SK602001A3 - Detergent tablet - Google Patents

Abstract

A multi-phase detergent tablet comprising: a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, wherein the tablet composition comprises one or more detergent actives which is predominantly concentrated in the second phase, and wherein the second phase additionally comprises a disrupting agent. The multi-phase tablets provide improved dissolution and cleaning characteristics together with excellent tablet integrity and strength.

Description

Detergent compositions in the form of tablets are known in the art. It is to be understood that detergent compositions in the form of tablets have several advantages over detergent compositions in particulate form, such as ease of dosing, transport and storage.

Detergent tablets are most conveniently prepared by mixing the ingredients of the detergent composition and forming the mixed detergent ingredients in a tablet using any suitable device, preferably a tablet press. Tablets are typically formed by compressing the components of the detergent composition such that the tablets produced are strong enough to withstand handling and transportation without sustaining damage. While being solid, the tablets must dissolve rapidly enough to allow the detergent ingredients to be released from the wash water as soon as possible at the start of the wash cycle.

However, there is a dichotomy that when the compression pressure with which the tablets are compressed is increased, the dissolution rate of the tablets is slower. The present invention seeks to establish a balance between tablet stiffness and tablet dissolution.

Solutions to this problem, as seen in the prior art, include compressing the tablets with low compression pressure. However, tablets made in this manner, although relatively fast dissolution rate, tend to crush and thereby become damaged and unacceptable to the consumer. Another solution involves the preparation of tablets using a relatively high compression pressure to achieve the desired level of strength and includes a dissolution aid, for example effervescent agents.

The multi-phase detergent tablets described in the prior art are prepared by compressing the first composition in a tablet press to form a substantially planar first layer. Another detergent composition is then delivered to a tablet press on top of the first layer. The second composition is then compressed to form another substantially planar second layer. Thus, the first layer is in ·· ··· ·; In general, it is subjected to more than one compression, since it is also compressed when the second layer is compressed. Typically, the first and second compression pressures are of the same order of magnitude. The Applicant has discovered that in this case, since the compression pressure must be sufficient to bind the first and second compositions together, the pressure used in the first and second compression stages must be between about 4,000 and about 20,000 kg (assuming a tablet cross-section of about 10 cm) ² ). As a result, the dissolution rate of the tablet is slower. Other multiphase tablets having different dissolution are prepared such that the second layer is compressed at a lower pressure than the first layer. However, although the dissolution rate of the second layer is improved, the second layer is softer compared to the first layer and is then amenable to damage caused by handling and transportation.

EP-B-0 055 100 discloses a toilet block formed by combining a slowly dissolving, shaped body with a tablet. The toilet block is intended to be placed in a toilet bowl and dissolves over several days, preferably weeks. As slow toilet dissolution rate means, the document speaks of mixing one or more controlled solubility agents. Examples of such controlled-solubility agents are paradichlorobenzene, waxes, long-chain fatty acids and their alcohols and esters, and fatty acid alkyl amides. Detergent tablets for use in washing machines or automatic dishwashers must substantially dissolve within a single cycle of a washing machine or dishwasher, i. from 15 to 120 minutes.

SUMMARY OF THE INVENTION

According to a first aspect of the invention there is provided a multiphase detergent tablet for use in a washing machine, the tablet comprising:

a) a first shaped body having at least one mold therein; and

b) a second phase in the form of a particulate solid compressed in said form.

In preferred embodiments, the first phase compressed molding is prepared at an applied compression pressure of at least 40 kg / cm ² , preferably at least 250 kg / cm ² , more preferably at least 350 kg / cm ² (3.43 kN / cm ² ), more preferably still from 400 to about 2000, and in particular from about 600 to about 1200 kg / cm ² (the compression pressure applied here is divided by the cross-sectional area of the tablet in a plane transverse to the applied pressure - essentially, the transverse cross-sectional area of the rotary die dies. preferably, the second-phase particulate solid (whose terminology is intended to include the possibility of multiple "second" phases, sometimes referred to herein as "optional additional phases") will be compressed into said mold at an applied lower compression pressure than is applied to a first phase and preferably at a compression pressure of less than about 350 kg / cm ² , preferably in the range of about 40 kg / cm ² to about 300 kg / cm ^2, and preferably more preferably from about 70 to about 270 kg / cm ² , such tablets are preferred herein in terms of providing optimal tablet integrity and strength (as measured, for example, by the Child Bite Strength [CBS] test) and dissolution properties of the product. The tablets according to the invention preferably have a CBS of at least 6 kg, preferably greater than about 8 kg, more preferably greater than about 10 kg, especially greater than about 12 kg, and especially greater than 14 kg, the CBS being measured according to the US Security Commission for Consumer Product Test Specification. The compression pressures applied to the first and second phases will also generally be in a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1.

Thus, according to another aspect of the present invention, there is provided a multi-phase detergent tablet for use in a washing machine, the tablet comprising:

a) a first phase in the form of a compressed shaped body having at least one mold therein, the shaped body being prepared at a compression pressure of at least about 350 kg / cm ² ; and

b) a second phase in the form of a particulate solid compressed in said form, the second phase being compressed at a pressure of less than about 350 kg / cm ² .

In further preferred embodiments, the second phase in the form of a compressed or shaped body is contained adhesively, for example by physical or chemical adhesion, in at least one form of the first body. It is also preferred that the first and second phases have a relatively high weight ratio to each other, for example at least about 6: 1, preferably at least about 10: 1, and also that the tablet composition comprises one or more detergent active agents (e.g. enzymes, bleaching agents). bleach activators, bleach catalysts, surfactants, chelating agents, etc.) which are predominantly concentrated in the second phase, for example at least about 50 wt. %, preferably at least about 1 wt. 60%, in particular about 80 wt. % of the active ingredient (based on the total weight of active agent in the tablet) is in the second phase of the tablet. Again, such compositions are optimal for tablet strength, dissolution, cleansing and pH control characteristics providing, for example, tablet compositions capable of dissolving in aqueous solution to deliver at least 50 wt. %, Preferably at least 60 wt. % and more preferably at least 80 wt. % of the detergent active ingredient into the aqueous solution for 10, 5, 4 or even 3 minutes from the start of the washing procedure.

Thus, according to another aspect of the present invention, there is provided a multi-phase detergent tablet for use in washing machines, or a dishwasher, the tablet comprising:

a) a first shaped body having at least one mold therein; and

b) a second phase in the form of a particulate solid compressed in said form, characterized in that the tablet comprises at least one detergent active ingredient and is formulated such that at least 50 wt. %, preferably at least 60 wt. %, more preferably at least wt. 80% of the detergent active ingredient is delivered to the wash or wash in the first ten minutes, preferably in the first five minutes, and more preferably in the first three minutes of the washing process.

A further benefit of the invention is its ability to achieve different phase dissolution such that one phase of the tablet dissolves more strongly before the next phase and can dissolve completely before the next phase dissolves. This is particularly important in the different delivery of detergent active ingredients.

Thus, according to another aspect of the present invention, a multi-phase detergent tablet is provided, the tablet comprising:

a) a first shaped body having at least one mold therein; and

b) a second phase in the form of a compressed body contained adhesively in said form, and wherein the tablet composition comprises one or more detergent active substances which are predominantly concentrated in the second phase, and wherein the second phase further comprises a disrupting agent.

According to a further aspect of the present invention there is provided a multi-phase detergent tablet, the tablet comprising:

a) a first shaped body having at least one mold therein; and

b) a second phase in the form of a compressed body contained adhesively in said form, characterized in that the tablet composition comprises one or more detergent active substances which are predominantly concentrated in the second phase and wherein the second phase further comprises a binder.

with • · · · • · · • · · • · · ·· ····

Suitably, the one or more detergent active agents are selected from enzymes, bleaching agents, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof, the enzyme active ingredients being particularly preferred for promoting cleansing performance in very cold water in the initial stage of washing the washing or washing operation. Highly preferred for use herein are then enzyme detergent active ingredients, and in particular enzymes and enzyme compositions comprising one or more enzymes having enhanced or optimal activity in the temperature range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10 (e.g. Nataláza)

Thus, according to yet another aspect of the present invention, a multi-phase detergent tablet is provided, the tablet comprising:

a) a first shaped body having at least one mold therein; and

b) a second phase in the form of a compressed body contained adhesively in said form and characterized in that the second phase further comprises an enzyme.

DETAILED DESCRIPTION OF THE INVENTION

It is an object of the present invention to provide a detergent tablet that is not only strong enough to withstand handling and transportation, but also at least a significant portion of which dissolves rapidly in the wash water to ensure rapid delivery of the detergent active ingredient. It is preferred that at least one phase of the tablet dissolves in the wash water in the first ten minutes, preferably five minutes, more preferably four minutes, of the washing or washing cycle of the automatic dishwasher or washing machine. Preferably, the washing device is either an automatic dishwasher or an automatic washing machine. The time at which the multiphase tablet or its phase or detergent active ingredient dissolves is determined according to DIN 44990 using a dishwasher available from Bosha to a normal 65 ° C wash program with a water hardness of 18 ° H using at least six repetitions or sufficient number to ensure reproducibility.

The multi-phase detergent tablet of the present invention comprises a first phase, a second phase and optional further phases. The first phase is in the form of a shaped body of a detergent composition comprising one or more detergent ingredients, which will be described below. Preferred detergent ingredients include a parent compound, bleaching agents, enzymes, and a surfactant. The components of the detergent composition are mixed together, for example by mixing the dry ingredients or by spraying

· · «· • · · e · · · • · • * • · • • · • • · • · • · * • · · ·· ···· • · ·· • · · ·

Liquid components. The components are then shaped in a first phase using any suitable device, but preferably by compression, for example in a tablet press. Alternatively, the first phase may be prepared by extrusion, casting, etc. The first phase may also have various geometric shapes such as spheres, cubes, etc., but preferred embodiments generally have an axially symmetrical shape with a generally circular, square or rectangular cross-section.

The first phase is prepared to include at least one mold on the surface of the shaped body. The mold or molds may be different in size and shape with respect to the first phase and their location, orientation and topology. For example, the form or forms may generally be circular, square or oval in cross-section; they may form an internally closed cavity or recess on the surface of the molded body, or may extend between unconnected areas of the body surface (e.g., axially opposed face surfaces) to form one or more topological "holes in the molded body"; and may be axially or otherwise symmetrically distributed relative to the first phase, or may be asymmetrically distributed. In a preferred embodiment, the mold is formed using a specially designed tablet press, wherein the surface of the punch in contact with the detergent composition is shaped such that when it is in contact and compresses the detergent composition, it compresses the mold, or multiplied forms, into the first phases of a multi-phase detergent tablet. Preferably, the mold will have an inwardly concave or generally concave surface to provide improved adhesion to the second phase. Alternatively, the mold may be formed by compressing a preformed body of the detergent composition spaced annularly around a central dye to form a shaped body having a cavity-shaped form extending axially between opposing surfaces of the body.

The tablets of the invention may also contain one or more additional phases prepared from a composition or compositions comprising one or more detergent ingredients as described below. The at least one phase (referred to herein as the second phase) preferably has the form of a particulate solid (which includes powders, granules, agglomerates and other particulate solids including mixtures thereof with liquid binders, meltable solids, sprays, etc.) compressed into / in one or a plurality of forms of the first phase of the detergent tablet such that the second phase itself has the shape of a shaped body. Optional further phases comprise one or more compositions in the form of a separate layer or layers. Preferred Detergent Ingredients ··

They contain basic compounds, dyes, binders, surfactants, disrupting agents and enzymes, in particular enzymes amylase and protease. In a further preferred aspect of the present invention, the second phase and the optional further third phase comprise a disrupting agent which may be selected from either a disintegrant or an effervescent agent. Suitable disintegrants include agents which swell or facilitate the inflow and / or outflow of water in contact with water by forming channels in the detergent tablet. All known disintegrating or effervescent agents suitable for use in the washing machine are contemplated for use herein. Suitable disintegrants include starches (e.g., natural, modified or pregelatinized starches, i.e., those derived from cereals, rice and potato starch), starch derivatives such as U-Sperse (trade name), Primojel (trade name) and Explotab (trade name). cellulose, microcrystalline celluloses and cellulose derivatives such as Arbocel (tradename) and Vivapur (tradename) both available from Rettenmaier, Nymcel (tradename) available from Metsserla, Avicel (tradename), Lattice NT (tradename) and Hanfloc (tradename) alginates, acetate trihydrate, burkeite, monohydrated carbonate of the formula N2CO3.H2O, hydrated STPP with a phase I content of at least 40%, carboxymethylcellulose (CMC), polymers based on carboxymethylcellulose, sodium acetate, alumina. Suitable effervescent agents are those which form a gas in contact with water. Suitable effervescent agents may be oxygen generators, nitrogen dioxide or carbon dioxide. Examples of preferred effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate, di-carbonate in combination with a carboxylic or other acid, such as citric, sulfamic, malonic or maleic acid.

The components of the detergent composition are mixed together, for example by mixing dry ingredients and mixing by spraying the liquid ingredients. The components of the second and optional further phases are then fed and left in the form provided by the first phase.

A preferred embodiment of the present invention comprises two phases; first and second phases. The first phase will normally comprise one form and the second phase will normally consist of one detergent active composition. However, it is contemplated that the first phase may comprise more than one form and the second phase may be prepared from more than one detergent active composition. It is further contemplated that the second phase may comprise more than one detergent active composition contained in a single form. It is also contemplated that some detergent active compositions may be contained in separate forms. In this way, potentially chemically sensitive detergent ingredients can be separated to prevent loss of their effect due to ingredients interacting with and potentially becoming inactive or leaking.

In a preferred aspect of the present invention, the first, second and / or optional further phases may comprise a binder. When present, the binder is selected from the group consisting of organic polymers, for example polyethylene and / or polypropylene glycols, especially with molecular weights of 4,000, 6,000 and 9,000, paraffins, polyvinylpyrrolidone (PVP), especially polyvinylpyrrolidones with molecular weight of 90,000, polyacrylates, sugars and sucrose derivatives, starch and starch derivatives such as hydroxypropylmethylcellulose (HPMC) and carboxymethylcellulose (CMC); and inorganic polymers such as hexametaphosphate. The binder is important for its tablet cohesion and also helps to achieve different dissolution of the first and second phases, as will be described below.

In a preferred aspect of the present 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. The second and optionally further phases have a weight of less than 4 g. More preferably, the second and / or optional further phase has a weight between about 0.1 g and about 3.5 g, preferably between about 1 g and about 3.5 g, most preferably from about 1.3 g to about 2.5 g.

In another embodiment of the present invention, the barrier layer comprising the barrier layer composition is disposed between the first and second phases and / or the optional further phase or, of course, between the second and the optional further phases. The barrier layer composition comprises at least one binder selected from the group described above. The advantage of the presence of a barrier layer is to prevent or reduce the movement of the components from one phase to the next, for example from the first phase to the second and / or optional further phase and vice versa.

The components of the second and optional subsequent phases are preferably compressed at a very low compression pressure relative to the compression pressure commonly used to prepare the tablets. Thus, the advantage of the present invention is that low compression pressure is applied, heat, pressure or chemically sensitive detergent ingredients can be incorporated into the detergent tablet without exhibiting the consequent loss of action encountered in incorporating such ingredients into the tablets. Alternatively, it may be the second • · ··

a phase or phases compressed at the same or higher compression pressure than the first phase in order to achieve different phase dissolution as described below.

A further advantage of the present invention is the improved protection of the second phase against damage caused, for example, by handling or transportation. As described, multiphase detergent tablets were prepared when the second layer was compressed at a lower compression pressure than the first layer. However, by improving the dissolution rate, the second layer of these tablets becomes accessible to damage, in contact with the tendency to disintegrate or cleave. However, the lightly compressed phase (s) of the detergent tablets of the present invention is protected in the form performed by the first phase.

Yet another advantage of the present invention is the ability to prepare a multi-phase detergent tablet characterized in that one phase may be intended for dissolution, preferably significantly before the next phase. In the present invention it is preferred that the second and optional further phase (s) dissolve before the first phase. According to the preferred weight ranges described above, it is preferred that the first phase dissolve from 5 to 20 minutes, more preferably from 10 to 15 minutes and the second and / or optional further phase dissolves in less than 5 minutes, more preferably in less than 4.5 minutes , preferably in less than 4 minutes. Alternatively, the second phase may dissolve after the first or subsequent phases, for example, when it is necessary to impart cleaning or washing properties to the end of the washing operation. The times at which the first, second and / or optional further phases dissolve are independent of each other. Thus, in a particularly preferred aspect of the present invention, different phase dissolution is achieved. The significant benefit of the ability to achieve different dissolution of a multiphase detergent tablet is that the component that is chemically deprived of the presence of the other component can be separated at another stage. In this case, the deprived ingredient is preferably placed in the second phase and optionally further phase (s).

Yet another advantage of the present invention is improved adhesion between phases of a multiphase tablet. Improved adhesion is believed to be achieved by reducing the action of the second phase as compared to the prior art multi-phase tablets, making the tablets of the present invention less susceptible to breakage along a line in which there is contact between the phases.

·· ··

DETAILED DESCRIPTION OF THE INVENTION

Multiphase detergent tablets are prepared using any suitable tabletting equipment, for example Courtoy R253. Preferably, the tablets are prepared by compression in a tablet press to prepare a tablet by compression of the mold. In a particularly preferred embodiment of the present invention, the first phase is prepared using a specially designed tablet press according to the method described below. The punch (s) of this tablet press are modified so that the surface of the punch that contacts the detergent composition has a convex surface.

The first detergent composition is supplied to the die of the tablet press and the punch is lowered to touch and then compress the detergent composition to form the first phase. The first detergent composition is compressed using an applied pressure of generally at least 250 kg / cm ² , preferably between about 350 kg / cm ² and about 2000 kg / cm ² , more preferably from about 500 to about 1500 kg / cm ² , and most preferably from about 600 to about 1200 kg / cm ² . The punch is then lifted by uncovering the first phase containing the mold. The second and optional additional detergent composition (s) is then delivered to the mold. The specially designed tablet press punch is then lowered for the second time to gently squeeze the second and optional further composition (s) to form a second and optionally further phase (s). In a further embodiment of the present invention, where an optional additional phase is present, the optional additional phase is prepared essentially in the optional further compression step and a similar second compression step described above. The second and optional additional detergent composition (s) are compressed at a pressure of preferably less than about 350 kg / cm ² , more preferably up to about 40 to about 300 kg / cm ² , most preferably from about 70 to about 270 kg / cm ² . After compression of the second detergent composition, the punch is lifted a second time and the multi-phase detergent tablet is punched out of the tablet press.

Detergent compositions

The first and second and / or third optional further phases of the multi-phase detergent tablet described herein are prepared by compressing one or more of the ingredients including the detergent active ingredients. Suitably, the composition used in any of these phases may contain a variety of different detergent ingredients, including basic compounds, surfactants, enzymes, bleaching agents, alkaline sources, dyes, perfumes, lime soap dispersants, as follows: : ·· ::. ··: · .........

organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion separators, metal ion salts, enzyme stabilizers, corrosion inhibitors, soap suds suppressors, solvents, emollients, and optical brighteners.

Highly preferred first phase detergent components comprise a base component, a surfactant, an enzyme, and a bleaching agent. Highly preferred components of the second phase comprise a parent component, enzymes, crystal growth inhibitors, and disrupting agents and / or binder.

Base compound

The tablets of the present invention preferably contain a compound, typically present in an amount of from 1 wt. % to 80 wt. %, preferably from 10 wt. % to 70 wt. %, most preferably from 20 wt. % to 60 wt. % of the composition of the active detergent ingredients.

Water-soluble parent compound

The water-soluble parent compounds comprise water-soluble monomeric polycarboxylates, or acid forms thereof, homo- or copolymeric polycarboxylic acids or salts thereof, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, carbonates, carbonates, borates , phosphates and mixtures of the foregoing compounds.

The carboxylate or polycarboxylate base may be monomeric or oligomeric, although monomeric carboxylates are generally preferred for cost and effect reasons.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid, and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, ethylenedioxydiacetic acid, diglycolic acid, tartaric acid, tartronic acid, fumaric acid, as well as other carboxylates and sulfinylcarboxylates. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble citrates, aconititrates and citraconates, as well as succinic acid derivatives such as the carboxymethyloxysuccinates described in British Patent No. 5,960,549. 1,379,241, the lactoxysuccinates disclosed in British Patent No. 5,367,249; 1,389,732

And the aminosuccinates disclosed in Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-1,1,3-propane-tricarboxylates described in British Patent No. 5,201,573. 1,387,447.

Polycarboxylates containing four carboxyl groups include the oxydisuccinates disclosed in British Patent No. 5,201,549. 1,261,829, 1,1,2,2-ethane-tetracarboxylates, 1,1,3,3-propane-tetracarboxylates and 1,1,2,3-propane-tetracarboxylates. Polycarboxylates containing sulfosubstituents include the sulfosuccinate derivatives disclosed in British Pat. No. 1,398,421 and 1,398,422, and U.S. Pat. No. 3,936,448, and the sulfonated pyrolysis citrates described in British Patent No. 3,936,448. 1 439 000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis-cis-cis-tetracarboxylates, cyclopentadiene-pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis-cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the derivatives of melitic acid, pyromellitic acid, and phthalic acid described in British Patent No. 5,201,549. 1,425,343.

Of the above polycarboxylates, hydroxycarboxylates containing up to three carboxyl groups per molecule, in particular citrates, are preferred.

The starting acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example citric acid or citrate / citric acid mixtures, are also considered to be useful parent compounds.

Borate base compounds as well as borate-containing base materials that can produce borate under detergent storage or washing conditions can also be used, but are not preferred under washing conditions at less than 50 ° C, especially less than 40 ° C.

Examples of carbonate base compounds are alkali metal and alkaline earth carbonates, including sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, as described in German Patent Application Ser. No. 2,321,001, published November 15, 1973.

Highly preferred base compounds for use in the present invention are water-soluble phosphate base components. Specific examples of water-soluble phosphate bases are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium pyrophosphates. · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · And potassium and ammonium, sodium and potassium orthophosphates, sodium polymetaphosphates, in which: is a degree of polymerization ranging from 6 to 21, and a phthalic acid salt.

Specific examples of the water-soluble phosphate base compounds are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium pyrophosphates, sodium and potassium orthophosphates, and the sodium polymethyphosphates in the range from 6 to 21, where the acid.

Partially soluble or insoluble parent compound

The tablets of the present invention may contain a partially or insoluble parent compound. Partially soluble or insoluble base compounds are particularly suitable for use in tablets ready for use in laundry washing processes. Examples of partially water-soluble bases include crystalline layered silicates as disclosed, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are crystalline layered sodium silicates of the general formula

NaMSixO ₂₊ i .yH ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "foil structure", e.g. a layered structure as described in EP 0 164514 and EP 0 293640. Methods for preparing crystalline layered silicates of this type are disclosed in DE-A-3147649 and DE-A-3742043. For purposes of the present invention, x in the general formula is 2, 3 or 4, and is preferably 2.

The most preferred crystalline layered sodium silicate compound has the formula δ-Na ₂ SiO ₂ s known as NaSKS-6 (trade name) available from Hoechst AG.

The crystalline layered sodium silicate material is preferably present in the granular detergent composition as a particulate well blended admixture with the solid, water-soluble ionizable substance disclosed in PCT Patent Application No. 6,030,549. WO92 / 18,594th The solid, water-soluble ionizable substance is selected from organic acids, salts of organic and inorganic acids and mixtures thereof, preferably with citric acid.

Examples of the more water-insoluble basic ingredients include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having a unit formula of Na2 [(AlO2) z (SiO2) yJ]. xhfeO, wherein z and y are at least 6; the molar ratio of z / y is from 1.0 to 0.5 and is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%. %, preferably from 18% to 22% of water in bound form.

The aluminosilicate zeolites may be naturally occurring substances, but are preferably synthetically derived. Ion exchange synthetic crystalline aluminosilicates 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 that described by Schoeman et al. (published in Zeolite (1994) 14 (2), 110-116) in which the author describes a process for preparing colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should be such that no more than 5% of the particles have a size greater than 1 µm in diameter, and no more than 5% of the particles have a size greater than 0.05 µm in diameter. Preferably, the aluminosilicate zeoite particles have a mean particle diameter of between 0.01 µm and 1 µm, more preferably between 0.05 µm and 0.9 µm, most preferably between 0.1 µm and 0.6 µm.

Zeolite A has the formula

Nai _{2 [(AlO2)} i2 _(SiO2) and _2]. XH 2 O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AlO ₂ ) 86 (SiO ₂ ) 106]. 276H ₂ O. The zeolite MAP as disclosed in EP-B-384 070 is the preferred zeolite of the parent compound herein.

Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. When a component of the detergent composition is a colloidal aluminosilicate zeolite, in particular colloidal zeolite A, this provides an enhanced component effect in performing improved stain removal. An increased component effect is also seen with reduced fabric coverage and improved fabric whiteness maintenance; problems are anticipated in conjunction with poorly formulated detergent compositions.

A surprising finding is that the mixed aluminosilicate zeolite detergent compositions comprising colloidal zeolite A and colloidal zeolite Y exert the same calcium ion release effect over the same weight of commercially available zeolite A.

Another surprising finding is that the mixed aluminosilicate zeolite detergent compositions described above exert an improved magnesium ion release effect over the same weight of commercially available zeolite A.

Surfactant

Surfactants are the preferred detergent active ingredients of the compositions described herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and oboionic surfactants and mixtures thereof. Automatic dishwashers should have a low foaming property, and thus the foaming of the surfactant system for use in the washing process should be suppressed or more preferably the foaming, typically non-ionic property, should be reduced. The foaming caused by the surfactant systems used in the washing process need not be suppressed to the same extent as is necessary for a dishwasher. The surfactant is typically present in an amount of from 0.2 to 30 wt. %, more preferably from 0.5 to 10 wt. %, most preferably from 1 to 5 wt. % of the composition of the active detergent ingredients.

Typical lists of anionic, nonionic, ampholytic, and oboionic classes and types of these surfactants are given in U.S. Patent 3,929,678 issued to Laughlin and Heuring on December 30, 1975. A list of suitable cationic surfactants is given in U.S. Patent 4,259,217 issued to Murphy 31 Lists of surfactants typically contained in automatic dishwasher detergent compositions are given, for example, in EP-A0414 549 and PCT applications no. WO93 / 08876 and WO93 / 08874.

· ·

Non - ionic surfactants

Essentially, any nonionic surfactant useful for washing purposes may be included in the detergent tablet. Preferred, non-limiting classes of useful nonionic surfactants are listed below.

Nonionic ethoxylate alcohol surfactants

Suitable condensation products of aliphatic alcohol alkyl ethoxylates with 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohols may be either straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per molecule of alcohol.

Alkyl alkoxylate-terminated surfactants

Suitable alkylalkoxylate-terminated surfactants are epoxy-terminated poly (oxyalkylate) alcohols represented by the formula:

R 10 [CH 2 CH (CH ₃ ) O] x [CH 2 CH ₂ O] y [CH ₂ CH (OH) R ₂ ] (I) wherein R 1 is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R 2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is a number having an average value of from 0.5 to 1.5, more preferably 1 _: and y is a number having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I has at least 10 carbon atoms in the final epoxy unit [CH 2 CH (OH) R 2j. Suitable surfactants of the formula I according to the present invention are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants as described, for example, in WO94 / 22800 published October 13, 1994 by Olin Corporation.

Ether-terminated poly (oxyalkylated) alcohols

Preferred surfactants for use herein include ether-terminated poly (oxyalkylated) alcohols having the formula:

R ¹ O [CH 2 CH (R ³ ) O] x [CH 2] k CH (OH) [CH ² ] jOR ² • · * ·· ** ··· ·· í

.................

wherein R ¹ and R ² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R ³ is hydrogen, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is a number having an average value of from 1 to 30, when x is 2 or greater, R ³ may be the same or different and k and j are numbers having an average value of from 1 to 12, and more preferably 1 to 5.

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

As described above, when it is a preferred embodiment and x is greater than 2, R ³ may be the same or different. That is, R ³ may vary between each of the alkyleneoxy units as described above. For example, if x is 3, R ³ may be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and may be varied in the order of (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO) (EO); (PO) (EO) (PO);

(PO) (PO) (EO) and (PO) (PO) (PO). Of course, number 3 is selected by way of example only, and variations may be larger with a higher number x and include, for example, multiple (EO) units and a much smaller number (PO) units.

Particularly preferred surfactants described above include those having a low cloud point below 20 ° C. These low cloud point surfactants may then be involved in association with the high cloud point surfactant, as described in more detail below, for higher ointment cleansing effects.

Most preferred ether-terminated poly (oxyalkylated) alcohol surfactants are those wherein k is 1 and j is 1 such that the surfactants have the formula:

R ¹⁰ O [CH 2 CH (R ³ ) O] x CH ₂ CH (OH) CH ₂ OR ² wherein R ¹ , R ² and R ³ are as defined above and x is a number with an average value of 1 to 30, preferably 1 to 20, and preferably from 6 to 18. Most preferred are surfactants in which R ¹ and R ² are in the range of from 9 to 14, R ³ is hydrogen-forming ethyleneoxy and r is in the range of from 6 to 15.

· ·

The ether-terminated poly (oxyalkylated) alcohol surfactants include three general components, namely a linear or branched alcohol, an alkylene oxide and a terminal alkyl ether. The capping alkyl ether and alcohol serve as the hydrophobic, oil-soluble portion of the molecule, wherein the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.

These surfactants show marked improvements in stain and coating properties and in the removal of greasy soils than conventional surfactants when used in conjunction with high cloud point surfactants.

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

Preparation of C12 / 14 alkyl glycidyl ethers

C12 / 14 fatty alcohols (100.00 g, 0.515 mol) and tin tetrachloride (058 g, 2.23 mmol, available from Aldrich) are combined in a 500 ml three-necked round-bottomed flask with attached condenser, argon inlet, funnel added, magnetic stirrer and internal temperature sensor. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise to maintain the temperature between 60-65 ° C. After stirring for an additional hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated by mechanical stirring with 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%). After the addition is complete, the mixture is heated at 90 ° C for 1.5 hours, cooled and filtered with ethanol. The filtrate is separated and the organic phase is washed with water (100 mL), dried over MgSO 4, filtered and concentrated. Distillation of the oil at 100-120 ° C (0.1 mm Hg) affords glycidyl ether as an oil.

Preparation of Cwu alkyl-Cg / n ether-terminated alcohol surfactants

Neodol® 91-8 (20.60 g, 0.0393 mol ethoxylate alcohol available from Shell Chemical Co.) and tin tetrachloride (058 g, 2.23 mmol) are combined in a 250 ml three-necked round-bottomed flask with a condenser attached, with an argon inlet, added via a funnel, a magnetic stirrer, and an internal temperature sensor. The mixture is heated to 60 ° C at which C12 / 14 alkyl glycidyl ether (110.00 g, 0.0393 mol) is added dropwise over 15 minutes. After stirring at 60 ° C for 18 hours, the mixture is cooled to room temperature and dissolved in an equal portion of dichloromethane. The solution was passed through a 2.5 cm block of silica gel eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then collected in a round oven (100 ° C, 0.5 mm Hg) to yield a surfactant as an oil.

Nonionic ethoxylated / propoxylated fatty alcohol surfactants

Ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated / propoxylate fatty alcohols are suitable surfactants for use herein, especially when they are water soluble. The ethoxylate fatty alcohols are preferably C10-C18 ethoxylate fatty alcohols having an ethoxylation degree of from 3 to 50, most preferably C12-C18 ethoxylate fatty alcohols having an ethoxylation degree of from 3 to 40. Preferably, the mixed ethoxylate / propoxylate fatty acids have an alkyl chain of 10 to 18 atoms carbon, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Nonionic EO / PO condensates with propylene glycol

Suitable hydrophobic base ethylene oxide condensation products formed by the condensation of propylene oxide and propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from 1,500 to 1,800 and exhibits water insolubility. Examples of compounds of this type include some of the commercially available Pluronic ™ surfactants sold by BASF.

Nonionic EO condensation products with propylene oxide / ethylenediamine addition compounds

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of from 2,500 to 3,000.

• ·

·· ·· ·· ····

Examples of this type of nonionic surfactant include some of the commercially available Tetronic ™ compounds sold by BASF.

Mixed nonionic surfactant system

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

The "cloud point" as used herein is a well-known property of nonionic surfactants, which implies that the surfactant becomes less soluble as the temperature rises; the temperature at which the appearance of the second phase is observable is referred to as the "cloud point" (see Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed. Vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is defined as an additive of a surfactant system having a cloud point below 30 ° C, preferably below 20 ° C, and most preferably below 10 ° C. Typical low cloud point nonionic surfactants include nonionic alkoxylate surfactants, especially primary alcohol ethoxylates, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Such low-cloud nonionic surfactants also include, for example, ethoxylate-propoxylate alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy-terminated poly (oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionic, described e.g. (WO94 / 22800 published October 13, 1994 by Olin Corporation) and ether-terminated poly (oxyalkylated) alcohol surfactants.

The nonionic surfactants may optionally contain propylene oxide in an amount of up to 15 wt. %. Other preferred nonionic surfactants may be prepared by the methods described in U.S. Patent 4,223,163, issued September 16, 1980, to Builloty, incorporated herein by reference.

Low-point nonionic surfactants additionally include a polymer compound with a polyoxyethylene, polyoxypropylene block. Polymeric compounds with polyethylene, polypropylene block include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiators of the reaction hydrogen compound. Certain of block ·· · · ···· · · · ·· ····

polymers of surfactant compounds labeled PLURONIC®, REVERSED PLURONIC®, and TETRONIC® from BASF-Wyandotte Corp., Wyandotte, Michigan are suitable for the ADD compositions of the invention. Preferred examples include REVERSED PLURONIC ® 25R2 and TETRONIC ® 702. Such surfactants are typically useful herein as low cloud point nonionic surfactants.

As used herein, a "high cloud point" nonionic surfactant is defined as a component of a surfactant system having a cloud point greater than 40 ° C, preferably greater than 50 ° C, and most preferably greater than 60 ° C. The nonionic surfactant system preferably comprises ethoxylate surfactants derived from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol on average. Such "high cloud point" nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhône Poulenc) and Neodol 91-8 (supplied by Shell).

It is also preferred for the purposes of this invention that the high cloud point nonionic surfactant has a hydrophilic-lipophilic equilibrium ("HLB"; see Kirk Othmer mentioned above) value in the range of 9-15, preferably 11-15. Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhône Poulenc) and Neodol 91-8 (supplied by Shell).

Another high ionic point nonionic surfactant is derived from a straight or preferably branched chain or a secondary fatty alcohol containing from 6 to 20 carbon atoms (C 6 -C 12 alcohol), including secular and branched chain primary alcohols. Preferably, the high-cloud nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed Cg / n or C n / ε 5 branched alcohol ethoxylates condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant has a narrow diameter ethoxylate derivative thus derived.

Anionic surfactants

In principle, all anionic surfactants useful for cleaning purposes are suitable. These may include salts (including, for example, sodium, potassium,

ammonium and substituted ammonium salts such as salts of mono-, di- and triethanolamine) anionic sulfates, sulfonates, carboxylates, and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C diesters ₄ ), Nacylsarcosinates. Also suitable are resin acids and hydrogenated resin acids such as resin, hydrogenated resin, and resin acids and hydrogenated resin acids present or derived from tallow fat.

Anionic sulphate surfactant

Anionic sulfate surfactants suitable for use herein include straight and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenolethylene oxide ether sulfates, C5-C17 acyl-h- (C1-C2 alkyl) and -N- (CC hydroxyalkyl) glucamines alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (nonionic non-sulfide compounds described herein).

The alkyl sulphate surfactants are preferably selected from straight or branched primary C 1 -C 16 alkyl sulphates, more preferably branched chain C 11 -C 15 alkyl sulphates and straight chain C 12 -C 14 alkyl sulphates.

The alkyl ethoxysulfate surfactants are preferably selected from the group consisting of C 1 -C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the surfactant is a C 11 -C 16 alkyl ethoxy sulfate, more preferably a C 11 -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention includes mixtures of preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT patent application no. WO93 / 18,124th

Anionic sulphonate surfactant

Anionic sulfonate surfactants for use herein include C5-C20 salts of direct alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkylglycerol sulfonates, fatty acid glycerol sulfates, fatty acyl glycerols.

Ammonium carboxylate surfactant

Suitable anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkylpolyethoxypolycarboxylate surfactants and soaps ('alkylcarboxylates'), in particular certain secondary soaps as described herein.

Suitable alkyl ethoxycarboxylates include those having the formula RO (CH 2 CH 2 O) _X CH 2 COO'IV 1, wherein R is a C 6 to C 18 alkyl group, x is from 0 to 10 and the ethoxylate distribution is such that on a mass basis when x is 0, the amount of the substance is less than 20% and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula RO- (CHR ₁ -CHR ₂ O-) - R 3, wherein R is a C ₆ to C ₁₈ alkyl group, x is from 1 to 25, R 1 and R ₂ are selected from a group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants which contain a carboxyl unit attached to the secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali sarcosinate surfactants

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

·············································· 9 9 9 9 9 9 · ·

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkylamphocarboxylic acids.

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

A suitable example of an alkylaphodicarboxylic acid is Miranol ™ C2M Conc. manufactured by Miranol, Inc., Dayton, N.J.

Oionic surfactant

Oboionic surfactants can also be incorporated into these detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betalin and sultain surfactants are exemplary obionic surfactants for use herein.

Suitable betaines are those compounds having the formula R (R ') 2 N ⁺ R ² COO · in which R is a C 6 -C 16 hydrocarbon group, each R ¹ is typically C 1 -C 3 alkyl, and R ² is a C 1 -C 5 hydrocarbon group . Preferred betaines are C12-18 dimethylammonium hexanoate and C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants

The cationic ester surfactants used in the present invention are preferably water dispersible compounds having surfactant properties comprising at least one ester (i.e., -COO-) moiety and at least one cationic charged group. Other suitable cationic ester surfactants, including choline ester surfactants, have been disclosed, for example, in U.S. Pat. 4228042, 4239660 and 4260529.

* * * * * · · · · · · * * * * * * * * * * · ·

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

enzymes

Enzymes are preferred detergent components of the first phase and especially of the second and / or optional additional phases. When present, said enzymes are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenase, lipoxygenase, lipoxygenase, lipoxygenase, lipoxygenase, tannases, pentosanases, malanas, βglucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, or mixtures thereof.

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

Cellulases useful in the present invention include bacterial or fungal cellulase. They preferably have an optimum pH between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307 to Barbesgoard et al. J + 1078384 and WO96 / 02653 which disclose fungal cellulases produced from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2,095,275; DE-OS-2,247,832 and WO95 / 26398.

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola grisea var. Thermoidea), in particular Humicola DSM 1800. Other suitable Humicola insolens derived cellulases having a molecular weight of 50 KDa, an isoelectric point of 5.5 and contain 415 amino acids; a ~ 43 kD endoglucanase derived from Humicola insolens, DSM 1800 showing cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application no. WO91 / 17,243th Also suitable cellulases are EGIII cellulases from Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published Sep. 29, 1994. Particularly suitable cellulases are cellulases having color preservation benefits. Examples of such cellulases are cellulases described in European patent application no. No. 91202879.2 filed November 6, 1991 (Novo).

·· ·· ·· _ • · · · a a · • · · · • · · ; · · · · · · · 26 • · · ·· ···· • · · ·· ····

·· · · · · · · · · · · · ·

Carenzyme and cellulose (Novo Nordisk A / s) are particularly useful. See also WO91 / 17244 and WO91 / 21801. Other suitable cellulases for fabric care and / or cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

Said cellulases are normally incorporated in the detergent composition in an amount of from 0.0001 wt. % to 2 wt. % of the active enzyme by weight of the detergent composition.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used for the "bleaching solution", i.e. to prevent transfer of dyes or pigments taken from substrates during washing operations to substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO89 / 099813, WO89 / 09813, and in European Patent Application No. EP-A-030813. No. 91202882.6 filed November 6, 1991 and EP no. No. 96870013.8, filed Feb. 20, 1996. The enzyme lactase is also suitable.

Preferred accelerators are substituted phenothiazine- and phenoxazine-10-phenothiazine-propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazine-propionic acid (POP) and 10-methylphenoxazine (described in WO94 / 12621) and C3 substituted. -C5 substituted alkylsyringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

Suitable cellulases and / or peroxidases are normally incorporated in the detergent compositions in an amount of from 0.0001 wt. % to 2 wt. % of the active enzyme by weight of the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the present invention include a lipase. Suitable lipase enzymes for detergent use include those produced by Pseudomonas family microorganisms, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those that exhibit a positive immunological cross reaction with a fluorescent antibody P produced by the microorganism. IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P 'Amano', hereinafter 'Amano-P'. Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum • ·

99 99 9 9 • · · 9 9 9 · · 9 9 9 • • • • 9 9 9 • e • 9 9 9 • • • 99 9999 · · • ·

• · · · · · · ·

NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Lipases such as M1 lipase ^R and Lipomax ^R (GistBrocades) and lipolase ^R and Lipolase Ultra ^R (Novo) have been found to be particularly effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO92 / 05249 and WO95 / 22615 belonging to Novo Nordisk and WO94 / 03578, WO95 / 35381 and WO96 / 00292 belonging to Unilever.

Also suitable are cutinases [EC 3.1.1.50], which can be considered as a particular type of lipase, particularly lipases that do not require interphase activation. Other cutinases for detergent compositions have been described e.g. WO-A-88/09367 (Genencor); WO90 / 09446 (Plant Genetic System) and WO94 / 14963 and WO94 / 14964 (Unilever).

Lipases and / or cutinases are commonly incorporated in detergent compositions in an amount of from 0.001 wt. % to 2 wt. % of the active enzyme by weight of the detergent composition.

Suitable proteases are subtilisins that are obtained from individual strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease is obtained from a Bacillus strain having an action in the pH range of 8 to 12, developed and sold as ESPERASE® from Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in British Patent 1,243,784 to Novo. Other suitable proteases include KANNASE®, ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein designed by Macaxal) from Gist-Brocades. Proteolytic enzymes also contain modified bacterial serine proteases as described in European Patent Application 199,404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme referred to herein as "Protease A". Suitably, it is named "Protease C", which is a variant of the alkaline serine protease from Bacillus, in which lysine replaced arginine at position 27, tyrosine replaced threonine at position 274. Protease C is described in EP 909115958: 4 corresponding to WO91 / 06637 published May 16, 1991. Genetically modified variants, particularly Protease C, are also contemplated herein.

A preferred protease related to "Protease D" is a carbonyl hydrolase variant having amino acid sequences not found in nature, it is derived from a carbonyl hydrolase precursor by substituting various amino acids for an amount of stve · · · · · · · · · Amino acid residues of said carbonyl hydrolase at a position equivalent to position +76, preferably also in combination with one or more positions of amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218 , +222, +260, +265 and / or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, described in WO95 / 10591 and in Patent Application C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes" having the serial number US 08/322 677 filed 13 October 1994.

Also suitable for the present invention are the proteases described in patent application EP 251 446 and WO91 / 06637, the BLAP® protease described in WO91 / 02792, and variants thereof described in WO95 / 23211.

See also high pH protease from Bacillus sp. NCIMB 40338 described in WO93 / 18140 A by Novo. Enzyme detergents comprising a protease, one or more enzymes and a reversible protease inhibitor are described in WO92 / 03529 A to Novo. If desired, a protease having reduced adsorption and increased hydrolysis is accessible as described in WO95 / 07791 to Procter & Gambia. A recombinant trypsin-like protease suitable for the detergents herein is described in WO94 / 25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

Other preferred protease enzymes include enzymes that are a variant of carbonyl hydrolase having non-naturally occurring amino acid sequences that are derived by replacing a plurality of amino acid residues of the carbonyl hydrolase precursor with different amino acids, wherein said plurality of amino acid residues has been replaced in the +2 precursor enzyme of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, + 158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions correspond to naturally occurring Bacillus amyloliquefaciens subtilisin or equivalent amino acid residues in other carbonyl hydrolases or subtilisins ( such as Bacillus lentus subtilisin). Preferred enzymes of this type include those having position changes of +210, +76, +103, +104, +156 and +166.

Proteolytic enzymes are incorporated in the detergent compositions of the present invention in an amount of 0.0001 wt. %, preferably from 0.001 wt. %

Up to 0.2 wt. %, more preferably from 0.005 wt. % to 0.1 wt. % pure enzyme by weight of the composition.

Amylases (and and / or β) may be included to remove carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S published February 3, 1994, discloses cleaning compositions incorporating mutant amylases. See also WO95 / 10603, Novo Nordisk A / S published April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-amylases are known in the art and include those disclosed in U.S. Pat. 5,003,257; EP 252,666; WO91 / 00353; FR 2,676,456; EP 285 123; EP 525,610; EP 368,341; and British patent specification no. 1,296,839 (Novo). Other suitable amylases are the improved stability amylases described in WO94 / 18314 published August 18, 1994 and WO96 / 05295, Genencor published February 22, 1996, and amylase variants having further immediate modification modifications available from Novo Nordisk A / S, published in WO95 / Also suitable are the amylases described in EP 277 216, WO95 / 26397 and WO96 / 23873 (all from Novo Nordisk).

Examples of commercial α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, Natalase®, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: aamylases, characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® in a temperature range of 25 ° C to 55 ° C and at a pH value in the range of 8-10 measured by activity Phadebas® α-amylase samples. Variants of the above enzymes described in WO96 / 23873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties regarding activity and a combination of thermostability and higher activity are described in WO95 / 35382.

Preferred amylase enzymes include those described in WO95 / 26397 and in co-pending application Novo Nordisk PCT / DK96 / 00056.

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

In a particularly preferred embodiment, the detergent tablets of the present invention include amylase enzymes, particularly those described in

WO95 / 26397 and co-pending application Novo Nordisk PCT / DK96 / 00056 in combination with supplementary amylase.

By "complementary" is meant the addition of one or more amylases suitable for detergent purposes. Examples of complementary amylases (α- and / or β) are described below. WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S disclose cleaning compositions incorporating mutant amylases. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-amylases are known in the art and include those disclosed in U.S. Pat. 5,003,257; EP 252,666; WO91 / 00353; FR 2,676,456; EP 285 123; EP 525,610; EP 368,348; and British patent specification no. 1,296,839 (Novo). Other suitable amylases are the improved stability amylases described in WO94 / 18314 published August 18, 1994 and WO96 / 05295, Genencor published February 22, 1996, and amylase variants having additional immediate-modification modifications available from Novo Nordisk A / S, published in WO95 / 10,603th Also suitable are amylases described in EP 277 216 (Novo Nordisk).

Examples of commercial α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amylases, characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® in a temperature range of 25 ° C to 55 ° C and at a pH value in the range of 8-10 measured according to the activity of the Phadebas® α-amylase sample. Variants of the above enzymes described in WO96 / 23873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties regarding activity and a combination of thermostability and higher activity are described in WO95 / 35382. Preferred additional amylases for the present invention are amylases sold under the tradename Purafect Ox Am ^R described in WO94 / 18314, WO96 / 05295 sold by Genecor; Termamyl®, Fungamyl®, Ban®, Natalase® and Duramyl®, all available from Novo Nordisk A / S and Maxamyl® from Gist-Brocades.

Said additional amylases are generally incorporated in the detergent compositions of the present invention in an amount of from 0.0001 wt. % to 2 wt. %, preferably from 0.00018 wt. % to 0.06 wt. %, more preferably from 0.00024 wt. % to 0.048 wt. % pure enzyme by weight of the composition. Preferably, the ratio of pure specific amylase enzyme to supplemental amylase is between 9: 1 to 1: 9, more preferably between 4: 1 to 1: 4, and most preferably between 2: 1 and 1: 2.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and cereal origin. The origin may be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes may also be used. Mutants can be obtained e.g. protein and / or genetic engineering, chemical and / or physical modifications of natural enzymes. Equally common practice is the expression of the enzyme through host organisms in which the genetic material responsible for the production of the enzyme has been cloned.

Said enzymes are normally incorporated in the detergent composition in an amount of from 0.0001 wt. % to 2 wt. % of the active enzyme by weight of the detergent composition. Enzymes may be added as separate individual ingredients (samples, granulates, stabilized liquids, etc. containing one enzyme) or mixtures of two or more enzymes (e.g. cogranulates).

Other suitable detergent builders that may be supplied are the enzyme oxidation scrubbers described in co-pending European patent application 92870018.6 filed January 31, 1992. Examples of such enzyme oxidation scrubbers are ethoxylated tetraethylene polyamines.

A range of enzyme substances and compositions for incorporating them into synthetic detergent compositions are also disclosed in WO93 / 07263 A and WO93 / 07260 A by Genencor International, WO89 / 08694 A by Novo and US 3,553,139 of January 5, 1971 by Mc Carty et al. . Enzymes are further disclosed in US 4 101 457, Plače et al, July 18, 1978 and in US 4 507 219, Hughes, March 26, 1985. Enzymes useful for liquid detergent formulations and their incorporation into such formulations are disclosed in US 4,261 868, Hora et al., April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US 3,600,319, Aug. 17, 1971, Gelde et al, EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas. Useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases is described in WO 94/01532 A to Novo.

Bleaching agent

A highly preferred component of the detergent builder composition is a bleaching agent. Suitable bleaching agents include chlorine and oxygen releasing bleaching agents.

· · · · · · · · · · · ·

In one preferred aspect, the oxygen releasing bleaching agent comprises a hydrogen peroxide source and organic peroxyacid bleach precursor compounds The production of organic peroxyacids occurs through the in situ reaction of the precursor with the hydrogen peroxide source. Preferred sources of hydrogen peroxide include inorganic perhydrate bleach solutions. In an alternative preferred aspect, the preformed organic peroxyacid is incorporated directly into the composition. Compositions comprising mixtures of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a preformed organic peroxyacid are also contemplated.

Inorganic perhydrate bleach solutions

Preferably, detergent builder compositions include a source of hydrogen peroxide, and an oxygen releasing bleaching agent. Suitable sources of hydrogen peroxide include inorganic perhydrate salts.

Inorganic perhydrate salts are commonly incorporated in the form of the sodium salt in an amount of from 1 wt. % to 40 wt. %, more preferably from 2 wt. % to 30 wt. % and most preferably from 5 wt. % to 25 wt. % of compositions.

Examples of inorganic perhydrate salts include salts of perborate, percarbonate, phosphate, persulfate, and persilicate. Inorganic perhydrate salts are normally alkali metal salts. Inorganic perhydrate salts may be included as crystalline solids without further protection. For certain perhydrate salts, however, a preferred embodiment of such granular compositions utilizes a coated form of the material that provides better storage stability for the perhydrate salts in the granular product.

Sodium perbotate may be in the form of a monohydrate of the formula NaBO ₂ H ₂ O ₂ or NABO ₂ H ₂ O _{2. 3} H ₂ O tetrahydrate.

Alkali metal percarbonates, in particular sodium percarbonate, are preferred perhydrates for inclusion in the compositions of the invention. Sodium percarbonate is an addition compound having the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Sodium percarbonate as a hydrogen peroxide addition compound tends to release hydrogen peroxide quite rapidly upon dissolution, which may increase the intention to increase localized bleaching concentrations. Percarbonate is most preferably incorporated into such compositions in a coated form that provides stability in the product.

• · · · · · · · · · · · · ·

• · ··

A suitable coated material to provide stability in the product includes mixed salts of water-soluble alkali metal sulphates and carbonates. Such coatings, together with coating processes, have been previously described in GB 1 466 799, issued to Interox on March 9, 1977. The weight ratio of the mixed salt of the coated material to the percarbonate is in the range of 1: 200 to 1: 4, more preferably 1: 99 to 1. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the general formula Na ₂ SO ₄ .n.Na ₂ CO 3, wherein n is from 0.1 to 3, preferably n is from 1: 49 to 1: 19. 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Another suitable coated material to provide stability in the product comprises a ratio of sodium silicate SiO ₂ : Na ₂ O from 1.8: 1 to 3.0: 1, preferably 1.8: 1 to

2.4: 1, and / or metasilicate, preferably used in an amount of from 2 wt. % to 10 wt. % (typically from 3 wt% to 5 wt%) of SiO ₂ inorganic perhydrate salt. Magnesium silicate may also be included as a coating. Coatings which contain salts of silicate and borate or boric acid or other inorganic substances are also suitable.

Also other coatings containing waxes, oils, fatty soaps can be used in the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt for use in the compositions herein.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form the peroxyacid. In general, peroxyacid bleach precursors may be represented as

II

XCL in which L is a leaving group and X is essentially any function such that in perhydrolysis the structure of the peroxyacid formed is ··· ·· ·· · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Ο

II

X — C — ΟΟ Η

The peroxyacid bleach precursor is preferably incorporated in an amount of from 0.5 wt. % to 20 wt. %, more preferably from 1 wt. % to 10 wt. %, most preferably from 1.5 wt. % to 5 wt. % of compositions.

A suitable peroxyacid bleach precursor typically contains N or O-acyl groups, the precursors of which may be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful substances in these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Cleavage groups

The leaving group, the L group herein, must be sufficiently reactive in the perhyrolysis reaction to occur within the optimal time frame (i.e., the wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in the bleaching composition.

Preferred L groups are selected from the group consisting of:

-ABOUT' 0 H -NCR ¹ A ¹ R ⁵ 1 Y A o -y 7 —NC-CH — R ⁴ L 1, 1 R ³ Y

··························

R ³

I-O-CH = C = CH = CH ₂

Y

I

-Ο-c H = c - CH = CH ₂

about

II

CH-C

ABOUT

R ³ = O-C = CHR ⁴ , and

OY ^{11 1} —N — S — CH — R ⁴

·· ·· · • • • · · · · · • and mixtures thereof, wherein R ¹ is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R ³ is an alkyl chain containing from 1 to 8 carbon atoms, R ⁴ is hydrogen or R ³ , R ⁵ is an alkenyl chain containing from 1 to 8 carbon atoms and Y is hydrogen or a soluble group. Each R ¹ , R ^3, and R ⁴ may be substituted with substantially each functional group including, for example, an alkyl, hydroxyl, halogen, amine, nitrosyl, amide, ammonium or alkylammonium group.

Preferred soluble groups are -SO ₃ 'M ⁺ , -CO ₂ ' M *, -SO / M *, -N ⁺ (R ³ ) 4X 'and O < -N (R ³ ) 3 and most preferably -SOa'M * and CO ^{2 '} M ⁺ , in which R ³ is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which assures the solubility of the bleach activator, and X is the anion which ensures the solubility of the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium are most preferably, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor

The perbenzoic acid precursor compound provides perbenzoic acid in perhydrolysis.

··································

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, including, for example, benzoyloxybenzenesulfonate:

Also suitable are benzoylation products of sorbitol, glucose and all carbohydrates with benzoylating agents, including, for example:

OAc

And what

OBzl

Ac = _COCH3; Bz = Benzoyl

Compounds of the imide-type perbenzoic acid precursor include Nbenzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include Nbenzoylimidazole and N-benzoylbenzimidazole and other useful N-acyl groups containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Other perbenzoic acid precursors include benzoyldiacylperoxides, benzoyltetraacylperoxides and a compound having the formula:

COOH · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

ABOUT

Suitable precursors of N-acylated lactamic perbenzoic acid have the formula:

C-Chg-Chg-R-C ⁶ N I

CH-ÍCHJh wherein n is 0-8, preferably 0-2, and R ^p is benzoyl.

Perbenzoic acid derivatives precursors

Perbenzoic acid derivative precursors provide substituted perbenzoic acids for hydrolysis.

Suitable prodrugs of substituted perbenzoic acid derivatives include all of the perbenzoic prodrugs disclosed herein, in which the benzoyl group is substituted with essentially any non-positively charged (i.e., non-cationic) functional group, including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl and nitro.

Preferred classes of precursors of substituted perbenzoic acid derivatives are amido substituted compounds of the following general formula:

^R1-C - ^N-R2-C - LR ¹ - C - ^C-R2-C - L

II II II II II

OR ^D OR OO or ⁵ wherein R ¹ is an aryl or alkaryl group with from 1 to 14 carbon atoms, ^R2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R ⁵ is · '' · · · · e ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · hydrogen or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms and L may be essentially any leaving group. R preferably contains 4 to 8 carbon atoms. R ¹ may be aryl, substituted aryl or alkylaryl containing a branching, substitution, or both, and may be derived from synthetic sources or natural sources, including, for example, tallow fat. The permissible Analogous structural variations are the R ^second The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably hydrogen or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amido substituted bleach activators of this type are described in EPA-0170386.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds provide cationic peroxyacids for perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting a portion of the peroxyacid of a suitable positively charged peroxyacid precursor, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as a halide ion or methylsulfate ion.

The peroxyacid precursor, which is thus cationically substituted, may be perbenzoic acid, or substituted derivatives thereof, as described above. Alternatively, the peroxyacid precursor may be an alkylpercarboxylic acid precursor or an amido substituted alkylperoxyacid precursor as described below.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; UK1 382 594; EP 475,512; 458396 and 284 292; and JP87-318 332.

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

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

··························

A preferred cationically substituted alkyloxybenzenesulfonate has the formula:

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams, especially trimethylammonium methylenebenzoylcaprolactam:

Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium-methylalkylcaprolactams:

wherein n is from 0 to 12, especially from 1 to 5.

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

· ·

• • · · • • · • · • · · • • · • • ····

Alkyl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in perhydrolysis.

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

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

Amido substituted alkylperoxyacid precursors

Also suitable are amido substituted alkylperoxyacid precursors including those having the following formulas:

I. Ii clay

R ⁵ OO or wherein R ¹ is an alkyl group of from 1 to 14 carbon atoms, R ² is an alkylene group of from 1 to 4 carbon atoms, and R ⁵ is hydrogen or an alkyl group of 1 to 10 carbon atoms and L may be represented by a leaving group. R ¹ preferably contains from 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ may be a straight chain or branched alkyl containing branching, substitution, or both, and may be derived from synthetic sources or natural sources, including, for example, tallow fat. The permissible Analogous structural variations are the R ^second The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably hydrogen or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amido substituted bleach activators of this type are described in EP-A-0170386.

Precursors of benzoxazine organic peroxyacids

Also suitable are prodrugs of the benzoxazine-type compounds as disclosed, for example, in EP-A-332 294 and EP-A-482 807, especially those having the formula:

including substituted benzoxazines of type

wherein R ¹ is hydrogen, alkyl, alkaryl, aryl, arylalkyl, and wherein R ² , R ³ , R ⁴ , and R ⁵ may be the same or different substituents selected from hydrogen, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy , amino, alkylamino, COOR ⁶ (wherein R ⁶ is hydrogen or alkyl) and carbonyl.

A particularly preferred benzoxazine-type precursor is:

Preformed organic peroxyacids

The organic peroxyacid bleach system may contain, in addition to or as an alternative to the organic peroxyacid bleach precursor, a preformed organic peroxyacid typically in an amount of from 0.5 wt. % to 25 wt. %, more preferably from 1 wt. % to 10 wt. % of the composition.

A preferred class of organic peroxyacid compounds are amido substituted compounds of the following formulas:

^R1-C - N - ^R2 - C - OOH ^R1 N - C - ^R2 - C - ^00H '! L ii i ₅ ii

OR ⁵ o R ⁵ OO or wherein R ¹ is an alkyl group of from 1 to 14 carbon atoms, R ² is an alkylene, arylene and alkarylene group of from 1 to 14 carbon atoms, and R ⁵ is hydrogen or an alkyl, aryl or aralkyl a group containing 1 to 10 carbon atoms. R ¹ preferably contains from 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ may be a straight chain or branched alkyl containing branching, substitution, or both, and may be derived from synthetic sources or natural sources, including, for example, tallow fat. The permissible Analogous structural variations are the R ^second The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably hydrogen or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amido substituted bleach activators of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. The dibenzoyl peroxide is in said preferred organic peroxyacid. Also suitable are mono- and diperazelaic acid, mono-diperbrasilic acid, and N-phthaloylaminoperoxycaproic acid.

Controlled release rate - means

The compositions may be designed to control the rate of release of the bleach, particularly oxygen bleach, into the wash solution.

Means for controlling bleach release rate can provide controlled release of peroxides into the wash solution.

Another mechanism for controlling the rate of bleach release may be by coating the bleach with a coating designed to effect controlled release. The coating may then, for example, comprise a poorly water-soluble material, or be a coating of sufficient thickness to provide a controlled release rate of the coarse coating dissolution kinetics.

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

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

Other suitable coating materials may include alkali metal and alkaline earth sulphates, silicates and carbonates, including calcium carbonate and silicas.

Preferred coating materials, particularly bleach sources for inorganic perhydrate salts, include sodium silicate SiO ₂ : Na ₂ O in a ratio of from 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 and / or sodium metasilicate %, preferably used in an amount of from 2 wt. % to 10 wt. % (typically from 3 wt% to 5 wt%) of SiO ₂ by weight of the inorganic perhydrate salt.

All inorganic salt coating materials may be combined with an organic binder material to provide a composite inorganic salt / organic binder coating. Suitable binders include C10-C20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole of alcohol and more preferably C15-C20 primary alcohol ethoxylates containing 20-100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 70,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 x 10 ⁶ , preferably 1,000 to 400,000, most preferably 1,000 to 10,000 are examples of such polymeric materials. Other examples of polymeric materials useful as binder agents are maleic anhydride-ethylene copolymers, methyl vinyl ether or methacrylic acid, maleic anhydride forming at least 20 moles. These polymeric materials can be used as such or in combination with solvents such as water, polypropylene glycol and the aforementioned.

C10-C20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole. Other examples of binders include C10-C20 mono- and diglycerol ethers as well as C10-C20 fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric carboxylic acids or salts thereof are other examples of binders suitable for use herein.

One method of using the coating material requires agglomeration. Preferred agglomeration processes include the use of any of the organic binder materials described herein. Any conventional agglomerator / mixer may be used, including, but not limited to, pan, rotary drum types and vertical mixers. The melted coating compositions can also be applied, either by pouring or spraying onto a moving bed of bleaching agent.

Other means of performing the desired controlled release include mechanical means for altering the physical properties of the bleach to control its solubility and release rate. Suitable protocols may include compression, mechanical injection, manual injection, and adjustment of the whitening compound by selecting the particle size of each particulate component.

If the selection of the particle size will depend on both the composition of the particulate component and the requirement to meet the desired controlled release kinetic, it is desirable that the particle size be greater than 500 microns, preferably having a particle diameter of 800 to 1200 microns.

Additional protocols for carrying out controlled release means include selecting all other components of the matrix of the detergent composition such that when the composition is introduced into the wash solution, the ionic strength of the medium in the solution allows the desired release kinetics to be achieved.

Metal containing bleach catalyst

The compositions described herein which contain a bleach as a detergent component may additionally comprise as a preferred component a bleach catalyst-containing metal. Preferably, the metal-containing bleach catalyst is a transition element comprising a bleach catalyst, more preferably manganese or cobalt-containing bleach catalyst.

• ·

A suitable type of bleaching catalyst is a catalyst comprising a heavy metal cation of defined bleaching catalytic activity, such as copper, iron cations, an additional metal cation having little or no bleaching catalytic activity, such as zinc or aluminum, and a preservative having defined stability constants for catalytic and additional metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonium acid) and their water-soluble salts. Such catalysts are disclosed in U.S. Patent 4,430,243.

Preferred types of bleach catalysts include the manganese complexes disclosed in U.S. Patent Nos. 5,246,621 and 5,244,594. Preferred examples of such catalysts include Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (PF6) 2, Mn ^III 3 (µO) i (µ-Oac) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (CIO 4) 2, Mn ^IV 4 (µO) 6 ( 1,4,7-triazacyclononane) 4- (ClO4) 2, Mn ¹¹¹ Mn ^IV 4 (µO) i (µ-Oac) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- ( And mixtures thereof. Others are described in European patent publication no. 549 272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2 , 4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

Bleach catalysts useful for use may be selected as appropriate for the present invention. For example, suitable bleach catalysts see U.S. Patents 4,246,612 and 5,227,084. See also U.S. Patent 5,194,416, which refers to mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-, 4.7). -triazacyclononane) (OCH3) 3- (PF6) 3 Yet another type of bleach catalyst, as disclosed in US Patent 5,114,606, is a water-soluble manganese (III) and / or (IV) ligand complex that is a hecarboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose, and mixtures thereof.

US Patent 5,114,611 discloses a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a non-macrocyclic ligand. Said ligands have the formula:

R ² R ³

R ¹ -N = CBC = NR ⁴ • wherein each R ¹ , R ² , R ³ and R ⁴ may be selected from hydrogen, a substituted alkyl or aryl group such that R ¹ -N = CR ² and R ³ - C = NR ⁴ form a five or six membered ring. Said ring may be further substituted. B is a bridging group selected from oxygen, sulfur. CR ⁵ R ⁶ , NR ⁷ and C = O, wherein each R ⁵ , R ⁶ and R ⁷ may be hydrogen, alkyl or aryl, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole groups. Optionally, said rings may be substituted with substituents such as alkyl, alkoxy, halide and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , Di (isothiocyanato) bispyridylamine-cobalt (II), trispyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ O2ClO 4, Bis- (2,2 ' (bis) pyridyl amine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

Preferred examples include the dinuclear manganese complexes of stetra-Ndentate and bi-N-dentate ligands, including N4Mn ^HI (µ-0) 2Mn ^{1 in} N4) and [Bipy2Mn ^HI (µO) 2Mn ^{1 in} bipy2] - (CIO4) 3 ·

If the structures of the bleaching catalyzed manganese complexes of the present invention have not been elucidated, they may be considered to include chelates or other hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Similarly, the oxidation state of the manganese cation during the catalytic process is not known with certainty and may be in the (+ II), (+ III), (+ IV) or (+ V) valence state. Since six manganese cation attachment points are possible, it can reasonably be considered that there may be multinuclear species and / or "cage" structures in the aquatic environment. Any form of active Mn-ligand species that currently exists functions clearly in a catalytic manner to provide improved whitening effects in a durable color such as tea, ketchup, coffee, wine, juice and the like.

Other bleach catalysts are described, for example, in European Patent Application, Publication No. WO 97/32711. 408 131 (cobalt complex catalysts), European Patent Application, Publication Nos. 384,503 and 306,089 (metal-porphyrin catalysts), US 4,711,748, and European Patent Application, Publication No. Ser. 224 952 (absorbed manganese and aluminosilicate catalysts), US 4 601 845 (aluminosilicate carrier with manganese and zinc or magnesium salts), US 4 ··

626,373 (manganese / ligand catalysts), US 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelate catalyst), Canadian 866,191 (transition metal salts), US 4,430,243 (manganese cation chelants) and non-catalytic metal cations) and US 4,728,455 (manganese gluconate catalysts).

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

Co [(NH ₃₎ nM'mB'bT'tQqPpjYy wherein cobalt is in the +3 oxidation state; n is a number from 0 to 5 (preferably 4 or 5; most preferably 5); M 'represents a monodentate ligand m is a number from 0 to 5 (preferably 1 or 2; most preferably 1); B * represents a bidentate ligand; b is a number from 0 to 2; T * represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; an + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counter anions present in a number of y, wherein y is a number from 1 to 3 (preferably 2 to 3; most preferably 2, when Y is a charged-anion -1) to obtain a balanced charge salt, preferably Y is selected from the group consisting of chloride, sulfate nitrate, citrate, acetate, carbonate and combinations thereof; and wherein at least one of the coordination points attached to the cobalt is labile under conditions of use in an automatic dishwasher and the remaining coordination points stabilize the cobalt in an automatic dishwasher condition so that the reduction potential for cobalt (III) and cobalt (II) under alkaline conditions is less 0.4 volts (preferably less than 0.2 volts) over a conventional hydrogen electrode.

Preferred cobalt catalysts of this type have the formula:

[Co (NH ₃ ) _n (M ') _m ] Y _y wherein n is the number 4 or 5 (preferably 4 or 5; most preferably 5); M 'is a labile coordination bond, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) combinations thereof m is a number from 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6; and Y is one correspondingly selected counter anion present in a number of y, which is a number from 1 to 3 (preferably 2) (preferably 2). Preferably up to 3, most preferably 2, when Y is a charged anion -1) to obtain a balanced charge salt.

Preferred cobalt catalysts of this type useful herein are the cobalt pentaamine chloride salts having the formula [Co (NH ₃ ) 5 C] Y _y, and in particular [Co (NH ₃ ) ₅ Cl] Cl 2.

More preferably, the compositions of the present invention employ cobalt (III) bleach catalysts having the formula:

[Co (NH ₃ ) _n (M) ni (B) b] T _y in which the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0) and if b = 0 then m + n = 6, a and b = 1 then m = 4; and T is one or more of the appropriately selected counter anions present in the number y, where the number is to obtain a balanced charge salt (preferably, y is 1 to 3; most preferably 2 when Y is a charged anion -1); and wherein said catalyst has a base hydrolysis rate constant of less than 0.23 M ^-1 s ^-1 (25 ° C) to obtain a balanced charge salt.

Preferred T are selected from the group consisting of chloride, iodide, I, format, nitrate, sulfate nitrite, sulfite, citrate, acetate, carbonate, bromide, PF ₆ ', BF ₄ ', B (Ph) ₄ ; phosphate, phosphite, silicate, tosylate, methanesulfonate and combinations thereof. Alternatively, T can be protonated if there is more than one anionic group in T, for example HPO ₄ ² ; HCO ₃ ', H ₂ PO ₄ , etc. Further, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ethoxy sulfonates (AES), etc.) and / or anionic polymers (e.g. polyacrylates, polymethacrylates, etc.).

The moieties of M include, but are not limited to, for example, F ', SO ₄ ² ', NCS; SCN ', S203 ² ; NH 3 ΡΟΛ and carboxylates (which are preferably monocarboxylates but more than one carboxylate may be present in the moiety only when bound to the cobalt by one carboxylate per moiety, in this case the second carboxylate in moiety M may be protonated or in salt form). Alternatively, M may be protonated if there is more than one anionic moiety in M (e.g., HPO ₄ ² ; HCO ₃ ', HCO ₃ ', HCO ₃ ', HCO ₃ ', HCO ₃ ', HCO ₃ ', · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Η ₂ ΡΟ ₄ ·, HOC (O) CHC (O) O-, etc. Preferred moieties of M are substituted and unsubstituted C 1 -C 30 carboxylic acids having the formula:

RC (O) Ov wherein R is preferably selected from the group consisting of hydrogen and C 1 -C 30 (preferably _C-8 C) unsubstituted and substituted alkyl, C ₃ -C ₆ a (preferably Ce-Cie) unsubstituted or substituted aryl, and C3-C3Q (preferably C5-Cw) unsubstituted and substituted heteroaryl wherein the substituents are selected from the group consisting of NR3, -NR '/, -CO (O) R', -OR ', -C (O) NR' Such substituted R then includes the moieties - (CH 2) n OH and - (CH ₂ ) n NR 'Z, in which n is a number from 1 to 16 , preferably from 2 to 10, and most preferably from 2 to 5.

Most preferably, M is a carboxylic acid having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C 4 -C 12 alkyl, and benzyl. Most preferably R is methyl. Preferred proportions of M carboxylic acid include formic, benzoic, octanoic, nonanoic, decinoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthalic, oleic, palmitic, triftal, butyric, tartaric, stearic, tartaric, stearic, teary , aspatam, fumaric, lauric, linoleum, dairy, apple and especially acetic.

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

The cobalt bleach catalysts disclosed herein are known, for example, from describing the rate of base hydrolysis in M.L. Tobe, &quot; Base Hydrolysis of Transition-Metal Complexes &quot;, Adv. Inorg. Bioinoro, Mech. (1983), 2, pp. 1-94. For example, Table 1 on page 17 provides base hydrolysis rates (referred to herein as koH) for cobalt pentamine catalysts complexed with oxalate (koH = 2.5 x 10 ^-4 M ^-1 s * ¹ (25 ° C)), NCS (kOH = 5.0 x 10 ^-4 M ^-1 s ^-1 (25 ° C)), format (kOH = 5.8 x W ⁴ M ^-1 s ¹ (25 ° C)), and acetate (kOH = 9, 6 x 10 ⁴ M ^-1 s ^-1 (25 ° C)). The most preferred cobalt catalysts useful herein are the cobalt penatminacetate salts having the formula [Co (NH 3) ₅ OAc] Those in which OAc represents the acetate moiety, and in particular cobalt pentamine acetate, [Co (NH ₃ ) ₅ OAc] CI ₂ ; as well as [Co (NH ₃ ) ₅ OAc] (OAc) ₂ ; [Co (NH ₃ ) ₅ OAc] (PF ₆ ) 2; (Co (NH ₃ ) ₅ OAc] (SO ₄ ); [Co (NH ₃ ) ₅ OAc] (BF ₄ ) ₂ ; and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (here "PAC") .

These cobalt catalysts are readily coupled according to known procedures, such as e.g. in the aforementioned Tobe article and references cited therein, in U.S. Patent 4,810,410 to Diakun et al, issued Mar. 7, 1989, J, Chem. Ed. (1989) 66 (12), 1043-45; The Sythesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), p. 461-3; Inorq. Chem., 18, 1497-1502 (1979); Inorq. Chem., 21, 2881-2885 (1982); Inorq, Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistrv. 56, 22-25 (1952); as well as the synthetic examples provided below.

Cobalt catalysts suitable for incorporation in the detergent tablets of the present invention can be produced according to the synthetic procedures disclosed in U.S. Pat. 5,559,261, 5,581,005, and 5,597,936, the disclosure of which is incorporated herein by reference.

These catalysts may be treated together with complementary materials to reduce the color impact, if desired for product aesthetics, or be included in enzyme-containing particles as explained below, or the compositions may be made to contain catalyst "spots".

Organic polymeric compounds

Organic polymeric compounds may be added as preferred ingredients of detergent tablets in accordance with the invention. Organic polymeric compound means substantially any organic polymeric compound commonly found in detergent compositions having dispersing, anti-reinsert, soil release agents or detergent properties.

The organic polymer compound is typically incorporated in the detergent compositions of the invention in an amount of from 0.1 wt. % to 30 wt. %, preferably from 0.5 wt. % to 15 wt. %, most preferably from 1 wt. % to 10 wt. % of the composition.

Examples of organic polymeric compounds include water-soluble organic homo- or copolymeric polycarboxylic acids, modified polycarboxylates, or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 2,000-10,000 and their copolymers with any other substituted monomeric units including modified acrylic, fumarate, maleic, itaconic, atconite , mesaconic, citroconic and methylene malonic acid or salts thereof, maleic anhydride, acrylamide, alkylene, vinyl methyl ether, styrene and all mixtures thereof. Preferred are copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.

Preferred commercially available acrylic acid-containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 from BASF and those sold under the tradename Acusol 45N, 480N, 460N from Rohm and Haas.

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

Useful polyamine and modified polyamine compounds herein include those derived from aspartic acid as disclosed in EP-A-305282, EP-A-305283 and EP-A-351 629.

Other optional polymers may include polyvinyl alcohols and acetates, both modified and unmodified, cellulosic and modified celluloses, polyoxyethylenes, polyoxypropylenes and copolymers thereof, modified and unmodified, terephthalate esters of ethylene or propylene glycol, or mixtures thereof with polyoxyalkylene units.

· · · · ·· ·· · · • · • · • · • · · · • · • • · • ···· • · · · • · · • · · · • · · ·· ···· • · • · • · • · · ·

Dirt-releasing agents

Suitable polymeric soil release agents include those soil release agents having: a) one or more nonionic hydrophilic components consisting essentially of i) polyoxyethylene segments having a degree of polymerization of at least 2, or ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 10 wherein said hydrophilic segment contains no oxypropylene unit when bound to adjacent portions at each end by ether bonding, or iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophilic segments preferably comprising at least 25 oxyethylene units and more preferably, in particular, for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate to C3 oxyethylene terephthalate units is 2: 1 or less; (ii) C4-C4 alkylene segments Iii) polyvinyl ester segments, preferably polyvinyl acetate having a degree of polymerization of at least 2, or iv) C1-C4 alkyl ether or C4 hydroxy ether substituents, or these mixtures wherein said substituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures thereof, or a) and b) combinations.

Typically, polyoxyethylene segments a) i) will have a degree of polymerization of from 200, although higher grades may be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable oxy C4-C6 alkylene hydrophobic segments include, but are not limited to, terminated with polymeric soil release agents such as MO ₃ S (CH ₂ ) n OCH ₂ CH ₂ O-, wherein M is sodium and n is a number from 4 to 6 as disclosed in US Patent 4,721,580 issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful herein include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulose soil release agents for use herein also include those selected from the group consisting of C 1 -C ₄ alkyl and C ₄ hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol et al.

Soil release agents characterized by polyvinyl ester hydrophobic segments include attached polyvinyl ester copolymers, e.g. C1-C6 vinyl esters, preferably polyvinyl acetate linked to a polyalkylene oxide backbone, such as a polyethylene oxide backbone. See European Patent Application 0 219 048 published April 22, 1987 by Kud et al.

Another suitable soil release agent is a copolymer having irregular blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent ranges from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, and U.S. Patent 3,893,929 to Basadur, issued July 8, 1975.

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

Another suitable polymeric soil release agent is the sulfonated product of a substantially linear oligomer ester composed of oligomeric esters of terephthaloyl backbone and oxyalkyleneoxy repeating units and terminated by moieties covalently attached to the backbone. These soil release agents are fully described in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include terephthalate polyesters of U.S. Patent 4,711,730 issued December 8, 1987 to Gosselink et al, anionically terminated oligomeric esters of U.S. Patent 4,721,580 issued January 26, 1988 to Gosselink, and block polyester oligomeric compounds of U.S. Patent 4,702 857 issued October 27, 1987 to Gosselink. Other polymeric soil release agents also include soil release agents according to U.S. Patent 4,877,896 issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaryl, terephthalate terminated esters.

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

• ·

• φ ·· · · φ ·· ·· ···· ·· ·

Heavy metal ion separators

The tablets of the invention preferably contain an optional heavy metal ion separator component. Here, the heavy metal ion separator means components that act to separate (chelate) the heavy metal ions. These components may also have a chelating capacity of calcium and magnesium, but preferably may exhibit selectivity for binding heavy metal ions such as iron, manganese, and copper.

Heavy metal ion separators are generally present in an amount of from 0.005 wt. % to 20 wt. %, preferably from 0.1 wt. % to 10 wt. %, more preferably from 0.25 wt. % to 7.5 wt. % and most preferably from 0.5 wt. % to 5 wt. % of the composition.

Acidic heavy metal ion scavengers having, for example, phosphonium or carboxylic acid functionalities, may be present in their acid form or as a complex / salt with a suitable counterion such as an alkali or alkali metal ion, ammonium, or substituted ammonium ion or any mixtures thereof. Preferably all the water-soluble salts / complexes are present. The molar ratio of said counterionion of the heavy metal ion sequester is preferably at least 1: 1.

Suitable heavy metal ion scavengers for use herein include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), 1-hydroxydiphosphonates, and alkali metal nitrilotrimethylphosphonates. Preferred of the above are diethylenetriamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate.

Other suitable heavy metal ion separators for use herein include nitrilotriacetic acid and polyaminocarboxylic acid, such as ethylenediaminotetraacetic acid, ethylenetriamine-pentaacetic acid, ethylenediamine-disuccinic acid, ethylenediamine-di-diaminic acid, or their 2-diaminocarboxylic acid, 2-diene.

Particularly preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or an alkali metal, alkaline earth, ammonium, or substituted ammonium salt thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form or the sodium or magnesium salt or complex thereof.

·······················

Crystal growth inhibitor component

The detergent tablets preferably comprise a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably in an amount of from 0.1 wt. % to 5 wt. %, more preferably from 0.1 wt. % to 2 wt. % of compositions.

Organodiphosphonic acid here means an organodiphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition then excludes organoaminophosphonates, which may, however, be included in the compositions of the invention as components of heavy metal ion separators.

The organo acid is preferably a C1 -C4 diphosphonic acid, more preferably C ₂ diphosphonic acid, such as ethylene acid aleboetán-

1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partial or fully ionized form as a salt or complex.

Water-soluble sulfate salts

The detergent tablet optionally comprises a water-soluble sulfate salt. If a water-soluble sulfate salt is present, it is present in an amount of from 0.1 wt. % to 40 wt. %, more preferably from 1 wt. % to 30 wt. %, most preferably from 5 wt. % to 25 wt. % of compositions.

The water-soluble salt may be substantially any salt of a counter-cation sulfate. Preferred salts are selected from alkali metal and alkaline earth sulphates, especially sodium sulphate.

Alkali metal silicates

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

The alkali metal silicate may also be present as a component of the basic system.

• ·

··· ··· ··· ···

The basic system may preferably contain sodium metasilicate present in an amount of at least 0.1 wt. % S1O2. Sodium metasilicate has a nominal S1O2: Na2O ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO2, 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

The term "dyes" as used herein means all substances that absorb specific wavelengths of light from the visible light spectrum. Such dyes, when added to the detergent composition, cause a change in the visible color and hence the appearance of the detergent composition. Preferably, the dyes are stable in the composition in which they are incorporated. Thus, in a high pH composition, the dye is preferably alkaline stable, and in a low pH composition, the dye is preferably acid stable.

The first and / or second and / or optional further phases may comprise a dye, a dye mixture, colored particles of the colored particle mixture such that the different phases have a different visual appearance. Preferably one of the first or second phases comprises a colorant. When both the first and second phases and / or the next phase comprise a dye, it is preferred that the dyes have a different visual appearance.

Examples of suitable dyes include reaction dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline dyes, monoazo, diazo and polyazo dyes. More preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-hrl, 180% (trade name), SANDOLAN MILLING BLUE, TURQUOISE ACID BLUE and SANDOLAN BRILLIANT GREEN (trade name), all available from Clariant UK, HEXANOL QUINOLINE YELLOW name) and HEXANOL BRILLIANT BLUE (trade name), both available from Pointings, UK, ULTRAMARINE BLUE (trade name) available from Holliday or LEVAFIX TURQUISE BLUE EBA (trade name) available from Bayer, USA.

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

·· • ·

The colorant, when present as a first phase component, is in an amount of from 0.001 wt. % to 1.5 wt. %, preferably from 0.01 wt. % to 1.0 wt. %, most preferably from 0.1 wt. % to 0.3 wt. %. When present as a component of the second phase and / or optional additional phases, the dye is generally in an amount of from 0.001 wt. % to 0.1 wt. %, more preferably from 0.005 wt. % to 0.05 wt. %, most preferably from 0.007 wt. % to 0.02 wt. %.

Corrosion inhibitor component

Tablets of the present invention suitable for use herein in the washing methods may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen containing corrosion inhibitor compounds, and Mn (II) compounds, especially Mn (II) salts of organic ligands.

Organic silver coating agents are described in PCT publication no. WO94 / 16047 and co-pending European application no. EP-A-690,122th Nitrogen-containing corrosion inhibitor compounds are described in co-pending European application EP-A-634 478. Mn (II) compounds for use herein for corrosion inhibition are described in co-pending European application no. EP-A-672,749.

The organic silver coating agent may be incorporated in an amount of from 0.05 wt. % to 10 wt. %, preferably from 0.1 wt. % to 5 wt. % by weight of the total composition.

The functional role of the silver coating agent is to provide a &quot; in use &quot; protective coating on all components of the silver articles of the washing device in which the compositions of the invention are used. Thus, the silver coating agent should have a high affinity for attaching to the solid silver surfaces, especially when they are present as a component of an aqueous washing or bleaching solution with which the solid silver surfaces are in contact.

Suitable organic silver coating agents herein include fatty esters of mono- or polyhydroalcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester may be obtained from mono- or polycarboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid, and β-glycolic acid. 1-dihydroxyisobutyric acid. Examples of suitable carboxylic acids include: n-butyl malonic acid, isocitronic acid, citric acid, maleic acid, malonic acid and succinic acid.

The fatty alcohol radical in fatty esters may be mono- or polyhydroalcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include: behenyl, arachidyl-cocoyl-, oleyl- and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol and sorbitan.

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

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

Glycerol esters are also highly preferred. These are mono-, di- or triesters of glycerol and fatty acids as defined above.

Specific examples of fatty acid esters for use herein include: stearyl acetate, palmityldilactate, cocoyl isobutyrate, oleyl maleate, oleyldimalate, and tallow propionate. Fatty acid esters for use herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monohydrate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan disistearate, sorbitan dibearate, sorbitan dioleate, and also mixed mono diesters.

Preferred glycerol esters herein are glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate.

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

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

Alginates and gelatin are suitable organic silver coating agents herein.

Also suitable are dialkylamino oxides such as C12-C20 methylamine oxide and dialkyl quaternary ammonium compounds and salts such as C12-C20 methylammonium halides.

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

Certain perfume ingredients, especially those that exhibit high substantivity for metallic surfaces, are useful herein as organic silver coating agents.

The polymeric soil release agent is paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a carbon number ranging from 20 to 50; the preferred paraffin oil is selected from the group of predominantly branched C25-C45 species with a ratio of cyclic and non-cyclic hydrocarbons of from 1:10 to 2: 1, preferably from 1: 10 to 2: 1. 5 to 1: 1. Paraffin oil having these properties and a 32:68 ratio of cyclic to non-cyclic hydrocarbons is sold from Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Nitrogen containing corrosion inhibitor compounds

Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and its derivatives, such as benzimidazole, 2-heptadealkylimidazole, and those imidazole derivatives described in Czech Patent No. 5,960,549. 139,279 and British Patent GB-A-1,137,741, which also disclose a process for the preparation of imidazole compounds.

·····································

Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and derivatives thereof, especially those in which pyrazole is substituted in each of positions 1, 3, 4 or 5 with substituents R ¹ , R ³ , R ⁴ and R ⁵ , wherein R ¹ is each hydrogen, CH 2 OH, CO 2 NH or COCH 2, R ³ and R ⁵ are each C 1 -C 20 alkyl or hydroxyl, and R ⁴ is each hydrogen, NH 2 or NO 2.

Other suitable nitrogen containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoylstearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.

Nitrogen-containing compounds such as amines, in particular distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrocitrate are also suitable.

Manganese (II) corrosion inhibitor compounds

The detergent tablets may contain an Mn (II) corrosion inhibitor compound. The manganese (II) compound is preferably incorporated in an amount of from 0.005 wt. % to 5 wt. %, more preferably from 0.01 wt. % to 1 wt. %, most preferably from 0.02 wt. % to 0.4 wt. % of the composition. Preferably, the manganese (II) compound is incorporated in an amount to correspond to from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of ions (II) ions in any bleaching solution.

The manganese (II) compound may be an inorganic salt in unhydrated or hydrated form. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The manganese (II) compound may be a salt or organic fatty acid complex such as manganese acetate or manganese stearate.

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

Other corrosion inhibitor compounds

Other other suitable corrosion inhibitor compounds include mercaptans and diols, especially mercaptans having 4 to 20 carbon atoms, including lauryl mercaptan, thiophenol, thionophenol, thionalide, and thioantranol. Saturated or unsaturated are also suitable

999 · ·· ·· 9999

9 9 9 9 9 9 9 9 99

9

9

9999 99 9999 ·····

C10-C20 fatty acids or their salts, especially aluminum tristearate. Also suitable are C10-C20 hydroxy fatty acids, or salts thereof. Phosphonated octadecane and other antioxidants such as beta-hydroxytoluene (BHT) are also suitable.

Butadiene-maleic acid copolymers, especially those sold under the trade number 07787 or Polysciences Inc., are considered to be particularly useful as corrosion inhibitor compounds.

Hydrocarbon oils

Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain aliphatic hydrocarbon, having a carbon number ranging from 20 to 50; the preferred hydrocarbon oil is selected from the predominantly branched C25-C45 species with a cyclic hydrocarbon ratio of from 1: 10 to 2: 1, preferably from 1: 5 to 1: 1. The preferred hydrocarbon oil is paraffin. Paraffin oil having the characteristics outlined above and having a 32:68 cyclic to non-cyclic hydrocarbon ratio is sold from Wintershall, Salzbergen, Germany under the trade name WINOG 70.

Water-soluble bismuth compound

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

The water-soluble bismuth compound may be substantially any salt of the bismuth complex with substantially any inorganic or organic counter anion. Preferred inorganic bismuth salts are selected from bismuth trihalide, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with an organic counter anion.

Enzyme stabilizing system

Preferred enzyme containing compositions herein may comprise from 0.001 wt. % to 10 wt. %, preferably from 0.005 wt. % to 8 wt. %, most preferably from 0.01 wt. % to 6 wt. % enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system that is compatible with the detergent enzyme. Such stabilizing systems may include calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boric acid, bleach chlorine scavengers, and mixtures thereof. Such stabilizing systems may also include reversible enzyme inhinators, such as reversible protease inhibitors.

Lime Soap Dispersant Compound

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

The lime soap dispersant is a substance that prevents the precipitation of alkali metal, ammonium or amine salts of calcium or magnesium ions. Preferred lime soap dispersant compounds are disclosed in PCT application no. W093 / 08,877th

Foam suppressing systems

The detergent tablets of the present invention, when formulated for use in washing machine or dishwasher compositions, preferably comprise a foam suppressing system present in an amount of from 0.01 wt. % to 15 wt. %, preferably from 0.05 wt. % to 10 wt. %, most preferably from 0.1 wt. % to 5 wt. % of the composition.

Suitable foam suppression systems for use herein include substantially all known antifoam compounds, including, for example, antifoam silicone compounds, antifoam 2-alkyl and alkanol compounds. Preferred foam suppressing systems and antifoam compounds are disclosed in PCT application WO93 / 08876 and EP-A-705 324.

Polymeric dye transfer inhibiting agents

The detergent tablets herein may comprise from 0.01 wt. % to 10 wt. %, preferably from 0.05 wt. % to 0.5 wt. % dye transfer inhibiting polymeric agents.

· ·

The dye transfer inhibiting polymeric agents are preferably selected from polyamine N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole polymers, polyvinylpyrrolidone polymers or combinations thereof.

Optical brighteners

Detergent tablets suitable for use herein in the laundry washing processes described herein also optionally contain from 0.005 wt. % to 5 wt. % certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R ¹ is selected from anilino, Ν-2-bis-hydroxyethyl and ΝΗ-2-hydroxyethyl; R ² is selected from Ν-2-bis-hydroxyethyl; N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino and M is a salt-forming cation such as sodium or potassium.

When in the above formula R ¹ is anilino, R ² is Ν-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2- bis-hydroxyethyl) -s-triazine

2-yl) amino] -2,2'-stilbenedisulfonic acid and the disodium salt. This major type of brightener is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNGA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula R ¹ is anilino, R ² is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino-6- (N- 2-hydroxyethyl-N-methylamino) -5-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This significant type of brightener is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula R ¹ is anilino, R ² is morpholino and M is a cation such as sodium, the brightener is the sodium salt of 4 ₁ 4 ^, -bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid. This major brightener is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNGA-GX

Clay Softening System

Detergent tablets suitable for use in a laundry washing process may comprise a clay softening system comprising a mineral clay compound and optionally a clay flocculating agent.

The mineral clay compound is preferably a smectite clay compound. Smectite clays are disclosed in U.S. Pat. 3 862 058, 3 948 790m 3 954 632 and 4 062 647. European patents no. EP-A-299 575 and EP-A-313 146 of the Procter and Gambia Company describe organic polymeric clay flocculating agents.

Cationic tissue softening agents

Cationic tissue softening agents can also be incorporated into compositions in accordance with the present invention that are suitable for use in laundry methods. Suitable cationic fabric softening agents include water-insoluble tertiary amines or two long chain amide materials are disclosed in GBA-1 514 276 and EP-B-0 011 340.

Cationic fabric softening agents are typically incorporated in a total amount of from 0.5 wt. % to 15 wt. %, typically from 1 wt. % to 5 wt. %.

Other optical additives suitable for inclusion in the compositions of the invention include pafrems and filler salts, with sodium sulfate as the preferred filler salt.

PH compositions

The detergent tablets of the present invention are preferably formulated so as not to have a disproportionately high pH, preferably having a pH measured as a 1% solution in distilled water of from 8.0 to 12.5, more preferably from 9.0 to 11.8, most preferably from 9, 5 to 11.5.

Method of washing in the dishwasher

All suitable methods of washing or cleaning soiled dishes in the dishwasher are envisaged.

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J · · · · ············

A preferred dishwashing method comprises treating a soiled dish selected from stoneware, glass, silverware, cutlery, and mixing them with an aqueous liquid having dissolved or dispensed an effective amount of a detergent tablet in accordance with the present invention. An effective amount of a detergent tablet is from 8 g to 60 g of product dissolved or dosed in an aqueous solution having a volume of 3 to 10 liters, such as typical product doses and volumes of washing solution commonly used in conventional dishwashing methods. Preferably, the detergent tablets have a weight of from 15 g to 40 g, more preferably from 20 g to 35 g.

Machine wash method

The machine washing methods herein typically involve treating a soiled laundry with an aqueous wash solution in a washing machine having a dissolved or dispensed effective amount of a detergent tablet composition in the washing machine in accordance with the invention. An effective amount of a detergent tablet composition is from 40 g to 300 g of product dissolved or dispersed in a wash solution of 5 to 65 liters, such as typical product doses and wash solution volumes commonly used in conventional washing machine processes.

In a preferred aspect of the use, the dispensing device operates in a washing manner. The dispensing unit is filled with detergent product and is used to introduce the product directly into the lever drum before the start of the wash cycle. Its bulk capacity should be such that it can contain sufficient detergent product as commonly used in washing processes.

After the washing machine has been filled with laundry, the dispensing unit containing the detergent product is placed in a drum. At the beginning of the wash cycle, water is introduced into the drum and the drum rotates periodically. The design of the dosing unit should be such as to allow the contents of the dry detergent product to be contained, but then allow the product to be released during the wash cycle due to its mixing during rotation of the drum and also as a result of its contact with the wash water.

To allow release of the detergent product upon washing, the unit may have a plurality of openings through which the product may pass. Alternatively, the unit may be made of a material that is liquid-permeable, but impermeable to solids, which will allow release of the dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle, and thereby, the detergent product will be released rapidly. Ensure temporarily localized high product concentrations in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing units are reusable and are designed in such a way that the integrity of the container is maintained both dry and during the wash cycle.

Alternatively, the dosage unit may be a flexible container, such as a sachet or pouch. The bag may be constructed of fiber coated with a water impervious protective material so as to retain the content as described in European Published Patent Application no. Alternatively, it may be formed from a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in an aqueous environment as disclosed in European Published Patent Applications Nos. 0011500, 0011501, 0011502 and 001968. A conforming form of a water-frangible closure includes a water-soluble adhesive disposed along the edge and sealing one edge of a housing formed of a water-impermeable polymer film such as polyethylene or polypropylene.

Examples

Abbreviations used in the Examples

In detergent compositions, the abbreviations of the components have the following meanings: STPP: sodium tripolyphosphate

Dicarbonate: sodium bicarbonate

Citric acid: anhydrous citric acid Carbonate: anhydrous sodium carbonate

Silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0 ratio) SKS-6: crystalline layered silicate of the formula 5-Na ₂ Si ₂ Ss

PB 1: anhydrous sodium perborate monohydrate

Non-ionic: 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 from BASF

TAED: tetraacetylethylenediamine

·· ·· · · · · ·· · • · · · • • • · • · • * • · · • · • • · • • · · • · • • • ·! • • · · ·· ···· • · ·· • ···· e e ·· e ···

HEDP : ethane-1-hydroxy-1,1-diphosphonic acid PAAC : cobalt (III) salt of pentaamine acetate paraffin : paraffin oil sold under the trade name Winog 70 by Wintershall protease : proteoytic enzyme Amylase BTA : amylolytic enzyme : benzotriazole sulphate : anhydrous sodium sulphate PEG 3000 : polyethylene glycol with a molecular weight of about 3000 available from Hoechst PEG 6000 : polyethylene glycol with a molecular weight of approximately 6000 Available from Hoechst pH : measured as a 1% solution in distilled water at 20 ° C

In the following examples, all amounts are parts by weight:

Examples 1-IV

The following illustrates examples of a detergent tablet of the present invention in a washing apparatus.

I II III IV IN VI Phase 1 STPP 9.62 9.62 10.45 9.57 9.57 11.47 silicate 0.50 0.67 1.60 1.00 1.00 2.40 SKS-6 1.5 1.50 2.30 2.25 carbonate 2.33 2.74 3.5 3.59 4.10 5.25 HEDP 0.18 0.18 0.18 0.28 0.28 0.28 PB1 2.45 2.45 2.45 3.68 3.68 3.68 PAAC 0,002 0,002 0,002 0,003 0,004 0,004 amylase 0,148 0,110 0,110 0,252 0,163 0,163 protease 0.06 0.06 0.06 0.09 0.09 0.09 nonionic 0.40 0.80 0.80 1.20 1.20 1.20 PEG 6000 0.4 0.26 0.26 0.38 0.39 0.39 BTA 0.04 0.04 0.04 0.06 0.06 paraffin 0.10 0.10 0.10 0.15 0.15 0.15 part 0.02 0.02 0.02 0.02 0.02 0.02 sulphate 0,502 0.05 2,843 Pretty 17.75 g 18.55 g 19.57 g 23.0 g 23.0 g 23.0 g

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Phase 2 amylase 0.30 0.35 0.25 0.30 0.35 0.25 protease 0.25 0.22 0.30 0.25 0.22 0.30 Citric acid 0.3 0.30 0.3 0.30 Sulfamic acid 0.3 0.3 dicarbonate 1.09 0.45 0.45 1.09 0.45 0.45 carbonate 0.55 0.55 silicate 0.64 0.64 CaCl ₂ 0.07 0.07 PEG 3000 0 ^ 6 0.06 0.06 0.06 0.06 0.06 Pretty 2.0 g 2.0 g 2.0 g 2.0g 2.0 g 2.0 g

Multiphase tablet compositions are prepared as follows. The phase 1 detergent active composition is prepared by mixing the granular and liquid components and then passes to a conventional rotary press die. The press comprises a punch suitably shaped to form a mold. The die cross-section is approximately 30 x 38 mm. The composition is then subjected to a compression force of 940 kg / cm ² and the punch is then lifted by uncovering the first phase of the tablet containing the mold on its top surface. The phase 2 detergent active composition is prepared in a similar manner and passes into a die. The particulate active composition is then subjected to a compression force of 170 kg / cm ² , the punch is then lifted, and the multiphase tablet is punched out from a tablet press. The resulting tablets dissolve or disintegrate in the washing machine and dishwasher as described above within 12 minutes, phase 2 tablets dissolving within 5 minutes. The tablets provide excellent dissolution and washing properties along with good cohesiveness and firmness of the tablet.

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Claims (14)

A multiphase detergent tablet comprising: a) a first shaped body having at least one mold therein; and b) a second phase in the form of a compressed body contained adhesively in said form, characterized in that the tablet composition comprises one or more detergent active substances which are predominantly concentrated in the second phase and wherein the second phase further comprises a disrupting agent. The multi-phase detergent tablet of claim 1, wherein the second phase is compressed at a pressure of less than about 350 kg / cm ² . 3. A multi-phase detergent tablet comprising: a) a first phase in the form of a compressed shaped body having at least one mold therein, the shaped body being prepared at a compression pressure of at least about 350 kg / cm ² ; and b) a second phase in the form of a compressed body contained adhesively in said form, the second phase being compressed at a pressure of less than about 350 kg / cm ² and characterized in that the tablet composition comprises one or more detergent active substances predominantly concentrated in the second and wherein the second phase further comprises a disrupting agent. The multi-phase detergent tablet according to any of the preceding claims, wherein the second phase dissolves more rapidly than the first phase. The multi-phase detergent tablet according to any one of the preceding claims, characterized in that the second phase dissolves in the dishwasher within 5 minutes. 6. A multi-phase detergent tablet for use in a washing machine, comprising: a) a first shaped body having at least one mold therein; and ················································ · · · ····························· b) a second phase in the form of a compressed body contained adhesively in said form, characterized in that the tablet composition comprises one or more detergent active substances which are predominantly concentrated in the second phase and wherein the second phase further comprises a disintegrant and the tablet is formulated so as to wherein at least 50 wt. %, preferably at least 60 wt. %, more preferably at least 80 wt. % of one or more detergent active agents is delivered to the wash within 10 minutes, preferably within 5 minutes, and most preferably within 3 minutes. A multi-phase detergent tablet according to any preceding claim wherein the one or more detergent active ingredients are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors, and mixtures thereof. A multi-phase detergent tablet according to any one of the preceding claims, characterized in that the disrupting agent is selected from disintegrants, effervescent agents and mixtures thereof. A multi-phase detergent tablet according to any one of the preceding claims, characterized in that the first and / or second phase comprises a binder. The multi-phase detergent tablet of claim 9, wherein the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers. The multi-phase detergent tablet of any preceding claim, further comprising a barrier phase between the first and second phases. The multi-phase detergent tablet of claim 11, wherein the barrier layer comprises a binder used in liquid form. ················································ ·· ··· A washing machine method comprising loading a rinsing device with one or more multiphase tablets according to any one of the preceding claims. The method of claim 13, wherein the multiphase detergent tablet dissolves or comminutes in a dishwasher in less than 15 minutes in accordance with the solubility testing method described herein.