided, for example, in EP-A-0414549 and PCT applications WO 93/08876 and WO 93/08874.

 Nonionic surfactants.

 Essentially any non-ionic surfactants suitable for washing purposes can be included in detergent tablets. Preferred non-limiting classes of suitable nonionic surfactants are listed below.

 Non-ionic surfactants based on ethoxylated alcohol.

 For use in the present invention, alkyl ethoxylate condensation products of aliphatic alcohols with 1-25 mol of ethylene oxide are suitable. The alkyl chain of an aliphatic alcohol can be either unbranched or branched, primary or secondary and, as a rule, contains from 6 to 22 carbon atoms. Especially preferred are the condensation products of alcohols, the alkyl group of which contains from 8 to 20 carbon atoms with 2-10 moles of ethylene oxide per mole of alcohol.

Functional End-Alkyl Alkoxylate Surfactants
Suitable alkyl end-functional surfactants with functional end groups are poly (oxyalkylated) alcohols with epoxy end groups 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 containing from 4 to 18 carbon atoms; R ₂ represents a linear or branched aliphatic hydrocarbon radical containing from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably 1; and y represents an integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I contains at least 10 carbon atoms in the terminal epoxy moiety [CH ₂ CH (OH) R ₂ ]. Suitable surfactants of formula (I) according to the present invention are nonionic surfactants ^{Olin Corporation's POLY-TERGENT ® SLF} -18B, as disclosed, e.g., in WO 94/22800, published October 13, 1994 Olin Corporation.

Poly (oxyalkylated) esters with ether terminal groups
Preferred surfactants for use in the present invention include poly (oxyalkylated) esters with ester terminal groups of 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 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals containing from 1 to 30 carbon atoms; R ³ represents H or a linear aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms; x represents an integer having an average value of from 1 to 30, wherein if x = 2 or more, R ³ may be the same or different; k and j are integers taking average values from 1 to 12, and more preferably from 1 to 5.

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

As indicated above, if in preferred embodiments of the present invention x ≥ 2, R ³ may be the same or different. That is, R ³ may vary between any of the alkyleneoxy units mentioned above. For example, if x = 3, R ³ can be chosen to form ethyleneoxy (EO) or propyleneoxy (PO), and can be changed in the order of (EO) (PO) (EO), (EO) (EO) (PO) ; (EO) (EO) (EO); (RO) (EO) (RO); (RO) (RO) (EO) and (RO) (RO) (RO). Naturally, the integer 3 is chosen only as an example, and there may be much more options with higher integer values for x, and include, for example, a plurality of (EO) units and a much smaller number (PO) of units.

Most preferred surfactants, as described above, include those with a cloud point below 20 ^° C. Such low cloud point surfactants can then be used with high cloud point surfactants, as described in detail below. , to improve fat removal.

The most preferred poly (oxyalkylated) alcohol surfactants with ester end groups are those in which k = 1 and j = 1, so that such surfactants have the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²
where R ¹ , R ² and R ³ have the above meanings, x represents an integer with 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 take values from 9 to 14, R ³ represents H forming ethyleneoxy, and x takes values from 6 to 15.

 The ether-terminated poly (oxyalkylated) alcohol surfactants comprise three main components, namely, linear or branched alcohol, alkylene oxide and terminal alkyl ether. The terminal alkyl ether and alcohol serve as the hydrophobic, oil-soluble part of the molecule, while the alkylene oxide group forms the hydrophilic, water-soluble part of the molecule.

 Such surfactants show significant improvements in stain and film removal and grease removal characteristics when used together with high cloud point surfactants compared to conventional surfactants.

Generally speaking, poly (oxyalkylene) alcohol surfactants with ester terminal groups of the present invention can be prepared by reacting an aliphatic alcohol with an epoxide to produce an ester, which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to give the new compounds of the present invention. The following are examples of methods for producing surfactants based on poly (oxyalkylene) alcohols with ether end groups:
Getting C _12/14 alkyl glycidyl ether
C _12/14 fatty alcohol (100 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol from Aldrich) are combined in a 500 ml three-necked round-bottom flask equipped with a refrigerator, an argon inlet opening, and a droplet funnel, magnetic stirrer and internal temperature probe. This mixture was heated to 60 ^° C., epichlorohydrin (47.70 g, 0.515 mol from Aldrich) was added dropwise so as to maintain a temperature of 60 to 65 ^° C. After stirring for an additional hour at 60 ^{° C., the} mixture was cooled to room temperature. temperature. The mixture is 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 resulting filtrate was isolated and the organic phase was washed with water (100 ml), dried over magnesium sulfate, filtered and concentrated. As a result of the distillation of the oil at 100-120 ^o C (0.1 mm RT.article) get glycidyl ether in the form of oil.

Obtaining a surfactant based on alcohol with a terminal C _12/14 alkyl-C _9/11 ether group
Neodol ^(R) 91-8 (20.6 g, 0.0393 mol ethoxylated alcohol from Shell chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) are combined in a 250 ml three-necked round bottom flask equipped with a refrigerator, an argon inlet opening, a dropping funnel, a magnetic stirrer and an internal temperature probe. This mixture was heated to 60 ^° C and at this moment C _12/14 alkyl glycidyl ether (11.0 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 amount of dichloromethane. The solution was passed through a silica gel layer of 2.54 cm, eluting with dichloromethane. The filtrate was concentrated in a rotary evaporator and then distilled off in a round-bottom furnace (100 ^{° C.} , 0.5 mm Hg) to give a surfactant in the form of an oil.

 Non-ionic surfactant based on ethoxylated / -propoxylated fatty alcohol.

Ethoxylated C ₆ -C ₁₈ fatty alcohols and C ₆ -C ₁₈ mixed ethoxylated / propoxylated fatty alcohols are suitable surfactants for use in the present invention, especially if they are soluble in water.

Preferred ethoxylated fatty alcohols are C ₁₀ -C ₁₈ ethoxylated fatty alcohols with an ethoxylation degree of 3 to 50, most preferably C ₁₂ -C ₁₈ ethoxylated fatty alcohols with an ethoxylation degree of 3 to 40. Preferably, the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length from 10 to 18 carbon atoms, the degree of ethoxylation from 3 to 30 and the degree of propoxylation from 1 to 10.

 Nonionic EO / PO condensates with propylene glycol.

The hydrophobic base ethylene oxide condensation products resulting from the condensation of propylene oxide with propylene glycol are suitable for use in accordance with the present invention. The hydrophobic part of such compounds preferably has a molecular weight of from 1500 to 1800 and is not soluble in water. Examples of compounds of this type include some commercially available Pluronic ^™ surfactants sold by BASF.

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

The condensation products of ethylene oxide with products obtained by the reaction of propylene oxide and ethylene diamine are suitable for use in the present invention. The hydrophobic moiety of these products consists of the reaction product of ethylene diamine and excess propylene oxide and usually has a molecular weight of from 2500 to 3000. Examples of non-ionic surfactants of this type include some commercially available Tetronic ^™ compounds sold by BASF.

Mixed nonionic surfactant system
In a preferred embodiment of the present invention, the detergent tablets comprise a mixed nonionic surfactant system 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", as used in the description, is a well-known property of non-ionic surfactants, resulting from the fact that surfactants become less soluble with increasing temperature, and the temperature at which the appearance of the second phase is observed , called the "cloud point" (See Kirk Othmer's Encyclopedia of Chtmical Technology, 3 ^rd Ed. Vol. 22, pp. 360-379).

As used herein, a “low cloud point” non-ionic surfactant is defined as an ingredient in a non-ionic surfactant system with a cloud point below 30 ^{° C.} , preferably below 20 ^{° C.} and more preferably below 10 ^° C. Typical nonionic surfactants low cloud point actives include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) inverted block olimers. Further, such low-cloud point nonionic surfactants include, for example, ethoxylated / propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent ^® SLF18), poly (oxyalkylated) epoxy terminal alcohols (e.g., Olin Corporation's Poly-Tergent ^® SLF18B series of non-ionic surfactants in-in, as disclosed, for example, in WO 94/22800, published October 13, 1994 Olin Corporation) and surfactants based on poly (oxyalkylated) alcohol with ether terminal groups.

 Nonionic surfactants may optionally contain propylene oxide in an amount up to 15 wt.%. Other preferred non-ionic surfactants can be obtained by the methods disclosed in US patent 4223163, issued September 16, 1980, Builloty (included in the description by reference).

Low cloud point nonionic surfactants further include polyoxyethylene / polyoxypropylene block polymeric compounds. Block polyoxyethylene / polyoxypropylene polymer compounds include polymers based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as the active hydrogen initiating compound. Some block polymer surfactant compounds designated PLURONIC ^®, REVERSED PLURONIC ^® and TETRONIC ^® from BASF-Wyandotte Corp., Wyandotte, Michidan , suitable for ADD (automatic dishwashing detergent for the machine) of the compositions of the present invention. Preferred examples include REVERSED PLURONIC ^® 25R2 and TETRONIC ^® 702. Such surfactants are commonly used here as non-ionic surfactants with a low cloud point.

As used herein, a “high cloud point” non-ionic surfactant is defined as an ingredient in a non-ionic surfactant system with a cloud point above 40 ^{° C.} , preferably above 50 ^{° C.} and more preferably above 60 ^° C. Preferably, the nonionic surfactant system -active substance includes an ethoxylated surfactant obtained by reacting monohydroxy alcohol or alkyl phenol containing from 8 to 20 carbon atoms with 6-15 mol of ethylene oxide per mole alcohol or alkyl phenol based on the average. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (from Union Carbide), Rhodasurf TMD 8.5 (from Rhone Poulenc), and Neodol 91-8 (from Shell).

 For the purposes of the present invention, it is also preferable that the non-ionic surfactants with a high cloud point additionally have a hydrophilic-lipophilic balance value ("HLB"; see Kirk Othmer previously) in the range from 9 to 15, preferably from 11 to 15. Such materials include, for example, Tergitol 15S9 from Union Carbide), Rhodasurf TMD 8.5 (from Rhone Poulenc) and Neodol 91-8 (from Shell).

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

 Anionic surfactants.

 Almost any anionic surfactants suitable for washing purposes are suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and tri-ethanolamine 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, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinates monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), especially sulfosuccinates diesters saturated and unsaturated 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 that are present in or derived from tall oil are also suitable.

Anionic Sulfate Surfactants
Anionic sulfate surfactants suitable for use in the present invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide sulfates, C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) and N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfates, and alkyl polysaccharide sulfates such as alkyl polyglucoside sulfates (non-ionic non-sulfated compounds disclosed herein).

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

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

 In a most preferred aspect of the present 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 Surfactants
Anionic sulfonate surfactants suitable for use in the present invention include salts of C ₅ -C ₂₀ linear alkyl benzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Anionic Carboxylate Surfactants
Anionic carboxylate surfactants suitable for the purposes of the present invention include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"), especially some secondary soaps, as disclosed herein.

Suitable alkyl ethoxy carboxylates include compounds of the formula RO (CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , where R is a C ₆ -C ₁₈ alkyl group, x ranges from 0 to 10, and the distribution of ethoxylate is such that it is calculated by weight, the amount of material in which x = 0 is less than 20% and M represents a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include compounds of the formula RO- (CHR ₁ —CHR ₂ —O) —R ₃ where R is 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, methyl acyl 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 containing from 1 to 8 carbon atoms, and mixtures thereof.

 Suitable soap-based surfactants include secondary soap-based surfactants that contain a carboxy moiety attached to the secondary carbon. Preferred secondary soap surfactants for use in the present invention are water-soluble compounds 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. Some soaps may also be included as anti-foaming agents.

 Surfactants based on alkali metal sarcosinates.

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 alkyl group, and M represents an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactants
Suitable amphoteric surfactants for use in the present invention include amine oxide surfactants and alkyl amphocarboxylic acids.

где R³ выбирают из алкильной, гидроксиалкильной, ациламидопропильной и алкилфенильной групп, или их смесей, содержащих от 8 до 26 атомов углерода; R⁴ представляет алкиленовую или гидроксиалкиленовую группу, содержащую от 2 до 3 атомов углерода, или их смеси; х принимает значения от 0 до 5, предпочтительно от 0 до 3; каждый R⁵ представляет алкильную или гидроксиалкильную группу, содержащую от 1 до 3 атомов углерода, или полиэтиленоксидную группу, содержащую от 1 до 3 этиленоксидных групп. Предпочтительны С₁₀-C₁₈ алкил диметиламиноксид и С₁₀-C₁₈ ациламидо алкил диметиламиноксид.Suitable amine oxides include compounds of the formula

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

 A suitable example of alkyl amphodicarboxylic acid is Miranol (TM) C2M Cone manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactants
Zwitterionic surfactants may also be included in the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants for use in the present invention are betaine and sultaine surfactants.

Suitable betaines are compounds of the formula R (R ') ₂ N ⁺ R ² COO ^- wherein R is a C ₆ -C ₁₈ hydrocarbyl group, each R ¹ is usually a C ₁ -C ₃ alkyl, and R ² is a C ₁ -C ₅ hydrocarbyl group. Preferred betaines are C ₁₂ -C ₁₈ dimethylammonio hexanoate and C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants can also be used.

Cationic Surfactants
The cationic ester surfactants used in the present invention are preferably water-dispersible compounds having surface-active properties, including at least one ester (i.e., -COO-) bond and at least one cationically charged group. Other suitable cationic ester surfactants, including choline ester surfactants, for example, are disclosed in US patents 4228042, 4239660 and 4260529.

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

Enzymes
Enzymes are preferred detergent components of the first phase and especially the second and / or optionally subsequent phases. If present, 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, ligna tannase, pentosanase, malanase, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccase or mixtures thereof.

 Preferred enzymes include proteases, amylases, lipases, peroxidases, cutinases and / or cellulases together with one or more enzymes that destroy the cell wall of plants.

 Cellulases suitable for the purposes of the present invention include both bacterial cellulases and fungal cellulases. Preferably, they have an optimum pH of 5 to 12 and activity above 50 CEVU (Cellulose Viscosity Unit = cellulose viscosity unit). Suitable cellulases are disclosed in US Pat. Nos. 4,435,307, Barbesgoard et al., J 61078384 and WO 96/02653, in which fungal cellulases obtained from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively, are disclosed. EP 739982 discloses 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), especially Humicola strain DSM 1800. Other suitable cellulases are cellulases derived from Humicola insolens with a molecular weight of 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; and ~ 43 kDa endoglucanase obtained from Humicola insolens, DSM 1800 showing cellulase activity; the preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO 91/17243. Also suitable cellulases are EGIII cellulases from Trichoderma longibrachiatum, disclosed in WO 94/21801, Genencor, published September 29, 1994. Cellulases having a color retention property are particularly suitable. Examples of such cellulases are cellulases described in European Patent Application 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are particularly suitable. See also WO 91/17244 and WO 91/21801. Other suitable cellulases having tissue stain and / or cleansing properties are disclosed in WO 96/34092, WO 96/17994 and WO 95/24471.

 These cellulases are usually included in detergent compositions 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, such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used to "bleach in solution", that is, to prevent the transfer of dyes or pigments removed from the substrates during washing to other substrates in the washing solution. Peroxidase enzymes are known to those skilled in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chloro and bromoperoxidases. Detergent compositions containing peroxidases are disclosed, for example, in PCT international application WO 89/099813, WO 89/09813, and in EP 91202882.6, filed November 6, 1991 and EP 96870013.8, filed February 20, 1996. Laccase enzyme can also be used.

Preferred enhancing agents are substituted phenyazine and phenoxazine 10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-methylphenoxazine (disclosed in WO 94/12621) and substituted (C ₃ -C ₅ substituted alkyl syringates) and phenols. A preferred source of hydrogen peroxide is sodium 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 for detergent use include enzymes produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in UK patent 1372034. Suitable lipases include those that exhibit a positive immunological cross-reaction with the lipid antibody produced by microcentonomas Pomeudomonas p. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipase P "Amano," hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, ex Chromobacker viscosum lipases, e.g. 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 ex Pseudomonas gladioli lipases. Particularly suitable lipases are lipases such as Ml Lirase ^R and Lipomax ^R (Gist-Brocades) and Lipolase ^R and Lipolase Ultra "(Novo), which, as it turned out, are very effective when used in combination with the compositions of the present invention. You can also use lipolytic enzymes disclosed in EP 258068, WO 92/05249 and WO 95/22615 Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 Unilever.

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

 Lipases and / or cutinases are 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.

Suitable proteases are subtilisins, which are obtained from specific strains of B. subtllls and B. licheniformis (subtilisin BPN and BPN '). One suitable protease is obtained from a strain of Bacillus, having maximum activity in the pH range of 8-12, developed and sold as ^{ESPERASE ® Novo Industries A / S of} Denmark, hereinafter as "Novo". The preparation of this enzyme and similar enzymes is disclosed in GB 1243784 Novo. Other suitable proteases include KANNASE ^®, ALCALASE ^®, DURAZYM ^® and SAVINASE ^® from Novo and MAXATASE ^®, MAXACAL ^®, PROPERASE ^® and MAXAPEM ^® (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application 87303761.8, filed on April 28, 1987 (in particular p. 17, 24 and 98) and which are referred to herein as “Protease B” and in the European Patent application 199404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, which is here called "protease A". Also suitable is one called “protease C” which is a variant of the alkaline serine protease from Bacillus, in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, series replaces asparagine at position 123 and alanine replaces threonine at position 274 Protease C is disclosed in EP 90915958: 4, which corresponds to WO 91/06637 published May 16, 1991. Genetically modified variants are also included, especially proteases C.

A preferred protease called “protease D” is a carbonyl hydrolase variant whose amino acid sequence is not found in nature and which is derived from a carbonyl hydrolase precursor by substituting for various amino acids a plurality of amino acid residues at a position in 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 Bacillus amyloliquefaciens subtilisin, as disclosed in WO 95/10591 and in patent application C. Ghosh, et al., "Bleaching Compositions Comprising Protease Enzymes" 08/322677, filed October 13, 1994. The proteases disclosed in patent applications EP 251446 and WO 91 are also suitable for the purposes of the present invention. / 06637, protease BLAP ^® disclosed in WO 91/02792, and variants thereof are disclosed in WO 95/23221. See also high pH protease from Bacillus sp. NCIMB 40338 disclosed in WO 93/18140 A, Novo. Enzymatic detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are disclosed in WO 92/03529 A, Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available, as disclosed in WO 95/07791, Procter & Gamble. Recombinant trypsin-like detergent protease suitable for use in the present invention is disclosed in WO 94/25583, Novo. Other suitable proteases are disclosed in EP 516200, Unilever.

 Other preferred protease enzymes include protease enzymes, which are carbonyl hydrolase variants whose amino acid sequence is not found in nature and which are obtained by replacing the multiple amino acid residues of the carbonyl hydrolase precursor with different amino acids, where the specified many amino acid residues substituted in the enzyme precursor correspond to the + 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, +1 35, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the position numbering corresponds to the natural subtilisin from Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those in which substitutions have occurred 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 of carbohydrate origin. WO 94/02597, Novo Nordisk A / S, published February 03, 1994, discloses a cleaning composition that includes mutant amylases. See also WO 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-amylases are known to those skilled 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 UK Patent Application 1296839 (Novo). Other suitable amylases are stability enhancing amylases disclosed in WO 94/18314, published August 18, 1994 and WO 96/05295, Genencor, published February 22, 1996, and amylase variants having an additional modification in the starting material directly available from Novo Nordisk A / S disclosed in WO 95/10603 published in April 1995. Amylases disclosed by EP 277216, WO 95/26397 and WO 96/23873 (all Novo Nordisk) are also suitable.

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

 Preferred amylase enzymes include those disclosed in WO 95/26397 and in the pending application Novo Nordisk PCT / DK 96/00056.

 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 specific preferred embodiment, the detergent tablets of the present invention include amylase enzymes, in particular those disclosed in WO 95/26397 and in the pending application Novo Nordisk PCT / DK 96/00056 in combination with complementary amylase.

By the term “complementary” is meant the addition of one or more amylases suitable for washing purposes. Examples of complementary amylases (α and / or β) are disclosed below. WO 94/02597 and WO 95/10603, Novo Nordisk A / S disclose cleaning compositions that include mutant amylases. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-amylases are known to those skilled 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 stability enhancing amylases disclosed in WO 94/18314, and WO 96/05295, Genencor, and amylase variants with further modification in the starting material directly available from Novo Nordisk A / S disclosed in WO 95/10603. Amylases disclosed in EP 277216 (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 available from Novo Nordisk A / S Denmark. Other suitable amylases are disclosed in 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 of 25-55 ^{° C.} , and at a pH in the range of 8 to 10 measured by analysis of the α-amylase activity of Phadebas ^® . Variants of the above enzymes disclosed in WO 96/23873 (Novo Nordisk) are also suitable. Other amylolytic enzymes with improved characteristics in terms of activity level and a combination of thermal stability and higher activity level are disclosed in WO 95/35382. Preferred complementary amylases for the purposes of the present invention are amylases sold under the trademark Purafect Ox Am ^R , disclosed in WO 94/18314, WO 96/05295 and supplied by Genencor; Termarnyl ^® , Fungarnyl ^® , Ban ^® Natalase and Duramyi ^® are all available from Novo Nordisk A / S and Maxamyl ^® from Gist-Brocades.

 Said complementary amylases are usually included in detergent compositions in an amount of from 0.0001 to 2%, preferably from 0.00018 to 0.06%, more preferably from 0.00024 to 0.48% of the pure enzyme by weight of the composition. Preferably, the weight ratio of the pure specific amylase enzyme to the complementary amylase is from 9: 1 to 1: 9, more preferably from 4: 1 to 1: 4, and most preferably from 2: 1 to 1: 2.

 The above enzymes can be of any suitable origin, such as plant, animal, bacterial, fungal origin, or from yeast. The source may be additionally mesophilic or extremophilic (psychrophilic, psychrotropic, thermophilic, barophilic, alkaline, acidophilic, halophilic, etc.). You can use purified or unrefined forms of these enzymes, as well as mutants of natural enzymes. Mutants can be obtained, for example, as a result of protein and / or genetic engineering, as a result of chemical and / or physical modifications of natural enzymes. It is also common practice to express the enzyme at the expense of the host organisms into which the genetic material responsible for the production 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. These enzymes can be added as individual single ingredients (granules, granules, stabilized liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (e.g. co-granules).

 Other suitable detergent ingredients that can be added are enzymatic oxidative acceptors, which are disclosed in co-pending EP 92870018.6, filed January 31, 1992. Examples of such enzymatic oxidative acceptors are ethoxylated tetraethylene polyamines.

 A wide range of enzyme materials and means for incorporating them into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A Genencor International, WO 8908694 A Novo, and in US patent 3,553139 of January 5, 1971 McCarty et al. Enzymes are further disclosed in US Pat. Nos. 4,101,457, Place et al., July 18, 1978, and 4,507,219, Hughes, March 26, 1985. Enzyme materials suitable for liquid detergent compositions and methods for incorporating them into such compositions are disclosed in US Pat. No. 4,261,868, Leg. et al. April 14, 1981. Enzymes for use in detergents can be stabilized in various ways. Methods for stabilizing enzymes are disclosed, for example, in US Pat. No. 3,600,319, August 17, 1971, Gedge et al., In EP 199405 and EP 200586, October 29, 1986, Venegas. Enzyme stabilizing systems are also disclosed, for example, in US Pat. No. 3,519,570. Suitable Bacillus, sp. AC 13 producing proteases, xylanases and cellulases are disclosed in WO 9401532 A, Novo.

 Bleaching agents.

 A highly preferred component composition of detergent components is a whitening agent. Suitable whitening agents include chlorine and oxygen releasing whitening agents.

 In one preferred aspect, the oxygen-releasing whitening agents comprise a hydrogen peroxide source and an organic peroxy acid precursor whitening compound. The formation of organic peroxyacid occurs as a result of the in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred aspect, the preformed organic peroxy acid is included directly in the composition. Compositions containing mixtures of a source of hydrogen peroxide and a precursor of organic peroxyacid in combination with a preformed organic peroxyacid are also possible.

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

 Inorganic perhydrate salts are usually included 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 even more 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. Inorganic perhydrate salts may be included as crystalline solids without additional protection. However, for some perhydrate salts, preferred embodiments of such granular compositions use the form of a coated material, which provides us with better storage stability for the perhydrate salt in the granular product.

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

Alkali metal percarbonates, in particular sodium percarbonate, are preferred perhydrates for inclusion in the compositions of the present invention. Sodium percarbonate is an additional compound of the formula which corresponds to 2Na ₂ CO _s • 3H ₂ O _2, and is available commercially as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound, tends to dissolve with fairly rapid evolution of hydrogen peroxide, which may increase the tendency for localized high bleach concentrations to occur. Percarbonate is most preferably included in such compositions in a coated form that provides stability in the product.

Suitable coating material for stability in the product includes a mixed salt of water-soluble sulfate and alkali metal carbonate. Such coatings along with processes for their application were previously disclosed in GB Patent GB-1466799, issued March 9, 1977, Infcerox. The weight ratio of the coating material of the mixed salt to percarbonate ranges from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt consists of sodium sulfate and sodium carbonate of the general formula Na ₂ SO ₄ • n • Na ₂ CO ₃ , where n is from 0.1 to 3, preferably from 0.3 to 1.0, and most preferably from 0, 2 to 0.5.

Another suitable coating material for stability in the product includes sodium silicate with a SiO ₂ : Na ₂ O ratio of from 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably used in an amount of from 2 to 10% (usually from 3 to 5%) of SiO _{2 by} weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganic substances can also be used.

 In the framework of the present invention, other coatings that contain waxes, oils, and oily soaps can also be successfully used.

 Another inorganic perhydrate salt that may find application in the compositions of the present invention is potassium peroxymonopersulfate.

 Peroxyacid whitening precursors.

где L представляет уходящую группу, и Х представляет по существу любую функциональность, так что после пергидролиза структура полученной пероксикислоты оказывается

Пероксикислотные отбеливающие соединения-предшественники предпочтительно включают в количестве от 0,5 до 20 вес.%, более предпочтительно от 1 до 10 вес.% и наиболее предпочтительно от 1,5 до 5 вес.% композиции.Peroxyacid whitening precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form peroxyacid. Typically, a peroxyacid whitening precursor can be represented as

where L represents a leaving group, and X represents essentially any functionality, so that after perhydrolysis, the structure of the obtained peroxyacid is

Peroxyacid whitening precursor compounds preferably include in an amount of from 0.5 to 20 wt.%, More preferably from 1 to 10 wt.% And most preferably from 1.5 to 5 wt.% Of the composition.

 Suitable peroxyacid whitening precursor compounds typically contain one or more N- or O-acyl groups, and the precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, 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, 1147871, 2143231 and EP-A-0170386.

Outgoing groups
The leaving group, hereinafter the L group, must be sufficiently reactive so that the perhydrolysis reaction proceeds in an optimal time period (for example, during the washing cycle). However, if L is too reactive, such an activator will be difficult to stabilize for use in the whitening composition.

и их смесей, где R¹ представляет алкильную, арильную или алкарильную группу, содержащую от 1 до 14 атомов углерода, R³ представляет алкильную цепочку, содержащую от 1 до 8 атомов углерода, R⁴ представляет Н или R³, R⁵ представляет алкенильную цепочку, содержащую от 1 до 8 атомов углерода, и Y представляет Н или солюбилизирующую группу. Любые из R¹, R³ и R⁴ могут быть замещены по существу любыми функциональными группами, включая, например, алкильную, гидрокси, алкокси, галоген, амин, нитрозильную, амидную и аммонийную или алкиламмонийную группы. Предпочтительными солюбилизирующими группами являются -SO₃ ^-M⁺, -СО₂ ^-M⁺, -SO₄ ^-М⁺ -N⁺(R³)₄X^- и O<--N(R³)₃ и наиболее предпочтительно -SO₃ ^-M⁺ и -СО₂ ^-М⁺, где R³ представляет алкильную цепочку, содержащую от 1 до 4 атомов углерода, М представляет катион, который обеспечивает растворимость активатора отбеливания, а Х представляет анион, который обеспечивает растворимость активатора отбеливания. Предпочтительно М представляет катион щелочного металла, аммония или замещенного аммония, причем наиболее предпочтительны натрий и калий, а Х представляет галогенид, гидроксид, метилсульфатный или ацетатный анион.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 groups, including, for example, alkyl, hydroxy, alkoxy, 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 preferably -SO ₃ ^- M ⁺ and —CO ₂ ^- M ⁺ , where R ³ represents an alkyl chain containing from 1 to 4 carbon atoms, M represents a cation that provides the solubility of the bleach activator, and X represents the anion that provides the solubility of the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid during perhydrolysis.

Пригодны также продукты бензоилирования сорбита, глюкозы и всех сахаридов агентами бензоилирования, включая, например:

Ас=СОСН₃; Bz=бензоил
Предшественники пербензойной кислоты имидного типа включают N-бензоил сукцинимид, тетрабензоил этилендиамин и N-бензоил замещенные мочевины. Подходящие предшественники пербензойной кислоты имидазольного типа включают N-бензоил имидазол и N-бензоил бензимидазол, а другие подходящие предшественники пербензойной кислоты, содержащие N-ацильную группу, включают N-бензоил пирролидон, дибензоил таурин и бензоил пироглутамовую кислоту.A suitable precursor of O-acylated perbenzoic acid includes substituted and unsubstituted benzoyl hydroxybenzenesulfonates, including, for example, benzoyl hydroxybenzenesulfonate:

Benzoylation products of sorbitol, glucose and all saccharides with benzoylation agents are also suitable, including, for example:

Ac = COSH ₃ ; Bz = benzoyl
Imide-type perbenzoic acid precursors include N-benzoyl succinimide, tetrabenzoyl ethylenediamine and N-benzoyl substituted urea. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole, and other suitable N-acyl group containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Фталевый ангидрид является еще одним подходящим предшественником пербензойной кислоты для настоящего изобретения:

Подходящие предшественники N-ацилированной лактам пербензойной кислоты имеют формулу

где n принимает значения от 0 до 8, предпочтительно от 0 до 2, a R⁶ представляет бензоильную группу.Other perbenzoic acid precursors include benzoyl diacyl peroxides, benzoyl tetraacyl peroxides and compounds of the formula

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

Suitable precursors of N-acylated lactam perbenzoic acid have the formula

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

 Perbenzoic acid derivative precursors.

 Perbenzoic acid derivative precursors provide protective perbenzoic acids during hydrolysis. Suitable precursors of substituted perbenzoic acid derivatives include any of the perbenzoic acid precursors disclosed herein in which the benzoyl group is substituted by essentially any non-positively charged (i.e., non-cationic) functional group, including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.

или

где R¹ представляет арильную или алкарильную группу, содержащую от 1 до 14 атомов углерода, R² представляет ариленовую или алкариленовую группу, содержащую от 1 до 14 атомов углерода, а R⁵ представляет Н или алкильную, арильную или алкарильную группу, содержащую от 1 до 10 атомов углерода, и L может быть по существу любой уходящей группой. R предпочтительно содержит от 6 до 12 атомов углерода, R² предпочтительно содержит от 4 до 8 атомов углерода. R¹ может быть арилом, замещенным арилом или алкиларилом, содержащим разветвление, замещение или то и другое, и может быть получен либо из синтетических источников либо из природных источников, включая, например, талловый жир. Аналогичные структурные варианты допустимы для R². Замещение могут включать алкил, арил, галоген, азот, серу и другие типичные замещающие группы или органические соединения. R⁵ предпочтительно представляет Н или метил. R¹ и R⁵ не должны содержать более чем 18 атомов углерода в сумме. Амидзамещенные активаторы отбеливания такого типа раскрыты в ЕР-А-0170386.A preferred class of substituted perbenzoic acid precursors are amide substituted compounds of the following general formulas:

or

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, and R ⁵ represents H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms, and L may be essentially any leaving group. R 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 alkylaryl containing branching, substitution, or both, and may be obtained either from synthetic sources or from natural sources, including, for example, tall oil. Similar structural options are valid 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 should not contain more than 18 carbon atoms in total. Amide substituted bleach activators of this type are disclosed in EP-A-0170386.

 Cationic peroxyacid precursors.

 Cationic peroxyacid precursors provide cationic peroxyacids during perhydrolysis.

 Typically, cationic peroxyacid precursors are formed by replacing the peroxyacid moiety of a suitable peroxyacid precursor with a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in the compositions in the form of salts with a suitable anion, such as, for example, a halide ion or methyl sulfate ion.

 The precursors of peroxyacids to be cationically substituted may be precursors of perbenzoic acid or its substituted derivatives, as described above. Alternatively, the peroxy acid precursor compound may be an alkyl percarboxylic acid precursor or an amide substituted precursor of an alkyl peroxy acid precursor, as described below.

 Cationic peroxyacid precursors are disclosed in US patent 4904406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5127852; 5093022; 5,106,528; in UK patent 1382594; in EP 475512; 458396 and 284292 and in JP 87-318332.

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

Предпочтительный катионно замещенный алкил оксибензол сульфонат имеет формулу:

Предпочтительные катионные пероксикислотные предшественники класса N-ацилированных капролактамов включают триалкил аммоний метилен бензоил капролактамы, особенно триметил аммоний метилен бензоил капролактам

Другие предпочтительные катионные предшественники пероксикислот класса N-ацилированных капролактамов включают триалкил аммоний метилен алкил капролактамы

где n принимает значения от 0 до 12, особенно от 1 до 5.A preferred cationically substituted benzoyl hydroxybenzene sulfonate is 4- (trimethylammonium) methyl derivative of benzoyl hydroxybenzene sulfonate

A preferred cationically substituted alkyl hydroxybenzene sulfonate has the formula:

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

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

where n takes values from 0 to 12, especially from 1 to 5.

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

Alkyl Percarboxylic Acid Whitening Precursors
Alkyl percarboxylic acid bleaching precursors form percarboxylic acids upon perhydrolysis. Preferred precursors of this type provide peracetic acid during perhydrolysis.

Preferred imide type alkylpercarboxylic acid precursor compounds include N, N, N ¹ , N ¹ tetraacetylated alkylenediamines 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. Most preferred is tetraacetyl ethylenediamine (TAED).

 Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (ISO-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

или

где R¹ представляет алкильную группу, содержащую от 1 до 14 атомов углерода, R² представляет алкиленовую группу, содержащую от 1 до 14 атомов углерода, R⁵ представляет 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 неразветвленным или разветвленным алкилом, содержащим разветвление, замещение или и то и другое, и может быть получен либо из синтетических источников либо из природных источников, включая например, талловый жир. Аналогичные структурные варианты допустимы для R². Замещение может включать алкил, галоген, азот, серу и другие типичные замещающие группы или органические соединения. R⁵ предпочтительно представляет Н или метил. R¹ и R⁵ не должны содержать более чем 18 атомов углерода в сумме. Амидзамещенные активаторы отбеливания такого типа раскрыты в ЕР-А-0170386.Amide Substituted Alkyl Peroxy Acid Precursors
Amide substituted alkyl peroxy acid precursor compounds are also suitable, including those having the following general formulas:

or

where R ¹ represents an alkyl group containing 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 unbranched or branched alkyl containing branching, substitution, or both, and may be obtained either from synthetic sources or from natural sources, including, for example, tall oil. Similar structural options are valid 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 should not contain more than 18 carbon atoms in total. Amide substituted bleach activators of this type are disclosed in EP-A-0170386.

включая замещенные бензоксазины типа

где R₁ представляет Н, алкил, алкарил, арил, арилалкил и где R₂, R₃, R₄ и R₅ могут быть одинаковыми или различными заместителями, выбранными из Н, галогена, алкила, алкенила, арила, гидроксила, алкоксила, амино, алкиламино, СООR₆ (где R₆ представляет Н или алкильную группу) и карбонила.Benzoxazine Organic Peroxy Acid Precursors
Benzoxazine-type precursor compounds are also suitable, as disclosed, for example, in EP-A-332294 and EP-A-482807, especially compounds of 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, alkenyl, aryl, hydroxyl, alkoxyl, amino , alkylamino, COOR ₆ (where R ₆ represents H or an alkyl group) and carbonyl.

Предварительно полученные органические пероксикислоты
Система отбеливателей на основе органических пероксикислот может содержать, в дополнение к или в качестве альтернативы отбеливающим соединениям-предшественникам на основе органических пероксикислот предварительно полученные органические пероксикислоты обычно в количестве от 0,5 до 25 вес. %, более предпочтительно от 1 до 10 вес.% композиции.A particularly preferred benzoxazine-type precursor is

Preformed Organic Peroxy Acids
The organic peroxy acid bleach system may contain, in addition to or as an alternative to the organic peroxy acid precursor bleach compounds, preformed organic peroxy acids, typically in an amount of 0.5 to 25 weight. %, more preferably from 1 to 10 wt.% of the composition.

или

где R¹ представляет алкильную, арильную или алкарильную группу, содержащую от 1 до 14 атомов углерода, R² представляет алкиленовую, ариленовую или алкариленовую группу, содержащую от 1 до 14 атомов углерода, R⁵ представляет 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 неразветвленным или разветвленным алкилом, замещенным арилом или алкиларилом, содержащим разветвления, замещения или и то и другое, и может быть получен либо из синтетических источников либо природных источников, включая, например, талловый жир. Аналогичные структурные варианты допустимы для R². Замещение может включать алкил, арил, галоген, азот, серу и другие типичные замещающие группы или органические соединения. R⁵ предпочтительно представляет Н или метил. R¹ и R⁵ не должны содержать более чем 18 атомов углерода в сумме. Амидзамещенные органические пероксикислоты такого типа раскрыты в ЕР-А-170386.A preferred class of organic peroxyacids are amide substituted compounds of the following general formulas:

or

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 an alkyl, aryl or alkaryl 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 unbranched or branched alkyl substituted with aryl or alkylaryl containing branches, substitutions or both, and can be obtained either from synthetic sources or natural sources, including, for example, tall oil. Similar structural options are valid 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 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacids of this type are disclosed in EP-A-170386.

 Other organic peroxyacids include diacyl and tetra acyl peroxides, especially diperoxide, decanedioic acid, diperoxytetradecandioic acid and diperoxyhexa-decanedioic acid. For the purposes of the present invention, a preferred organic peroxy acid is dibenzoyl peroxide. Mono- and diperazelaic acid, mono- and di-brassilic acid, and N-phthaloylaminoperoxicaproic acid are also suitable.

Controlled Release Funds
Means may be provided to control the rate of release of the bleaching agent, especially oxygen bleach, into the washing solution.

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

 Another mechanism for controlling the bleaching rate of a bleach may be to coat a bleach to provide controlled release. Therefore, such a coating may include slightly water-soluble material, or the coating may 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 in a weight ratio of coating material to bleach from 1:99 to 1: 2, preferably from 1:49 to 1: 9.

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

 Other suitable coating materials may include sulfates, silicates, and carbonates of alkali and alkaline earth metals, including calcium carbonate and silicon dioxide.

A preferred coating material, especially for a bleach based on inorganic perhydrate salts, includes sodium silicate with a SiO ₂ : Na ₂ O ratio of from 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 and / or sodium metasilicate, preferably in an amount of from 2 to 10% (usually 3 to 5%) of SiO ₂ by weight of inorganic perhydrate salt. Magnesium silicate may also be included in the coating.

Any coating materials based on inorganic salts can be combined with an organic binder material to create inorganic salt / organic binder composite coatings. Suitable binders include C ₁₀ -C ₂₀ alcohol ethoxylates containing 5 to 100 moles of ethylene oxide per mole of alcohol, and more preferably C ₁₅ -C ₂₀ ethoxylates of primary alcohols containing 20 to 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include some 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, and most preferably from 1000 to 10,000. Other examples of polymeric materials are can be used as binding agents are copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, with maleic anhydride comprising at least 20 molar percent of the polymer. These polymeric materials can be used as they are or in combination with solvents such as water, propylene glycol and the aforementioned C ₁₀ -C ₂₀ alcohol ethoxylates containing from 5 to 100 mol of ethylene oxide per mole. Other examples of binders include C ₁₀ -C ₂₀ mono- and diglyceric esters, as well as C ₁₀ -C ₂₀ fatty acids.

 Other examples of binders that can be used in the present invention are cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, and homo- or co-polymeric polycarboxylic acids or their salts.

 One way to use the coating material involves agglomeration. A preferred agglomeration process involves the use of any of the organic binder materials described above. Any agglomerators / mixers may be used, including but not limited to pallets, rotary drums, and upright mixers. The molten coating composition can also be applied either by pouring method or by atomized spraying on a moving layer of a bleaching agent.

 Other means of providing the necessary controlled release include mechanical means to change the physical characteristics of the bleach to control its solubility and rate of release. Suitable schemes may include compression, mechanical injection, manual injections, and control of the solubility of the bleach by selecting the particle size of any particulate component.

 Although the choice of particle size will depend both on the composition of the component in the form of particles and on the desire to correspond to the necessary kinetics of controlled release, it is desirable that the particle size be more than 500 μm, preferably the average particle diameter is from 800 to 1200 μm.

 Additional schemes for providing means for controlled release include the appropriate selection of any other matrix components of the detergent composition, so that when the composition is introduced into the washing solution, the ionic strength of the environment will provide the ability to achieve the necessary kinetics of controlled release.

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

 A suitable type of bleaching catalyst is a catalyst comprising a heavy metal cation of a certain catalytic bleaching activity, such as copper, iron cations, an auxiliary metal cation having little or no bleaching catalytic activity, such as zinc or aluminum cation, and a binding agent with defined stability constants for catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylene phosphones acid) and their water-soluble salts. Such catalysts are disclosed in US Pat. No. 4,430,243.

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

Whitening catalysts that can be used in the compositions of the invention can also be selected in accordance with the present invention. For example, suitable whitening catalysts are disclosed in US Pat. Nos. 4,246,612 and 5,227,084. See also US Pat. ) (OCH ₃ ) ₃ - (RF ₆ ).

 Another type of whitening catalysts, as disclosed in US Pat. No. 5,114,606, is a water-soluble complex of manganese (III) and / or (IV) with a ligand, which is a non-carboxylate polyhydroxy compound containing at least three consecutive C — OH groups. Preferred ligands include sorbitol, idit, dulcite, mannitol, xylitol, arabitol, adonite, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

где R¹, R², R³ и R⁴ каждый может быть выбран из Н, замещенных алкильных и арильных групп, так что каждый R¹-N=C-R² и R³-C=N-R⁴ образует пяти- или шестичленное кольцо. Указанное кольцо может быть дополнительно замещено. В представляет мостиковую группу, выбранную из О, S, CR⁵R⁶, NR⁷ и С=О, где R⁵, R⁶ и R⁷ каждый может представлять Н, алкильную или арильную группу, включая замещенные или незамещенные группы. Предпочтительные лиганды включают пиридиновое, пиридазиновое, пиримидиновое, пиразиновое, имидазольное, пиразольное и триазольное кольца. Необязательно, указанные кольца могут быть замещены такими заместителями как алкил, арил, алкокси, галогенид и нитро. Особенно предпочтительным лигандом является 2,2'-биспиридиламин. Предпочтительные катализаторы отбеливания включают комплексы Со, Сu, Mn, Fe, -биспиридилметана и -биспиридиламина. Особенно предпочтительные катализаторы включают Со(2,2'-биспиридиламин)Cl₂, ди(изотиоцианато)-биспиридиламин-кобальт (II), трисдипиридиламин-кобальт(II)перхлорат,
Со(2,2биспиридиламин)₂O₂СlO₄, бис-(2,2'-бис-пиридиламин)-медь(II)перхлорат, трис(ди-2-пиридиламин)железо(II) перхлорат и их смеси.US 5,114,611 discloses a whitening 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 R ¹ , R ² , R ³ and R ⁴ each can be selected from H, substituted alkyl and aryl groups, so that each 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 R ⁵ , R ⁶ and R ⁷ may each represent H, an alkyl or aryl group, including substituted or unsubstituted groups. Preferred ligands include the pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. A particularly preferred ligand is 2,2'-bispyridylamine. Preferred whitening catalysts include complexes of Co, Cu, Mn, Fe, β-bispyridylmethane and β-bispyridylamine. Particularly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate,
Co (2,2 bispyridylamine) ₂ O ₂ ClO ₄ , bis- (2,2'-bis-pyridylamine) -copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

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

 Although the structures of the manganese whitening catalyst complexes of the present invention have not been elucidated, it can be assumed that they include chelates or other hydrated coordination complexes resulting from the interaction of the carboxyl and ligand nitrogen atoms with the manganese cation. Similarly, the oxidation state of the manganese cation during the catalytic process is not known exactly, and the valence state can be (+ II), (+ III), (+ IV) or (+ V). Due to the six possible points of attachment of the ligand to the manganese cation, it is reasonable to assume that multicore compounds and / or cell-type structures may exist in an aqueous bleaching medium. Whatever the form of the active Mn ligand of the compound that actually exists, it acts obviously in a catalytic manner, providing improved whitening characteristics of resistant stains such as tea, ketchup, coffee, wine, juice, and the like.

 Other whitening catalysts are disclosed, for example, in European Patent Publication 408131 (cobalt complex catalysts), European Patent Publications 384503 and 306089 (metal-porphyrin catalysts), in US Patent 4,728,455 (manganese / multidentate ligand catalyst), in US Patent 4,711,748 and European Patent publication 224952, (manganese adsorbed on an aluminosilicate catalyst), in US Pat. No. 4,601,845 (aluminosilicate carrier with manganese and zinc or a magnesium salt), in US Pat. No. 4,626,373 (manganese / ligand catalyst), in US 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 (chelates with manganese cations and non-catalytic metal cations) and US Pat. No. 4,728,455 (catalysts with manganese gluconate).

Other preferred examples include cobalt (III) catalysts of the formula
Co [(NH ₃ ) _n M ' _m B' _b T ' _t Q _q P _p ] Y _y
where cobalt is in oxidation state +3; n represents an integer from 0 to 5 (preferably 4 or 5; more preferably 5), M 'represents a monodentate ligand, m represents an integer from 0 to 5 (preferably 1 or 2; most preferably 1); B ′ is a bidentate ligand; b represents an integer from 0 to 2; T represents a tridentate ligand; t is 0 or 1; Q represents a tetradentate ligand; q is 0 or 1; P represents a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y represents one or more appropriately selected counter anions that are present in an amount of y, where y represents an integer from 1 to 3 (preferably 2-3; most preferably 2 if Y represents a -1 charged anion) to produce a neutrally charged salt; preferred Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and where additionally, at least one of the coordination sites attached to cobalt is labile in conditions of using an automatic dishwasher, and the remaining coordination places are stabilized by cobalt in conditions of using an automatic dishwasher, so that the reduction potential for cobalt (III) to cobalt ( Ii) under alkaline conditions, it is less than 0.4 volts (preferably less than 0.2 volts) with respect to the normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula
[Co (NH ₃ ) _n (M ') _m ] Y _y
where n represents an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M 'represents a labile coordinating fragment, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (if m is greater than 1) combinations thereof; m represents an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6; a Y represents an appropriately selected counteranion, which is present in an amount of y that represents an integer from 1 to 3 (preferably 2-3; most preferably 2, if Y represents a -1 charged anion), to obtain a neutrally charged salt.

A preferred cobalt catalyst of this type, suitable for the purposes of the present invention, is cobalt pentamine chloride salt of the formula [Co (MH ₃ ) ₅ Cl] Y _y , and especially [Co (NH ₃ ) ₅ C1] C1 ₂ .

More preferred are compositions of the present invention in which cobalt (III) whitening catalysts of the formula are used
[Co (NH ₃ ) _n (M) m (B _b )] T _y
where cobalt is in oxidation state +3; n is 4 or 5 (preferably 5); M represents one or more ligands coordinated with cobalt at one site; m = 0, 1 or 2 (preferably 1), B represents a ligand coordinated with cobalt at two sites; b = 0 or 1 (preferably 0), and if b = 0, then m + n = 6, and if b = 1, then m = 0 and n = 4; T represents one or more appropriately selected counter-anions present in an amount of y, where y represents an integer to obtain a neutrally charged salt (preferably y = 1-3; more preferably 2, if T represents a -1 charged anion); and where additionally the specified catalyst has a constant rate of basic hydrolysis of 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. Optionally, T can be protonated if there is more than one anionic group in T, for example, HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- , etc. Further, T can be selected from the group consisting of unconventional inorganic anions, such as anionic surfactants (e.g. linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or anionic polymers (e.g. polyacrylates, polymethacrylates, etc.).

-C(O)OR', -OR', -C(O)NR'₂, где R' выбирают из группы, состоящей из водорода и С₁-С₆ фрагментов. Поэтому такие замещенные R включают фрагменты -(СН₂)_nОН и

где n представляет целое число от 1 до 16, предпочтительно от 2 до 10, и наиболее предпочтительно от 2 до 5.M fragments include, but are not limited to, for example, F ^- , SO ₄ ^-2 , NCS ^- , SCN ^- , S ₂ O ₃ ^-2 , NH ₃ , PO4 ^-3 , and carboxylates (which are preferably monocarboxylates, but in the fragment more than one carboxylate may be present if only cobalt binding is carried out with only one carboxylate per fragment, in which case other carboxylates in fragment M may be protonated or may be in the form of their salts). Optionally, M can be protonated if there is more than one anionic group in M (e.g., НРО ₄ ^-2 , НСО ₃ ^- , Н ₂ РО ₄ ^- , НСО (O) СН ₂ С (O) O-, etc. .). Preferred M fragments are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids of 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, where the substituents are selected from the group consisting of —NR ′ ₃ ,

-C (O) OR ', -OR', -C (O) NR ' ₂ , where R' is selected from the group consisting of hydrogen and C ₁ -C ₆ fragments. Therefore, such substituted Rs include fragments - (CH ₂ ) _n OH and

where n represents an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.

Most preferred M are carboxylic acids of the above formula, where R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, unbranched or branched C ₄ -C ₁₂ alkyl and benzyl. Most preferred R is methyl. Preferred carboxylic acids of fragments M include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenic, oleic, palmitic, triflate, tartrate, lemon, stear, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

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

Suitable cobalt whitening catalysts for the purposes of the present invention are known and disclosed, for example, along with their basic hydrolysis rates, in M. L. Tobe, Base Hydrolysis of Transition-Metal Complexes, Adv. Inorg. Bioinorg. Mech (1983), 2, p. 1-94. For example, table 1 on page 17 shows the rates of basic hydrolysis (designated here as k _OH ) for cobalt pentamine catalysts complexed with oxalate (k _OH = 2.5 • 10 ^-4 M ^-1 s ^-1 (25 ^o С) ), NCS ^- (k _OH = 5.0 • 10 ^-4 M ^-1 s ^-1 (25 ^o С)), formate (k _OH = 5.8 • 10 ^-4 M ^-1 s ^-1 (25 ^o С )), and acetate (k _OH = 9.6 • 10 ^-4 M ^l s ^-l (25 ^o С)). The most preferred cobalt catalysts suitable for the purposes of the present invention are cobalt pentamine acetate salts of the formula [Co (NH ₃ ) ₅ OAc] T _y , where OAc represents an acetate fragment, and especially cobalt pentamine acetate chloride [Co (NH ₃ ) ₅ OAc] Cl ₂ ; a also [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, "RAS").

 Such cobalt catalysts are readily prepared by known methods such as those disclosed, for example, in the Tobe article cited earlier and references cited therein, in US Pat. No. 4,810,410 to Diakun et al., Issued 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, 1497-1502 (1979); Inorg. Chem. 21, 2881-2885 (1982); Inorg. Chem. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952); as well as in the following synthesis examples.

 Cobalt catalysts suitable for inclusion in the detergent tablets of the present invention can be obtained in accordance with the synthesis methods disclosed in US patents 5559261, 5581005, and 5597936, the disclosure of which is incorporated into the description by reference. These catalysts can be prepared in conjunction with additional materials in order to reduce the color effect if required for product aesthetics, or which need to be incorporated into the enzyme containing particles, as shown below, or compositions can be prepared to contain catalytic spots.

 Organic polymer compounds.

 Organic polymer compounds can be added as preferred components of the detergent tablets of the present invention. By the term “organic polymer compounds” is meant essentially any polymer organic compound commonly found in detergent compositions having dispersant properties, anti-re-deposition properties, dirt-repellent properties, or other detergent properties.

 Organic polymer compounds are usually included in the detergent compositions of the present invention in an amount of from 0.1 to 30%, preferably from 0.5 to 15%, and most preferably from 1 to 10 wt.% Of the compositions.

 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 carboxyl radicals separated from each other by no more than two carbon atoms. The latter type of polymers are disclosed in GB-A-1596756. Examples of such salts are polyacrylates with a molecular weight of 2000-10000 and their copolymers with any suitable other monomer units, including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, 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 with 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 under the trademark Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 from BASF GmbH, and those sold under the Acusol 45N trademark , 480N, 460N by Rohm and Haas.

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

 The polyamine and modified polyamine compounds are suitable for the purposes of the present invention, including those derived from aspartic acid, such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

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

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

Dirt repellent agents
Suitable polymeric dirt-repellent agents include those dirt-repellent agents that contain: (a) one or more non-ionic hydrophilic components consisting essentially of (i) segments of polyoxyethylene with a degree of polymerization of at least 2, or (ii) segments of hydroxypropylene or polyoxypropylene with the degree of polymerization from 2 to 10, where the specified hydrophilic segment does not include any oxypropylene units, if it is not connected with neighboring fragments at each end with ether bonds, 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, where if said hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is 2: 1 or less, (ii) C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene segments, or mixtures thereof, (iii) segments of a poly (vinyl ester), preferably polyvinyl acetate, with a degree of polymerization of at least 2, or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substitute whether or mixtures thereof, wherein said substituents are present 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) will have a degree of polymerization of from 2, although higher values can be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable hydroxy C ₄ -C ₆ alkylene hydrophobic segments include, but not limited to, terminal functional group polymeric dirt-repellent agents, such as MO ₃ S (CH ₂ ) nOCH ₂ CH ₂ O-, where M is sodium, n is an integer from 4 to 6, as disclosed in US Pat. No. 4,721,580, issued January 26, 1988 Gosselink.

Polymeric dirt-repellent agents suitable for the purposes of the present invention also include cellulose derivatives such as polymers of hydroxyether cellulose, block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include cellulose hydroxyesters such as METHOCEL (Dow). Cellulosic dirt repellent agents for use in the present invention also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose, see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Dirt-repellent agents characterized by hydrophobic segments of poly (vinyl ester) include grafted copolymers of poly (vinyl ester), for example, C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate), grafted onto a polyalkylene oxide backbone, such as a backbone polyethylene oxide, see European Patent Application 0219048, published April 22, 1987, Kud, et al.

 Another suitable dirt repellent agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric dirt-repellent agent is in the range of 25,000 to 55,000, see US Pat. No. 3,959,230, Hays, May 25, 1976, and US Pat. No. 3,893,929, Basadur, July 8, 1975.

 Another suitable polymeric dirt-repellent agent is a polyester with repeating units of ethylene terephthalate containing 10-15 wt.% Units of ethylene terephthalate together with 90-80 wt.% Units of polyoxyethylene terephthalate obtained from polyoxyethylene glycol with an average molecular weight of 300-5000.

 Another suitable polymeric dirt-repelling agent is a sulfonated product of a substantially linear ester oligomer, consisting of an oligomeric ester chain of terephthaloyl and oxyalkyleneoxy repeating units, and end moieties covalently linked to the main chain. These dirt repellent agents are fully disclosed in US Pat. No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.R. Gosselink. Other suitable polymeric dirt-repellent agents include terephthalate polyesters of US Pat. No. 4,711,730 issued December 8, 1987 to Gosselink et al., Anionic oligomeric esters with functional terminal groups of US Pat. No. 4,721,580, issued January 26, 1988 to Gosselink, and block polyester oligomeric compounds of US Pat. 4702857, issued October 27, 1987 by Gosselink. Other polymeric dirt-repellent agents also include dirt-repellent agents of US Pat. No. 4,877,896, issued October 31, 1989 to Maldonado et al. In which anionic, especially sulfoaryl, terephthalate ester-terminated functional groups are disclosed.

 Another dirt-repellent agent is an oligomer with repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethylene and oxy-1,2-propyleneoxy units. The repeating units form the skeleton of an oligomer and preferably terminate with modified isethionate end groups. A particularly preferred dirt-repelling agent of this type includes one sulfoisophthaloyl unit, 5 terephthaloyl units, hydroxyethylene ethoxy and hydroxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two terminal functional units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

 Binding agents of heavy metal ions.

 The tablets of the present invention preferably contain, as an optional component, a binding agent for heavy metal ions. By a binding agent for heavy metal ions is meant components that bind (chelate) heavy metal ions. These components may also have the ability to chelate calcium and magnesium ions, but preferably they exhibit selectivity for the binding of heavy metal ions such as iron, manganese and copper.

 Binding agents for heavy metal ions are usually 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 wt.% Of the composition.

 Binding agents for heavy metal ions that are acidic in nature, containing, for example, phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or in the form of complexes / salts with suitable anti-cations, such as alkali or alkaline earth metal ions , ammonium or substituted ammonium ions, or any mixtures thereof. Preferably, any salts / complexes are water soluble. The molar ratio of said protocation to a binding agent for heavy metal ions is preferably at least 1: 1.

 Suitable heavy metal ion binding agents for the present invention include organic phosphonates such as amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrile trimethylene phosphonates. Preferred among the above are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1-diphosphonate.

 Other suitable heavy metal ion binding agents for the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediamine pentaacetic acid, ethylenediamine di-succinic acid, ethylenediamine di-glutaric acid, 2-hydroxypropylenediamine di-diamine any.

 Ethylene diamine-N, N'-di-succinic acid (EDDS), or its salts of alkali metals, alkaline earth metals, ammonium or substituted ammonium, or a mixture 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 tablets preferably contain crystal growth inhibitors, preferably an organodiphosphonic acid-based component, preferably included in an amount of from 0.01 to 5%, more preferably from 0.1 to 2% by weight of the composition.

 By organodiphosphonic acid is meant organodiphosphonic acid, which does not contain nitrogen as part of its chemical structure. Therefore, this definition excludes organoaminophosphonates, which, however, can be included in the compositions of the present invention as components of a binding agent of heavy metal ions.

Organodiphosphonic acid is preferably C ₁ -C ₄ diphosphonic acid, more preferably C ₂ diphosphonic acid, such as ethylene diphosphonic acid or more preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), and may be present in partially or fully ionized form, in particular in the form of a salt or complex.

 Water soluble sulfate salt.

 Detergent tablets optionally contain a water soluble sulfate salt. In those cases when it is present, it is present in an amount of from 0.1 to 40%, more preferably from 1 to 30%, most preferably from 5 to 25 wt.% Of the composition.

 The water-soluble sulfate salt may be essentially any sulfate salt with any anti-cation. Preferred salts are selected from sulfates of alkali and alkaline earth metals, especially sodium sulfate.

Alkali metal silicate
An alkali metal silicate is a preferred component of the tablets of the present invention. A preferred alkali metal silicate is sodium silicate,
having a SiO ₂ : Na ₂ O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, and most preferably 2.0. Sodium silicate is preferably present in an amount of less than 20%, preferably from 1 to 15%, most preferably from 3 to 12 wt.% SiO ₂ . The alkali metal silicate may be in the form of either an anhydrous salt or a hydrated salt.

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

The alkalinity system also preferably contains sodium metasilicate in an amount of at least 0.4% SiO _{2 by} weight. The nominal ratio of SiO ₂ : Na ₂ O in sodium metasilicate is 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO ₂ , is preferably from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, and most preferably from 10: 1 to 5: 2.

 Coloring agent.

 The term "coloring agent", as used in the description, means any substance that absorbs specific wavelengths of light in the visible part of the spectrum. Such coloring agents, when added to the detergent composition, have the effect of changing the visible color, and thus the general appearance of the detergent composition. Coloring agents can be, for example, either dyes or pigments. Preferably, coloring agents are stable in the composition in which they should be included. Thus, in compositions with high pH values, coloring agents are preferably stable with respect to alkalis, and in compositions with low pH values, coloring agents should preferably be stable with respect to acids.

 The first and / or second, and / or optionally further phases may contain a coloring agent, mixtures of coloring agents, coloring particles or mixtures of coloring particles, so that the various phases have a different appearance. Preferably, one of either the first or second phases comprises a coloring agent. If both the first and second and / or subsequent phases include coloring agents, it is preferred that these coloring agents have a different appearance.

 Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo, diazo and polyazo. More preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-HRL 180% (trademark), SANDOLAN MILLING BLUE (trademark), TURQUOISE ACID BLUE (trademark) and SANDOLAN BRILLIANT GREEN (trademark), all available from Clariant UK, HEXACOL QUINOLINE YELLOW (trademark brand) and HEXACOL BRILLIANT BLUE (brand), both are available from Pointings, UK, ULTRA MARINE BLUE (brand) is available from Holliday or LEVAFIX TURQUISE BLUE EVA (brand) is available from Bayer, USA.

 Coloring agents can be incorporated into phases by any suitable means. Suitable methods include mixing all or selected detergent components with coloring agents in a drum, or spraying all or selected detergent components of coloring agents in a rotary drum.

 The coloring agent, if present as a component of the first phase, is present in an amount of from 0.001 to 1.5%, preferably from 0.01 to 0.1%, and most preferably from 0.1 to 0.3%. If it is present as a component of the second and / or optionally subsequent phases, the coloring agent is usually present 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%.

Corrosion inhibitors
Tablets of the present invention for use in dishwashers may contain corrosion inhibitors, preferably selected from silver-coating organic agents, in particular paraffins, nitrogen-containing corrosion inhibitors and Mn (II) compounds, especially Mn (II) salts of organic ligands.

 Silver-plating organic agents are disclosed in PCT Publication WO 94/16047 and pending EP-A-690122. Nitrogen-containing corrosion inhibitors are disclosed in pending EP-A-634478. Mn (II) compounds for use in corrosion inhibitors are disclosed in pending EP-A-672749.

 Silver-plating organic agents may be included in an amount of from 0.05 to 10%, preferably from 0.1 to 5% by weight of the total composition.

 The functional role of the silver coating agent is to provide a “in use” protective coating layer on any silver containing wash loading components that utilize the composition of the present invention. Therefore, the silver-coating agent must have a high affinity for bonding to solid silver surfaces, especially when it is present as a component of an aqueous detergent and bleach solution that treats solid silver surfaces.

 Suitable silver-plating organic agents include fatty esters of mono- or polyhydric alcohols containing from 1 to 40 carbon atoms in the hydrocarbon chain.

 Part of the fatty acid 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 acids include: n-butyl malonic acid, isolimonic acid, citric acid, maleic acid, malic acid and succinic acid.

 The radical of a fatty alcohol in a fatty ester can be represented by mono- 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, glycerin, ethanol, isopropanol, vinyl alcohol, diglycerin, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitol.

 Preferably, the group of a fatty acid and / or fatty alcohol of a fatty ester of an auxiliary material contains from 1 to 24 carbon atoms in the alkyl chain.

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

 Glycerol esters are also highly preferred. They are mono-, di- or tri-esters of glycerol and the above fatty acids.

 Specific examples of fatty alcohol esters for the purposes of the present invention include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl di-maleate, and tallyl propionate. Fatty acid esters for the purposes of the present invention include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobegenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed di-ethyl esters.

 For the purposes of the present invention, preferred glycerol esters are glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobegenate and glycerol distearate.

 Suitable silver-plating organic agents include triglycerides, mono or diglycerides and their fully or partially hydrogenated derivatives, as well as any mixtures thereof. Suitable sources of fatty acid esters include vegetable oils, fish oil 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.

Waxes, including microcrystalline waxes, are silver-plating organic compounds suitable for the purposes of the present invention. Preferred waxes have a melting point in the range of 35 to 110 ^{° C.} and typically contain 12 to 70 carbon atoms. Paraffin and microcrystalline type petroleum waxes, which are composed of long chain saturated hydrocarbon compounds, are preferred.

 Suitable silver-plating organic compounds for the purposes of the present invention are alginates and gelatin.

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

 Other suitable silver-plating organic agents include some polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of 12,000 to 7,000,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole and cellulose derivatives such as methylcellulose , carboxymethyl cellulose and hydroxyethyl cellulose.

 As perfume coating agents for the purposes of the present invention, certain perfume materials (perfumes) can be used, especially those that exhibit high affinity for metal surfaces.

 Polymeric dirt-repellent agents can also be used as silver-coating organic agents.

A preferred silver-coating organic agent is paraffin oil, usually a predominantly branched aliphatic hydrocarbon with a carbon number in the range of 20 to 50; a preferred paraffin oil selected from predominantly branched C _25-45 compounds with a ratio of cyclic to non-cyclic from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A paraffin oil corresponding to these characteristics, with a cyclic to non-cyclic hydrocarbon ratio of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trademark WINOG 70.

Nitrogen Corrosion Inhibitors
Suitable nitrogen-containing corrosion inhibitors include imidazole and its derivatives, such as benzimidazole, 2-heptadecylimidazole and those imidazole derivatives, which are disclosed in Czech patent 139279 and GB patent A-1137741, which also discloses methods for preparing imidazole compounds.

As suitable nitrogen-containing corrosion inhibitors, pyrazole compounds and derivatives thereof are suitable, especially those in which pyrazole is substituted in any of 1, 3, 4 or 5 positions with substituents R ₁ , R ₃ , R ₄ and R ₅ , where R ₁ represents any of H, CH ₂ OH, CONH ₃ or COCH ₃ , R ₃ and R ₅ are any of C ₁ -C ₂₀ alkyl or hydroxyl, R ₄ is any of H, NH ₂ or NO ₂ .

 Other suitable nitrogen-containing corrosion inhibitors include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotriazole.

 You can also use nitrogen-containing compounds, such as amines, especially distearylamines, and ammonium compounds, such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrocytrate.

Corrosion Inhibitors - Mn (II) Compounds
Detergent tablets may contain corrosion inhibitors - compounds of Mn (II). Compounds Mn (II) preferably include in an amount of from 0.005 to 5 wt.%, More preferably from 0.01 to 1%, and most preferably from 0.02 to 0.4 wt.% Of the composition. Preferably, the Mn (II) compounds are included in such an amount as to provide a Mn (II) ion content in any whitening solution of from 0.1 to 250 ppm, more preferably from 0.5 to 50 ppm (ppm), and most preferably from 1 to 20 parts per million 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. The compound Mn (II) may be a salt or complex of an organic fatty acid, such as manganese acetate or manganese stearate.

 The compound Mn (II) may be a salt or complex of an organic ligand. In one preferred aspect, the organic ligand is a binding agent for heavy metal ions. In another preferred aspect, the organic ligand is a crystal growth inhibitor.

 Other corrosion inhibitors.

Other suitable additional corrosion inhibitors include mercaptans and diols, especially mercaptans containing from 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 ₁₂ -C ₂₀ hydroxy fatty acids or their salts are also suitable. Phosphonated octadecane and other antioxidants such as betahydroxytoluene (BHT) can also be used.

 Copolymers of butadiene and maleic acid have been found to be particularly suitable as corrosion inhibitors, especially those sold under the trade 07787 Polysciences Inc.

 Hydrocarbon oils.

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

 Water soluble bismuth compounds.

 The detergent tablets of the present invention suitable for use in dishwashing may contain water-soluble bismuth compounds, which are preferably present in an amount of from 0.005 to 20%, more preferably from 0.01 to 5% and most preferably from 0.1 to 1 wt.% compositions.

 Water-soluble bismuth compounds can be virtually any bismuth salts or complexes with virtually any inorganic or organic counter-anion. Preferred inorganic bismuth salts are selected from bismuth trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and bismuth citrate are preferred salts with an organic counter anion.

Enzyme Stabilizing System
Preferred enzyme containing compositions may include from 0.001 to 10%, preferably from 0.005 to 8%, and most 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 detergent enzymes. Such stabilizing systems may include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acid, chlorine bleach acceptors, and mixtures thereof. Such stabilizing systems may also include reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap dispersants
The tablets of the present invention may contain lime soap dispersants, which are preferably present in an amount of from 0.1 to 40 wt.%, More preferably from 1 to 20 wt.%, And most preferably from 2 to 10 wt.% Of the compositions.

 A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts and fatty acids with calcium or magnesium ions. Preferred dispersants of lime soap are disclosed in PCT Application WO 93/08877.

Foam suppression system
The detergent tablets of the present invention, when designed for use in washing machine compositions, preferably include a foam suppression system present in an amount of 0.01 to 15%, preferably 0.05 to 10%, and most preferably 0.1 to 5 wt.% composition.

 Suitable foaming suppression systems for the purposes of the present invention may include virtually any known antifoam agents, including, for example, silicone antifoam agents, 2-alkyl and alkanol antifoam agents. Preferred foam suppression systems and defoamers are disclosed in PCT application WO 93/08876 and in EP-A-705324.

Dye Transfer Inhibiting Polymeric Agents
The detergent tablets of the present invention may also include from 0.01 to 10%, preferably from 0.05 to 0.5% by weight of polymeric dye transfer inhibiting agents.

 The dye transfer inhibiting polymer agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinyl pyrrolidone polymers and combinations thereof.

Optical brighteners
Detergent tablets suitable for washing, as disclosed herein, optionally also contain from 0.005 to 5% by weight of certain types of hydrophilic optical brighteners.

где R₁ выбирают из анилино, N-2-бис-гидроксиэтила и NH-2-гидроксиэтила; R₂ выбирают из N-2-бис-гидроксиэтила, N-2-гидроксиэтил-N-метиламино, морфолино, хлора и амино; и М представляет солеобразующий катион, такой как натрий или калий.Hydrophilic optical brighteners suitable for the purposes of the present invention include compounds of the structural 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, morpholino, chlorine and amino; and M represents a salt-forming cation, such as sodium or potassium.

If in the above formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation, such as sodium, the bleach is 4,4'-bis [(4-anilino-6- (N- 2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid. This particular bleach is commercially available under the brand name Tino-pal-UNPA-GX from Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener for the detergent compositions of the present invention.

If 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 bleach is the disodium salt of 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N- methylamino) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid. This particular bleach is commercially available under the brand name Tinopal-5BM-GX from Ciba-Geigy Corporation.

If in the above formula, R ₁ is anilino; R ₂ is morpholino and M is a cation, such as sodium, the bleach is the 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -2,2'-stilbendisulfonic sodium salt acids. This particular bleach is commercially available under the brand name Tinopal-AMS-GX from Ciba-Geigy Corporation.

Clay-based softening system
The detergent tablets of the present invention for use in washing processes may comprise a clay-based softening system that includes a clay mineral compound and optionally a clay flocculant.

 The clay mineral compound is preferably smectite clay. Smectite clays are disclosed in US Pat. Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patent applications EP-A-299575 and EP-A-313146 to Procter and Gamble Company describe suitable organic polymer flocculants for clay.

Cationic fabric softeners
Cationic fabric softeners that can be used for washing can also be included in the compositions of the present invention. Suitable cationic fabric softeners include water-insoluble tertiary amines or di (long chain) amides, as disclosed in GB-A-1514276 and in EP-B-0011340.

 Cationic fabric softeners typically include in a total amount of from 0.5 to 15% by weight, usually from 1 to 5% by weight.

Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of the present 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 not formulated to have an excessively high pH, preferably the axes have a pH, measured as a 1% solution in distilled water, from 8.0 to 12.5, more preferably from 9.0 to 11.8, and most preferably from 9.5 to 11.5.

The method of washing dishes in the dishwasher
You can use any suitable method of washing or cleaning dirty dishes in the dishwasher. A preferred method of washing in a dishwasher involves treating contaminated items selected from earthenware, glassware, silverware, metal items, cutlery and mixtures thereof, with an aqueous solution in which an effective amount of the detergent tablet of the present invention is dissolved or distributed. 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 doses of the product and the volumes of the washing solution commonly used in traditional dishwashers. Preferably, the weight of the detergent tablets is from 15 to 40 g, more preferably from 20 to 35 g.

Machine Wash Method
Machine wash methods typically include treating the soiled laundry with an aqueous washing solution in a washing machine in which an effective amount of the machine wash detergent tablet composition of the present invention is dissolved or dispensed. By an effective amount of a detergent tablet composition is meant 40 to 300 g of a product dissolved or dispersed in a washing solution of 5 to 65 liters in volume, which corresponds to typical product doses and volumes of washing solutions commonly used in machine wash.

 In a preferred embodiment, a machine switchgear is used. A detergent product is loaded into the dispenser and used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. The volumetric capacity of this device must be such that it contains a sufficient amount of detergent, which is usually used for washing.

 After the laundry is loaded into the washing machine, the dispenser containing the detergent is placed inside the drum. At the beginning of the washing cycle of the washing machine, water is supplied to the drum, and it begins to rotate periodically. The design of the dispenser must be such as to provide a dry detergent content, but then it must ensure that the product is released during the washing cycle as a result of mixing during rotation of the drum and also as a result of its contact with washing water.

 To ensure the release of detergent during the washing process, this appliance may have a series of holes through which the product can pass. Alternatively, this device can be made of a material that is permeable to liquid, but not permeable to a solid product, which will ensure the release of the dissolved product. Preferably, the detergent product will be rapidly released at the beginning of the wash cycle, thereby temporarily localizing high product concentrations in the drum of the washing machine at this stage of the cycle.

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

 Alternatively, the dispenser may be a flexible container, such as a bag or bag.

 The bag may be made of fiber coated with a waterproof protective material so that its contents are preserved, as disclosed in European Patent Application Publication 0018678. Alternatively, it may be made of a water-insoluble synthetic polymer material provided with closed edges or closures made so that disclose in an aqueous medium as described in published European patent applications 0011500, 0011501, 0011502 and 0011968. A convenient form of a water-disruptive shutter includes water-soluble adhesion c, applied along one edge of the bag and sealing it, the bag being made of a waterproof polymer film, such as polyethylene or polypropylene.

EXAMPLES
Abbreviations used in the examples:
In detergent compositions, the determining constituents of contraction have the following meanings:
STPP: sodium tripolyphosphate
Bicarbonate: Sodium Bicarbonate
Citric Acid: Anhydrous Citric Acid
Carbonate: Anhydrous Sodium Carbonate
Silicate: Amorphous sodium silicate (ratio SiO ₂ : Na ₂ O = 2.0)
SKS-6: crystalline layered silicate of the formula δ-Na ₂ Si ₂ O ₅
PB1: Anhydrous Sodium Perborate Monohydrate
Non-ionic: C ₁₃ -C ₁₅ mixed ethoxylated / propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and with an average degree of propoxylation of 4.5, sold under the trademark Plurafac, BASF
TAED: tetraacetyl ethylenediamine
HEDP: ethane 1-hydroxy-1,1-diphosphonic acid
RASS: salt of pentamine cobalt (III) acetate
Paraffin: paraffin oil, sold under the Winog 70 brand from Wintershall
Protease: proteolytic enzyme
Amylase: amylolytic enzyme
BTA: benzotriazole
Sulfate: anhydrous sodium sulfate
PEG 3000: polyethylene glycol with a molecular weight of approximately 3000 from Hoecht
PEG 6000: approximately 6,000 polyethylene glycol from Hoecht
pH: measured as 1% solution in distilled water at 20 ^o C
In the following examples, all quantities are given as weight. parts.

Examples I-IV
Examples of detergent tablets of the present invention suitable for use in a dishwasher are shown in the table.

Compositions of multiphase tablets are prepared as follows. The active detergent composition of phase 1 is obtained by mixing granular and liquid components, and then placed in a matrix of a conventional rotary press. The press includes a punch designed in such a way that allows you to create a form. The cross section of the matrix is approximately 30 • 38 mm. Then the composition is pressed under a pressure of 940 kg / cm ² , the punch is lifted and the first phase of the tablet is obtained, on the upper surface of which a shape is created. The active detergent composition of phase 2 is obtained in a similar manner and placed in a matrix. Then the particles of the active composition are pressed under a pressure of 170 kg / cm ² , the punch is lifted and the multiphase tablet is removed from the tablet press. The resulting tablets dissolve or disintegrate in a washer, as described above, in 12 minutes, with a phase of 2 tablets dissolving in 5 minutes. The tablets provide excellent solubility and cleaning properties along with good tablet integrity and strength.

Claims (14)

1. A multiphase detergent tablet for use in a washing machine, characterized in that it comprises: a) a first phase in the form of a shaped body containing at least one form; and b) the second phase in the form of solid particles pressed into the inside of the specified form, and the formed body of the first phase is obtained at a pressing 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 the second phase dissolves faster than the first phase.  3. Multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that the second phase dissolves in the dishwasher in 5 minutes.  4. Multiphase detergent tablet according to claim 1, characterized in that the tablet contains at least one detergent active substance and is formulated so that at least 50%, preferably at least 60%, more preferably at least 80% by weight of the detergent active substance is flushed for 10 minutes, preferably for 5 minutes, and more preferably for 3 minutes.  5. Multiphase detergent tablet according to claim 1, characterized in that the tablet composition contains one or more detergent active substances selected from enzymes, bleaches, bleaching activators, bleaching catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof , and mainly concentrated in the second phase.  6. Multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that the second phase further comprises a destructive agent.  7. Multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that the second phase contains an enzyme.  8. Multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that the first and / or second phases contain a binder.  9. Multiphase detergent tablet according to claim 8, 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.  10. Multiphase detergent tablet according to any one of the preceding paragraphs, characterized in that it further comprises a barrier layer between the first and second phases.  11. Multiphase detergent tablet according to claim 10, characterized in that the barrier layer contains a binder used in liquid form. 12. The method of producing multiphase detergent tablets according to claims 1-11, characterized in that the method comprises the steps of: a) compressing at a pressure of at least about 350 kg / cm of the first detergent active composition to form a first phase containing at least at least one form; b) placing the second detergent active composition in the form of solid particles in the specified form; and c) pressing at a pressure of less than about 350 kg / cm ^{2 the} second detergent active composition in the form of solid particles inside the specified form to form a second phase.  13. A method of washing in a washing machine, comprising loading one or more multiphase detergent tablets into the washer, characterized in that multiphase detergent tablets according to claims 1 to 11 are used.  14. The method according to item 13, wherein the multiphase detergent tablet is dissolved or destroyed in less than 15 minutes in the dishwasher. Priorities for items:
July 17, 1998 according to claims 1-12;
05/17/1999 according to paragraphs 13 and 14.

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