PL189559B1 - Detergent tablet - Google Patents

Abstract

1 . Multi-phase dishwasher detergent tablet, weighing 15-40 grams, comprising a first phase in the form of a compressed, shaped body formed from a first detergent composition, and a second phase in the form of a pressed body formed from a second detergent composition, characterized in that a) the first phase has at least one nest on the surface of the shaped element and b) the second phase, held in the nest by adhesion, has a mass of less than 4 grams and contains an enzyme. PL

Description

The present invention relates to a multiphase detergent tablet for dishwashers.

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

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

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

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

Known multiphase detergent tablets are made by compressing the first composition in a tablet press to form a substantially planar first layer. The next detergent composition is then fed to the tablet press on top of the first layer. This second composition is then compressed to form a further, substantially flat, second layer. Accordingly, the first layer is generally compressed more than once as it is also compressed during compression of the second composition. Typically, the first and second compressive forces are of the same order of magnitude.

189 559

It has been found that in this case, since the compressive force must be sufficient to bond the first composition to the second, the force applied in the first and second pressing steps must be between about 40 and 200 kN (assuming the cross section is tablet is about 10 cm ² ). This causes the tablet to dissolve slowly. Other multiphase tablets with different dissolution rates are produced by compressing the second layer with a lower pressure than the first layer. However, while the dissolution rate of the second layer increases, the second layer is softer than the first layer and is therefore susceptible to damage during handling and shipping.

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

Thus, there is a need for a detergent tablet which is strong enough to withstand handling and transport, and at least a significant portion of which dissolves rapidly in the wash water, ensuring rapid delivery of the detergent active ingredient. Preferably, at least one phase of the tablet should dissolve in the wash water within the first 10 minutes, preferably 5 minutes and more preferably within the 4 minutes of the automatic dishwasher cycle. The time for which the multiphase tablet or its phase or the detergent active ingredient dissolves is determined in accordance with DIN 44990 using a dishwasher available from Bosch in a normal washing program at 65 ° C in water hardness 18 ° H with a repetition number of at least 6 or sufficient to ensure repeatability.

Accordingly, the invention relates to a multi-phase dishwasher detergent tablet weighing 15-40 grams comprising a first phase as a compressed, shaped body formed from a first detergent composition and a second phase as a compressed body formed from a second composition det ^^^ <^^ The first phase is characterized in that a) the first phase has at least one cavity on the surface of the shaped element and b) the second phase, held in the seat by adhesion, has a weight of less than 4 grams and contains the enzyme.

Preferably the multiphase detergent tablet according to the invention comprises the enzyme mainly concentrated in the second phase.

Preferably, in the multi-phase detergent tablet according to the invention, the first and / or second phase comprises a binder.

Preferably, the multiphase detergent tablet according to the invention comprises a binder selected from the group consisting of sugar and sugar derivatives, starch and sugar derivatives, and inorganic and organic polymers.

Preferably, the multiphase detergent tablet according to the invention additionally comprises a barrier phase between the first and second phases.

Preferably, the barrier phase is a binder applied in liquid form.

In preferred embodiments of the inventive tablet, the first phase is a compressed, shaped member formed under an applied pressure of at least about 3.9 MPa, preferably at least about 24.5 MPa, more preferably at least about 34.3 MPa, more preferably from about 39.2 MPa to about 39.2 MPa. about 196.1 MPa, and more preferably from about 58.8 to about 117.7 MPa (as used herein, pressure is the applied force divided by the cross-sectional area of the tablet in a plane perpendicular to the applied force, i.e. the cross-sectional area of the die in the rotary press). It is also preferred that the particulate solid of the second phase (which term also includes the possibility of using multiple "second" phases, sometimes referred to herein as "optional second phases") is compressed in the cavity at a pressure less than the pressure applied to the second phase. first phase,

189,559 and preferably at a pressure less than about 34.3 MPa, preferably in the range from about 3.9 to about 29.4 MPa, more preferably from about 6.9 to about 26.5 MPa, as such tablets are preferred in this respect, that optimal tablet integrity and strength (as measured by e.g. Child Bite Strength [CBS]) and dissolution characteristics of the product are achieved. The tablets of the invention preferably exhibit a CBS of at least about 60 N, preferably more than about 80 N, more preferably more than about 100 N, more preferably more than about 120 N and most preferably greater than about 140 N, CBS measured according to US Consumer Product Safety Standard. Commission Test Specification. Furthermore, the ratio of pressures applied to the first and second phases is typically at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1.

Particularly preferably, a shaped member formed from the first phase is produced at a pressure of at least about 34.3 MPa and the second, particulate solid phase is pressed at a pressure below about 34.3 MPa.

The second phase is held in the form of a compressed or shaped element by physical or chemical adhesion.

Preferably, the weight ratio of the first to the second phase is high, e.g. at least about 6: 1 and preferably at least about 10: 1.

The tablet may contain one or more detergent active ingredients (e.g. enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, etc.) which are mainly concentrated in the second phase such that e.g. at least about 50%, preferably at least about 60%, especially about ¹ to 80% active ingredient (based on the total weight of active ingredients in tablet) is in the second phase of the tablet. Such compositions are optimal with regard to tablet strength, dissolution, washing properties, and pH adjustment characteristics, whereby e.g. tablets dissolving in the washing liquid are obtained such that they provide at least 50%, preferably at least 60%, more preferably at least 80%. wt.% detergent actives into the washing liquid within 10, 5, 4 or even 3 minutes from the start of washing.

An additional advantage of the invention is the possibility of achieving differential dissolution of the phases whereby one phase of the tablet will dissolve much earlier than the other phase, and even essentially completely before the dissolution of the other phase. This is especially valuable due to the differential delivery of detergent active ingredients.

A preferred multiphase detergent tablet in the second phase contains, in addition to the one or more detergent actives mainly concentrated in the second phase, an additional disintegrant.

Another preferred second phase multiphase detergent tablet comprises, in addition to one or more detergent actives mainly concentrated in the second phase, an additional binder.

Suitably the one or more detergent actives are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors, and mixtures thereof, with enzyme actives being particularly preferred for enhancing cleaning performance. in cold water. In this regard, enzymatic detergent actives are highly preferred, and in particular enzymes and enzyme mixtures containing one or more enzymes with enhanced or optimal activity in the temperature range from 25 ° C to 55 ° C and at a pH value in the range from 8 to 10 (e.g. Natalase).

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

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

The tablets of the invention may also contain one or more additional phases made of one or more compositions which contain one or more detergent ingredients, as described below. At least one phase (herein referred to as "second phase") preferably takes the form of a particulate solid (which includes powders, granules, agglomerates, and other particulate solids, including mixtures thereof with liquid binders, solids, spray mixtures etc.), pressed into one or more cavities in the first phase of the detergent tablet, or compressed in these cavities so that the second phase itself takes the form of a shaped body. The optional additional phases include one or more compositions in the form of separate layer or layers.

The preferred detergent ingredients include builders, colorants, binders, surfactants, disintegrants and enzymes, especially amylase and proteinase enzymes.

The second phase and any optional subsequent phases may additionally contain a disintegrant which may be selected from a disintegrant and an effervescent agent. Suitable disintegrants include those which swell on contact with water or facilitate the flow in and / or outflow of water by creating channels in the detergent tablet. Any known disintegrants or effervescent agents suitable for use in dishwashing are suitable. Suitable disintegrating agents include starches (such as natural modified or pregelatinized starches, e.g. corn, rice and potato), starch derivatives such as U-Sperse (tradename), Primojel (tradename) and Explotab. (trade name), celluloses, microcrystalline celluloses and cellulose derivatives such as Arbocel (trade name) and Vivapur (trade name) available from Rettenmaier, Nymcel (trade name) available from Mctsa-serla, Avicel (trade name), Lattice NT (trade name) and Hanfloc (trade name), alginates, acetate trihydrate, burkeite, carbonate monohydrate formula Na2CO3-12O, hydrated sodium tripolyphosphate (STPP) with a ί phase content of at least about 40%, carboxymethiocelliosis (CMC), polymers based on CMC, Sodium Acetate, Alumina. Suitable effervescent agents include those which generate a gas on contact with water. A suitable effervescent agent can be oxygen, nitrogen dioxide or carbon dioxide evolving agent. Exemplary effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with carboxylic acids or other acids such as citric, sulfamic, malic or maleic.

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

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

As mentioned above, the first, second and optional additional phases may include a binder. When present, the binder is selected from the group consisting of organic polymers, e.g. polyethylene and / or polypropylene glycols, especially molecular weight 4,000, 6,000 and 9,000, paraffins, polyvinylpyrrolidone (PVP), especially PVP with a molecular weight of 90,000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, e.g. hydroxypropylmethyl cellulose (HPMC) and carboxymethyl cellulose (CMC); and inorganic polymers such as hexametaphosphate. The role of the binder is to ensure tablet integrity and achieve differential dissolution of the first and second phases as described below.

In a preferred embodiment of the invention, the weight of the first phase is greater than about 3 g, preferably greater than about 4 g, more preferably greater than about 5 g. More preferably, the weight of the first phase is from about 10 g to about 30 g, more preferably from about 15 g to about 25 g, and most preferably from about 18 g to about 24 g. The second phase and any subsequent phases weigh less than 4 g. More preferably the second and / or optional further phases weigh from about 0.1 g to about 0.1 g.

3.5 g, preferably from about 1 g to about 3.5 g, most preferably from about 1.3 g to about 2.5 g.

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

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

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

Yet another advantage of the invention is the possibility of producing a multiphase detergent tablet in which one phase can be designed to dissolve, preferably

189,559 significantly ahead of the second phase. According to the invention, it is preferred that the second phase and any further phases dissolve before the first phase. Within the preferred weight ranges given above, the first phase preferably dissolves within 5 to 20 minutes, more preferably 10 to 15 minutes, and the second phase and / or any subsequent phases dissolve in less than 5 minutes, more preferably less than 4.5 minutes. and most preferably less than 4 minutes. Alternatively, the second phase may dissolve after the first phase or other phases, e.g. in case it is desired to provide a beneficial cleaning or rinsing effect at the end of washing. The times at which the first, second and / or any subsequent phases dissolve are independent of each other. Accordingly, in a particularly preferred embodiment according to the invention, a differential phase dissolution is achieved. A particular advantage of being able to achieve differential dissolution of a multiphase detergent tablet is that a component that is chemically inactivated in the presence of another component may be introduced into a separate phase. In this case, the component that is deactivated is preferably in the second phase and in an optional next phase (s).

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

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

The first detergent composition is introduced into the die of the tablet press and the punch is lowered into contact with the detergent composition and compressed to form a foam phase. The first detergent composition is typically compressed under an applied pressure of at least about 24.5 MPa, preferably from about 34.3 to about 196.1 MPa, more preferably about 49 to about 147.1 MPa, and most preferably about 58.8 to about 117.7 MPa. The punch is then lifted so that the first phase containing the cavity is exposed. In turn, a second and possibly further detergent compositions are introduced into the seat. The specially designed tablet press punch is then lowered a second time to lightly compress the second and possibly subsequent detergent compositions to form the second phase and any subsequent phases. In another embodiment of the invention, when any optional further phases are present, such an optional next phase is formed in an optional subsequent pressing step substantially similar to the second pressing step described above. The second and optional subsequent detergent compositions are compressed at a pressure of preferably less than about 34.3 MPa, more preferably from about 3.9 to about 29.4 MPa, most preferably from about 6.9 to about 26.4 MPa. After the second detergent composition has been compressed, the punch is lifted a second time and the multi-phase tablet is pushed out of the tablet press.

Detergent ingredients

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

The very preferred detergent ingredients of the first phase are builder, surfactant, bleach and optionally an enzyme. To very much

Preferred second phase detergent ingredients in addition to the enzyme include builder, crystal growth inhibitors, and disintegrants and / or binders.

active

The tablets of the invention preferably contain a builder, typically present in an amount of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight. detergent compositions ^^ ibs ^ ta ^ <active ingredients.

Dissolve the a7 in water builder

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

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

Suitable carboxylates containing one carboxyl group include the water-soluble salts of lactic acid, glycolic acid, and their ether derivatives. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing 3 carboxyl groups include, in particular, water-soluble citrates, aconitates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in GB 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732, and the aminosuccinates described in GB patent No. 1,389,732. Dutch Patent Application No. 7205873, and oxypolycarboxylic materials. such as

The 2-oxa-1,1 J-propanetricarboxylates described in British Patent No. 1,387,447.

The polycarboxylates containing 4 carboxyl groups include the oxydisuccinates described in the block of patent no. 1261829, 1,1,2,2-eltmolthic lkkkboxide, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-) petroleum < anotetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in United Kingdom Patent No. 1,439,000.

The alicyclic and heterocyclic polycarboxylates include cyclopentanocis, cis, cis-telracarboxy] any, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuranocis, cis, cis-tetracarboxylates, 2.5-telrahydroftlrano-cis-cis-cis-carboxylates, 2,2,5-carboxylates, tetrahydrofuranetetracarboxylates, 1CJNJ6-hexanehexacarboxylates, and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. The aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in Patent No. 1,425,343.

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

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

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

Examples of carbonate builders include the alkaline earth metal and alkali metal carbonates, including carbonate and sesquicarbonate, and mixtures thereof with H1 189 559 traditional calcium carbonate, disclosed in German Patent Application No. 2321001 published November 15, 1973.

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

Partially soluble or insoluble active filler

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

NaMSi _x O2 + 1 yH2O where M is a: ohm sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. Crystalline sodium layered silicates of this type preferably have a two-dimensional "lamellar" structure · such as the so-called eight-layer structure disclosed in EP 0164514 and EP 0293640. Methods for producing crystalline layered silicates are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the invention, x in the above general formula is 2, 3 or 4, preferably 2.

The most preferred crystalline layered sodium silicate has the formula 6-INa2Si2O5, known as NaSKS-6 (tradename), available from Hoechst AG.

The crystalline layered sodium silicate material is preferably present in granular detergent compositions as particles in intimate admixture with a solid water-soluble ionizable material as described in PCT Patent Application No. WO92 / 18594. The solid water-soluble ionizable material is selected from organic acids, salts of organic and inorganic acids, and mixtures thereof, with citric acid being preferred.

Examples of significantly water-insoluble builders include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having the unit cell formula Na _z [(AlO2) _z (SiO2) y] · ΧΗ2Ο, wherein z and y are at least 6; the molar ratio z to y is from 10 to 0.5, with x being at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is hydrated and is preferably crystalline, containing from 10% to 28 %, more preferably from 18% to 22% of bound water.

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

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

VII ζ_ιννιιΐ o k vruvoivuj ..........

Nai2 [[(AlO2) i2 ((3iO2) i2] * ΧΗ2Ο where x is from 20 to 30, especially 27. Zeolite X is defined by the formula Na _S 6 [(AlO2) s6 (SiO2) i06] '276 H ^ O Zeolite MAP, disclosed in EP-B-384070, is a preferred zeolite builder.

Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. The use of colloidal aluminosilicate zeolites, especially colloidal zeolite A as a component of the detergent composition, provides increased effectiveness of

189 559 filler active in ensuring effective soil removal. The increased efficiency of the builder can also be seen as reduced soil clogging and increased whiteness maintenance; these problems are believed to be related to detergent compositions with inadequate builder content.

It has been surprisingly found that mixed zeolite aluminosilicate detergent compositions containing colloidal zeolite A and colloidal zeolite Y provide the same calcium ion complexing efficiency as an equal weight amount of commercially available zeolite A. Furthermore, it has surprisingly been found that the mixed zeolite aluminosilicate detergent compositions described hereinbefore above, will provide enhanced efficiency in complexing magnesium ions as an equal weight amount of commercially available zeolite A.

Surfactant

Surfactants are the preferred detergent actives of the compositions of the invention. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants, and mixtures thereof. The dishwasher products should be low-foaming and therefore the foaming of the surfactant system to be used in dishwashing needs to be suppressed or, more preferably, they should be low-foaming systems, usually non-ionic in nature. The surfactant is typically present in an amount of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight. detergent active ingredient compositions.

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

Non-ionic surfactant

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

Non-ionic surfactant of the ethoxylated alcohol type

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

A surfactant of the terminally capped alkyl alkoxide

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

R, O [CH 2 CH (CH 3) O] _x [CH ₂ CH 2 O] _y [CH 2 CH (OH) R2] (I) wherein R1 is a linear or branched aliphatic hydrocarbon radical containing from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon group containing from 2 to 26 carbon atoms; χ is an integer with an average value from 0.5 to 1.5, more preferably 1; and y is an integer with an average value of at least 15, more preferably at least 20.

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

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Poly (oxyalkylated) alcohols terminated with ether groups

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

R ¹ O [2 H 2 CH (R ³ ) O] _x [(2 H 2] kCH (OH) [CH 2] _J OR 2 wherein R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups containing from 1 up to 30 carbon atoms; R is H or a linear aliphatic hydrocarbon group containing 1 to 4 carbon atoms; x is an integer with an average value from 1 to 30, whereby when x is 2 or more, R ³ may be the same or different, ak and j are ^^ and a ^ integers with a mean value from 1 to 12, more preferably from 1 to 5.

R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups containing from 6 to 22 carbon atoms, most preferably from 8 to 18 carbon atoms. R3 is most preferably H or a linear aliphatic hydrocarbon group having from 1 to 2 carbon atoms. Preferably, x is an integer with an average value of from 1 to 20, more preferably from 6 to 15.

As noted above, when, in preferred embodiments, x is greater than 2, R ³ may be the same or different. Thus, r3 may be any of the alkyleneoxy groups described above. For example, when x is 3, R3 may be selected as to form an ethyleneoxy (EO) or propyleneoxy (PO) moiety, and may vary in the order of (EO) (PO) (EO), (EO) (EO) ( AFTER); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the number 3 is chosen by way of example only, so that the fluctuation can be much greater at higher values of x and include e.g. a number of (EO) units and a much smaller number of (PO) units. Particularly preferred surfactants described above include those that exhibit low cloud point, below 20 ° C. These low cloud point surfactants can then be used in conjunction with a high cloud point surfactant as detailed below to provide more favorable cleaning of greasy soil.

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

R ¹ O [CH 2 CH (R 3) O] _x CH ₂ CH (OH) CH ₂ OR 2 12 3 where R, R and R are as defined above, and x is an integer with an average value from 1 to 30, preferably from 1 to 20, more preferably from 6 to 18. The most preferred surfactants are surfactants wherein R1 and R2 are in the range of 9 to 14, R3 is H such that an ethyleneoxy moiety is formed, and x is from 6 to 15.

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

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

In general, the poly (oxyalkylene) type alcohol ether terminated alcohol surfactants of the present invention can be prepared by reacting an aliphatic alcohol having ~ "r ---— -----> ---- ---- C? J ------------------ J - with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with the alkoxylated alcohol to provide the novel compound of the invention. Exemplary methods for the preparation of ether terminated poly (oxyalkoxylated) alcohol surfactants are described below:

Preparation of C1 2/14 alkyl glycidyl ether

189 559

Fatty alcohol _Ci2 / i4 (100.00 g, 0.515 mol) and tin chloride (IV) (0.58 g, 2.23 mmol, available from Aldrich) are combined in a 500 ml three-necked round bottom flask equipped with a condenser, argon inlet, , dropping funnel, magnetic stirrer and internal temperature probe. The mixture was heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) was added dropwise at such a rate as to maintain the temperature at 60-65 ° C. After being stirred for an additional hour at 60 ° C, the mixture was cooled to room temperature. A 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) was added to the mixture with mechanical stirring. After the addition was complete, the mixture was heated to 90 ° C for

1.5 hours, cooled and filtered using ethanol as an aid. The filtrate was separated and the organic phase was washed with water (100 mL), dried over MgSO 4, filtered and concentrated. The oil was distilled at 100-120 ° C (0.1 mm of Hg) to obtain glycidyl ether as an oil.

Preparation of an alcohol type surfactant terminated with C12 / 14 alkyl 10 -C9 / 11 ether

Neodol® 91-8 (20.60 g, 0.0393 mol, ethoxylated alcohol available from Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) were combined in a 250 mL three-necked round bottom flask, equipped with a cooler, argon inlet, dropping funnel, magnetic stirrer and a probe for measuring internal temperature. The mixture was heated to 60 ° C and a C 12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) was added dropwise over 15 minutes. After stirring for 18 hours at 60 ° C, the mixture was cooled to room temperature and dissolved in an equal amount of dichloromethane. The solution was passed through a silica gel cartridge (2.5 cm) eluting with dichloromethane. The filtrate was concentrated on a rotary evaporator and chased on a kugelrohr (100 ° C, 0.5 mm Hg) to afford the surfactant as an oil.

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

C6-C8 ethoxylated fatty alcohols and mixed ethoxylated / propoxylated C6-C8 fatty alcohols are suitable surfactants for use in the present invention, particularly when water-soluble. Preferably the ethoxylated fatty alcohols are C10-C8 fatty alcohol ethoxylates with a degree of ethoxylation of 3 to 50, most preferably C12-C18 ethoxylated fatty alcohols with a degree of ethoxylation of 3 to 40. Preferably the mixed ethoxylated / propoxylated fatty alcohols contain an alkyl chain of 10 to 18 atoms. carbon, with a degree of ethoxylation from 3 to 30 and with a degree of propoxylation from 1 to 10.

Non-ionic EO / PO condensates with propylene glycol

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

Nonionic EO condensation products with propylene oxide / ethylene diamine adducts

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

System in the form of a mixture of surfactants

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

Cloud point, as used herein, means the well-known property of nonionic surfactants that the surfactant

189 559 active becomes less soluble with increasing temperature, the temperature at which the appearance of the second phase is observed is referred to as the "cloud point" (see Kirk Othmer's Encyclopedia of Chemical Technology, 3rd edition, vol. 22, p. 360). -379).

As used herein, a "low cloud point" nonionic surfactant is defined as a component of a nonionic 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 alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) inverse block polymers. In addition, such low cloud point nonionic surfactants include e.g. ethoxylated propoxylate alcohol (e.g. Poli-Tergent® SLF18 from Olin Corporation), poly (alkoxylated) epoxy terminated alcohols (e.g. Poli-Tergent® SLF18B series of nonionic surfactants actives from Olin Corporation, described e.g. in WO 94/22800, published October 13, 1994, Olin Corporation) and poly (alkoxylated) alcohol surfactants terminated with ether groups.

The nonionic surfactants may optionally contain propylene oxide in an amount up to 15 wt.%. Other preferred nonionic surfactants can also be prepared by the methods described in U.S. Patent No. 4,223,163, September 16, 1980, Buillots, which is hereby incorporated by reference.

Low cloud point nonionic surfactants further include polyoxyethylene-polyoxypropylene polymer blocking agents. Polyoxyethylene-polyoxypropylene block polymers include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylene diamine as an initiator of a compound with active hydrogen atoms. Certain surface-active block polymers, designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC®, from BASF-Wyandotte Corp., Wyandotte, Michigan, are useful in automatic dishwasher detergent compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactants are typically useful in compositions as low cloud point nonionic surfactants.

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

Furthermore, it is preferred in the present invention that the high cloud point non-ionic surfactant further exhibits a hydrophilic lipophilic balance ("HLB"; see Kirk Othmer, supra) value in the range from 9 to 15, preferably from 11 to 15. Such rhaterials include e.g. Tergitol 15S9 (available from Union Carbide), Rhodasurf TMD 8.5 (available from Rhone Poulenc) and Neodol 91-8 (available from Shell).

Other preferred high cloud point surfactants are derived from a straight or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon atoms (C6-C20 alcohol), including secondary alcohols and branched-chain primary alcohols. Preferably the high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9 / 11 or C1 1/15 branched alcohol ethoxylates, condensed on average to 6-15 moles, preferably 6-12 moles, and most preferably 6-9 moles. moles of ethylene oxide per mole of alcohol. Favorable

The ethoxylated nonionic surfactant thus obtained has a narrow ethoxylation distribution with respect to the average.

Anionic surfactant

In principle, any anionic surfactants useful for detersive purposes are suitable. These include the salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts) of anionic sulfate, sulfonate, carboxylate, and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides derived from methyl tauride, alkylsuccinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-C18 monoesters), unsaturated C12-C18 unsaturated diesters (especially C6-unsaturated unsaturated sulfosuccinates) C _{] 4} diesters), N ^^ <^^^ ios ^ l ^ (^: zy ^ ians. Resin acids and hydrogenated resin acids are also useful, such as rosin, hydrogenated rosin, and the resin acids and hydrogenated resin acids present in tallow oil.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use in the invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycer sulfates, alkylphenol ether sulfates with ethylene oxide, C5-C17 acyl-N- (C1-C4) sulfates. and -N-C1-4 hydroxyalkyl) glucamines; and alkyl polysaccharide sulfates such as alkypolyglucoside sulfates (non-ionic unsulfated compounds mentioned herein).

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

Alk ^ ^ ^ ^ ^ and ^ [beta] sulfate surfactants are preferably selected from the group consisting of C1-10 alkyl sulfates ethoxylated with 0.5-20 moles of ethylene oxide per molecule. More preferably the alkyl ethoxy sulfate surfactant is a C 11 -C 18 alkyl sulphate ethoxylated with 0.5-7, preferably 1-5 moles of ethylene oxide per molecule.

In a particularly preferred embodiment of the invention, mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants are used. Such mixtures are disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sufonate Surfactant

Anionic sulfonate surfactants suitable for use in the present invention include C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic fatty acids, alkylglycerin sulfonates fatty acid glycerin sulfonates, and any mixtures thereof.

Anionic carboxy / anic surfactant

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

Suitable alkyl ethoxycarboxylates include compounds of the formula RO (CH2CH2O) xCH2COO'M ⁺ , where R is a C6-C18 alkyl group, x is from 0 to 10, the distribution of the ethoxylate is such that by weight, the strength of the x-ratio is equal to 0%. n will be less than 20% and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula RO - CHRrCHR2-O) -R3 where R is C6-C18 alkyl, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid, a succinic acid group, a hydroxysuccinic acid group, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon groups having 1 to 8 carbon atoms, and mixtures thereof.

189 559

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl group attached to a secondary carbon atom. Preferred secondary soap surfactants for use in the present invention include water-soluble ingredients selected from the group consisting of water-soluble acid salts

2-methyl-1-octanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as foam suppressants.

An alkali metal sarcosinate surfactant

Other suitable anionic surfactants include alkali metal sarcosinates of formula R-COlNfRjCHiCOOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Ri is a C1-C4 alkyl group, and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactant

Suitable amphoteric surfactants for use in the invention include. amine oxide surfactants and alkylamphocarboxylic acids. 4 0 5 Suitable amine oxides include compounds of formula R ³ (OR) _X N (R) 2, wherein R ³ is selected from the group consisting of alkyl, hydr <^^^ ss ^ and ^ H ^ ^ 1, acylamidopropoyl and alkylphenyl or mixtures thereof containing from 8 to 26 carbon atoms; R ⁴ is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁵ is an alkyl or hydroxyalkyl group containing 1 to 3, or a polyethylene oxide moiety containing 1 to 3 ethylene oxide groups. Preference is given to using a C 10 -C 8 alkyldimethylamine oxide and a C 10 -C 8 acyl] amidoalkyl oxide. Kimee ^ ^ 3amine oxide.

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

Bipolar surfactant. Active agent

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

Suitable betaines are compounds of the formula R (R ^r ) 2N ⁺ R ² COO ', wherein R is a C 6 -C 18 hydrocarbyl group, each Ri is usually C 1 -C 3 alkyl and R ² is a C ₁ -C ₅ hydrocarbyl group. Preferred betaines include C12-8 dimethyl camcic acid hexanoate and C10-18 acylkamidoplkpank (or ethane) dimethyl (or diethyl betaine) Complex betaine surfactants are also suitable for use in the invention.

Canonical surfactants

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

Suitable cationic surfactants include quaternary ammonium surfactants selected from mono-C6-C16, preferably C6-Ck, N-alkyl or alkenyl ammonium surfactants in which the remaining positions on the nitrogen atom are substituted with methyl, hydroxyl s ^^ t ^ dl ^ s or hydroxypropyl Io s.

189 559

Enzymes

The enzymes used in the present invention are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, ligninoxidases, ligninases, ligninases, ligninases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases and mixtures thereof.

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

Cellulases useful in the compositions of the invention include both bacterial and fungal cellulases. Preferably they will exhibit optimal performance at a pH of 5 to 12, and an activity greater than 50 CEVU (cellulose viscosity units). Suitable cellulases are disclosed in U.S. Patent No. 4,435,307 to Barbesgoard et al. In JP 61078384 and WO 96/02653, which disclose fungal cellulases produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275, DE-OS-2247832 and WO 95/26398.

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

Other suitable cellulases with cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

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

Peroxidases are useful with oxygen sources such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used to "bleach the solution", i.e. to prevent transfer of dyes or pigments removed from the substrates during washing to other substrates in the washing solution. Peroxidases are known and these include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Detergent compositions containing peroxidases are disclosed, for example, in PCT International Applications Nos. WO 89/099813, WO 89/099813 and in EP-A-540784, and in WO 97/30143. Laccase is also suitable.

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

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

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

Suitable lipases for use in detergents include enzymes produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, disclosed in British Patent No. 1,372,034. Suitable lipases include those which show a positive cross-reactivity with the lipase antibody produced

189 559 by the microorganism Pseudomonas f7uores'cen / LAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the tradename Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Amano-CES, lipases from Chromobacter viscosum, e.g., Chromobacter viscosum var. / ipo / yticum NRRLB 3673 ex Toyo Jozo Co., Tagata, Japan; Chromobacter ν / scosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases from Pseudomonas g / adio / i '. Particularly suitable lipases include lipases such as Ml Lipase® and Lipomax® (GistBrocades) as well as Lipolase® and Lipolase Ultra® (Novo) which have been found to be very effective when used in conjunction with the compositions of the invention. Also useful are the lipolytic enzymes described in EP 258068. WO 92/05249 and WO 95/22615 to Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 to Unilever.

Also useful are the cutinases [EC 3.1.1.50], which can be considered as a special type of lipase, namely as lipases that do not require activation at the interface. The addition of cutinases to detergent compositions is described e.g. in WO-A-88/09367 (Genencor), WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).

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

Suitable proteases are subtilisins, obtained from respective strains of B subtilis and B. / icAenlforwi's (BPN and BPN 'subtilisin). One suitable protease is an enzyme obtained from a Bacillus strain with a maximum activity in the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A / S, Denmark, hereinafter referred to as "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1243784 to Novo. Other suitable proteases include KANNASE®, ALCALASE®, DURAZYM® and SAVINASE® from Novo and MaXATASE®, MaXaCAL®, PROPERASE® and MAXAPEM® (Maxacal with protein modified by genetic engineering techniques) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in EP-A-251441 (especially on pages 17, 24 and 98), herein referred to as "Protease B", and European Patent Application No. 199404, Venegas, with October 29, 1986, concerning a modified bacterial proteolytic serine enzyme, referred to herein as "Protease A". Also useful is an enzyme, referred to herein as "Protease C," which is a variant of the BaciY / us alkaline serine protease in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, serine replaces asparagine at position '23, and alanine replaces threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants are also useful, especially Protease C.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant containing a non-naturally occurring amino acid sequence obtained from a precursor carbonyl hydrolase by substituting a series of amino acid residues at a position corresponding to position +76 of a carbonyl hydrolase, preferably in combination with one or more amino acid residues in positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156 , +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274, according to Bacillus awy subtilisin numbering ' / o / iqu &lt; faj7e &apos; s, described in WO 95/10591 and in US-A-6066611.

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

See also the high pH range protease from Bac / llus sp. NCIMB 40338, described in WO 93/18140 A to Novo.

Enzymatic detergents containing a protease, one or more other enzymes, and an inverse protease inhibitor are described in WO 92/03529 A to Novo. If desired, a protease with reduced adsorption capacity and increased hydrolysis capacity is available, as described in WO 95/07791, by Procter & Gamble. Recombinant trypsin-like

A detergent protease suitable for use in the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 to Unilever.

Other preferred protease enzymes include the carbonyl hydrolase variant protease enzymes containing an amino acid sequence not found in nature, derived from a carbonyl hydrolase precursor by substituting a series of amino acid residues at a position corresponding to position +210, in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, + 129, +130, +132, +135, +156, +158, +164 , +166, +167, +170, +209, +215, +217, +218 and +222, with the item numbering corresponding to the naturally occurring subtilisin from Bacz / lws amy ^ o / zą ^ efa ^ ciens, or the corresponding amino acid residues in other carbonyl hydrolases or subtilizines (such as BaciY / uslentus subtilisin). Preferred enzymes of this type include. enzymes containing changes in positions +210, + 76, + 103, + 104, + 156 and +166.

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

Amylases (α and / or β) may be included to remove carbohydrate type soils. WO 94/02597, Novo Nordisk A / S, published February 3, 1994, describes cleaning compositions which contain mutant amylases. See also WO 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include a- and β-amyazases. a-Amylazv are known and include the enzymes disclosed in US Patent No. 5,003,257; EP 252666; WO / 91/00353; FR 2676456; EP 285123; EP 525610; EP 368341; and in British Patent No. 1,296,839 (Novo). Other suitable amylases are. Stability-enhanced amylases described in WO 94/18314, published August 18, 1994 and WO 96/05295, Genencor, published February 22, 1996, and amylase variants containing an additional modification in the immediate parent enzyme, available from Novo Nordisk A / S, disclosed in WO 95/10603, published April 1995. Also useful are the amylases described in EP 277216, WO 95/26397 and WO 96/23873 (all by Novo Nordisk).

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

Preferred amylase enzymes include those described in WO 95/26397 and WO 96/23873.

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

In a particularly preferred embodiment, the detergent tablets according to the invention contain amylase enzymes, especially those described in WO 95/26397 and in co-pending Novo Nordisk PCT / DK96 / 00056, in combination with complementary amylases.

The term "complementary" refers to the addition of one or more amylases suitable for detergent purposes. Examples of complementary amylases (a and / or (!) Are described below. WO 94/02597 and WO 95/10603, Novo Nordisk A / S, describe cleaning compositions which contain the amylase mutant. Other amylases known for use in cleaning compositions, include both α- and (1-amylase. α-amylases are known and include the enzymes described in U.S. Patent No. 5003257; EP 252666; WO / 91/00353; FR 2676456; EP 285123; EP 525610 ; EP 368341; and in British Patent No. 1,296,839 (Novo). Other suitable amylases are

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

Such complementary amylase is typically included in the detergent compositions of the invention in an amount from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% by weight. pure enzyme in relation to the composition. Preferably, the weight ratio of pure specific amylase enzyme to complementary amylase is from 9: 1 to T9, more preferably from 4: 1 to 1: 4, and most preferably from 2: 1 to 1: 2.

The aforementioned enzymes may be of any suitable origin, e.g. vegetable, animal, bacterial, fungal and yeast origin. They can also be mesophilic or extremophilic (psychrophilic, psychrotrophilic, tenmophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes can be used. Also included are mutants of native enzymes. Mutants can be obtained e.g. by protein and / or genetic modification, chemical and / or physical modification of native enzymes. It is common practice to express the enzyme in the host organism whose genetic material responsible for producing the enzyme has been cloned.

Such enzymes are usually included in the detergent composition in an amount from 0.0001% to 2% by weight. active enzyme in relation to the detergent composition. The enzymes may be added as separate individual components (lumps, granules, stabilized liquids, etc., containing one enzyme) or as mixtures of two or more 'enzymes (e.g. co-granules).

Other suitable detergent ingredients that can be added include enzyme oxidation inhibitors which are described in EP-A-553607. Examples of enzyme oxidation inhibitors include ethoxylated tetraethylene polyamines.

A number of enzyme materials and methods for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A, to Genencor International, in WO 8908694 A to Novo, and in U.S. Patent No. 3,553,139, filed January 5, 1971, McCarty and others. Enzymes are further disclosed in U.S. Patent No. 4,101,457, Place et al., July 18, 1978, and U.S. Patent No. 4,507,219, Hughes, issued March 26, 1985. Enzymatic materials suitable for liquid detergent formulations, and methods for their incorporation into such formulations are disclosed in US Patent No. 4,261,868 to Hora et al., April 14, 1981. Enzymes for use in detergents are stabilized with a variety of different compounds. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent No. 3,600,319, issued on 17 si ^^^^^^ 1971, Gedge et al., EP 199405 and EP 200586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent No. 3,519,570. A suitable species Bac / l / s ·, sp. AC 13, producing proteases, xylanases and cellulases, is described in WO 9401532 A, to Novo.

189 559

Bleaching agent

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

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

Inorganic perhydral bleaching agents

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

The inorganic salt perhydrate is usually introduced as the sodium salt in an amount of from 1% to 40% by weight, more preferably from 2% to 30% by weight, and most preferably from 5% to 25% by weight. relative to the composition.

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

Sodium perborate may be in the monohydrate form with the nominal formula NaBCĘlbO? or NaBO2CP3 tetrahydrate < 3H2O2.

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

A suitable coating material ensuring stability in the product is a mixed salt of a water-soluble alkali metal sulphate and carbonate. Such coatings and coating methods are known and described in GB-1466799, issued to Interox on March 9, 1977. The weight ratio of mixed salt coating material to percarbonate is from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9. and most preferably from 1:49 to 1:

19. Preferably the mixed salt is sodium sulfate and sodium carbonate, having the general formula Na2SO4 · n Na2CO3, where n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 up to 0.5.

Another suitable coating material for product stability is sodium silicate with a SiO2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate. preferably applied in an amount of from 2% to 10% by weight. (typically from 3% to 5%) S1O2 based on the inorganic salt perhydrate. Magnesium silicate may also be included in the coating. Coatings with silicate and borate salts or boric acids or other inorganic acids are also suitable.

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

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

189 559

A precursor to a peroxyacid bleach

Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form a peracid. Typically, peroxyacid bleach precursors can be represented as

ABOUT

II

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

II

X-C-OOH

The pre-emir compounds of the peroxy acid bleach are preferably incorporated in an amount of from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight, based on the composition. .

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

Cleavage groups

The cleavage group, below group L, must be sufficiently reactive in re-perhydrolysis for this reaction to occur within an optimal time interval. However, if L is too reactive, the activator will be too difficult to stabilize to be used in a bleach composition.

Preferred L groups are selected from the group consisting of:

189 559

Υ

R

-Ο

Λ —Ν Ν and

-Ο

R ⁵ Y

Ο ¹¹ 4 —NC-CH-R

U ¹ R Υ

R —O-CH = C — CH = CH,

-O-CH = C — CH = CH,

Ο ¹¹ ι — OCR

CH, —C -Ν _χ ^? NO. ⁴

II

O 'N .NR

C.

II o

R —OC = CHR ⁴

About Y

II and and

-N — S — CH — R> 3 ¹¹

RO, and mixtures thereof, wherein R1 is alkyl, aryl, or alkaryl containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, ^R4 is H or R3, R5 is an alkenyl chain containing from 1 is 8 carbon atoms and Y is H or a solubilizing group. Any of R 1 R ³ and R ⁴ may be substituted by essentially any functional group, e.g.,. Alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl, amide and ammonium or alkylammonium group.

Preferred solubilizing groups include -SO3M ⁺ , -CO2M ⁺ , -SO4-M + -N + (R ³ ) 4X 'and ON (R ³ ) 3, and most preferably -SO3'M ⁺ and -CO2'M ⁺ , where R ³ represents an alkyl chain of 1 to 4 carbon atoms, M is a cation which provides solubility of the bleach activator and X is an anion which provides solubility of the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds form perbenzoic acid by perhydrolysis.

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

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

189 559

ΟΒζ

OAc where Ac = COCH3; Bz = Benzoyl

The imide-type perbenzoic acid precursors include N- < 3 &gt; &lt; 3 &gt; Suitable imidazole-type perbenzoic acid precursors include N-benzoyimidazole and N-benzoylbenzimidazole, and other N-acyl-containing perbenzoic acid precursors such as N-been: oil pyrrolidone, dibenzoylthaurine and benzodopyroglutamic acid.

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

COOH

Phthalic anhydride is another suitable perbenzoic acid precursor:

ABOUT

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

O C-CH -— CH, _s II I ^{2 2}

R-C-N

Γζ — 1T T d

vn ₂ - j ₁ ou _{2 n} wherein n is a number from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.

Precursors of perbenzoic acid derivatives

Perhydrolysis precursors to perbenzoic acid derivatives form substituted perbenzoic acids.

189 559

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

A preferred class of substituted perbenzoic acid precursor compounds are. compounds in the form of substituted amides with general formulas:

R ¹ - C — N — R — C — L

R — N — C — R — C — L

ORO l _u b

II o

wi in which R 1 is an aryl or alkaryl group containing 1 to 14 carbon atoms, R ² is an aryl or alkarylene group containing 1 to 14 carbon atoms, R ² is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms, and L can be essentially any cleavable group. Ri preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R? it may be aryl, substituted aryl, or alkylaryl, containing branching and / or substitution, and may be derived from synthetic or natural sources such as tallow. Similar structural variants are also possible in the case of R2. The substituents may include alkyl, aryl, halogen, nitrogen, sulfur, and other conventional substituents or organic compounds. R3 is preferably H or methyl. Ri and R5 should contain no more than 18 carbon atoms in total. Substituted amide bleach activators of this type are described in EP-A-01703 86.

Precursors of cationic peroxy acids

Cationic peroxyacid precursor compounds form cationic peroxyacids by perhydrolysis.

Typically, cationic peracid precursors are formed by substituting the peroxyacid portion of the corresponding peroxyacid precursor with a positively charged group with a functional group such as an ammonium or alkylammonium group, preferably an ethyl or methyl ammonium group. The cationic peroxy acid precursors are typically present in the compositions in the form of a salt with a suitable anion, such as, for example, a halide ion or a methyl sulfate ion.

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

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

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

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

189 559

S0 ₃

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

SO,

Preferred cationic peroxyacids precursors of the N-acylated caprole class include triclkylmethyltobeτzoylkprolactams, especially trimethylammoniummethylenebenzoylkprolactam:

Other preferred cationic peroxyacids precursors from the class of N-acylated caprolactam include triclklloammoniometγlenoklkllotapr () lkktanly:

where n is a number from 0 to 12, especially from 1 to 5.

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

Alkylpercarboxylic acid type bleaching agent precursors

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

Preferred imide-type talkyboxylic acid precursors include N, N, N · N ¹ -telracetyl alkylene dicmines. in which the alkylene group contains from 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 atoms

Γο Qc ^ / e <-7ογτΑ1 6iio * elno etcf ^ · ί: lt * ^, jlaea ^ fxt1l ^ o + l71 ^ o ^ i-ammm- (t * a Ε'Τ 'Λ ΙΡΤΛλ lVl. LJUłU J ivu UUVVlj lVllV / tXXUXlXXlltX X

Other preferred alkyl percarboxylic acid precursors include 3,5,5-trimethylhexaτoyloxybeIT'enesulfonikτ sodium (iso-NOBS), sodium τonanoyloxybeIτzenosulfoτikτ (NOBS), sodium acetoxybermrnosulfoTate (ABS) and pentaacetyl glucose.

Precursors of amide-substituted clycloperoxycxides

Also useful are compounds that are precursors to amide-substituted clavyl-peroxide oxyxes, including compounds having the following general formulas

189 559

R — C — Ν — R — C — L

II l ₅ II

O R O or

R — N — C — R — C — L ₁₅ II II Roo / 2 in which R 1 is an alkyl group containing 1 to 14 carbon atoms, R is an alkylene group containing 1 to 14 carbon atoms, R ⁵ is H or alkyl having from 1 to 10 carbon atoms and L can be essentially any cleavable group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, containing branching and / or substitution, and may be derived from synthetic or natural sources such as tallow. Structural variants of s1, analogous and also permitted for R2 ^. The substituents may include alkyl, halogen, nitrogen, sulfur, and other conventional substituents or organic compounds. R ⁵ is preferably H or methyl. R1 and ^R5 should not contain more than 18 carbon atoms. Substituted amide bleach activators of this type are described in EP-A-0170386.

Benzoxazine precursors of an organic peroxyacid

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

n ^c_r , including substituted benzoxazines of the type

ABOUT

C4

R, where R1 is H, alkyl, alkaryl, aryl, arylalkyl, and R2, R3, R4 and R5 may be the same or different, selected from the group consisting of H, halogen, alkyl, alkenyl, aryl, hydroxy, alkoxy, amino group, alkylamino group, COOR5 (where R6 is H or alkyl) and carbonyl group. A particularly preferred precursor of the benzoxazine type is the compound:

189 559

Pre-formed organic peroxy acid

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

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

R — C — N — R — C—

II

ABOUT

II o

OOH or

R — N — C — R — C — OOH I ₃ II II where R? is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, aryerKową or alkarylene containing from 1 to 14 carbon atoms, and R ⁵ is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms . R1 preferably contains from 6 to 12 carbon atoms. r2 preferably has from 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl, containing branching and / or substitution, and may be derived from synthetic or natural sources such as tallow. Similar structural variants are also possible in the case of R2. The substituents may include alkyl, aryl, halogen, nitrogen, sulfur, and other conventional substituents or organic compounds. R5 is preferably H or methyl. R1 and r5 should not contain more than 18 carbon atoms in total. Compounds of this type in the form of amide-substituted organic peroxyacids are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacytoperoxides, especially diperoxydodecanedioic acid, diperoxyhexadecanedioic acid, and d-peroxyhexadecanedioic acid. Dibenzoyl peroxide is the preferred organic peroxyacid for use in the invention. Mono- and dinadazelaic acid, mono- and dinadabrasylic acid, and N ^^^^ t ^^loaminc ^ p ^^ r ^ ok ^ sycaproic acid are also useful.

Adjustable release rate - measures

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

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

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

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

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

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

A preferred coating material, especially in the case of an inorganic salt perhydrate as bleach source, is sodium silicate with a S1O2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied in an amount

From 2% to 10% by weight (typically from 3% to 5%) of S1O2 based on the inorganic salt perhydrate. Magnesium silicate may also be included in the coating.

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

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight from 600 to 5 x 10 ⁶ , preferably from 1,000 to 400,000, most preferably from 1,000 to 10,000, are examples of such polymeric mats. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid in which maleic anhydride is at least 20 mole% of the polymer are further examples of polymeric materials useful as binders. Such polymeric materials can be used alone or in combination with solvents such as water, propylene glycol, and the above-mentioned C10-C20 ethoxylated alcohols containing 5-100 moles of ethylene oxide per mole of alcohol. Additional exemplary binders include C1O-C20 mono- and diether glycerol and C10-C20 fatty acids.

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

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

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

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

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

Catalysts containing me / ia /

The compositions according to the invention which will contain a bleach as a detergent component may additionally contain, as a preferred component, a metal-containing bleach catalyst. Preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt containing bleach catalyst.

A suitable type of bleach catalyst is a heavy metal cation with a defined bleach catalytic activity, such as a copper or iron cation, an auxiliary metal cation with no or invisible bleach catalytic activity, such as a zinc or aluminum cation, and a complexing agent with defined constants. stability against cations of catalytic and auxiliary metals, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic) acid and their water-soluble salts. Such catalysts are disclosed in U.S. Patent No. 4,430,243.

189 559

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Patent Nos. 5,246,621 and 5,244,594. Preferred examples of such catalysts include Mn ^ Cu-Oj] 1,4,7-trirpetyl-1,4,7-triazacyclononants. -CPFńty, Mn ^nl 2 (uO) and (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononan) 2- (C1O4) 2, Mn ^ u-Ojó (1,4, 7-triazacyclononan) 4- (ClO4) 2, Mn ' ⁿ Mn' ^v (uO) and (u-OAc) ₂ - (1,4,7-trimethyl-1,4,7-triazacyclononan) ₂ - (004) 3 and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1 , 4,7-triazacyclononan, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

Bleach catalysts useful in compositions of this type are also suitable according to the invention. Examples of suitable bleach catalysts are given in U.S. Patent Nos. 4,246,612 and 5,227,084. See also U.S. Patent No. 5,194,416, which discloses single-ring manganese (IV) complexes such as Mn (1,4,7-trimethyl-1, 4,7-triazacyclononane) (OCH3) 3- (PF6).

Yet another type of bleach catalyst disclosed in U.S. Patent No. 5,114,606 is a water-soluble manganese (III) and / or (IV) complex with a ligand that is a non-carboxylate polyhydroxy compound containing at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulzyitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose, and mixtures thereof.

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

R ² R ³ r'-n = cb-æ = No. ⁴ wherein each of R ¹ , R ² , R ³ and R ⁴ may be selected from the group consisting of hydrogen and substituted alkyl and aryl, such that R'-N = CR ² and R ³ -C = NR ⁴ form a five or six membered ring. Moreover, such a ring may be substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C = O, wherein each of R ⁵ , R ⁶ and R ⁷ may be hydrogen, alkyl or aryl, including substituted or unsubstituted groups. Preferred ligands include the pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. The rings may be optionally substituted with substituents such as alkyl, aryl, alkoxy, halogen, and nitro. A particularly preferred ligand is 2,2'-bispyridyl amma. Preferred bleach catalysts include complexes of bispyridimethane and bispyridylamine with Co, Cu, Mn or Fe. Highly preferred catalysts include Co (2,2'-bispyridylamine) C12, di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ O ₂ ClO4, bis perchlorate - Copper (II) - (2,2'bispyridylamine), tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

Preferred examples include bicyclic Mn complexes with tetra-N-tick and bi-N-tick ligands such as N ₄ Mn ⁱⁿ (uO) 2Mn ^rV N ₄ ) + and [Bipy ₂ Mn ^m (u-O) 2Mn ^lv N4bips ₂ ] - (C10 ₄ ) 3.

Although the structure of the manganese bleach catalysing complexes of the present invention has not been established, it can be assumed that they are chelates or other hydrated coordination complexes resulting from the interaction of carboxyl groups and nitrogen atoms of the ligand with the manganese cation. Likewise, the degree of oxidation of the manganese cation during the catalytic process is not known with certainty, so that it may be the degree of valence (+11), (+ III), (+ IV) or (+ V). Due to the 6 possible points of attachment of the ligands to manganese katicrtiu, it can be assumed with a high degree of probability that multi-ring and / or "cage" structures may exist in aqueous bleaching media. Regardless of the form of the Mn-ligand structures that are actually present, they do function in a catalysed manner30

189 559 tic and provide enhanced bleaching performance against stubborn soiling e.g. tea, ketchup, coffee, wine, juice etc.

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

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

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

Preferably, cobalt catalysts of this type have the formula:

Co [(NH3) n (M ') _m ] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M 'is a labile coordination group, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6; and Y is a suitably selected counter-anion of y which is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is an anion with a charge of -1) such that a charge balanced salt is formed.

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

More preferred are compositions according to the invention in which they are used as katahzatoij υινινιιια z> vvic | Zivi auDatiu V ^11JL 7 ^v ννζ, ϋιζΛ ,.

[6o (NH 3) n (M) _m (B) _b ] Ty in which the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more cobalt-coordinated ligands at one site; m is 0, 1 or 2 (preferably 1); B is a cobalt-coordinated ligand at two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more appropriately selected quadrates in the number of y, where y is an integer such as to result in a balanced charge salt (preferably y is 1-3; most preferably 2 when T is an anion with a charge -1); in addition, such a catalyst has an alkaline hydrolysis rate constant of 0.23 M "s" (25 ° C).

Preferably, T is selected from the group consisting of chloride, iodide, I3, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6 ', BF4-B (Ph) 4, phosphate, phosphite, silicate, tosylate, methanesulfonate. and their combinations. T may be optionally protonated when more than one anionic group is present in T, e.g. HPO4 ', HCO3, H2PO4' etc. Furthermore, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g. linear alkyl benzene sulfonates) (LAS), alkyl sulfates (AS), alkyl ethoxysulfonates (AES) etc.) and / or anionic polymers (e.g. polyacrylates, polymethacrylates etc.).

The M groups include, but are not limited to, e.g., F ', SO4' ² , NCS-SCN-S2O3 ', NH3, PO4 and carboxylates (which are preferably monocarboxylates, but more than one carboxylate may be present in group where the linkage to the cobalt may be through one carboxylate in the group, then the other carboxylate in the M group may be protonated or in the form of a salt). M may be optionally protonated, when M is more than one anionic group (eg. HPO4- ² - HCO3 ', H2PO4- HOC (O) CH 2 C (O) O, etc.) Preferred M groups are substituted and unsubstituted C1-C30 acids carboxylic compounds of the formula:

RC (0) 0 wherein R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C1-C18) unsubstituted and substituted alkyl, C6-C30 (preferably C6-Cis) unsubstituted and substituted aryl and C3-C30 (preferably C5 -C18) unsubstituted and substituted heteroary, wherein the substituents are selected from the group consisting of -NR-, -NR-4- -C (O) OR-OR ', -C (O) NR-, wherein R' is selected from the group consisting of hydrogen and C1-C- groups. Such substituted R therefore include the group - (CH2) n OH and - (CH ₂₎ nNR- ⁺ wherein n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.

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

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

Cobalt bleach catalysts useful in the compositions of the invention are known, and are described, for example, with their base hydrolysis rates, in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg Bioinorg. Mech., (1983), 2, pp. 1-94. For example, Table 1 on page 17 shows the basic hydrolysis rates (denoted as kOH) for pentaaminocobalt catalysts complexed with oxalate (kOH = 2.5 x 10 ^ ''M''s'1 (25 ° C)), NCS '(kOH ⁼ 5.0 x 1 (P ⁴ M' * s '* (25 ° C)), formate (koO ⁼ 5.8 x 10- M' * s (25 ° C)), and with acetate (kOH = 9.6 x 10 ^{4 M-s-1} (25 ° C)). the most preferred cobalt catalysts for use in the invention are salts of acetate pentaaminokobaltu of the formula [Ca-NIkNOAejT.y wherein OAc represents an acetate moiety, and especially chloride, acetate pentfflrninokobfltn , [Co (NH 3) 5OAc] Cl ₂ and also [Co (NH ₃ ) ₅ OAc] (OAc) ₂ ;

[Co (NH ₃ ) ₅ OAc] (PF ₆ ) 2 [Co (NH ₃ ) 5OAc] (SO4);

iCofNikkOdAcjCBF.jk; and [Co (NH ₃ ) 5OAc] (nO3) 2 (in the "PAC" description). Such cobalt catalysts are readily prepared by known methods, such as those set forth in the aforementioned Tobe article and the references cited therein, US Patent No. 4,810,410, Diakun et al., March 7, 1989, J Chem. Ed. (1989), 66 (12), 1043-45; TAe Synthesis and Charactcrzzahon of / norganic Compounds, WL Jolly

189 559 (Prentice-Hall; 1970) pp 461-3; Inorg Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and. Journa / of Chemistry, 56, 22-25 (1952); and also in the synthesis examples provided below.

Cobalt catalysts suitable for inclusion in detergent tablets of the invention can be prepared by the synthetic methods disclosed in US Patent Nos. 5,559,261, 5,581,005 and 5,597,936, the disclosure of which is hereby incorporated by reference.

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

Organic polymeric compound

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

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

Examples of the organic polymeric compounds include water-soluble organic homo- or copolymeric polycarboxylic acids, modified polycarboxylates or their salts, wherein the polycarboxylic acid contains at least two carboxylic acid groups separated by no more than two carbon atoms. The latter type of polymers are disclosed in GB-A-1596756. Examples of such salts include the polyacrylates with a molecular weight of 2,000-10,000 and their copolymers with any suitable other monomers, including polymers modified with acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic, and methyliomalonic acid or their salts, maleic acrylamide anhydride, , alkylene, vinyl methyl ether, styrene, and any mixtures thereof. Copolymers of acrylic acid and maleic anhydride with a molecular weight of 20,000 to 100,000 are preferred.

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

The preferred acrylic acid-containing copolymers are those having as units: a) from 90% to 10%, preferably from 80% to 20% by weight. of acrylic acid or a salt thereof, and b) from 10% to 90%, preferably from 20% to 80% by weight. a substituted acrylic monomer or a salt thereof, of the general formula - (R 2 - 2 R 1 (CO-O-R 3)] - wherein at least one of R 1, R 2 and R 3, preferably R 1 or R 2 is alkyl or hydroxyalkyl of 1 - 4 carbon atoms, R1 or R2 may be hydrogen and R3 may be hydrogen or an alkali metal salt Most preferably a substituted acrylic monomer where R1 is methyl, R2 is hydrogen (i.e. methacrylic acid monomer). Most preferred copolymer. of this type has a molecular weight of 3500 and comprises 60% -80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.

Polyamine compounds and modified polyamine compounds, including those derived from aspartic acid, such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-3 51629 are also useful.

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

189 559

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

Means uók'τ / k / ą ^ cc dirt

Suitable soil release agents include those soil release agents which comprise: (a) one or more nonionic hydrophytic 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 from 2 to 10, wherein this hydrophyte segment does not include oxypropylene units, unless they are linked to adjacent groups at each end by ether bonds, or (iii) a mixture of oxya] kileT units containing an oxyethylene mer and from 1 to 30 oxypropylene units, wherein these hydrophilic segments preferably contain at least 25% oxyethylene units, more preferably, especially for components having from 20 to 30 oxypropylene units, at least 50% oxyethylene units;

or (b) one or more of the hydrophobic components of obelmJąeyeh (i) segments of C3 oxyalkylene terephthalate, in which, when such hydrophobic components also include oxyethylTu terephthalate, the ratio of oxyethyl terephthalate: C3 oxyalkyl terephthalate units is 2: 1 or below, (ii) C4-C6 alkylene or C4-C6 alkylene oxy, or mixtures thereof, (iii) a poly (vinyl ester) segment, preferably polyvinyl acetate, with a degree of polymerization of at least 2, or (iv) C1-C4 cycloether or C4 hydroxyckylether substituents, or mixtures thereof, wherein said substituents are present in the form of C1-C4 γ1Μο616 or C4 hydroxy cycloclioether cellulose derivatives, or mixtures thereof, or a mixture of (a) and (b).

Typically, the polyoxyethylene segments in (a) (i) will have a polymerization degree of up to 200, although the levels may be higher, preferably from 3 to 150, more preferably from 6 to 100. Suitable hydrophobic C4-C6 alkyl segments include but not limited to, end-capped polymeric soil release agents such as MO3S (CH2) nOCH2CH ₂ Or. where M is sodium and n is an integer 4-6, as disclosed in U.S. Patent 4,721,580, Jan.26, 1988, Gosselink.

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

Dirt release agents containing hydrophobic polyvinyl ester segments include graft copolymers of polyvinyl ester, e.g. Cr-C vinyl esters, preferably polyvinyl acetate, grafted onto a polycyclene polyethylene backbone such as a polyethylene oxide backbone. See European Patent Application No. 0219048, published April 22, 1987 by Kud et al.

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

Another suitable polymer is a polyester with ethylene terephthalate containing 10-15 wt. % of this ^^ 't: ^^ ^ ^ i in ethylene and 90-80 wt. polyoxyethylene tereHa / mu mers, derived from polyoxyethylene glycol with an average molecular weight of 300-5000.

Another suitable polymeric soil agent is the product of a sulfoτowkτik essentially linear ester oligomer with an oligomeric ester backbone with terephthaloyl and oxyalkyleneoxy units and end groups covalently attached to the backbone. Such soil release agents are further described in U.S. Patent No. 4,968,451,

189 559 of November 6, 1990, J. J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include polyesters of terephthalate as described in U.S. Patent No. 4,711,730, issued Dec. 8, 1987, Gosselink et al., Anionic terminated oligomeric esters of U.S. Patent No. 4,721,580, issued January 26, 1988. , Goss ^^ ink, and block polyester oligomeric compounds as described in US Patent No. 4,702,857, issued October 27, 1987, Gosselink. Other polymeric soil release agents also include the soil release agents of US Pat. No. 4,877,896, issued October 31, 1989 to Maldonado et al, which disclose anionic, especially sulfoaroyl terminated terephthalate esters.

Another soil release agent is an oligomer with terephthalate units, sult'oisotereitayoyl units, oxyethyleneoxy units and oxy-1,2-propy tones. The mers form the backbone of the oligomer, which is preferably terminated with modified isethionate end groups. A particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthalic meters, oxyethyleneoxy and oxy1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two end groups 2- (2-hydroxyethocta) et ^^^ n ^^ sodium ulphonate.

Mask / ions of heavy metal ions

The tablets of the invention preferably contain as an optional ingredient a heavy metal ion sequestrant.

The term heavy metal ion sequestrant refers to ingredients which act as heavy metal ion sequestering (chelating) agents. These components may also exhibit calcium and magnesium chelating ability, but will selectively show se ^^^ binding to heavy metal ions such as iron, manganese and copper.

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

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

Suitable heavy metal ion masking agents for use in the present invention include organic phosphonates such as aminoalkylene polypol ((alkytophosphonates), ethno-1-hydroxydisphosphonates, and alkali metal nitrilotπmethytonephosphonates. ^^ mp ^^ tra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for use in the present invention include nitrilotriacetic acid and polyamino-carboxylic acids, such as ethylenediaminetetrocetic acid, ethylenediaminetaminopentacetic acid, ethylenediaminodisuccinic acid, ethylenediaminodiglutaric acid, 2-hydroxypropylenediamine or any diamino diamine salts. .

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

A component that is a crystal growth inhibitor

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

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

Acid, organo acid is preferably a C1-C4 diphosphonic acid, preferably C ₂ diphosphonic acid, such as etylenodifosfonowy, or most preferably ethane-1-hydroksy1,1-diphosphonic acid (HEDP) which may be present in partially or fully ionized, in particular as salt or complex.

Water-soluble sulfate salt

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

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

Alkali metal silicate

An alkali metal silicate is a preferred component of the tablet of the invention. The preferred alkali metal silicate is sodium silicate with a SiO ₂ : Na ₂ O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, most preferably 2.0. Sodium silicate is preferably present in an amount of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight. SiO ₂ . The alkali metal silicate can be in the form of the anhydrous salt or the hydrated salt.

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

Coloring agent

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

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

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

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

189 559

When a colorant is used as a component of the first phase, its amount is from 0.001% to 1.5%, preferably from 0.01% to 1.0%, most preferably from 0.1% to 0.3%. When used as a component of the second phase and / or any subsequent phases, the amount of colorant is typically from 0.001% to 0.1%, more preferably from 0.005% to 0.05%, most preferably from 0.007% to 0.02%.

Compound Coarse inhibitor; korotyi

The tablets according to the invention suitable for dishwashing use may contain corrosion inhibitors, preferably selected from organic silver coating agents, especially 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 in European Patent Application No. EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are disclosed in European Patent Application No. EP-A-634478. Mn (II) compounds for use as corrosion inhibitors are described in European Patent Application No. EP-A-672 749.

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

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

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

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

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

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

Preferred fatty esters for use according to the invention are esters of ethylene glycol, glycerin and the n-^ ^ ^ jiton, wherein the fatty acid portion of the ester is typically derived from a compound selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

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

Specific examples of fatty alcohol esters for use in the present invention include: steayl acetate, dipalmityl lactate, cocoyl isobutyrate, oleyl maleate, dioleyl maleate, and tallow-derived alcohol propionate. Specific examples of fatty acid esters for use in the invention include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glyceryl monostearate, ethylene glycol monostearate, sorbitan esters. To the appropriate esters

189,559 of sorbitan include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distcarinate, sorbitan dibehenate and sorbitan dioleate derived from sorbitan and sorbitan dioleates.

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

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

Waxes, including microcrystalline waxes, are suitable organic silver coating agents for use in the present invention. Preferred waxes have a melting point ranging from 35 ° C to 110 ° C, and contain from 12 to 70 carbon atoms per molecule.

Petroleum waxes of the paraffinic and microcrystalline types, consisting of long chain saturated hydrocarbon compounds, are preferred.

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

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

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

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

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

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

Nitrogen-containing compounds as corrosion inhibitors

Suitable nitrogen-containing compounds as corrosion inhibitors include imidazole and its derivatives, such as benzimidazole, 2-heptadecylimidazole and the imidazole derivatives described in Czech Patent Specification No. 139,279 and GB-A-1,137,741, which also discloses a process for the preparation of imidazole compounds. .

Suitable nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, especially those wherein the pyrazole is substituted at any of the 1, 3, 4 or 5 positions with R _h R ₃ , R 4 and R ₅ , wherein R 1 is H, CH2OH, CONH3 or COCH3, each of R3 and R5 is C1-C20 alkyl or hydroxy and R4 is Η, NH2 or NO2.

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

189 559

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

Mn (7I) compounds as corrosion inhibitors

Detergent tablets may contain a compound Mn (II) as a corrosion inhibitor. Compound Mn (II) is preferably introduced in an amount of 0.005% to 5% by weight, more preferably 0.01% to 1%, most preferably 0.02% to 0.4% by weight. relative to the composition. Preferably, the compound Mn (II) is introduced in an amount ranging 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. Mn (II) ions in any bleach solution.

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

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

Other corrosion inhibitors

Other suitable corrosion inhibitor compounds include mercaptans and diols, especially mercaptans containing 4-20 carbon atoms, including lauryl mercaptan, thiophenol, thionaphthol, thionalide and thioanthranol. Also suitable are C10-C20 saturated or unsaturated fatty acids or their salts, especially aluminum tristearate. C12-C20 hydroxy fatty acids or their salts are also useful. Phosphonated octadecane and other antioxidants such as betahydroxytoluene (BHT) are also useful.

Butadiene maleic acid copolymers, especially those supplied under Trade Designation No. 07787 by Polisciences Inc., have been found to be particularly useful as corrosion inhibitor compounds.

Hydrocarbon oils

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

A water-soluble compound of bismuth

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

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

Uk ^^^ .s7 <a / blϊzjj'ąjy enzyme

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

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Nydio calcium compound

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

The calcium soap dispersant is a material that prevents the precipitation of alkali metal, ammonia or amine salts of fatty acids with calcium or magnesium ions. Preferred calcium soap dispersant compounds are disclosed in PCT Application No. WO 93/08877.

Foam extinguishing system

The detergent tablets according to the invention preferably contain the foam suppression system present in an amount of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight. relative to the composition.

Suitable foam extinguishing systems for use in accordance with the invention may contain any known antifoam such as, e.g., silicone antifoam compounds,

2-aUklic and alkanol antifoam compounds. Preferred foam extinguishing systems and anti-defogging compounds are disclosed in PCT Application No. WO 93/08876 and in EPrAr705 324.

7 other additional ingredients

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

PH value of the compositions *

The detergent tablets of the invention are preferably not formulated such that their pH is undesirably high, such that their pH as measured in a 1% solution in distilled water is preferably from 8.0 to 12.5, more preferably from 9.0 to 11.8. most preferably from 9.5 to 11.5.

Washing method in dishwashers

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

A preferred method of washing in a dishwasher involves treating soiled items selected from porcelain dishes, glassware, silverware, metalware, cutlery, and mixtures thereof with an aqueous liquid in which an effective amount of the detergent tablet of the invention is dissolved or dispersed. An effective amount of a detergent tablet means from 8 to 60 g of product dissolved or dispersed in a dishwashing liquid with a volume of 3 to 10 liters, as these are typical product doses and dishwashing solution volumes commonly used in conventional dishwasher washing methods. Detergent tablets weighing from 15 to 40 g, more preferably from 20 to 35 g, are preferred.

Examples

Abbreviations used in the examples

In detergent compositions, the abbreviations used to identify the ingredients have the following meanings:

STTP: Bicarbonate: Citric acid: Carbonate: Silicate:

SKS-6:

PB 1:

Non-ionic:

TAED:

HEDP:

PAAC:

Paraffin:

Sodium tripolitbflbran

Hydrocarbonate of sodium

Anhydrous carmine acid

Anhydrous sodium carbonate

Anhydrous sodium silicate (ratio SiO2: Na2O - 2. ^^) Crystalline layered silicate of formula 8-Na2Si2O5 Anhydrous Tty sodium perborate monohydrate

C13-C15 m ^^ sz ^ amy rtoksγlowaτv / propoxylated fatty alcohol with average 3.8 and medium s ^^ o ^^ u propoxylation 4.5, sold under the trade name P / nafac by BASF

Tetrtkertylortylrτodikmmk

Ethane-1-hydroxy-1,1-diphosphoic acid

Salt, cobalt (III) pentktminoacetate

Paraffin oil, sold under the tradename Winog 70 from Wintershall.

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Protease: Enzyme

Amylase: Amylitol enzyme

BtA: Benzotriazole

Sulfate: Anhydrous sodium sulfate

PEG 3000: Polythene glycol with a molecular weight of about 3000, available from Hoechst

PEG 6000: Glycol p ^^ and ^^ y ^^ n ^^ with a molecular size of kodo 6000, available from Hoechst pH: Measured in 1% solution in water, (^^ tPl ^^ important at 20 ° C

In the examples below, all amounts are given in parts by weight:

Examples I-IV

The following are illustrative examples of detergent tablets according to the invention suitable for use in dishwashers.

AND II III IV V VI Phase 1 STPP 9.62 9.62 10.45 9.57 9.57 11.47 Silicate 0.50 0.67 1.60 100 100 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 Non-ionic 0.40 0.80 0.80 120 120 120 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 Fragrance 0.02 0.02 0.02 0.013 0.013 0.013 Sulfate - - - 0.502 0.05 2.843 Together 17.75 g 18.55 g 19.57 g 23.0 g 23.0 g 23.0 g 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 - Bicarbonate 109 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 0.06 0.06 0.06 0.06 0.06 0.06 Together 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g

189 559

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

189 559

Publishing Department of the Polish Patent Office. Circulation 50 copies

Price PLN 6.00.

Claims (6)

Patent claims A multiphase dishwasher detergent tablet having a weight of 15-40 grams comprising a first phase as a compressed, shaped body formed from a first detergent composition and a second phase as a compressed body formed from a second detergent composition characterized in that a) a first the phase has at least one cavity on the surface of the shaped body and b) the second phase held in the seat by adhesion is less than 4 grams and contains the enzyme. 2. Multiphase detergent tablet according to claim 1 The enzyme according to claim 1, characterized in that the enzyme is mainly concentrated in the second phase. 3. The multiphase detergent tablet according to claim 1 The method of claim 1, wherein the first and / or second phase comprises a binding agent. 4. The multiphase detergent tablet according to claim 1 The composition of claim 3, characterized in that the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, and inorganic and organic polymers. 5. Multiphase detergent tablet according to claim 5; The method of claim 1, further comprising a barrier phase between the first and second phases. 6. The multiphase detergent tablet according to claim 6 5. A method as claimed in claim 5, characterized in that the barrier phase is a binder applied in liquid form.