PL190559B1 - Detergent tablet - Google Patents

Abstract

1. A multi-phase detergent tablet for use in a dishwasher, characterized in that it has a mass of 15 - 40 g and contains a) a first phase in the form of a compressed shaped element containing at least one socket in its surface; and b) a second phase in the form of a compressed element held in the cavity by adhesion, made of a solid substance in the form of particles, weighing less than 4 g, the tablet containing in its composition one or more detergent active substances selected from the group consisting of fillers, coloring agents, surfactants and enzymes, which are concentrated primarily in the second phase, and the second phase additionally contains a binding agent, but the phases of this tablet have different dissolution rates during use. PL

Description

The present invention relates to a dishwasher safe multiphase detergent tablet.

Tablet detergent compositions are known. It will be appreciated that tablet detergent compositions have a number of advantages over particulate detergent compositions, such as being easy to dose, handle, transport and store.

Most often, detergent tablets are prepared by premixing the ingredients of the detergent composition and forming the pre-blend detergent ingredients into a tablet using any suitable equipment, preferably a tablet press. Tablets are typically formed by compressing the ingredients of a detergent composition such that the resulting tablets are sufficiently strong to withstand handling and transport without damage. In addition to being strong, the tablets also need to dissolve sufficiently quickly so that the detergent ingredients are released into the washing or washing water as soon as possible at the beginning of the washing or washing cycle.

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However, incompatibility occurs because as the compressive force increases, the dissolution rate of the tablets slows down. It is therefore an object of the invention to find a suitable balance between tablet strength and tablet dissolution.

Known solutions to this problem include compressing the tablets under low pressure. However, tablets prepared in this way, while dissolving relatively quickly, tend to crumble and become damaged, which is unacceptable to the consumer. Other approaches include making the tablets under relatively high pressure to achieve the required level of strength, with the addition of a dissolving aid such as an effervescent agent.

Known multiphase detergent tablets are made by compressing the first composition in a tablet press to form a substantially planar first layer. The next detergent composition is then fed to the tablet press on top of the first layer. This second composition is then compressed to form a further, substantially flat, second layer. Accordingly, the first layer is generally compressed more than once as it is also compressed during compression of the second composition. Typically, the first and second compressive forces are of the same order of magnitude. It has been found that in such a case, since the compressive force must be sufficient to bond the first composition to the second, the force applied in the first and second pressing steps must be between about 40,000 and 200,000 N (assuming the cross section is tablet is about 10 cm ² ). This causes the tablet to dissolve slowly. Other multiphase tablets with different dissolution rates are produced by compressing the second layer with a lower pressure than the first layer. However, while the dissolution rate of the second layer increases, the second layer is softer than the first layer and is therefore susceptible to damage during handling and shipping.

EP-B-0055100 describes a sanitary block obtained by combining a slowly dissolving shaped element with a tablet. The sanitary cube is intended to be placed in a toilet reservoir, where it dissolves within days, preferably weeks. As a means of reducing the dissolution rate of a sanitary block, the document discloses the addition of one or more solubility regulating agents. Examples of solubilizing agents include p-dichlorobenzene, waxes, long chain fatty acids and alcohols and their esters, and fatty alkylamides. Detergent tablets for use in washing machines and dishwashers must generally dissolve within one cycle of the washing machine or dishwasher, i.e. 15-120 minutes.

The invention therefore relates to a multiphase detergent tablet for use in a dishwasher, characterized in that it has a weight of 15-40 g and contains

a) a first phase in the form of a compressed shaped member including at least one cavity in its surface; and

b) a second phase in the form of a compressed element held in the seat by adhesion, made of a particulate solid, weighing less than 4 g, the tablet comprising one or more detergent active substances selected from the group consisting of fillers, colourants, surfactants and enzymes, which are primarily concentrated in the second phase, and wherein the second phase additionally comprises a binder, however, the phases of this tablet exhibit a different dissolution rate during use.

Preferably, the multiphase detergent tablet of the invention comprises a first phase produced at an applied pressure of at least 34.3 MPa and a second phase produced at a pressure less than 34.3 MPa.

Preferably the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, and inorganic and organic polymers.

Preferably the multiphase detergent tablet according to the invention additionally comprises a barrier layer between the first and second phases, more preferably the layer comprises a binder applied in liquid form, especially selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, and inorganic and organic polymers.

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Preferably, the first and second phases of the multiphase detergent tablet according to the invention dissolve independently of one another.

Preferably, the weight ratio of the first phase to the second phase is at least 6: 1. preferably, at least 10: 1.

Preferably, the dissolution rate of the second phase is faster than that of the first phase.

In preferred embodiments of the invention, the first phase is a compressed, shaped member under an applied pressure of at least about 3.9 MPa, preferably, at least about 24.5 MPa, more preferably. at least about 34.3 MPa (3.43 kN / cm '), more preferably from about 39.2 to about 196.2, and more preferably from about 58.9 to about 117.7 MPa. In the specification, pressure means the applied force divided by the cross-sectional area of the tablet in a plane perpendicular to the applied force, i.e. the cross-sectional area of the die in a rotary press.

It is also preferred that the particulate solid of the second phase (which term also includes the possibility of using multiple "second" phases, sometimes referred to herein as "optional second phases") is compressed in the seat at a pressure less than the pressure applied to the second phase. of the first phase, and preferably at a pressure below about 34.3 MPa, preferably in the range from about 3.9 MPa to about 29.4 MPa, more preferably from about 6.9 to about 26.5 MPa, as such tablets are preferred for this because optimal tablet integrity and strength (as measured by e.g. Child Bite Strength [CBS]) and dissolution characteristics of the product are achieved. The tablets of the invention preferably exhibit a CBS of at least about 6 kg, preferably more than about 8 kg, more preferably more than about 10 kg, more preferably more than about 12 kg, and most preferably more than about 14 kg, CBS measured according to the US Consumer Product Standard. Safety Commission Test Specification. Furthermore, the ratio of pressures applied to the first and second phases is typically at least about 1.2: 1, preferably at least about 2: 1, more preferably. at least about 4: 1.

The second phase is in the form of a compressed or shaped element, contained by adhesion, e.g. by physical or chemical adhesion, in at least one seat of the first element.

As mentioned above, the tablet comprises one or more detergent actives which are concentrated primarily in the second phase, such that e.g. at least about 50%, preferably at least about 60%, especially about 80% of the active ingredients ( based on the total weight of active ingredients in the tablet) is in the second tablet phase. Such compositions are optimal with regard to tablet strength, dissolution, cleaning properties and pH adjustment characteristics, whereby e.g. tablets dissolving in a washing liquid are obtained such that they provide at least 50%, preferably at least 60%, more preferably at least 80% by weight. . detergent actives into the washing liquid within 10, 5, 4 or even 3 minutes from the start of washing.

As stated above, it is an advantage of the invention to be able to achieve differential dissolution of the phases such that one phase of the tablet will dissolve significantly before the other phase, and may dissolve substantially completely before dissolving the other phase. This is especially valuable in view of the differential delivery of detergent actives.

A multiphase detergent tablet is preferred which comprises a first shaped member phase having at least one cavity in its surface and a second particulate solid phase compressed in the seat, the tablet containing one or more detergent actives. which are mainly concentrated in the second phase, the second phase additionally containing a binding agent.

As mentioned above, suitably the one or more detergent actives are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors, and mixtures thereof, the enzyme actives being particularly

190 559 advantageous for improving the cleaning properties in the initial cold water washing stage. In this regard, enzymatic detergent actives are highly preferred, and in particular enzymes and enzyme mixtures containing one or more enzymes with enhanced or optimal activity in the temperature range 25 ° C - 55 ° C and at a pH value in the range 8-10 ( e.g. Natalase).

Preferably, the multiphase detergent tablet comprises a first phase shaped member having at least one cavity in its surface and a second phase of particulate solid pressed in the seat, the second phase further comprising an enzyme.

The object of the invention is to provide a detergent tablet which is not only strong enough to withstand handling and transport, but at least a significant proportion which dissolves rapidly in the washing water, ensuring rapid delivery of the detergent active ingredient. Preferably, the at least one tablet phase is dissolved in the wash water within the first 10 minutes, preferably 5 minutes, more preferably within the 4 minute automatic dishwasher cycle. Preferably the washing device is an automatic dishwasher. The time during which the multiphase tablet or its phase or detergent active ingredient dissolves is determined in accordance with DIN 44990 using a dishwasher available from Bosch in a normal dishwashing program at 65 ° C in water hardness 18 ° H with a repetition number of every at least 6 or sufficient to ensure repeatability.

The multiphase detergent tablet according to the invention comprises a first phase and a second phase and optionally further phases. The first phase is in the form of a shaped body of a detergent composition containing one or more detergent ingredients as described below.

Preferred detergent compositions contain a builder, bleach, enzymes and a surfactant. The ingredients of the detergent composition are intimately mixed, e.g., by mixing the dry ingredients or spraying the liquid ingredients. The ingredients are then formed into a first phase using any suitable equipment, preferably by compression, e.g. in a tablet press. The first phase can also be produced by extrusion, casting etc. The first phase can take various geometrical shapes such as spheres, cubes etc. but in preferred embodiments they are essentially elements with an axis of symmetry, typically circular, square or rectangular in cross section. .

The first phase is produced in that it comprises at least one cavity in the surface of the shaped element. The socket or sockets may also differ in size and shape, and in position, orientation and topology with respect to the first phase /. For example, the socket or sockets may be substantially circular, square or oval in cross section; they may form an internally closed cavity or recess in the surface of the shaped element, or they may extend between non-interconnected surface areas of the element (e.g. between axially opposite faces), thus creating one or more topological "holes" in the shaped element , and may be axially or otherwise symmetrically disposed with respect to the first phase, or they may be asymmetrically disposed. In a preferred embodiment, the seats are formed using a tablet press with a special design in which the surface of the punch, which contacts the detergent composition, is shaped such that when it contacts and compresses the detergent composition, it forms a pocket or series of pockets in the first phase of the multi-phase tablet. detergent. Preferably, the seat will have an inwardly concave or generally concave surface to provide enhanced adhesion to the second phase. Alternatively, the seat may be made by compressing a preformed element of a detergent composition arranged in an annular pattern around a central die, thereby forming the shaped element containing the socket in the form of a cavity extending axially between opposite surfaces of the element.

The tablets of the invention also contain one or more additional phases made of one or more compositions which contain one or more detergent ingredients as described below. At least one phase (herein referred to as the second phase) preferably takes the form of a solid particulate

190 559 (which includes powders, granules, agglomerates and other particulate solids, including mixtures thereof with liquid binders, meltable solids, spray mixtures, etc.), pressed into one or more cavities in the first phase of the tablet detergent or compressed in these seats so that the second phase itself takes the form of a shaped body. The optional additional phases include one or more compositions in the form of separate layer or layers. The preferred detergent ingredients include builders, colorants, binders, surfactants, disintegrants and enzymes, especially amylase and proteinase enzymes.

In another preferred embodiment of the invention, the second phase and the optional further phases contain a disintegrant which may be selected from a disintegrant and an effervescent agent. Suitable disintegrants include those that swell on contact with water or facilitate the inlet and / or outflow of water by creating channels in the detergent tablet. Any known disintegrants or effervescent agents suitable for use in dishwashing are suitable. Suitable disintegrating agents include starches (such as natural, modified or pregelatinized starches, e.g., corn, rice and potato), starch derivatives such as U-Sperse (trade name), Primojel (trade name), and Explo. tab (trade name), celluloses, microcrystalline celluloses and cellulose derivatives such as Arbocel (trade name) and Vivapur (trade name), available from Rettenmaier, Nymcel (trade name) available from Metsa-serla, Avicel (trade name), Lattice NT (trade name) and Hanfloc (trade name), alginates, acetate trihydrate, burkeite, carbonate monohydrate of formula Na2CO3-H2C, hydrated sodium tripol phosphate (STPP) with a Phase I content of at least about 4C%, carboxymethylcellulose (CMC ), CMC-based polymers, sodium acetate, aluminum oxide. Suitable effervescent agents include those which generate a gas on contact with water. A suitable effervescent agent can be oxygen, nitrogen dioxide or carbon dioxide evolving agent. Exemplary effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with carboxylic acids or other acids such as citric, sulfamic, malic or maleic.

The ingredients of the detergent composition are mixed e.g. by mixing the dry ingredients and mixing or spraying the liquid ingredients. The components of the second phase and possibly the following phases are then introduced and held in the cavity formed in the first phase.

A preferred embodiment of the invention comprises two phases: a first and a second phase. The first phase will typically contain one cavity and the second phase will typically contain a single detergent active ingredient composition. However, it is acceptable that the first phase could contain more than one cavity and the second phase could be made of more than one detergent active ingredient. Furthermore, it is acceptable that the second phase may contain more than one detergent active ingredient composition in one seat. It is also acceptable for a number of the detergent active ingredient composition to be in different seats. In this way, potentially chemically sensitive detergent ingredients can be separated so as to avoid any deterioration in performance caused by the ingredients reacting with each other, such that they may be deactivated or exhausted.

The first, second and optionally additional phases may contain a binder which, as mentioned above, constitutes an essential component of the second phase. The binder is selected from the group consisting of organic polymers, e.g. polyethylene and / or polypropylene glycols, especially 4CCC, 6CCC and 9CCC molecular weight, paraffins, polyvinylpyrrolidone (PVP), especially PVP with a molecular weight 9CCCC, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, e.g. hydroxypropylmethyl cellulose (HPMC) and carboxymethyl cellulose (CMC); and inorganic polymers such as hexametaphosphate. The role of the binder is to ensure tablet integrity and achieve differential dissolution of the first and second phases as described below.

In a preferred embodiment of the invention, the weight of the first phase is greater than about 3 g, preferably greater than about 4 g, more preferably greater than about 5 g. More preferably the weight of the first phase is from

About 10 g to about 30 g, more preferably from about 15 g to about 25 g, and most preferably from about 18 g to about 24 g. As mentioned above, the weight of the second phase and any optional subsequent phases is less than 4 g. the second and / or optional subsequent phases is from about 0.1 g to about 3.5 g, preferably from about 1 g to about 3.5 g, most preferably from about 1.3 g to about 2.5 g.

As mentioned above, a barrier layer comprising the barrier layer composition is located between the first and second phases and / or any subsequent phases, or between the second phase and any optional subsequent phases. The barrier layer composition comprises at least one binder selected from the group described above. The barrier layer has the advantage of preventing or limiting migration of components from one phase to another phase, e.g., from the first to the second phase and / or possible subsequent phases, and vice versa.

The components of the second phase and any subsequent phases are preferably compressed using a very low compressive force compared to the compressive force normally used in the manufacture of tablets. Accordingly, it is an advantage of the invention that heat, force or chemically sensitive detergent ingredients can be incorporated into the detergent tablet due to the low compressive force being used without fear of the deterioration in performance normally associated with incorporating such ingredients into tablets. Alternatively, the second phase or phases may be compressed using the same or higher compressive force than the first phase so as to achieve differential phase dissolution as described below.

A further advantage of the invention is the increased protection of the second phase against damage caused e.g. by handling or transport. As described above, multiphase detergent tablets are produced where the second layer is compressed with a lower compressive force than the first layer. However, at an increased dissolution rate, the second layer of such tablets becomes susceptible to breakage, leading to disintegration or crushing on contact. However, the slightly compressed phase (s) of the detergent tablets according to the invention is secured in the seat, with the first phase being the detergent tablet.

Yet another advantage of the invention is the possibility of producing a multiphase detergent tablet in which one phase can be designed to dissolve, preferably significantly, before the other phase. Preferably the second phase and any possible further phases dissolve before the first phase. Within the preferred weight ranges given above, the first phase preferably dissolves within 5-20 minutes, more preferably 10-15 minutes, and the second phase and / or any subsequent phases dissolve in less than 5 minutes, more preferably less than 4.5 minutes and most preferably less than 4 minutes. Alternatively, the second phase may dissolve after the first phase or other phases, e.g. in case it is desired to provide a beneficial cleaning or rinsing effect at the end of washing. The times at which the first and second phases and / or any subsequent phases dissolve are independent of each other. Accordingly, differential phase dissolution is achieved. A particular advantage of being able to achieve differential dissolution of a multiphase detergent tablet is that a component that is chemically inactivated in the presence of another component may be introduced into a separate phase. In this case, the component that is deactivated is preferably in the second phase and in an optional next phase (s).

Yet another advantage of the invention is the increased interphase adhesion of the multiphase tablet. It is believed that the enhanced adhesion is achieved by reducing the exposure of the second phase compared to known multiphase tablets, making the tablets of the invention less prone to breaking along the contact lines.

Multiphase detergent tablets are made on any suitable tabletting machine such as e.g. Courtoy R253. Preferably tablets are made by compression in a tableting machine capable of producing a tablet having a pocket. In a particularly preferred embodiment of the invention, the first phase is produced on a specially designed tablet press as described below. The punch (s) of such a tablet press are modified so that the surface of the punch in contact with the detergent composition of the tablet is a convex surface.

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The first detergent composition is introduced into the die of the tablet press and the punch is lowered into contact with the detergent composition and compressed into the first phase. The first detergent composition is typically compacted under an applied pressure of at least about 24.5 MPa, preferably from about 34.3 to about 196.2 MPa, more preferably about 49.0 to about 147.1 MPa, most preferably about 58.9 to about 117 MPa. , 7 MPa! The punch is then raised so that the first phase containing the cavity is exposed. In turn, a second and possibly further detergent compositions are introduced into the seat. The specially designed tablet press punch is then lowered a second time to lightly compress the second and possibly subsequent detergent compositions to form the second phase and any subsequent phases. In another embodiment of the invention, when any optional further phases are present, such an optional next phase is formed in an optional subsequent pressing step substantially similar to the second pressing step described above. The second and optional subsequent detergent compositions are compressed at a pressure of preferably less than about 34.3 MPa, more preferably from about 3.9 to about 29.4 MPa, most preferably from about 6.9 to about 26.5 MPa. After the second detergent composition has been compressed, the punch is lifted a second time and the multi-phase detergent tablet is pushed out of the tablet press.

Detergent ingredients

The first, second and / or optionally subsequent phases of the multiphase detergent tablet according to the invention are prepared by compressing one or more compositions containing detergent actives. Conveniently, the compositions used in any of these phases may contain a variety of detergent ingredients, including builders, surfactants, enzymes, bleaches, alkalinity sources, colorants, perfume, calcium soap dispersants, organic polymeric compounds including polymeric inhibitors. dye transfer, crystal growth inhibitors, heavy metal ion complexing agents, metal salts, enzyme stabilizers, corrosion inhibitors, foam extinguishing agents, solvents, fabric softeners, optical brighteners and solubilizing agents.

The very preferred detergent ingredients of the first phase are builder, surfactant, enzyme and bleach. Highly preferred second phase detergent ingredients include builder, enzymes, crystal growth inhibitors, and disintegrants and / or binders.

Active filler

The tablets of the invention preferably contain a builder, typically in an amount of 1% - 80% by weight, preferably 10% - 70% by weight, most preferably 20% - 60% by weight. detergent active ingredient compositions.

Water-soluble builder

Suitable water-soluble builders include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid contains at least two carboxylic groups separated by no more than two carbon atoms, carbonates , bicarbonates, borates, phosphates, and mixtures of any of the above.

The carboxylate or polycarboxylate builder can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for reasons of cost and efficiency.

Suitable carboxylates containing one carboxyl group include the water-soluble salts of lactic acid, glycolic acid, and their ether derivatives. Polycarboxylates containing two carboxyl groups include the 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 3 carboxyl groups include, in particular, water-soluble citrates, aconitates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in GB 1,379,241, the lactoxysuccinates described in

190,559 of U.K. 1,389,732, and the aminosuccinates described in Dutch Patent Application No. 7205873, and oxypolycarboxylate materials such as the 2-oxa-1,1,3-propane tricarboxylates described in GB 1,387,447.

The polycarboxylates having 4 carboxyl groups include the oxydisuccinates described in British Patent No. 1261829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in United Kingdom Patent No. 1,439,000.

The alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene-pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2, 5,5-tetrahydrofuranetetracarboxylates, 1,2,3,4,5,6-hexanehexacarboxylates, and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxyl groups per molecule, especially citrates.

The parent acid of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate / citric acid mixtures are also contemplated as useful builder type ingredients.

Borate builders, as well as builders containing borate-forming materials that can form borate under detergent storage conditions or during washing, may also be used, but are not preferred when washing at temperatures below 50 ° C, especially below 40 ° C. .

Examples of carbonate builders include alkaline earth metal carbonates, and alkali metal carbonates including carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, disclosed in German Patent Application No. 2,321,001 published November 15, 1973.

Highly preferred builders for use in the present invention include water-soluble phosphate builders. Specific examples of water-soluble phosphate builders include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate with a degree of polymerization of 6-21, and acid salts phytic.

Partially soluble or insoluble builder

The tablets of the invention may contain a partially soluble or insoluble builder. Partially soluble or insoluble builders are particularly suitable for use in tablets intended for dishwashing use. Examples of partially water-soluble builders are the crystalline layered silicates disclosed, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Crystalline layered sodium silicates of formula are preferred

NaMSixO2 + i · yH ₂ O where M is sodium or hydrogen, x is 1.9 -4, and y is 0-20. Crystalline sodium layered silicates of this type preferably have a two-dimensional "lamellar" structure, such as The 5-layer structure is disclosed in EP 0164514 and EP 0293640. Methods for producing crystalline layered silicates are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the invention, x in the above general formula is 2, 3 or 4 and is preferably 2.

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The most preferred crystalline layered sodium silicate is represented by the formula Na-Na SSijOj, known as NaSKS-6 (trade name), available from Hoechst AG

The crystalline layered sodium silicate material is preferably present in granular detergent compositions as particles in intimate admixture with a solid water-soluble ionizable material as described in PCT Patent Application No. WO92 / 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 significantly water-insoluble builders include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having the unit cell formula Na _z [(AlO2) z (SiO2) y] xH2O, wherein z and y are at least 6; the molar ratio z to y is 1.0-0.5, with x being at least 5, preferably 7.5-276, more preferably 10-264. The alumino-silicate material is hydrated and is preferably crystalline, containing 10% -28 %, more preferably 18% - 22% of bound water.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetic. Synthetic, crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.

A preferred method of synthesizing aluminosilicate zeolites is described by Schoeman et al. (Zeolite (1994) 14 (2), 110-116) where the authors describe the preparation of colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should be such that no more than 5% of the particles have a diameter greater than 1 µm and no more than 5% of the particles are less than 0.05 µm. Preferably the aluminosilicate zeolite particles have an average diameter of 0.01 µm -1 µm, more preferably 0.05 µm - 0.9 µm, most preferably 0.1 µm - 0.6 µm.

Zeolite A is given by the formula

Na, 2 [AlO2) and2 (SiO2)] xH2O where x is 20-30, especially 27.

Zeolite X is defined by the formula

Na ^ tA ^ MSAbd · 276H20.

Zeolite MAP, disclosed in EP-B-384070, is a preferred zeolite builder.

Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. The use of colloidal aluminosilicate zeolites as a component of a detergent composition, particularly colloidal zeolite A, provides enhanced builder performance in providing effective stain removal. The increased efficiency of the builder can also be seen as reduced soil clogging and increased whiteness maintenance; these problems are believed to be related to detergent compositions with an inadequate builder content.

It has been surprisingly found that mixed zeolite aluminosilicate detergent compositions containing colloidal zeolite A and colloidal zeolite Y provide the same efficiency in complexing calcium ions as an equal weight amount of commercially available zeolite A. Another unexpected finding is that the mixed zeolite aluminosilicate detergent compositions , as described above, provide increased efficiency in complexing magnesium ions as an equal weight amount of commercially available zeolite A.

Surfactant

Surfactants are the preferred detergent actives of the detergent tablets of the invention. Suitable surfactants are selected from anionic, cationic, non-ionic, ampholytic and zwitterionic

190 559 surfactants and mixtures thereof. The dishwasher products should be low-foaming and therefore the foaming of the surfactant system to be used in dishwashing needs to be suppressed or, more preferably, they should be low-foaming systems, usually non-ionic in nature. Foaming caused by surfactant systems used in washing need not be suppressed to the same extent as in washing. The surfactant is typically present in an amount of 0.2-30 wt%, more preferably 0.5-10 wt%, most preferably 1-5 wt%. detergent active ingredient compositions.

A typical listing of the anionic, nonionic, ampholytic, and zwitterionic classes and grades of such surfactants is given in U.S. Patent No. 3,929,678 to Laughlin and Heuring, issued December 30, 1975. For a list of suitable cationic surfactants, see U.S. Patent No. 3,929,678. No. 4,259,217, Murphy, issued March 31, 1981. A list of surfactants conventionally used in automatic dishwasher detergent compositions is given, for example, in EP-A-0414 549 and in WO 93/08876 and WO 93/08874.

Non-ionic surfactant

Essentially any nonionic surfactant suitable for detersive purposes can be included in the detergent tablet. The preferred, non-limiting classes of nonionic surfactants are listed below.

Non-ionic surfactant of the ethoxylated alcohol type

According to the invention, alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and typically contains 6-22 carbon atoms. Particularly preferred are the condensation products of alcohols containing an alkyl group having 8-20 carbon atoms with 2-10 moles of ethylene oxide per mole of alcohol.

A surfactant of the terminally capped alkyl alkoxide

Suitable surfactants of the terminally blocked alkyl alkoxide type are epoxide blocked poly (alkoxylated) alcohols of the formula:

R _X O [CH2CH (CH3) O] χ [CH2CH2O] y [CH2CH (OH) R2] (I) where R | is a linear or branched aliphatic hydrocarbon group having 4 - 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon group having 2 to 26 carbon atoms; x is an integer with an average value of 0.5-1.5, more preferably 1; and y is an integer with an average value of at least 15, more preferably at least 20.

Preferably, the epoxy terminal [CH2CH (OH) R2] group in the surfactant of formula I contains at least 10 carbon atoms. Suitable surfactants of formula I include the nonionic surfactants of Olin Corporation, POLl-TERGENT® SLF-18B, described e.g. in WO 94/22800, published October 13, 1994 by Olin Corporation.

Poly (oxyalkylated) alcohols terminated with ether groups

According to the invention, the preferred surfactants used are poly (oxyalkylated) alcohols terminated with ether groups, having the formula:

Rio [CH2CH (r3) o] χ [CH2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 1-30 carbon atoms; R ³ is hydrogen or a linear aliphatic hydrocarbon group having 1-4 carbon atoms; x is an integer ranging from 1 to 30, with the proviso that when x is 2 or more,

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R ³ may be the same or different and k and j are integers with an average value of 1-1 ° C, more preferably 1-5.

R ¹ and R · are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 6 to 22 carbon atoms, most preferably 8-18 carbon atoms. R ³ is most preferably a hydrogen atom or a linear aliphatic hydrocarbon group having 1-2 carbon atoms. Preferably, x is an integer with an average value of 1-20, more preferably 6-15.

As noted above, when, in preferred embodiments, x is greater than 2, R ³ may be the same or different. Thus, R ' ³ may be any of the alkyleneoxy groups described above. For example, when x is 3, R3 may be selected to form an ethyleneoxy (EO) or propyleneoxy (PO) moiety, and may vary in the order of (EO) (PO) (EO), (EO) (EO) ( AFTER); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the number 3 is chosen by way of example only, so that the variation can be much greater at higher values of x and include, for example, a number of (EO) units and a much smaller number of (PO) units.

Particularly preferred surfactants described above are those that exhibit a low cloud point, below 20 ° C. These low cloud point surfactants may then be used in conjunction with a high cloud point surfactant as detailed below to provide more favorable cleaning of greasy soil.

The most preferred ether-terminated poly (oxyalkylated) alcohol surfactants are those where k is 1 and j is 1, i.e. the surfactants of formula

R ¹ O [CH 2 CH (R 2) O] _x CH ² CH (OH) CH ² OR ² where R ¹ , R ² and R 3 are as defined above, and x is an integer with an average value of 1-30, preferably 1-20, more preferably 6 -11 ?. Most preferred are surfactants in which R ¹ and R ² are in the range 9-14, R 3 is hydrogen such that an ethyleneoxy moiety is formed, and x is 6-15.

Poly (oxyalkoxylated) ether terminated alcohol surfactants contain 3 general components viz. Linear or branched alcohol, alkylene oxide and terminal alkyl ether group. The terminal alkylether group and the alcohol constitute the hydrophobic oil-soluble portion of the molecule, and the alkylene oxide group forms the hydrophobic, water-soluble portion of the molecule.

Such surfactants provide a significant improvement with respect to spot marking and film formation and the removal of greasy soil when used in conjunction with high cloud point surfactants, compared to conventional surfactants.

In general, poly (oxyalkylene) ether-terminated alcohol surfactants can be prepared by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with the alkoxylated alcohol to form a new compound. Exemplary methods for the preparation of ether terminated poly (oxyalkoxylated) alcohol surfactants are described below:

Preparation of C 12/14 alkyl glycidyl ether

C12 / 14 fatty alcohol (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol, available from Aldrich) were combined in a 500 mL three-necked round bottom flask equipped with an argon inlet, dropping funnel, magnetic stirrer and probe to measure internal temperature. The mixture was heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) was added dropwise at such a rate as to maintain the temperature at 60-65 ° C. After being stirred for an additional hour at 60 ° C, the mixture was cooled to room temperature. To the mixture

190,559 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) was added with mechanical agitation. After the addition was complete, the mixture was heated to 90 ° C for 1.5 hours, cooled, and filtered with ethanol as an aid. The filtrate was separated and the organic phase was washed with water (100 ml), dried over MgSO 4, filtered and concentrated. Glycidyl ether was obtained as an oil by distilling the oil at 100-120 ° C (0.1 mm Hg -13.33 Pa).

Preparation of an alcohol type surfactant terminated with C12 / 14 alkyl0-C9 / 11 ether

Neodol® 91-8 (20.60 g, 0.0393 mol, ethoxylated alcohol available from Shell chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) were combined in a 250 mL three-necked round bottom flask, equipped with a cooler, argon inlet, dropping funnel, magnetic stirrer and a probe for measuring internal temperature. The mixture was heated to 60 ° C and C 12/14 alkyl ghcidyl ether (11.00 g, 0.0393 mol) was added dropwise over 15 minutes. After stirring for 18 hours at 60 ° C, the mixture was cooled to room temperature and dissolved in an equal amount of dichloromethane. The solution was passed through a 1 inch (2.54 cm) silica gel cartridge eluting with dichloromethane. The filtrate was concentrated on a rotary evaporator and chased on a kugelrohr (100 ° C, 0.5 mm Hg -66.66 Pa) to afford the surfactant as an oil.

Non-ionic surfactant of the ethoxylated / propoxylated fatty alcohol type

Ethoxylated C6-C1 fatty alcohols and mixed ethoxylated / propoxylated C6-C18 fatty alcohols are suitable surfactants for use in the invention, especially when water-soluble. Preferably the ethoxylated fatty alcohols are C10-C18 fatty alcohol ethoxylates with a degree of ethoxylation of 3-50, most preferably C12-C18 fatty alcohols ethoxylated with a degree of ethoxylation of 3-40. Preferably the mixed ethoxylated / propoxylated fatty alcohols contain an alkyl chain of 10-18 carbon atoms with with a degree of ethoxylation of 3 - 30 and with a degree of propoxylation of 1-10.

Non-ionic EO / PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic base obtained by condensing propylene oxide with propylene glycol are suitable for use in the present invention. The hydrophobic part of these compounds preferably has a molecular weight of 1500-1800 and is insoluble in water. Examples of compounds of this type include certain of the commercially available Pluronic ™ surfactants, available from BASF.

Nonionic EO condensation products with propylene oxide / ethylene diamine adducts

The condensation products of ethylene oxide with the product obtained by reacting propylene oxide with ethylenediamine are suitable for use in the invention. The hydrophobic moiety in such products is the reaction product of ethylenediamine with an excess of propylene oxide, typically with a molecular weight of 2,500-3,000. Examples of nonionic surfactants of this type include certain commercially available Tetronic ™ compounds from BASF.

System in the form of a mixture of surfactants

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

"Cloud point", as used herein, means the well-known property of nonionic surfactants such that the surfactant becomes less soluble with increasing temperature, the temperature at which the appearance of the second phase is observed to be " cloud point ”(see Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Edition, Vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is defined as a component of a non-ionic surfactant system having a cloud point below 30 ° C, preferably below 20 ° C, and most preferably below

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10 ° C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) inverse block polymers. In addition, such low cloud point nonionic surfactants include e.g. ethoxylated propoxylated alcohol (e.g. Poli-Tergent® SLFl8 from Olin Corporation), poly (alkoxylated) epoxy terminated alcohols (e.g. Poli-Tergent® SLF18B series of nonionic surfactants actives from Olin Corporation, described e.g. in WO 94 / 228CC, published October 13, 1994, Olin Corporation); and ether terminated poly (alkoxylated) alcohol surfactants.

The nonionic surfactants may optionally contain propylene oxide in an amount up to 15 wt.%. Other preferred nonionic surfactants can also be prepared by the methods described in U.S. Patent No. 4,223,163, Oct.16, 198C, Buillots, which is hereby incorporated by reference.

Low cloud point nonionic surfactants further include polyoxyethylene-polyoxypropylene block polymers. Polyoxyethylene-polyoxypropylene block polymers include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane and ethylene diamine as an initiator of a compound with active hydrogen atoms. Certain surface active block polymers, designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC®, from BASF-Wyandotte Corp., Wyandotte, Michigan, are useful in automatic dishwasher detergent compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 7C2. Such surfactants are typically useful in the detergent tablets of the invention as low cloud point nonionic surfactants.

As used herein, a high cloud point nonionic surfactant is defined as a component of a nonionic surfactant system having a cloud point greater than 4C ° C, preferably greater than 5C ° C, more preferably greater than 6C ° C. Preferably, the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction product of a monohydroxy alcohol or alkylphenol having 8-20 carbon atoms, with an average of 6-15 moles of ethylene oxide per mole of alcohol or alkylphenol. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (available from Union Carbide), Rhodasurf TMD 8.5 (available from Rhone Poulenc), and Neodol 91-8 (available from Shell).

In addition, it is preferred in the present invention that the high cloud point nonionic surfactant further has a hydrophilic-lipophilic balance ("HLB"; see Kirk Othmer, supra) in the range 9-15, preferably 11-15. Tergitol 15S9 (available from Union Carbide), Rhodasurf TMD 8.5 (available from Rhone Poulenc) and Neodol 91-8 (available from Shell).

Other preferred high cloud point surfactants are derived from a straight or preferably branched chain or secondary fatty alcohol containing 6-20 carbon atoms (C6-C2C alcohol), including secondary alcohols and branched-chain primary alcohols. Preferably the high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9 / C11 or C11 / 15 branched alcohol ethoxylates, condensed on average to 6-15 moles, preferably 6-12 moles, and most preferably 6-9 moles. ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant thus obtained has a narrow ethoxylation distribution relative to the average.

Anionic surfactant

In principle any anionic surfactant suitable for detersive purposes is suitable. These include the anionic salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts)

190,559 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 derived from methyl tauride, alkylsuccinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-C13 monoesters), diesters (especially C12-C13 unsaturated and unsaturated sulfosuccinates) ₆ -Ci4 diesters), N-acylsarcosinates. Resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin, and the resin acids and hydrogenated resin acids present in tallow oil, are also useful.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use in the present invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycer sulfates, alkylphenol ether sulfates with ethylene oxide, C5-C17 acyl-N- (C1-C4 alkyl) sulfates ) and -N- (C1 -C2 hydroxyalkyl) glucamines; and alkyl polysaccharide sulfates such as alkyl polyglucoside sulfates (non-ionic unsulfated compounds mentioned herein).

The alkyl sulfate surfactants are preferably selected from linear and branched C10-C18 primary alkyl sulfates, more preferably C11-C15 branched chain alkyl sulfates and linear chain C12-C14 alkyl sulfates.

The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C10-C18 alkyl sulfate, ethoxylated with 0.5-20 moles of ethylene oxide per molecule. More preferably the alkyl ethoxy sulfate surfactant is a C11-C18, most preferably a C11-C15 alkyl sulfate ethoxylated with 0.5-7, preferably 1-5 moles of ethylene oxide per molecule.

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

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use in the present invention include C5-C20 linear alkyl benzene sulfonates, alkyl ester sulfonates, C6-C20 primary or secondary alkanesulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkylglycerin sulfonates, fatty glycerin sulfonates Fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps ("alkyl carboxylates"), especially certain secondary soaps described herein.

Suitable alkyl ethoxycarboxylates include compounds of formula RO (CH2CH2O) xCH2COO'M ⁺ where R is a C6-C18 alkyl group, x is 0-10, the distribution of ethoxylate is such that by weight, the amount of material where x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula RO- (CHR | -CHR2-O) -R3 where R is C6-C18 alkyl, x is 1-25, R1 and R2 are selected from the group consisting of hydrogen, g a methyl acid group, a succinic acid group, a hydroxysuccinic acid group, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon groups having 1-8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl group attached to a secondary carbon atom. Preferred secondary soap surfactants for use in the present invention include water-soluble ingredients selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-acid. -nonanoic acid

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2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as foam suppressants.

An alkali metal sarcosinate surfactant

Other suitable anionic surfactants include alkali metal sarcosinates of the formula R-CON (R ') CH2COOM, where R is a C5-C17 linear or branched alkyl or alkenyl group, r1 is a C1-C4 alkyl group, and M is a metal ion alkaline. Preferred examples are myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactant

Suitable amphoteric surfactants for use in the present invention include amine oxide surfactants and alkylamphcarboxylic acids.

Suitable amine oxides include compounds of formula R ³ (OR ⁴ ) xN ° (R ') 2, wherein R' is selected from the group consisting of alkyl, hydroxyalkyl, acylamidopropoyl, and alkylphenyl, or mixtures thereof, containing 8-26 carbon atoms; R4 is an alkylene or hydroxyalkylene group having 2-3 carbon atoms or mixtures thereof; x is 0-5, preferably 0-3; and each R ⁵ is an alkyl or hydroxyalkyl containing 1-3, or a polyethylene oxide moiety containing 1-3 ethylene oxide groups. Preference is given to using a C 10 -C 18 alkyldimethylamine oxide and a C 10 -C 1 acylamidoalkyldimethylamine oxide.

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

Bipolar surfactant

Bipolar surfactants can also be included in the detergent compositions of the invention. Such surfactants can generally be referred to as secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or quaternary ammonium derivatives, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultene surfactants are exemplary zwitterionic surfactants for use in the present invention.

Suitable betaines are compounds of formula R (R 1 N + RCOO ', wherein R is a C 6 -C 18 hydrocarbyl group, each r 1 is typically a C 1 -C 6 alkyl group and R 2 is a C 1 -C 5 hydrocarbyl group. and Cro-Cig acylamidopropane (or ethane) dimethyl (or diethyl) betaines Complex betaine surfactants are also suitable for use in the invention.

Cationic surfactants

The cationic ester surfactants used according to the invention are preferably water-dispersible compounds with surfactant properties which contain at least one ester group (i.e. -COO-) and at least one cationically charged group. Other suitable cationic ester surfactants include the choline ester surfactants, as disclosed in, for example, U.S. Patent Nos. 4,228,042, 4,239,660 and 4,260,529.

Suitable cationic surfactants include quaternary ammonium surfactants selected from mono-C 6 -C 18, preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants, where the remaining positions on the nitrogen atom are substituted with methyl, hrroxyethyl or hydroxypropyl.

Enzymes

Enzymes are the preferred detergent ingredients of the first phase, especially the second and / or possible subsequent phases. When present, enzymes are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, ligninases, ligninases, ligninases, pulmonases. , pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccase and mixtures thereof.

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Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase, and / or cellulase, in combination with one or more plant cell wall degrading enzymes.

Cellulases useful in the compositions of the invention include both bacterial and fungal cellulases. Preferably they will exhibit optimal performance at a pH of 5 to 12, and an activity greater than 50 CEVU (cellulose viscosity units). Suitable cellulases are disclosed in U.S. Patent No. 4,435,307 to Barbesgoard et al. In J61078384 and WO96 / 02653, which disclose fungal cellulases produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275, DE-OS-2247832 and WO 95/26398.

Such cellulases include, for example, cellulases produced by the strain Humicola insolens (Humicola grisea var. Thermoidea), especially the strain Humicola DSM 1800. Other suitable cellulases include cellulases derived from Humicola insolens having a molecular weight of about 50,000, an isoelectric point of 5.5 and containing 415 amino acids; and a ~ 43,000 endoglucanase derived from Humicola insolens DSM 1800 having cellulase activity, a preferred endoglucanase component comprises the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Suitable cellulases also include the EGIU cellulases from Trichoderma longibrachiatum, described in WO 94/21801, Genencor, published September 29, 1994. Particularly suitable cellulases include color-protecting cellulases. Such cellulases are, for example, those described in European patent application EP-A-495257. Carenzyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO 91/21801.

Other suitable textile protective and / or cleaning cellulases are described in WO 96/34092, WO 96/17994 and WO 95/24471.

Such cellulases are typically included in the detergent composition in an amount of 0.0001% - 2% by weight. active enzyme in relation to the detergent composition.

Peroxidases are useful with oxygen sources such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", that is, to prevent transfer of dyes or pigments removed from substrates during washing to other substrates in the wash solution. Peroxidases are known and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Detergent compositions containing peroxidases are disclosed, for example, in international PCT applications WO 89/099813, WO 89/09813 and in European patent application EP-A-540784 and in European patent application EP 96870013.8 corresponding to WO 97/30143. Laccase is also suitable.

Preferred enhancers include substituted phenothiazines and phenoxazines, 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinopropionic acid (POP), and 10-methylphenoxazine (described in WO 94/12621) and substituted syringans (C3-C5 alkyl substituted syringans) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

Such cellulases and / or peroxidases are usually included in the detergent composition in amounts of 0.0001% - 2% by weight of active enzyme, based on the detergent composition.

Other preferred enzymes that can be included in the detergent compositions of the invention are lipases.

Suitable lipases for use in detergents include enzymes produced by Pseudamonas microorganisms, such as Pseudomonas stutzeri ATCC 19.154, disclosed in British Patent No. 1,372,034. Suitable lipases include those which show a positive cross-reactivity with the lipase antibody produced by the Pseudomonas microorganism. fluorescent LAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the tradename Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Amano-CES, lipases from Chromobacter viscosum, e.g., Chromobacter viscosum var. lipolyticum

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NRRLB 3673 ex Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. Particularly suitable lipases include lipases such as Ml Lipase® and Lipomax® (GistBrocades) as well as Lipolase® and Lipolase Ultra® (Novo) which have been found to be very effective when used in conjunction with the compositions of the invention. Also useful are the lipolytic enzymes described in EP 258068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

Also useful are the cutinases [EC 3.1.1.50], which can be considered as a special type of lipase, namely as lipases that do not require activation at the interface. The addition of cutinases to detergent compositions is described e.g. 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 incorporated into the detergent composition in an amount of 0.0001% - 2% by weight of active enzyme, based on the detergent composition.

Suitable proteases are subtilisins, obtained from respective strains of B. subtilis and B. licheniformis (BPN and BPN subtilisin). One suitable protease is an enzyme obtained from a Bacillus strain with a maximum activity in the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / S, Denmark, hereinafter referred to as "Novo". The preparation of this enzyme and analogous enzymes is described in GB 12-43784 to Novo. Other suitable proteases include KANNASE®, ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal with genetically engineered protein) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Publication EP-A-251,441 (especially on pages 17, 24 and 98), herein referred to as "Protease B", and in European Patent Application No. 199404 , Venegas, October 29, 1986 concerning a modified bacterial proteolytic serine enzyme, referred to herein as "Protease A". Also useful is an enzyme, referred to herein as "Protease C," which is a variant of Bacillus alkaline serine protease in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, serine replaces asparagine at position 123, and alanine replaces threonine at position 123. at position 274. Protease C is described in EP 90915958.4, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants are also useful, especially Protease C.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant containing a non-naturally occurring amino acid sequence obtained from a precursor carbonyl hydrolase by substituting a series of amino acid residues at a position corresponding to position +76 of a carbonyl hydrolase, preferably in combination with one or more amino acid residues at positions equivalent to positions 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 Bacillus amyloliquefaciens subtilisin numbering , described in WO 95/10591 and in United States Patent Application Publication No. US-A-6066611 (Application 08/322677 filed October 13, 1994, C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes").

Also suitable for use in the invention are the proteases described in EP 251 446 and WO 91/06637, the BLAP® protease described in WO91 / 02792 and variants thereof described in WO 95/23221.

See also the high pH protease from Bacillus sp. NCIMB 40338, described in WO 93/18140 A to Novo. Enzymatic detergents containing a protease, one or more other enzymes, and an inverse protease inhibitor are described in WO 92/03529 A to Novo. If desired, a protease with reduced adsorption capacity and increased hydrolysis capacity is available, as described in WO 95/07791, by Procter & Gamble. A recombinant trypsin-like protease for detergents suitable for use in the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 to Unilever.

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Other preferred protease enzymes include the carbonyl hydrolase variant protease enzymes containing an amino acid sequence not found in nature, derived from a carbonyl hydrolase precursor by substituting a series of amino acid residues at a position corresponding to position +210, in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, + 104, +107, +128, +129, +130, +132, +135, +156, +158, +164 , +166, +167, +170, +209, +215. +217, +218 and +222, whereby the position numbering corresponds to the naturally occurring subtilisin from Bacillus amyloliquefaciens, or to the corresponding amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those having changes in positions +210, +76, +103, +104, +156, and +166.

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

Amylases (a and / or (5) may be included to remove stains of the carbohydrate type. WO 94/02597, Novo Nordisk A / S, published February 3, 1994 describes cleaning compositions which contain mutant amylases. See also WO 95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in cleaning compositions include α and β-amylases. Α-Amylases are known and include the enzymes disclosed in US Patent No. 5,003,257; EP 252666; WO / 91/00353; FR 2676456; EP 285123; EP 525610; EP 368341; and in British Patent No. 1,296,839 (Novo). Other suitable amylases are those with increased stability as described in WO 94/18314, published August 18, 1994 r. and in WO 96/05295, Genencor, published February 22, 1996, and variants of amylases with an additional direct parent enzyme modification available from Novo Nordisk A / S, disclosed in WO 95/10603, published April 1995. Useful are also amylases described in EP 277216, WO 95/26397 and WO 96/23873 (all for Novo Nordisk).

Examples of commercially available α-amylase products include Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, Natalase®, all available from Novo Nordisk A / S Denmark. WO 95/26397 describes other suitable amylases: α-amylases having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature in the range 25 ° C - 55 ° C and at a pH value in the range 8-10, as determined by the Phadebas® α-amylase activity. Useful are variants of the above enzymes as described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with regard to the activity level and the combination of thermostability and higher activity level are described in WO 95/35382.

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

The amylolytic enzymes are incorporated in the detergent compositions according to the invention in an amount of 0.0001% - 2%, preferably 0.00018% - 0.06%, more preferably 0.00024% - 0.048% by weight. pure enzyme in relation to the composition.

In a particularly preferred embodiment, the detergent tablets according to the invention contain amylase enzymes, especially those described in WO95 / 26397 and WO96 / 23873, in combination with complementary amylases.

The term "complementary" refers to the addition of one or more amylases suitable for detergent purposes. Examples of complementary amylases (a and / or (3) are described below. WO 94/02597 and WO 95/10603, Novo Nordisk A / S, describe cleaning compositions which contain mutant amylases. Other amylases known for use in cleaning compositions, include both α- and β-amylases. α-Amylases are known and include the enzymes described in US Patent No. 5003257; EP 252666; WO / 91/00353; FR 2676456; EP 285123; EP 525610; EP 368341; and in British Patent No. 1,296,839 (Novo). Other suitable amylases are the stability-enhanced amylases described in WO94 / 18314 and WO 96/05295, Genencor, and variants of the amylases containing additional modification in the immediate parent enzyme.

190,559 available from Νονο Nordisk A / S, disclosed in WO 95/10603. Also useful are the amylases described in EP 277216 (Νονο Nordisk). Examples of commercially available α-amylase products include Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Νονο Nordisk A / S Denmark. Other suitable amylases are described in WO 95/26397: α-amylases having a specific activity at least 25% higher than that of Termamyl® at a temperature in the range of 25 ° C - 55 ° C and at a pH value in the range of 8-10, in the Phadebas® α-amylase activity test. Useful are variants of the above enzymes as described in WO 96/23873 (Νονο Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and higher activity level, are described in WO 95/35382. Preferred complementary amylases for use in the present invention are the amylases sold under the trade names Purafect Ox Am®, described in WO 94/18314, WO 96/05295, available from Genencor; Termamyl®, Fungamyl®, Ban® Natalase® and Duramyl®, all available with Νονο Nordisk A / S, and Maxamyl® from GistBrocades.

Such complementary amylase is usually included in the detergent compositions of the invention in an amount of 0.0001% - 2%, preferably 0.00018% - 0.06%, more preferably 0.00024% - 0.048% by weight. pure enzyme in relation to the composition. Preferably, the weight ratio of pure specific amylase enzyme to complement 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 aforementioned enzymes may be of any suitable origin, e.g. vegetable, animal, bacterial, fungal and yeast origin. Moreover, they may be mesophilic or extremophilic (psychrophilic, psychrotrophilic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes can be used. Also included are mutants of native enzymes. Mutants can be obtained e.g. by protein and / or genetic modification, chemical and / or physical modification of native enzymes. It is common practice to express the enzyme in the host organism whose genetic material responsible for producing the enzyme has been cloned.

Such enzymes are usually included in the detergent composition in an amount of 0.0001% - 2% by weight. active enzyme in relation to the detergent composition. The enzymes can be added as separate individual components (lumps, 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 include enzyme oxidation inhibitors which are described in European Patent Application Publication EP-A-553607. Examples of enzyme oxidation inhibitors include ethoxylated tetraethylene polyamines.

A number of enzyme materials and methods for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A, to Genencor International, WO 8908694 A for Νονο, and in U.S. Patent No. 3,553,139, filed January 5, 1971, McCarty and others. Enzymes are further disclosed in U.S. Patent No. 4,101,457, Place et al., July 18, 1978, and U.S. Patent No. 4,507,219, Hughes, issued March 26, 1985. Enzymatic materials suitable for liquid detergent formulations, and methods for their incorporation into such formulations are disclosed in US Patent No. 4,261,868 to Hora et al., April 14, 1981. Enzymes for use in detergents are stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, August 17, 1971, Gedge et al, in EP 199405 and EP 200586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US Patent No. 3,519,570. A useful species of Bacillus, sp. AC 13, producing proteases, xylanases and cellulases, is described in WO 94/01532 A for Νονο.

190 559

Bleaching agent

A highly preferred ingredient in the detergent ingredient composition is a bleach. Suitable bleaching agents include chlorine and oxygen releasing bleaches.

In one preferred embodiment, the oxygen releasing bleach comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Organic peroxyacid is formed by an 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 embodiment, the preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a pre-formed organic peroxyacid are also possible.

Inorganic perhydrate bleaching agents

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

The inorganic salt perhydrates are usually introduced as sodium salt in an amount of 1% - 4C% by weight, more preferably 2% - 3C% by weight and most preferably 5% - 25% by weight. relative to the composition.

Examples of inorganic salt perhydrates include perborate, percarbonate, and perphosphate. persulfate and persilicate. Inorganic salt perhydrates are usually alkali metal salts. The inorganic salt perhydrate can be introduced as a crystalline solid without additional protection. However, in the case of certain salt perhydrate, the preferred forms of such granular compositions employ a coated material which provides greater stability of the salt perhydrate in the granular product.

The sodium perborate may be in the form of the monohydrate with the nominal formula NaBCh2Ch or the tetrahydrate of NaBC> 2H2O2 3H2O.

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrate for use in the compositions of the invention. Sodium percarbonate is the adduct of formula 2Na2CO3 · 3H2O2, commercially available as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide additive, tends to dissolve with a relatively rapid release of hydrogen peroxide, which may increase the propensity to produce high local concentrations of bleach. The percarbonate is most preferably incorporated into such compositions in a coated form to ensure its stability in the product.

A suitable coating material ensuring stability in the product is a mixed salt of a water-soluble alkali metal sulphate and carbonate. Such coatings and coating methods are known and described in GB-1466799, issued to Interox on March 9, 1977. The weight ratio of mixed salt coating material to percarbonate is from 1: 2CC to 1: 4, more preferably from 1:99 to 1: 9 and most preferably from 1:49 to 1:19. Preferably the mixed salt is sodium sulfate and sodium carbonate, having the general formula Na2SO4 · n Na2CO3, where n is C.1-3, preferably n is C.3-1, C, most preferably n is C.2 - C.5.

Another suitable coating material for product stability is sodium silicate with a SiO2: Na2O ratio of 1.8: 1 to 3, C: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied in an amount of 2% - 1C% by weight. (typically 3% - 5%) SiO2 based on the inorganic salt perhydrate. Magnesium silicate may also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganic acids are also suitable.

Other coatings that contain waxes, oils, soaps or salts of fatty acids can also be used successfully in the invention.

Potassium peroxymonopersulfate is another inorganic salt perhydrate useful in the tablets of the invention.

A precursor to a peroxyacid bleach

Peroxyacid bleach precursors are compounds that react

190 559 with hydrogen peroxide by perhydrolysis reaction to form the peroxyacid. Typically, peroxyacid bleach precursors can be represented as

About fl

X-C-L where L is a cleavable group and X is essentially any functional group such that the peroxyacid of formula

ABOUT

II

X-C-OOH

The peroxyacid bleach precursor compounds are preferably incorporated in an amount of 0.5-20 wt%, more preferably 1-10 wt%, most preferably 1.5-5 wt%, based on the composition.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, and precursors may be selected from a number of classes of compounds. Suitable classes include anhydrides, esters, imides, lactams, and acylated derivatives of imidazoles and oximes. Examples of suitable materials of these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Cleavable groups

The cleavable group, below the L group, must be sufficiently reactive with the perhydrolysis reaction such that the cleavage reaction takes place within an optimal time interval (e.g. a wash cycle). However, if L is too reactive, the activator will be too difficult to stabilize to be used in a bleach composition.

Preferred L groups are selected from the group consisting of:

-ABOUT

R

-ABOUT

Y and r ⁵ y

ABOUT

II — N-C-R

R ⁵

AND

Y

At ¹¹ 4

-N-C-CH-R

O-CH = C-C1I — CH ₂ —O-CH = C — CH = CH ₂

At ^{11 am} and —OCR

CIL — C

-N. NO ⁴

C.

II o

-N, NO

C '

II o

O — C = CHR, _O time and

OY ^{11 1} 4

N — S — CH — R

AT

R ³ O

190 559 and mixtures thereof, wherein R is alkyl, aryl or alkaryl containing 1-14 carbon atoms, R ³ is an alkyl chain containing 1 - 8 carbon atoms, R ⁴ is hydrogen or R ^J , R ¹ is the chain alkenyl containing 1-8 carbon atoms and Y is hydrogen or a solubilizing group. Any one of R 1, R 'and R ⁴ may be substituted with essentially any functional group, e.g., alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl, amide, and ammonium or alkylammonium.

Preferred solubilizing groups include -SO3-M +, -CO2M +, -SO / M +, -N ⁺ (R ³ ) 4X 'and O < - N (R ³ ) a, and most preferably -SO3'M + and -CO2 * M +. where R ³ is an alkyl chain of 1-4 carbon atoms, M is a cation that provides solubility of the bleach activator, and X is an anion that provides solubility of the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds form perbenzoic acid by perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzene sulfonates, including, for example, benzoyloxybenzene sulfonate:

c yr yr- ^s ° y

Also useful are benzoylation products of sorbitol, glucose, and all sugars with benzoylating agents, such as:

OBz

OAc where Ac = COCH3; Bz = Benzoyl

Imide-type perbenzoic acid precursors include N-benzoyl succinimide, tetrabenzoylethylenediamine and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl-containing perbenzoic acid precursors such as N-benzoylpyrrolidone, dibenzoylthaurine, and benzoylpyroglutamic acid.

Other precursors of perbenzoic acid include benzoyldiacyl peroxides, benzoyltetraacyl peroxides, and a compound of formula:

COOH

Phthalic anhydride is another suitable perbenzoic acid precursor:

190 559

Ο

Ο

Suitable N-acylated lactam perbenzoic acid precursors are given by the formula:

ABOUT

II

About C-CFL— CH,, ιι and | ²

RCN ^x chH <hJ "wherein n is 0-8, preferably 0-2, and R ⁶ is a benzoyl group.

Precursors of perbenzoic acid derivatives

Perhydrolysis precursors to perbenzoic acid derivatives form substituted perbenzoic acids.

Suitable substituted perbenzoic acid precursors include any of the disclosed perbenzoic precursors in which the benzoyl group is substituted with substantially any non-positively charged (or non-cationic) functional group including, e.g., alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl, and an amide group.

A preferred class of substituted perbenzoic acid precursor compounds are the substituted amide compounds of the general formulas:

R — C

II

N — R — C l ₅ II

R — N — C — R — C — L or

R ⁵ OO where R 1 is an aryl or alkaryl group containing 1-14 carbon atoms, R ² is an arylene or alkarylene group containing 1-14 carbon atoms, R ⁵ is hydrogen or alkyl, aryl or alkaryl containing 1-10 carbon atoms and L can be essentially any cleavable group. R1 preferably has 6-12 carbon atoms. R2 preferably contains 4-8 carbon atoms. R1 may be aryl, substituted aryl, or α-karyl, containing branching and / or substitution, and may be derived from synthetic sources or from natural sources such as tallow. Similar structural variants are also possible in the case of R2. The substituents may include alkyl, aryl, halogen, nitrogen, sulfur, and other conventional substituents or organic compounds. R5 is preferably hydrogen or methyl. R1 and R 'should not contain more than 18 carbon atoms in total. Substituted amide bleach activators of this type are described in EP-A-0170386.

Precursors of cationic peroxy acids

Cationic peroxyacid precursor compounds form cationic peroxyacids by perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid portion of the corresponding peroxyacid precursor with a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethyl or methyl ammonium group. Cationic peroxy acid precursors are typically present in the compositions

190 559 in the form of a salt with a suitable anion such as, for example, a halide ion or a methyl sulfate ion.

The peroxyacid precursor compound to be cationically substituted may be a perbenzoic acid precursor compound, or a substituted derivative thereof, as described above. Alternatively, the peroxyacid precursor compound can be an alkyl percarboxylic acid precursor compound or an amide-substituted alkylperoxy acid precursor as described above.

Cationic peroxy acid precursors are described in US Patent Nos. 4,904,406; 4,751015; 4,988,451; 4,397,757; 5269962; 5127852; 5,093,022; 5106528; in British Patent No. 1382594; EP 475512, 458396 and 284292; and in JP 87-318332.

Suitable cationic peroxyacid precursors include any of an ammonium or alkylammonium substituted alkyl or benzone-oxybenzenesulfonia, N-acylated caprolactams, and monobenzoiltetraacetyl glucose as a benzoyl peroxide precursor.

A preferred cationically substituted benzoyloxybenzenesulfonate is 4- (trimethylammonium) methyl benzoyloxybenzenesulfonate:

A preferred cationically substituted alkyloxybenzene sulfonate is given by the formula:

Preferred cationic peroxyacids precursors from the class of N-acylated caprolactam include trialkylammoniummethylene benzoyl caprolactams, especially trimethylammonium methylene benzoyl caprolactam:

X

Other preferred cationic peroxyacids precursors from the class of N-acylated caprolactam include trialkylammoniomethylenealkyl caprolactams:

'Ó where n is 0-12, especially 1-5.

195 959

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

Alkylpercarboxylic acid type bleaching agent precursors

Alkyl percarboxylic acid type bleaching agent precursors form percarboxylic acids by perhydrolysis. Preferred precursors of this type form peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic precursors include N, N, N-tetraacetylated alkylene diamms in which the alkylene group contains 1-6 carbon atoms, especially those in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylenediamine (TAED) is particularly preferred.

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

Amide-substituted alkylperoxyacids precursors

Amide-substituted alkylperoxyacid precursor compounds are also useful, including compounds having the following general formulas

R — C — N — R — C — L

R — N — C— R - C — i.

OR ⁵ O i _u b

R ⁵ OO

7 in which R is an alkyl group having 1-14 carbon atoms, R is an alkylene group having 1-14 carbon atoms, R ⁵ is hydrogen or alkyl containing 1-10 carbon atoms, and L can be essentially any cleavable group . R1 preferably has 6-12 carbon atoms. R2 preferably contains 4-8 carbon atoms. R1 may be straight chain or branched alkyl, containing branching and / or substitution, and may be derived from synthetic or natural sources such as tallow. Similar structural variants are also possible in the case of R2. The substituents may include alkyl, halogen, nitrogen, sulfur, and other conventional substituents or organic compounds. R ⁵ is preferably hydrogen or methyl. R ^r and R ⁵ should not contain more than 18 carbon atoms in total. Substituted amide bleach activators of this type are described in EP-A-0170386.

Benzoxazine precursors of an organic peroxyacid

Also suitable are the precursor compounds of the benzoxazine type, disclosed e.g. in EP-A-332,294 and EP-A-482,807, especially with the formula:

including substituted benzoxazines of the type

190 559 where R1 is hydrogen, alkyl, alkaryl, aryl, aralkyl, and R2, R3, R4 and R5 may be the same or different, selected from the group consisting of H, halogen, alkyl, alkenyl, aryl, hydroxy, alkoxy , amino, alkylamino, COOR6 (where Ro is hydrogen or alkyl), and carbonyl. A particularly preferred precursor of the benzoxazine type is the compound:

ABOUT

Pre-formed organic peroxy acid

The organic peracid bleach system may contain, in addition to or in place of the organic peracid bleach precursor compound, a preformed organic peroxyacid, typically in an amount of 0.5% - 25% by weight, more preferably 1% - 10% by weight, of the composition.

A preferred class of organic peroxyacid compounds are amide-substituted compounds having the following general formulas:

R — C — N — R — C — OOH

R ¹ —N — C — R — C — OOH

OR ⁵ O i _u b

II o

wherein R1 is an alkyl aryl or alkaryl group having 1-14 carbon atoms, R2 is an alkylene, arylene or alkarylene containing 1-14 carbon atoms, and R ⁵ is hydrogen or alkyl, aryl or alkaryl having 1-10 carbon atoms . R ¹ preferably has 6-12 carbon atoms. R2 preferably contains 4-8 carbon atoms. R ~ may be straight chain or branched alkyl, substituted aryl or alkylaryl, containing branching and / or substitution, and may be derived from synthetic or natural sources such as tallow. Analogous structural variations are permissible for R ^2. The substituents may include alkyl, aryl, halogen, nitrogen, sulfur, and other conventional substituents or organic compounds. R5 is preferably hydrogen or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. Compounds of this type in the form of amide-substituted organic peroxyacids are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is the preferred organic peroxyacid for use in the invention. Mono- and dinadazelaic acid, mono- and dinadbrasylic acid, and N-phthaloylaminoperoxicaproic acid are also useful.

Adjustable release rate - measures

Means may be used to control the rate of release of the bleach, especially oxygen bleach, into the washing solution.

Means for controlling the release rate of the bleach can be used, for the controlled release of peroxy compounds into the washing solution. Such measures may, for example, include controlling the release of any inorganic salt perhydrate to act as a source of hydrogen peroxide into the washing solution.

Another mechanism for controlling the rate of bleach release may include coating the bleach with a controlled release coating. Accordingly, the coating may be made of poorly water-soluble material, or it may be a coating of sufficient thickness so that the dissolution kinetics of the thick coating will provide a controlled release rate.

190 559

The coating material can be applied in various ways. Any material is typically present in an amount such that the weight ratio of coating material to bleach is from 1:99 to 1: 2, preferably from 1:49 to 1: 9.

Suitable coating materials include glycerides (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 alkali and alkaline earth metal sulfates, silicates, and carbonates, including calcium carbonate and silicas.

A preferred coating material, especially in the case of an inorganic salt perhydrate as bleach source, is sodium silicate with a SiO2: NaO ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied in an amount of from 2% to 10% by weight (typically from 3% to 5%) of SiO2 with respect to the inorganic salt perhydrate. Magnesium silicate may also be included in the coating.

Any inorganic salt coating materials can be combined with organic binder materials to produce inorganic salt / organic binder composite coatings. Suitable binders include ethoxylated C10-C20 alcohols containing 5-100 moles of ethylene oxide per mole of alcohol, more preferably C15-C20 ethoxylated primary alcohols containing 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 - 700,000 and polyethylene glycols (PEG) with an average molecular weight of 600 - 5 x 10 ⁶ , preferably 1,000 - 400,000, most preferably 1,000 - 10,000, are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid in which maleic anhydride is at least 20 mole% of the polymer are further examples of polymeric materials useful as binders. Such polymeric materials can be used alone or in combination with solvents such as water, propylene glycol, and the above-mentioned C10-C20 ethoxylated alcohols containing 5-100 moles of ethylene oxide per mole of alcohol. Additional exemplary binders include C10-C20 mono- and diether glycerol and C10-C20 fatty acids.

Cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, and hydroxyctyl cellulose, and homo- or copolymeric polycarboxylic acids or their salts are other examples of useful binders.

One method of applying the coating material involves agglomeration. Preferred agglomeration methods include the use of one or more organic binders as described above. Any suitable agglomeration equipment / mixer can be used, such as, but not limited to, pan, drum and vertical mixers. The molten coating compositions can also be applied by pouring or spraying onto a moving bed of bleach.

Other means of providing the required release rate include mechanical means for altering the physical characteristics of the bleaching agent so as to control its solubility and release rate. Suitable procedures may include compression, mechanical injection, manual injection, and adjusting the solubility of the bleach by selecting the particle size of any particulate component.

Although the selection of the particle size will depend on both the composition of the particulate component and the requirements for the desired controlled release kinetics, it is desirable that the particle size be greater than 500 µm, consequently the mean diameter of the particles should be 800-1200 µm.

Additional procedures to provide means to control the release include appropriate selection of any of the other components in the matrix of the detergent composition such that when the composition is incorporated into the washing solution, the ionic strength of the medium will allow the required release kinetics to be achieved.

Metal-containing bleach catalysts

Compositions of the invention that contain a bleach as detergent component may additionally contain, as a preferred component, a bleach catalyst comprising

190 559 metal. Preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt containing bleach catalyst.

A suitable type of bleach catalyst is a heavy metal cation with a specific bleach catalytic activity, such as a copper or iron cation, a supporting metal cation with no or little bleach catalytic activity, such as a zinc or aluminum cation, and a complexing agent with defined constants. stability against cations of catalytic and auxiliary metals, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic) acid and their water-soluble salts. Such catalysts are disclosed in US Patent No. 443C243.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Patent Nos. 5,246,621 and 5,244,594. Preferred examples of such catalysts include Mn ^IV 2 (u-O3 (1,4,7-trimethyl-1,4,7 -triazacyclononan) 2- (PF6) 2, Mn ^IU 2 (uO) and (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacykIononan2 (ClO4) 2, MIA (uO) 6 ( 1,4,7-triazacyclononan) 4- (C1O4) 2, MAn ^ (uO) and (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononan) 2- (C1O4) 3 and mixtures thereof. Others are described in European Patent Application Publication No. 549272. Other ligands useful for use include 1,5,9-trimethyl-1,5,9-tnazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

Bleach catalysts useful in compositions of this type are also suitable according to the invention. Examples of suitable bleach catalysts are found in US Patent Nos. 4,246,612 and 5227C84. See also U.S. Patent No. 5,194,416, which discloses monocyclic manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH3) 3- (PF6).

Yet another type of bleach catalyst disclosed in U.S. Patent No. 51146C6 is a water-soluble manganese (nI) and / or (IV) complex with a ligand that is a non-carboxylate polyhydroxy compound containing at least three consecutive C- groups OH. Preferred ligands include sorbitol, iditol, dulzyitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose, and mixtures thereof.

US Patent No. 5,114,611 discloses a bleach catalyst which is a complex of a metal such as Mn, Co, Fe or Cu with a non- (macro) cyclic ligand. Such ligands are defined by the formula:

R ² R ³ , 1 I.

R'-N = C -bcnr 'wherein each of R1, R2, R3 and R4 may be selected from the group consisting of hydrogen, and substituted alkyl and aryl, such that R 1 N = CR ^2, and RC = N-or six Riworząpięcio- ring. Moreover, such a ring may be substituted. B is a bridging group selected from O, S, CR ⁵ R 6, NR ⁷ and C = O, where each of ^R5, R6 and ^R7 may be hydrogen, alkyl or aryl, including substituted or unsubstituted groups. Preferred ligands include the pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. The rings may be optionally substituted with substituents such as alkyl, aryl, alkoxy, halogen, and nitro. A particularly preferred ligand is 2,2'-bispyridylamine. Preferred bleach catalysts include bispyridylmethane and bispyridylamine complexes with Co, Cu, Mn or Fe. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl2, dphysothiocyanate, ispyridylamine-cobaltCH), trisdipyridylamine-cobalt (GI) perchlorate, Cofy-bispyridylamine, CHC, bis (2,2'-bispyridylamine) perchlorate iron (II) tris (di-2-pyridylamine) and mixtures thereof.

Preferred examples include bicyclic Mn complexes with tetra-N-tick and bi-N-tick ligands such as N4Mn ⁱⁿ (uO) 2Mn'VN4) ⁺ and [Bipy2Mn ⁿ I (uO) 2lMnlVbipy2] - (ClQ4) 3 ·

190 559

Although the structure of the manganese bleach-catalyzing complexes used in the compositions of the present invention has not been established, it can be assumed that they are chelates or other hydrated coordination complexes resulting from the interaction of carboxyl groups and nitrogen atoms of the ligand with the manganese cation. Likewise, the degree of oxidation of the manganese cation during the catalytic process is not known with certainty, so that it may be the degree of valence (+11), (+ III), (+ IV) or (+ V). Due to the 6 possible points of attachment of the ligands to the manganese cation, it can be assumed with a high degree of probability that multi-ring and / or "cage" structures may exist in aqueous bleaching media. Regardless of the form of the Mn-ligand structures that are actually present, they do act catalytically and provide enhanced bleaching efficiency with respect to stubborn stains, e.g. from tea, ketchup, coffee, wine, juice etc.

Other bleach catalysts are described e.g. in European Patent Application, Publication No. 408131 (cobalt complex catalysts), European Patent Applications, Publications No. 384503 and 306089 (metalloporphyrin catalysts), in United States Patent No. 4,728,455 (manganese / multidentate ligand catalyst) , in U.S. Patent No. 4,711,748 and European Patent Applications, Publication No. 224952 (manganese absorbed on an aluminosilicate catalyst), in U.S. Patent No. 4601845 (an aluminosilicate support with a manganese zinc or magnesium salt), in U.S. Patent No. No. 4,626,373 (manganese / ligand catalyst), U.S. Patent No. 4,119,557 (iron complex type catalyst), German Patent No. 2,054,019 (cobalt chelant catalyst), Canadian Patent No. 866,191 (transition metal salts) , in U.S. Patent No. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and in U.S. Patent No. 4,728,455 (manganese gluconate catalysts).

Other preferred examples include the cobalt (Kl) catalysts of formula:

Co [(NH3) _n M ' _m B' _b T _t QqP _p ] Yy in which the cobalt is in the oxidation state +3; n is an integer from 0-5 (preferably 4 or 5; most preferably 5); M 'is a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; most preferably 1); B 'is a bidentate ligand; b is an integer from 0-2; T is a tridentate ligand; t is 0 or 1; Q is a tetridentate ligand; q is 0 or 1; P is a pentidentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more suitably selected y counter-anions, where y is an integer 1-3 (preferably 2-3; most preferably 2 when Y is an anion with a charge of -1) such that a balanced charge salt is formed; preferably Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; in addition, at least one of the coordination sites attached to the cobalt atom is labile under the conditions of the automatic dishwasher, and the remaining coordination sites stabilize the cobalt atom under the conditions of the automatic dishwasher, so that the cobalt (III) reduction potential to cobalt (n) under the conditions of alkali is below 0.4 V (preferably below 0.2 V) relative to a normal hydrogen electrode.

Preferably, cobalt catalysts of this type have the formula:

[Co (NH3) n (M ') _m ] Yy wherein n is an integer of 3-5 (preferably 4 or 5; most preferably 5); M 'is a labile coordinator group preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1-3 (preferably 1 or 2; most preferably 1); m + n = 6; and Y is respectively

190 559 a selected counter-anion of y, which is an integer of 1-3 (preferably 2 to 3; most preferably 2, when Y is an anion with a charge of -1), so that a salt with a balanced charge is formed.

A preferred cobalt catalyst of this type useful in the tablets of the invention is pentaaminocobalt chloride of the formula [Co (NH3) sCl] Yy, especially [Co (NH3) 5Cl] Cb

More preferred are compositions according to the invention which use cobalt (III) compounds of the formula:

[Co (NH3) n (M) _m (B) _b ] T _y in which the cobalt has an oxidation state of +3; n is 4 or 5 (preferably 5); M is one or more cobalt-coordinated ligands at one site; m is 0, 1 or 2 (preferably 1); B is a cobalt-coordinated ligand at two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b ^{1 0} , then m = 0 and n =; and T is one or more of a number of suitably selected counter-anions in y, where y is an integer so as to result in a balanced charge salt (preferably y is 1-33; most preferably 2 when T is an anion with a charge -1); in addition, such a catalyst has an alkaline hydrolysis rate constant of 0.23 M ' ¹ s' ¹ (25 ° C).

Preferably T is selected from the group consisting of chloride, iodide, I3, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ©, BP © B (Ph) 4 ', phosphate, phosphite, silicate, tosylate , methanesulfonate, and combinations thereof. T may be optionally protonated when more than one anionic group is present in T, e.g. HPO. 2 ', HCO3', H2PO4 'etc. Furthermore, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g. linear alkyl benzene sulfonates (LAS), alkyl sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or anionic polymers (e.g. polyacrylates, polymethacrylates, etc.).

M groups include, but are not limited to, e.g.,. P SO4'2 NCS ', SCN' S2O3- ^2, NH3, PO4'3 and carboxylates (which preferably are monocarboxylates, with the proviso that more than one carboxylate may be present in a group where the linkage to the cobalt may be through one carboxylate in the group, then the other carboxylate in the M group may be protonated or in the form of a salt). M may optionally be protonovar when there is more than one anionic group in M (e.g. HPO42 ', HCO3', H2PO4 ', HOC (O) CH2C (O) O' etc.). Preferred M groups are the substituted and unsubstituted C1-C30 carboxylic acids of the formula:

RC (O) Where R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C1-C18) unsubstituted and substituted alkyl, C6-C30 (preferably C ₍₎ -Cis) unsubstituted and substituted aryl and C3-C30 ( preferably C5-C18) unsubstituted and substituted heteroaryl, wherein the substituents are selected from the group consisting of -NR'3, -NR'4 +, -C (O) OR ', -OR', -C (O) NR'2, where R 'is selected from the group consisting of hydrogen and C1-C6 groups. Such substituted Rs therefore include - (CH2) _n OH and - (CH2) "NR'4 + groups, where n is an integer from 1-16, preferably 2-10, and most preferably 2-5.

Most preferably, M are carboxylic acids of the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 alkyl and benzyl. Most preferably R is methyl. Preferred carboxylic acids as M include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenic, oleic, palmitic, trifluoroic, methanesulfonic, tartaric, citric, stearic acids. acrylic, aspartic, fumaric, lauric, linolenic, lactic and malic acid, in particular acetic acid.

The B groups include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malate, succinate, maleate), picolinic acid, and α and β-amino acids (e.g., glycine, alanine, (3-alanine, phenylalanine).

190 559

Cobalt bleach catalysts useful in the compositions of the invention are known, and are described, for example, with their base hydrolysis rates, in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94. For example, Table 1 on p. 17 gives the basic hydrolysis rates (designated as koH) for pentaaminocobalt catalysts complexed with oxalate (koH = 2.5 x 10 ' 4 M'1s'1 (25 ° C)), NCS- (coH = 5.0 x 10 M ' ^l s' ¹ * (25 ° C)), formate (kOH = 5.8 x 10 ~ 4 M ⁴ s'1 (25 ° C)), and with acetate (coH = 9.6 x 10'4 M '4 (25 ° C)). The most preferred cobalt catalysts for use in the invention are pentaaminocobalt acetate salts of the formula [Co (NHj) 5OAc] Ty, where OAc is an acetate group, especially pentaaminocobalt acetate chloride, [Co (NH3) 5OAc] C-2; and also [Co (NH3) 5OAc] (OAcy ,;

[Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SC> 4);

[Co (NH3) OAc] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2 (in the description "PAC").

Such cobalt catalysts are readily prepared by known methods, such as those set forth in the aforementioned Tobe article and the references cited therein, US Patent No. 4,810,410, Diakun et al., Mar. 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); and also in the synthesis examples provided below.

Cobalt catalysts suitable for incorporation into detergent tablets of the invention can be prepared by the synthetic methods disclosed in US Patent Nos. 5,559,261, 5,581,005 and 5,597,936.

Such catalysts may be co-processed with auxiliary materials to reduce their color effect when an aesthetic product appearance is desired, or they may be incorporated into enzyme-containing particles as exemplified below, or compositions containing catalyst "spots" can be prepared.

Organic polymeric compound

Organic polymeric compounds can be added as preferred ingredients of the detergent tablets of the invention. Organic polymeric compound means essentially any polymeric organic compound commonly used in detergent compositions having dispersing properties, anti-redeposition, soil release agents, or other detergent properties.

The organic polymeric compound is usually incorporated in the detergent compositions of the invention in an amount of 0.1% - 30%, preferably 0.5% - 15%, most preferably 1% - 10% by weight, based on the composition.

Examples of the organic polymeric compounds include water-soluble organic homo- or copolymeric polycarboxylic acids, modified polycarboxylates or their salts, wherein the polycarboxylic acid contains at least two carboxylic acid groups separated by no more than two carbon atoms. The latter type of polymers are disclosed in GB-A-1596756. Examples of such salts include polyacrylates with a molecular weight of 2000-10,000 and their copolymers with any suitable other monomers, including polymers modified with acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic, and methylene malonic acid or their salts, maleic anhydride, acrylamide, alkenemamide. , vinyl methyl ether, styrene, and any mixtures thereof. Copolymers of acrylic acid and maleic anhydride with a molecular weight of 20,000-100,000 are preferred.

Preferred, commercially available acrylic acid-containing polymers with a molecular weight of less than 15,000 include the products sold under the trade names Sokalan PA30, PA20, PA15, PA 10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N, 480N, 460N by Rohm and Haas.

The preferred acrylic acid-containing copolymers are those having as units: a) 90% - 10%, preferably 80% - 20% by weight. acrylic acid or its salt, and b)

190 559

10% - 90%. preferably 20-80 wt.%. substituted acrylic monomer or a salt thereof, of general formula - [CR.2-CR |] (C0-0-R.3)] -, wherein at least one of R _t , R2 and R3, preferably R | or R2 is alkyl or hydroxyalkyl with 1-4 carbon atoms, R1 or R2 may be hydrogen and R3 may be hydrogen or an alkali metal salt. The most preferred is a substituted acrylic monomer, where Ri is methyl, R2 is hydrogen (i.e. methacrylic acid as monomer). The most preferred copolymer of this type has a molecular weight of 3500 and comprises 60-80 wt.%. of acrylic acid and 40 - 20 wt.%. methacrylic acid.

Polyamine compounds and modified polyamine compounds, including those derived from aspartic acid, such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629, are also useful.

Other optional polymers may include modified and unmodified polyvinyl alcohols and polyacetates, cellulose polymers and modified cellulose polymers, polyoxyethylenes, polyoxypropylenes, and copolymers, modified and unmodified, esters of ethylene or propylene glycol terephthalate or mixtures thereof with polyoxyalkyl groups.

Corresponding examples are disclosed in U.S. Patent Nos. 5,591,703, 5,597,789, and 4,490,271.

Dirt release agents

Suitable polymeric soil release agents include those soil release agents which comprise: (a) one or more nonionic hydrophilic components comprising essentially (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization 2-10 polymerization, wherein this hydrophyte segment does not include oxypropylene units, unless they are linked to adjacent groups at each end by ether bonds, or (iii) a mixture of oxyalkylene units containing an oxyethylene mer and 1-30 oxypropylene units, said segments the hydrophytes preferably contain at least 25% oxyethylene units, more preferably, especially for components containing 20-30 oxypropylene units, at least 50% oxyethylene units;

or (b) one or more hydrophobic components comprising (i) C3 oxyalkylene terephthalate segments in which, when such hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C3 oxyalkylene terephthalate units is 2: 1 or less, (ii) the segments C4-C6 alkylene or C4-C6 oxy alkylene or mixtures thereof, (iii) a poly (vinyl ester) segment, preferably polyvinyl acetate, with a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are present in the form of C1-C4 alkylether or C4 hydroxyalkylether cellulose derivatives, or a mixture thereof, or a mixture of (a) and (b).

Typically the polyoxyethylene segments in (a) (i) will have a degree of polymerization up to 200, although levels may be higher, preferably 3-150, more preferably 6-100. Suitable hydrophobic C4-C6 alkylene oxy segments include, but are not limited to at the ends, polymeric soil release agents such as MO3S (CH2) nOCH2CH20-, where M is sodium and n is an integer 4-6, disclosed in US Patent No. 4,721,580, Jan. 26, 1988, Gosselink.

Useful polymeric soil release agents also include cellulose derivatives such as cellulose hydroxyether type polymers, block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene terephthalate etc. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow) . Cellulosic soil release agents used also include those selected from the group consisting of C1-C6 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent No. 4,000,093, issued December 28, 1976 to Nicol et al.

Dirt release agents containing hydrophobic polyvinyl ester segments include graft copolymers of polyvinyl ester, e.g. C1 -C6 vinyl esters,

190 559 preferably polyvinyl acetate, grafted onto a polyalkylene oxide backbone, such as a polyethylene oxide backbone. See European Patent Application No. 0219048, published April 22, 1987 by Kud et al.

Another suitable soil release agent is a copolymer containing ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of such polymeric soil release agent is 25,000-55,000. See U.S. Patent No. 3,959,230, Hays, issued May 25, 1976 and U.S. Patent No. 3,893,929, Basadur, June 8, 1975.

Another suitable polymeric soil release agent is polyester with ethylene terephthalate units, containing 10-15 wt. % of ethylene terephthalate units and 90-80 wt. polyoxyethylene terephthalate units derived from polyoxyethylene glycol with an average molecular weight of 300-5000.

Another suitable polymeric soil release agent is the sulfonation product of an essentially linear ester oligomer with an oligomeric ester backbone with terephthaloyl and oxyalkyleneoxy units and end groups covalently attached to the backbone. Such soil release agents are further described in U.S. Patent No. 4,968,451, issued November 6, 1990, J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include polyesters of terephthalate as described in U.S. Patent No. 4,711,730, issued December 8, 1987, Gosselink et al., Anionic terminated oligomeric esters of U.S. Patent No. 4,721,580, issued January 26, 1988. , Gosselink, and block polyester oligomeric compounds as described in US Patent No. 4,702,857, issued October 27, 1987, Gosselink. Other polymeric soil release agents also include the soil release agents of US Pat. No. 4,877,896, issued Oct. 31, 1989, to Maldonado et al, which disclose anionic, especially sulfoaroyl terminated terephthalate esters.

Another soil release agent is an oligomer with terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy units and oxy-1,2-propylene units. The mers form the backbone of the oligomer which is preferably terminated with modified isethionate end groups. A particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two sodium 2- (2-hydroxyethoxy) ethanesulfonate end groups. .

Heavy metal ion masking agent

The tablets of the invention preferably contain as an optional ingredient a heavy metal ion sequestrant. The term heavy metal ion sequestrant refers to components that act as heavy metal ion sequestering (chelating) agents. These components can also chelate calcium and magnesium, but are selectively selective in binding heavy metal ions such as iron, manganese and copper.

The heavy metal ion sequestrants are generally used in an amount of 0.005% - 20%, preferably 0.1% - 10%, more preferably 0.25% - 7.5% and most preferably 0.5% - 5% by weight, based on to the composition.

Heavy metal ion complexing agents which are acidic in nature and contain, e.g., phosphonic acid or carboxylic acid functional groups, may be in acid form or as a complex / salt with a suitable countercation such as an alkali or alkaline earth metal ion, ammonium or substituted ammonium chloride or in the form of any mixtures thereof. Preferably any salts / complexes are water soluble. The molar ratio of the countercation to the heavy metal ion sequestrant is preferably at least 1: 1.

Suitable heavy metal ion sequestrants for use in the present invention include organic phosphonates such as aminoalkylene polyols, ethane-1-hydroxydisphosphomates, and alkali metal nitrilotrimetrylene phosphates. The preferred of the above compounds is diethylene triamine penta (methylene phosphonate),

190 559 ethylenediammotri (methylenephosphonate), hexamethylene diaminetetra (methylene phosphonate) and hydroxyethylene-1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for use in the present invention include nitrilotriacetic acid and polyamino carboxylic acids such as ethylenediaminetetrocetic acid, ethylenediaminepentacetic acid, ethylenediaminodisuccinic acid, ethylenediaminodiglutaric acid, 2-hydroxypropylene diaminodisuccinic acid or any of their salts.

Ethylenediamine-N, N'-di-succinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salt, or mixtures thereof is particularly preferred. The preferred EDDS compounds include the free acid form and the sodium or magnesium salt or a complex thereof.

A component that is a crystal growth inhibitor

The detergent tablets preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, preferably incorporated in an amount of 0.01% - 5%, more preferably 0.1% - 2% by weight, of the composition.

Organodiphosphonic acid as used herein means organodiphosphonic acid which does not contain a nitrogen atom as part of its chemical structure. Accordingly, this definition excludes organoaminophosphonates which, however, may be included in the compositions of the invention as heavy metal ion sequestering agent components.

The organodiphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid such as ethylenediphosphonic acid, or most preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), which may be present in a partially or fully ionized form, especially as a salt or complex.

Water-soluble sulfate salt

The detergent tablet optionally contains a water-soluble sulfate salt. When present, the water-soluble sulfate salt is 0.1% - 40%, more preferably 1% - 30%, most preferably 5% - 25% by weight. composition.

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

Alkali metal silicate

An alkali metal silicate is a preferred component of the tablet of the invention. A preferred alkali metal silicate is sodium silicate with a SiC2: Na2O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, most preferably 2.0. Sodium silicate is preferably present in an amount of less than 20%, preferably 1% - 15%, most preferably 3% - 12% by weight. SiC> 2. The alkali metal silicate may be in the form of the anhydrous salt or the hydrated salt. The alkali metal silicate may also be a component of the alkalinity providing system.

The alkalinity system preferably also contains sodium metasilicate, used in an amount of at least 0.4 wt.%. SiO2. In sodium metasilicate, the nominal SiO2: Na2O ratio is 1.0. The weight ratio of sodium silicate to sodium metasilicate, measured as S1O2, is preferably from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, most preferably from 10: 1 to 5: 2.

Coloring agent

The term "colorant" as used herein means any substance which absorbs certain wavelengths of light from the visible light spectrum. Such coloring agents, when added to a detergent composition, change the visible color and thus the appearance of the detergent composition. The colorants can be, for example, dyes or pigments. Preferably the coloring agents are stable in the composition to which they are to be added. Thus, in a high pH composition, the colorant is preferably alkali-resistant, and in a low pH composition, the colorant is preferably acid-resistant.

The first and / or second phase and / or optional additional phases may contain a colorant, a mixture of colorants, colored particles or a mixture of colored particles, so that the different phases have a different appearance. Preferably, one of the first and second phases comprises

190 559 coloring agent. When the first and second phases and / or the subsequent phases contain coloring agents, the coloring agents preferably have a different appearance.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline, monoazo, diazo and polyazo dyes. The more preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRfLLIANT GREEN (trade name), all available from Clariant UK, HEXACOL QUINOLINE YELLOW (trade name) (trade name) and HEXACOL BRILLIANT BLUE (trade name), both available from Pointings, UK, ULTRA MARINE BLUE (trade name) available from Holliday or LEVAFIX TURQUISE BLUE EBA (trade name) available from Bayer, USA.

The colorant can be introduced into the phases by any suitable method. Suitable methods include mixing all or selected detergent ingredients with the coloring agent in the drum, or spraying the coloring agent on all or selected detergent ingredients in the rotating drum.

When a colorant is used as an ingredient in the first phase. its amount is 0.001% - 15%, preferably 0.01% -1.0%, most preferably 0.1% - 0.3%. When used as a component of the second phase and / or any subsequent phases, the amount of colorant is typically 0.001% - 0.1%, more preferably 0.005% - 0.05%, most preferably 0.007% - 0.02%.

Corrosion inhibitor compound

The tablets according to the invention suitable for use in dishwashing may contain corrosion inhibitors, preferably selected from organic silver coating agents, especially paraffins, nitrogen-containing corrosion inhibitor compounds and Mn (II) compounds, especially Mn (n) salts of organic ligands.

Organic silver coating agents are described in WO94 / 16047 and in European patent application EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are disclosed in European Patent Application EP-A-634,478. Mn (II) compounds for use as corrosion inhibitors are described in European Patent Application EP-A-672 749.

The organic silver coating agent can be included in an amount of 0.05% -10%, preferably 0.1% -5% by weight. entire composition.

The effect of the silver coating agent is to create, during use, a protective coating layer on the components of the silver dishware during washing to which the compositions according to the invention have been added. Accordingly, the silver coating agent should exhibit a high affinity for attachment to a solid silver surface, especially when it is present as a component of an aqueous wash bath and bleach solution that treats silver solid surfaces.

Suitable for use according to the invention are fatty esters of monohydric or polyhydric alcohols having 1-40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester can be derived from mono- or polycarboxylic acids having 1-40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids are behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid, and 3, p '-dihydroxyisobutyric. Suitable examples of polycarboxylic acids include n-butylmalonic acid, isocitric acid, citric acid, maleic acid, malic acid, and succinic acid.

The fatty alcohol group of the fatty ester can be derived from mono- or polyhydric alcohols containing 1-40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include behenyl, arachidyl, colloyl, oleyl and lauryl alcohol, ethylene glycol, glycerin, ethanol, isopropanol, vinyl alcohol, diglycerin, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

190 559

Preferably, the fatty acid and / or fatty alcohol group of the fatty ester as auxiliary material contains 1-24 carbon atoms in the alkyl chain.

Preferred fatty esters for use in the invention are esters of ethylene glycol, glycerin and sorbitan, in which the fatty acid portion of the ester is usually derived from a compound selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

Glycerin esters are also highly beneficial. These include glycerol mono-, di- or triesters with the fatty acids mentioned above.

Specific examples of fatty alcohol esters for use in the invention include stearyl acetate, dipalmityl lactate, cocoyl isobutyrate, oleyl maleate, dioleyl maleate, and tallow alcohol propionate. Specific examples of fatty acid esters for use in the invention include xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glyceryl monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distezrinate, sorbitan dibehenate and sorbitan dioleate derived from sorbitan dioleate and dioleate derived from sorbitan.

Preferred glycerol esters for use in the invention are glyceryl monostearate, glyceryl monooleate, glyceryl monopalmitate, glyceryl monobehenate, and glyceryl distearate.

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

Waxes, including microcrystalline waxes, are suitable organic silver coating agents for use in the present invention. Preferred waxes have a melting point in the range of 35 ° C - 110 ° C, and contain 12-70 carbon atoms in the molecule. Petroleum waxes of the paraffinic and microcrystalline types, consisting of long chain saturated hydrocarbon compounds, are preferred.

Alginates and gelatin are also suitable organic silver coating agents for use in the present invention.

Dialkylammonium oxides such as C12-C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts such as C11-C20 methylammonium halides are also useful.

Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 - 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 - 10,000, amine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxycellulose, examples of such polymeric materials.

Certain perfume materials, especially those having high affinity for metal surfaces, are also useful as organic silver coating agents for use in the invention.

Polymeric soil release agents can also be used as organic silver coating agents.

A preferred organic silver coating agent is paraffin oil, typically a substantially branched aliphatic hydrocarbon having carbon numbers in the range of 20-50; a preferred paraffin oil is selected from substantially branched C25-45 compounds with a cyclic to non-cyclic hydrocarbon ratio of 1:10 to 2: 1, preferably 1: 5 to 1: 1. A paraffinic oil meeting these characteristics with a 32:68 cyclic to non-cyclic hydrocarbon ratio is sold by Wintershall, Salzbergen, Germany under the trade name WINOG 70.

190 559

Nitrogen-containing compounds as corrosion inhibitors

Suitable nitrogen-containing compounds as corrosion inhibitors include imidazole and its derivatives, such as the 2-heptadecylimide E az> and the lmidazoc derivatives described in Czech Patent Specification No. 139279 and British Patent Specification No. GB-Al 137,741, which also discloses a method for preparing the compounds. lmieazclowyhe.

As nitrogen-containing corrosion inhibitor compounds, olrazole compounds and derivatives thereof are useful, especially those in which the pyrazole is substituted at any of the positions 1, 3, 4 or 5 of the position 1, 3, 4, or 5 of the position 1, 3, 4 or 5, R 1, R 4, and R 5, where R j is a hydrogen atom, CH 6 OH, COIHIj or COCH3, each of R3 and R5 is C1C6 alkyl or hydroxy and R4 is hydrogen, NH2 or NO2.

Other suitable nitrogen-containing corrosion inhibitor compounds include benzotriazcl, 2-mcrcaotobenzothiazole, 1-phenylc-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylcamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.

Nitrogen containing compounds such as amines, especially distearylcamine, and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrogen citrate are also useful.

Mn (II) compounds as corrosion inhibitors

Detergent tablets may contain a compound Mn (II) as a corrosion inhibitor. Compound Mn (II) is preferably incorporated in an amount of C, CC5% - 5% by weight, more preferably 0.01% - 1%, most preferably 0.02% - 0.4% by weight. relative to the composition. Preferably, the compound Mn (II) is introduced in an amount to provide 0.1 ppm - 250 ppm, more preferably 0.5 ppm - 50 ppm, most preferably 1 ppm - 20 ppm by weight. Mn (II) ions in any bleach solution.

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

The Mn (II) compound may be a salt or an organic ligand complex. In one preferred embodiment, the organic ligand is a heavy metal ion sequestrant. In another preferred embodiment, the organic ligand is a crystal growth inhibitor.

Other corrosion inhibitors

Other corrosion inhibitor compounds include mercaptans and diols, especially mercaptans having 4-20 carbon atoms, including mercaptans lauryl, thiophenol, thionaphthol, thionalide and thioanthranol. Also suitable are C10-C20 saturated or unsaturated fatty acids or their salts, especially aluminum tristearate. C2-C20 hydroxy fatty acids or their salts are also useful. Phosphonated octadecane and other antioxidants such as betahydroxytoluene (BHT) are also useful.

Butadiene and maleic acid copolymers, especially those supplied under Trade Designation 07787 by Poliscienhcs Inc., have been found to be particularly useful as corrosion inhibitor compounds.

Hydrocarbon oils

Another preferred detergent component for use in the present invention is a hydrocarbon oil, usually in the form of substantially long-chain aliphatic hydrocarbons having carbon numbers in the range of 20-50; preferred hydrocarbons are saturated and / or branched; a preferred hydrocarbon oil is selected from substantially branched C25-45 products with a cyclic to non-cyclic hydrocarbon ratio of 1:10 to 2: 1, preferably 1: 5 to 1: 1. A preferred hydrocarbon oil is paraffin. Paraffin oil meeting the above characteristics, having a cyclic to non-cyclic hydrocarbon ratio of 32:68, is sold by Wintershall, Salzbergen, Germany under the trade name WINOG 70.

Water-soluble bismuth bundles

The detergent tablets of the invention for use in dishwashing may contain a water-soluble bismuth compound, preferably present in an amount of 0.005% - 20%, more preferably 0.01% - 5%, most preferably 0.1% - 1% by weight. relative to the composition.

190 559

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

Enzyme stabilizing system

Preferred enzyme-containing detergent tablets according to the invention may contain 0.001% - 10%, preferably 0.005% - 8%, most preferably 0.01% - 6% by weight. the enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with the detersive enzyme. Such stabilizing systems may include calcium ions, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach binders, and mixtures thereof. Such stabilizing systems may also include reversible enzyme inhibitors, such as reversible protease inhibitors.

Calcium soap dispersant

The tablets according to the invention may contain a calcium soap dispersant, preferably present in an amount of 0.1% - 40% by weight, more preferably 1% - 20% by weight, most preferably 2% - 10% by weight. relative to the composition.

Calcium soap dispersant is a material that prevents the precipitation of alkali metal, ammonia or amine salts of fatty acids with calcium or magnesium ions. Preferred calcium soap dispersant compounds are disclosed in WO93 / 08877.

Foam extinguishing system

The detergent tablets of the invention, made as dishwasher-safe compositions, preferably contain a foam extinguishing system, present in an amount of 0.01% - 15%, preferably 0.05% - 10%, most preferably 0.1% - 5% by weight. relative to the composition.

Suitable foam extinguishing systems for use in the invention may contain any known antifoam, such as, for example, silicone antifoam compounds, Z-alkyl and alkanol antifoams. Preferred foam extinguishing systems and antifoam compounds are disclosed in PCT Application No. WO93 / 08876 and in EP-A-705 324.

Polymeric dye transfer inhibiting agents

The detergent tablets according to the invention may also contain 0.01% - 10%, preferably 0.05% - 0.5% by weight. polymeric dye transfer inhibitors.

The polymeric dye transfer inhibiting agents are preferably selected from amine N-oxide polymers, N-wine-opiridone and N-vinylimidazole copolymers, vinylpyrrolidone polymers, and combinations thereof.

Other additional ingredients

Other additional ingredients suitable for incorporation in the compositions of the invention include flavorants and salt fillers, with sodium sulfate being the preferred filler salt.

The pH of the composition

The detergent tablets of the present invention are preferably not formulated such that their pH is undesirably high such that their pH as measured in a 1% solution in distilled water is preferably 8.0-12.5, more preferably 9.0-11.8, most preferably 9 , 5 - 11.5.

Washing method in dishwashers

Any methods of washing or cleaning soiled dishes and cutlery in the dishwasher are allowed.

A preferred method of washing in a dishwasher involves treating soiled items selected from porcelain dishes, glassware, silverware, metalware, cutlery, and mixtures thereof with an aqueous liquid in which an effective amount of the detergent tablet of the invention is dissolved or dispersed. An effective amount of a detergent tablet means 8-60 g of product dissolved or dispersed in a 3-10 liter washing liquid as these are typical product doses and washing solution volumes commonly used in common dishwashing methods. Detergent tablets with a weight of 20-35 g are preferred.

190 559

Examples

Abbreviations used in the examples

In detergent compositions, the abbreviations identifying the ingredients have the following meanings:

STTP:

Bicarbonate: Citric acid: Carbonate: Silicate: SKS-6:

PB1:

Non-ionic:

TAED:

HEDP:

PAAC:

Paraffin:

Protease: Amylase: BTA: Sulphate: PEG 3000:

PEG 6000:

pH:

Sodium tripolyphosphate

Sodium bicarbonate

Anhydrous citric acid

Anhydrous sodium carbonate

Anhydrous sodium silicate (ratio SiO2: Na2O = 2.0) Crystalline layered silicate of formula 5-Na2Si2O5 Anhydrous sodium perborate monohydrate

C13-C15 mixed ethoxylated / propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trade name Plurafac by BASF

Tetraacetyl ethylenediamine

Ethane-1-hydroxy-1,1-diphosphonic acid

Salt, cobalt pentaamine acetate (HI)

Paraffin oil, sold under the trade name Winog 70 by Wintershall.

Proteolytic enzyme Amylolytic enzyme Benzotriazole Anhydrous sodium sulphate

Polyethylene glycol with a molecular weight of about 3000 available from Hoechst

Polyethylene glycol with a molecular weight of about 6000 available from Hoechst

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

In the examples below, all amounts are in parts by weight. Examples I-IV

Illustrative examples of detergent tablets according to the invention suitable for use in dishwashers are given below.

AND II III IV V VI 1 2 3 4 5 6 7 Phase 1 STPP 9.620 9.620 10.450 9.570 9.570 11,470 Silicate 0.500 0.670 1,600 1,000 1,000 2,400 SKS-6 1,500 1,500 - 2,300 2,250 - Carbonate 2.330 2,740 3,500 3.590 4.100 5.250 HEDP 0.180 0.180 0.180 0.280 0.280 0.280 PB1 2,450 2,450 2,450 3.680 3.680 3.680 PAAC 0.002 0.002 0.002 0.003 0.004 0.004

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continued table

1 2 3 4 5 6 7 Amylase 0.148 0.110 0.110 0.252 0.163 0.163 Protease 0.060 0.060 0.060 0.090 0.090 0.090 Non-ionic 0.400 0.800 0.800 1,200 1,200 1,200 PEG 6000 0.400 0.260 0.260 0.380 0.390 0.390 BTA 0.040 0.040 0.040 - 0.060 0.060 Paraffin 0.100 0.100 0.100 0.150 0.150 0.150 Fragrance 0.020 0.020 0.020 0.013 0.013 0.013 Sulfate - - - 0.502 0.050 2.843 Together 17.75 g 18.55 g 19.57 g 23,000 g 23.0 g 23,000 g Phase 2 Amilaza 0.300 0.350 0.250 0.300 0.350 0.250 Protease 0.250 0.220 0.300 0.250 0.220 0.300 Citric acid 0.300 - 0.300 0.300 - 0.300 Sulfamic acid - 0.300 - - 0.300 - Bicarbonate 1.090 0.450 0.450 1.090 0.450 0.450 Carbonate - 0.550 - - 0.550 - Silicate - - 0.640 - - 0.640 CaCl2 - 0.070 - - 0.070 - PEG 3000 0.060 0.060 0.060 0.060 0.060 0.060 Together 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g

Multiphase tablet compositions were prepared as follows. The Phase 1 detergent active ingredient composition was prepared by mixing granular and liquid ingredients and then introduced into the die of an ordinary rotary press. The press contained a punch of an appropriate shape to form a nest. The die cross section was approximately 30 x 38 mm. The composition was then compressed at a pressure of 92.2MPa, after which the punch was lifted and the first tablet phase containing a seat in the top surface was exposed. A phase 2 detergent active ingredient composition was similarly prepared and incorporated into the matrix. The particulate active ingredient composition was then compressed at a pressure of 16.7 MPa, after which the punch was lifted and the multiphase tablet was pushed out of the tablet press. The resulting tablets dissolve or disintegrate in the dishwasher as described above within 12 minutes, the 2 tablet phase dissolving within 5 minutes. The tablets exhibit excellent dissolving and cleaning characteristics, along with good tablet integrity and strength.

190 559

Publishing Department of the UP RP. Mintage 50 copies. Price PLN 6.00.

Claims (9)

Patent claims 1. Multiphase detergent tablet for use in a dishwasher, weight 15-40 g and containing a) a first phase in the form of a compressed shaped member including at least one cavity in its surface; and b) a second phase in the form of a compressed element held in the seat by adhesion, made of a particulate solid, weighing less than 4 g, the tablet comprising one or more detergent active substances selected from the group consisting of fillers, colourants, surfactants and enzymes, which are primarily concentrated in the second phase, and wherein the second phase additionally comprises a binder, however, the phases of this tablet exhibit a different dissolution rate during use. 2. Multiphase detergent tablet according to claim 1 The process of claim 1, wherein the first phase is produced at an applied pressure of at least 34.3MPa and the second phase is produced at a pressure of less than 34.3MPa. 3. The multiphase detergent tablet according to claim 1 The method of claim 1 or 2, characterized in that the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, and inorganic and organic polymers. 4. The multiphase detergent tablet according to claim 1 The method of claim 1, further comprising a barrier layer between the first and second phases. 5. Multiphase detergent tablet according to claim 5; The method of claim 4, wherein the barrier layer comprises a binder applied in liquid form. 6. The multiphase detergent tablet according to claim 6 The method of claim 4, wherein the barrier layer comprises a binder selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, and inorganic and organic polymers. 7. Multiphase detergent tablet according to claim 7 The method of claim 1, wherein the first and second phases dissolve independently of each other. 8. The multiphase detergent tablet according to claim 1 The process of claim 1, characterized in that the weight ratio of the first phase to the second phase is at least 6: 1, preferably at least 10: 1. 9. The multiphase detergent tablet according to claim 9 The method of claim 1, wherein the dissolution rate of the second phase is greater than that of the first phase