CA2306388A1 - Performance-enhanced particulate dishwasher detergents - Google Patents

Abstract

Detergents with rapid and relatively long-lasting enzyme release and hence an improved enzyme effect contain enzyme particles of one or more coating material(s) with a melting point above 30°C, one or more liquid enzyme preparation(s) dispersed in the coating material(s) and optionally other carrier materials, auxiliaries and/or additives.

Description

Performance-enhanced Particulate Dishwasher Detergents Field of the Invention This invention relates generally to enzyme-containing detergents and, more particularly, to performance-enhanced multi-component deter-gents in which advantages in regard to detersive performance are obtained through division into several different ingredients. Detergents such as these include, in particular, powder-form or granular dishwasher detergents.
Background of the Invention Dishwasher detergents are at present marketed as powder-form or granular products, as tablets or as liquid products, each of these supply forms having technical and aesthetic advantages, but also disadvantages.
Compact detergent tablets have the largest market share and are enjoying increasing popularity among consumers by virtue of their simple dosing. In addition, tablets - through regions of different composition - enable certain ingredients only to be released under defined conditions in the washing/
cleaning process which improves the cleaning result. Besides the core/jacket tablets and ring/core tablets well known from the pharmaceutical field, multi-layer tablets in particular have been successful in this regard and are now available for use in many areas of washing, cleaning and hygiene.
The controlled release aspect of ingredients has been, and is still being, intensively investigated inter alia in the field of detergents, so that several publications are also available on the subject. In powder-form detersive products, this controlled release of certain ingredients can be achieved by coating individual particles which is both technically complicated and expensive.
Earlier German patent application DE 198 51 426.3 (Henkel KGaA) describes a process for the production of multi-phase detergent tablets in which a particulate premix is compressed to form tablets comprising a cavity which is subsequently filled with a separately prepared melt suspension or emulsion of a coating material and one or more active substances) dispersed or suspended therein. The coating materials mentioned in this document include paraffins and polyethylene glycols while the active substances mentioned include enzymes, bleaching agents, bleach activators, surfactants, corrosion inhibitors, scale inhibitors, co-builders and/or perfumes. Liquid enzyme preparations are not mentioned in this document. The teaching of this document is also confined to tablets.
Powder-form detergents containing a "second phase", which obtain certain effects through the controlled release of ingredients, are not disclosed.
Earlier German patent application DE 199 14 364.1 (Henkel KGaA) describes rinse aid particles for obtaining a clear rinse effect in domestic dishwashers which contain 30 to 90% by weight of one or more carrier materials, 5 to 40% by weight of one or more coating materials with a melting point above 30°C, 5 to 40% by weight of one or more active substances and 0 to 10% by weight of other active substances and auxiliaries. The rinse aid particles are advantageously produced by press agglomeration processes and are suitable for incorporation in powder-form dishwasher detergents. According to the teaching of this document, the coating materials ensure that the rinse aid particles are only significantly dissolved in the final rinse cycle and withstand the main wash cycle undamaged and without releasing any active ingredients. The accelerated and relatively long-lasting release of active substances is not mentioned in this document.
Dishwasher detergents producing a clear rinse effect in domestic dishwashers are also described in earlier German patent application DE
199 14 363.3 (Henkel KGaA). These powder-form detergents contain rinse aid particles which in turn contain 20 to 80% by weight of one or more coating materials with a melting point above 30°C, 20 to 80% by weight of one or more active substances and 0 to 20% by weight of other active substances and auxiliaries. The rinse aid particles are preferably incorporated in the detergents according to the invention in quantities of 0.5 to 30% by weight. According to this document, the problem addressed by the invention was again to ensure that the rinse aid particles would only dissolve significantly in the final rinse cycle and would withstand the main wash cycle undamaged and without releasing any active ingredients. The accelerated and relatively long-lasting release of active ingredients is not mentioned in this document either.
The problem addressed by the present invention was to make the advantages of the controlled release of ingredients available to powder-form detergents without any need for expensive process steps, such as single or multiple coating. The particulate detergents to be provided by the invention would be superior to conventional detergents above all in regard to stability in storage and in regard to the performance of enzymes.
Summary of the Invention It has now been found that particulate dishwasher detergents with the requisite properties can be obtained in a flexible and simple manner by processing liquid enzyme preparations with coating materials and optionally carrier materials and/or other ingredients to form melt dispersions which are then processed by forming/shaping and incorporated in particulate dishwasher detergents.
The present invention relates on the one hand to enzyme particles for dishwashing machines which contain a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials.
Description of the Invention According to the present invention, commercially available liquid enzyme preparations are embedded in a matrix or coating material(s), optionally together with carrier materials and other auxiliaries and/or active substances, and form enzyme particles. The enzymes are released from this matrix on the one hand more quickly and, on the other hand, surprisingly over a longer period so that a rapid and continuing release of the enzymes is achieved. By adopting the procedure according to the invention, the maximum enzyme activity is achieved at a much earlier stage in the wash cycle, enzyme activity remaining at a fairly high level throughout the remainder of the wash cycle.
The enzyme particles according to the invention may be formulated to contain carrier materials. The release kinetics can be influenced through the type and quantity of carrier material used. However, the most important aspect of using carrier materials lies in the increase in the bulk density of the enzyme particles. If particles with relatively high bulk densities are to be produced, carrier materials should be used in relatively large quantities.
Suitable carrier materials a) are any substances which are solid at room temperature. Substances which develop an additional effect in the wash cycle will normally be selected, builders being particularly appropriate in this regard. In preferred enzyme particles, substances from the group of water-soluble detergent ingredients, preferably carbonates, hydrogen carbonates, sulfates, phosphates and the organic oligocarboxylic acids solid at room temperature are present as carrier materials in quantities of 10 to 85% by weight, preferably 20 to 80% by weight and more preferably to 75% by weight, based on the weight of the particles.
25 The preferred carrier materials mentioned are described in detail hereinafter.
The enzyme particles according to the invention may also be produced without any carrier materials or substantially free from carrier materials. In this case, the enzyme particles according to the invention 30 preferably contain a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, more preferably 60 to 95% by weight and most preferably 70 to 90% by weight of one or more coating materials) with a melting point above 30°C, 5 b) 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably 2.5 to 30% by weight and most preferably 5 to 25% by weight of one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight and most preferably 0 to 5% by weight of optionally other carrier materials, auxiliaries and/or active substances.
Besides the carrier materials and other auxiliaries optionally used, coating materials and liquid enzyme preparations are present as essential ingredients in the enzyme particles according to the invention. Preferred coating materials have a melting range of 45 to 75°C. This melting range ensures the advantageous release of enzymes in the standard programs of dishwashing machines. According to the invention, the coating material is advantageously soluble in water.
Particularly preferred enzyme particles are those in which the coating material of the region contains at least one substance from the group of polyethylene glycols (PEGs) and/or polypropylene glycols (PPGs), polyethylene glycols with molecular weights of 1500 to 36,000 being preferred, those with molecular weights of 2000 to 6000 being particularly preferred and those with molecular weights of 3000 to 5000 being most particularly preferred.
Enzyme particles containing propylene glycols (PPGs) and/or polyethylene glycols (PEGs) as sole coating material are particularly preferred. Polypropylene glycols (PPGs) suitable for use in accordance with the invention are polymers of propylene glycol corresponding to general formula I:

H-(O- i H-CHZ)~-OH (I) where n may assume a value of 10 to 2000. Preferred PPGs have molecular weights of 1000 to 10,000 corresponding to values for n of 17 to about 170.
Polyethylene glycols (PEGs) preferably used in accordance with the invention are polymers of ethylene glycol corresponding to general formula (II):
H-(O-CH2-CH2)~-OH (I I) in which m may assume a value of 20 to about 1000. The preferred molecular weight ranges mentioned above correspond to preferred ranges for the value of n in formula II of about 30 to about 820 (exactly: 34 to 818), more preferably of about 40 to about 150 (exactly: 45 to 136) and, most preferably, of about 70 to about 120 (exactly: 68 to 113).
Besides the essential ingredients (coating material and liquid enzyme preparation), the enzyme particles according to the invention may contain other active substances and/or auxiliaries, for example those from the groups of anti-sedimenting agents, anti-settling agents, anti-floating agents, thixotropicizing agents and dispersants. Thus, certain enzyme particles according to the invention may contain other auxiliaries from the group of anti-sedimenting agents, anti-settling agents, anti-floating agents, thixotropicizing agents and dispersants in quantities of 0.5 to 8.0% by weight, preferably in quantities of 1.0 to 5.0% by weight and more preferably in quantities of 1.5 to 3.0% by weight, based on the weight of the enzyme particles.
According to the invention, the region may also contain emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and/or polyoxyalkylene siloxanes in quantities of 1 to 20% by weight, preferably in quantities of 2 to 15% by weight and more preferably in quantities of 2.5 to 10% by weight, based on the weight of the enzyme particles.
However, preferred enzyme particles are characterized in that, apart from the coating material(s), the constituents of the liquid enzyme prepara tions and optionally carrier materials, they contain no other ingredients.
The enzymes most commonly used in detergents include lipases, cellulases, amylases and proteases. In addition, hemicellulases, peroxi-dases and pectinases are used in special products. Proteases, amylases and lipases are of particular importance in dishwasher detergents. The enzymes are normally produced in a granulated an encapsulated form for use in powder products and are added to the detergent in that form. In water-containing liquid detergents, these granulated and encapsulated enzymes would partly dissolve so that, in general, liquid enzyme concentrates are preferably used in their case. Such liquid enzyme concentrates are based either homogeneously on propylene glycol/water or heterogeneously on a slurry or are present in microencapsulated form. The use of liquid enzyme products in solid detergents has never been described before.
Preferred liquid proteases are, for example, Savinase~ L, Durazym~ L, Esperase~ L and Everlase~ (Novo Nordisk); Optimase~ L, Purafect~ L, Purafect~ OX L, Properase~ L (Genencor International) and BLAP~ L (Biozym GmbH). Preferred amylases are Termamyl~ L, Duramyl~ L and BAN~ (Novo Nordisk) and Maxamyl~ WL and Purafect~
HPAm L (Genencor International). Preferred lipases are Lipolase~ L, Lipolase~ ultra L and Lipoprime~ L (Novo Nordisk) and Lipomax~ L
(Genencor International).
The Novo Nordisk products SL and LCC, for example, may be used as slurries or microencapsulated liquid products. The commercially available liquid enzyme preparations mentioned contain, for example, 20 to 90% by weight of propylene glycol or mixtures of propylene glycol and water. According to the present invention, preferred enzyme particles are characterized in that they contain one or more liquid amylase preparations and/or one or more liquid protease preparations.
The enzyme particles according to the invention can be produced in different ways, the processes for producing the enzyme particles differing slightly from one another according to whether or not the enzyme particles contain carrier materials. The present invention also relates to a process for the production of enzyme particles in which a melt dispersion of a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 5% by weight of other active substances and auxiliaries is processed by forming/shaping in the solidification range of the melt or is applied to one or more carrier materials and the mixture is processed by forming/shaping.
A melt dispersion of the enzyme particle ingredients (for a descrip tion see above) is initially prepared. It may either be directly processed by forming/shaping or may be applied to one or more carrier materials and then processed by forming/shaping.
There are no process-related restrictions on the forming/shaping process step for the melt dispersion or the mixture of melt and carrier material so that here, too, the expert may chose from the processes familiar to him. In tests conducted by applicants, processes in which the forming/shaping process step is carried out by granulation, compacting, pelleting, extrusion or tabletting have proved to be preferable. The granules, compactates, pellets, prills, extrudates, beads, flakes, tablets etc.
obtained in this way may then be added to powder-form or granular dishwasher detergents. The particle size of the enzyme particles may be adapted to the particle size of the "basic powder". According to the invention, the enzyme particles preferably have particle sizes of 200 to 2000 Nm, more preferably in the range from 400 to 1800 Nm and most preferably in the range from 600 to 1600 Nm, at least 90% by weight of the particles having sizes within these ranges.
In the process variant for the production of carrier-containing enzyme particles, a melt dispersion which may contain other active substances and auxiliaries is initially prepared. The melt dispersion is applied to a carrier material and is then processed by forming/shaping in admixture with that carrier material. The melt suspension or emulsion may be applied to the carrier material in any standard mixers. This variant of the process according to the invention comprises applying melts of coating materials and liquid enzyme preparations to carrier materials. In principle, melts and carrier materials) may be present in the resulting enzyme particles in varying quantities. Preferred processes are characterized in that a mixture of 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 15 to 40% by weight and most preferably 20 to 35% by weight of a melt dispersion and 50 to 95% by weight, preferably 55 to 90% by weight, more preferably 60 to 85% by weight and most preferably 65 to 80% by weight of carrier materials) is processed by forming/shaping.
Preferred variants of both the above-mentioned processes for producing the enzyme particles according to the invention are charac terized in that the coating material makes up from 25 to 85% by weight, preferably from 30 to 70% by weight and more preferably from 40 to 50%
by weight of the melt dispersion.
As already mentioned in the description of the enzyme particles according to the invention, polyethylene glycols are particularly suitable coating materials. Accordingly, preferred processes according to the invention are characterized in that the melt dispersion contains polyethylene glycols with molecular weights of 1500 to 36,000, preferably those with molecular weights in the range from 2000 to 6000 and more preferably those with molecular weights in the range from 3000 to 5000 as the coating material.
The foregoing observations apply in regard to the ingredients which 5 are used in the process according to the invention and processed to form the enzyme particles according to the invention. The melt suspension or emulsion to be prepared preferably satisfies certain criteria which were also described in the foregoing.
In principle, the enzyme particles according to the invention may be 10 directly placed in the hands of the consumer so that the consumer may add them to the detergent as required in order to obtain better cleaning results in the case of heavily soiled tableware. However, this option is often undesirable to the consumer because of the additional dosing step involved. Accordingly, the enzyme particles according to the invention are preferably incorporated in particulate dishwasher detergents.
Accordingly, the present invention also relates to a particulate dishwasher detergent containing builders and optionally other ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and perfumes and, in addition, enzyme particles which contain a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials, based on the weight of the enzyme particles.
As already mentioned in reference to the enzyme particles according to the invention, the composition of the enzyme particles is preferably within a relatively narrow range so that preferred particulate dishwasher detergents are also characterized in that the enzyme particles consist of a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, more preferably 60 to 95% by weight and most preferably 70 to 90% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably 2.5 to 30% by weight and most preferably 5 to 25% by weight or one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight and most preferably 0 to 5% by weight of optionally other carrier materials, auxiliaries and/or active substances.
The ingredients of the dishwasher detergents are described herein after. They may also be partly present as carrier materials in the enzyme particles according to the invention.
The most important ingredients of dishwasher detergents are builders. The dishwasher detergents according to the invention may contain any of the builders typically used in detergents, i.e. in particular zeolites, silicates, carbonates, organic co-builders and - as an important builder in dishwasher detergents - also phosphates. All the builders mentioned in the following are suitable as carrier materials for the enzyme particles according to the invention, as mentioned in the foregoing.
Suitable crystalline layered sodium silicates correspond to the general formula NaMSiXOZX+~y H20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layered silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium disilicates Na2Si205y H20 are particularly preferred, ~i-sodium disilicate being obtainable, for example, by the process described in International patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to encompass "X-ray amorphous". In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-44 00 024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing bound water used in accordance with the invention is preferably zeolite A and/or zeolite P.
Zeolite MAP~ (Crosfield) is a particularly preferred P-type zeolite.
However, zeolite X and mixtures of A, X and/or P are also suitable.
According to the invention, it is also preferred to use, for example, a co-crystallizate of zeolite X and zeolite A (ca. 80% by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under the name of VEGOBOND
AX~ and which may be described by the following formula:
nNa20 - (1-n)K20 - AI203 ~ (2 - 2.5)Si02 - (3.5 - 5.5) H20.
Suitable zeolites have a mean particle size of less than 10 ~m (volume distribution, as measured by the Coulter Counter Method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of bound water.
The generally known phosphates may of course also be used as builders providing their use should not be avoided on ecological grounds.
Among the large number of commercially available phosphates, alkali metal phosphates have the greatest importance in the detergent industry, pentasodium triphosphate and pentapotassium triphosphate (sodium and potassium tripolyphosphate) being particularly preferred.
"Alkali metal phosphates" is the collective term for the alkali metal (more particularly sodium and potassium) salts of the various phosphoric acids, including metaphosphoric acids (HP03)~ and orthophosphoric acid (H3P04) and representatives of higher molecular weight. The phosphates combine several advantages: they act as alkalinity sources, prevent lime deposits on machine parts and lime incrustations in fabrics and, in addition, contribute towards the cleaning effect.
Sodium dihydrogen phosphate (NaH2P04) exists as the dehydrate (density 1.91 gcm~, melting point 60°) and as the monohydrate (density 2.04 gcm-3). Both salts are white readily water-soluble powders which, on heating, lose the water of crystallization and, at 200°, are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na2H2P20~) and, at higher temperatures, into sodium trimetaphosphate (Na3P309) and Maddrell's salt (see below). NaH2P04 shows an acidic reaction. It is formed by adjusting phosphoric acid with sodium hydroxide to a pH value of 4.5 and spraying the resulting "mash". Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2P04, is a white salt with a density of 2.33 gcm~, has a melting point of 253° [decomposition with formation of potassium polyphosphate (KP03)X] and is readily soluble in water.
Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP04, is a colorless, readily water-soluble crystalline salt. It exists in water-free form and with 2 moles (density 2.066 gcm-3, water loss at 95°), 7 moles (density 1.68 gcm-3, melting point 48° with loss of 5 H20) and 12 moles of water (density 1.52 gcm~, melting point 35° with loss of 5 H20), becomes water-free at 100° and, on fairly intensive heating, is converted into the diphosphate Na4P20~. Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenol-phthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HP04, is an amorphous white salt which is readily soluble in water.
Trisodium phosphate, tertiary sodium phosphate, Na3P04, consists of colorless crystals which have a density of 1.62 gcm~ and a melting point of 73-76° (decomposition) as the dodecahydrate, a melting point of 100° as the decahydrate (corresponding to 19-20% P205) and a density of 2.536 gcm-3 in water-free form (corresponding to 39-4.0% Pz05). Trisodium phosphate is readily soluble in water through an alkaline reaction and is prepared by concentrating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH by evaporation. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3P04, is a white deliquescent granular powder with a density of 2.56 gcm~, has a melting of 1340° and is readily soluble in water through an alkaline reaction. It is formed, for example, when Thomas slag is heated with coal and potassium sulfate.
Despite their higher price, the more readily soluble and therefore highly effective potassium phosphates are often preferred to corresponding sodium compounds in the detergent industry.
Tetrasodium diphosphate (sodium pyrophosphate), Na4P20~, exists in water-free form (density 2.534 gcm-3, melting point 988°, a figure of 880°
has also been mentioned) and as the decahydrate (density 1.815 - 1.836 5 gcm-3, melting point 94° with loss of water). Both substances are colorless crystals which dissolve in water through an alkaline reaction. Na4P20~ is formed when disodium phosphate is heated to >200° or by reacting phosphoric acid with soda in a stoichiometric ratio and spray-drying the solution. The decahydrate complexes heavy metal salts and hardness 10 salts and, hence, reduces the hardness of water. Potassium diphosphate (potassium pyrophosphate), K4P20~, exists in the form of the trihydrate and is a colorless hygroscopic powder with a density of 2.33 gcm-3 which is soluble in water, the pH value of a 1 % solution at 25° being 10.4.
Relatively high molecular weight sodium and potassium phosphates 15 are formed by condensation of NaH2P04 or KH2P04. They may be divided into cyclic types, namely the sodium and potassium metaphosphates, and chain types, the sodium and potassium polyphosphates. The chain types in particular are known by various different names: fused or calcined phosphates, Graham's salt, Kurrol's salt and Maddrell's salt. All higher sodium and potassium phosphates are known collectively as condensed phosphates.
The industrially important pentasodium triphosphate, Na5P30~o (sodium tripolyphosphate), is a non-hygroscopic white water-soluble salt which crystallizes without water or with 6 H20 and which has the general formula Na0-[P(O)(ONa)-O]~-Na where n = 3. Around 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, around 20 g at 60° and around 32 g at 100°. After heating of the solution for 2 hours to 100°, around 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide in a stoichiometric ratio and the solution is spray-dried. Similarly to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K5P30~o (potassium tripolyphosphate), is marketed for example in the form of a 50% by weight solution (> 23% P205, 25% K20).
The potassium polyphosphates are widely used in the detergent industry.
Sodium potassium tripolyphosphates, which may also be used in accordance with the invention, also exist. They are formed for example when sodium trimetaphosphate is hydrolyzed with KOH:
(NaP03)3 + 2 KOH -~ Na3K2P30~o + H20 According to the invention, they may be used in exactly the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures thereof. Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate may also be used in accordance with the invention.
The particulate dishwashers according to the invention are preferably characterized in that they contain builders in quantities of 20 to 80% by weight, preferably in quantities of 25 to 75% by weight and more preferably in quantities of 30 to 70% by weight, based on the weight of the detergent.
Organic cobuilders suitable for use in the dishwasher detergents according to the invention are, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described in the following.
Useful organic builders are, for example, the polycarboxylic acids usable in the form of their sodium salts, polycarboxylic acids in this context being understood to be carboxylic acids which bear more than one acid function. Examples of such carboxylic acids are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), providing their use is not ecologically unsafe, and mixtures thereof.
Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
The acids per se may also be used. Besides their builder effect, the acids also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value in detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates such as, for example, the alkali metal salts of polyacrylic or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric polycarboxylates are weight-average molecular weights MW of the particular acid form which, basically, were determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which provides realistic molecular weight values by virtue of its structural similarity to the polymers investigated. These values differ distinctly from the molecular weights measured against polystyrene sulfonic acids as standard. The molecular weights measured against polystyrene sulfonic acids are generally higher than the molecular weights mentioned in this specification.
Particularly suitable polymers are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g/mole. By virtue of their superior solubility, preferred representatives of this group are the short chain polyacrylates which have molecular weights of 2,000 to 10,000 g/mole and, more particularly, 3,000 to 5,000 g/mole.
Also suitable are copolymeric polycarboxylates, particularly those of acrylic acid with methacrylic acid and those of acrylic acid or methacrylic acid with malefic acid. Acrylic acid/maleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have proved to be particularly suitable. Their relative molecular weights, based on the free acids, are generally in the range from 2,000 to 70,000 g/mole, preferably in the range from 20,000 to 50,000 g/mole and more preferably in the range from 30,000 to 40,000 g/mole.
The (co)polymeric polycarboxylates may be used either in powder form or in the form of an aqueous solution. The content of (co)polymeric polycarboxylates in the detergent is preferably from 0.5 to 20% by weight and more preferably from 3 to 10% by weight.
In order to improve solubility in water, the polymers may also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as monomer.
Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those which contain salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers.
Other preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Particular preference is attributed to polyaspartic acids or salts and derivatives thereof which, according to German patent application DE-A-195 40 086, are also said to have a bleach-stabilizing effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least three hydroxyl groups. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-aldehyde and mixtures thereof and from polyol carboxylic acids, such as gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates which may be obtained by partial hydrolysis of starches. The hydrolysis may be carried out by standard methods, for example acid- or enzyme-catalyzed methods. The end products are preferably hydrolysis products with average molecular weights of 400 to 500,000 g/mol. A polysaccharide with a dextrose equivalent (DE) of 0.5 to 40 and, more particularly, 2 to 30 is preferred, the DE being an accepted measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20 and dry glucose sirups with a DE of 20 to 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights of 2,000 to 30,000 g/mole may be used.
The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Dextrins thus oxidized and processes for their production are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and from International patent applications WO 92/18542, WO 93108251, WO 93116110, WO 94/28030, WO 95/07303, WO 95112619 and WO 95!20608. An oxidized oligosaccharide corresponding to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine-N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also 5 preferred in this connection. The quantities used in zeolite-containing and/or silicate-containing formulations are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids and salts thereof which may optionally be present in lactone form and which contain at least 4 carbon atoms, at least one 10 hydroxy group and at most two acid groups. Co-builders such as these are described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the phosphonates, more particularly hydroxyalkane and aminoalkane phos phonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1 15 diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used in the form of the sodium salt, the disodium salt showing a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9).
Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylenephosphonate 20 (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP. Of the phosphonates, HEDP is preferably used as a builder. In addition, the aminoalkane phosphonates have a pronounced heavy metal binding capacity. Accordingly, it can be of advantage, particularly where the detergents also contain bleach, to use aminoalkane phosphonates, more particularly DTPMP, or mixtures of the phosphonates mentioned.
In addition, any compounds capable of forming complexes with alkaline earth metal ions may be used as co-builders.
Besides the builders, substances from the groups of surfactants, bleaching agents, bleach activators, corrosion inhibitors and dyes and perfumes are important ingredients of detergents. Important representatives of the classes of compounds mentioned are described in the following.
Besides the builders, substances from the groups of surfactants, bleaching agents, bleach activators, enzymes, polymers and dyes and perfumes are important ingredients of detergents. Accordingly, preferred particulate dishwasher detergents contain one or more substances from the groups of bleaching agents, bleach activators, bleach catalysts, surfactants, corrosion inhibitors, polymers, dyes and perfumes, pH
regulators and enzymes. Important representatives of the classes of compounds mentioned are described in the following.
Normally, the only surfactants used in dishwasher detergents are low-foaming nonionic surfactants. Representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. In one particularly preferred embodiment, the dishwasher detergent tablets according to the invention contain nonionic surfactants.
In particularly preferred embodiments of the present invention, the detergent tablets according to the invention contain nonionic surfactants, more particularly nonionic surfactants from the group of alkoxylated alcohols. Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C~2_~4 alcohols containing 3 EO or 4 EO, C9_» alcohol containing 7 EO, C~3_~5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~2_~S alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2_~a alcohol containing 3 EO and C~2_~$ alcohol containing 5 EO. The degrees of ethoxylation mentioned represent statistical mean values which, for a special product, can be a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used, examples including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Suitable other nonionic surfactants are alkyl glycosides with the general formula RO(G)X where R is a primary, linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is a number of 1 to 10 and preferably 1.2 to 1.4.
Another class of preferred nonionic surfactants which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more especially the fatty acid methyl esters which are described, for example, in Japanese patent application JP 581217598 or which are preferably produced by the process described in International patent application WO-A-90113533.
Nonionic surfactants of the amine oxide type, for example N-coconutalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxy-ethylamine oxide, and the fatty acid alkanolamide type are also suitable.
The quantity in which these nonionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, more preferably, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides corresponding to formula (III):
R' R-CO-N-[Z] (I I I) in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms, R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds corresponding to formula (lU):
R~-O-R2 R-CO-N-[Z] (IV) in which R is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms, C» alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-alkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or -xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, for example in accordance with the teaching of International patent application WO-A-95107331.
Besides pure nonionic surfactants, other substances from the group of ionic surfactants, for example anionic or cationic surfactants, may of course also be present in the dishwasher detergents according to the invention.
According to the invention, preferred particulate dishwasher detergents contain surfactant(s), preferably nonionic surfactant(s), in quantities of 0.5 to 10% by weight, preferably in quantities of 0.75 to 7.5%
by weight and more preferably in quantities of 1.0 to 5% by weight, based on the detergent as a whole.
Among the compounds yielding H202 in water which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhy-drates and H202-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane dioic acid. Detergents according to the invention may also contain bleaching agents from the group of organic bleaching agents.
Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide for example. Other typical organic bleaching agents are the peroxy acids, of which alkyl peroxy acids and aryl peroxy acids are particularly mentioned as examples. Preferred representatives are (a) peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ~-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxy-caproic acid, N-nonenylamidoperadipic acid and N-nonenylamido-persuccinates. and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, 5 diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(6-amino-percaproic acid).
Other suitable bleaching agents in the dishwasher detergents acording to the invention are chlorine- and bromine-releasing substances.
10 Suitable chlorine- or bromine-releasing materials are, for example, heterocyclic N-bromamides and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations, such as potassium and sodium. Hydantoin compounds, such as 1,3-15 dichloro-5,5-dimethyl hydantoin, are also suitable.
The bleaching agents are normally used in dishwasher detergents in quantities of 1 to 30% by weight, preferably in quantities of 2.5 to 20% by weight and more preferably in quantities of 5 to 15% by weight, based on the detergent. In the context of the present invention, the quantities 20 mentioned are based on the weight of the basic powder, i.e. the detergent without the added enzyme particles according to the invention.
Bleach activators which support the effect of the bleaching agents can also be part of the basic powder. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as 25 substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetyl ethylenediamine (TAED), tetraacetyl methylenediamine (TAMD) and tetraacetyl hexylenediamine (TAHD) and also pentaacetyl glucose (PAG), 1,5-diacetyl-2,2-dioxohexaydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).
Suitable bleach activators are compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O-and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-urils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767, acetylated sorbitol and mannitol and the mixtures thereof (SORMAN), acylated sugar derivatives, more particularly pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example N-benzoyl caprolactam. Substituted hydrophilic acyl acetals are also preferably used. Combinations of conventional bleach activators may also be used. The bleach activators are normally used in dishwasher detergents in quantities of 0.1 to 20% by weight, preferably in quantities of 0.25 to 15% by weight and most preferably in quantities of 1 to 10% by weight, based on the detergent as a whole. In the context of the invention, the quantities mentioned are based on the weight of the basic powder.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleach catalysts may also be incorporated in the basic powder. These substances are bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-ammine complexes may also be used as bleach catalysts.
Bleach activators from the group of polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), N-acyl imides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or iso-NOBS), n-methyl morpholinium acetonitrile methyl sulfate (MMA) are preferably used, preferably in quantities of up to 10% by weight, more preferably in quantities of 0.1% by weight to 8% by weight, most preferably in quantities of 2 to 8% by weight and, with particular advantage, in quantities of 2 to 6% by weight, based on the detergent as a whole.
Bleach-boosting transition metal complexes, more particularly containing the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably selected from the group of manganese and/or cobalt salts and/or complexes, more preferably the cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate, are also present in typical quantities, preferably in a quantity of up to 5% by weight, more preferably in a quantity of 0.0025% by weight to 1 % by weight and most preferably in a quantity of 0.01 % by weight to 0.25% by weight, based on the detergent as a whole.
In special cases, however, more bleach activator may even be used.
The basic powder may of course also contain enzymes so that a conventional enzyme release and effect is achieved and is supported by the enzyme release and effect from the enzyme particles according to the invention. Corresponding detergents have as it were a "booster enzyme effect". The enzymes optionally used in the basic powder are preferably commercially available solid enzyme preparations.
Suitable enzymes in the basic powders are, in particular, those from the classes of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures thereof. All these hydrolases contribute to the removal of stains, such as protein-containing, fat-containing or starch-containing stains. Oxidoreductases may also be used for bleaching. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens and from genetically modified variants are particularly suitable. Proteases of the subtilisin type are preferably used, proteases obtained from Bacillus lentus being particularly preferred. Of particular interest in this regard are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease- and/or lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also been successfully used in some cases. Suitable amylases include in particular a-amylases, isoamylases, pullanases and pectinases.
The enzymes may be adsorbed to supports and/or encapsulated in shell-forming substances to protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme granules may be, for example, from about 0.1 to 5% by weight and is preferably from 0.5 to about 4.5% by weight. Preferred detergents according to the invention are characterized in that the basic powder contains protease and/or amylase.
By virtue of the fact that the detergents according to the invention may contain the enzymes) in two basically different regions, it is possible to provide detergents characterized by a very precisely defined enzyme release and effect. The following Table provides an overview of possible enzyme distributions in detergents according to the invention:
Basic powder Enzyme particles - Amylase - Protease - Lipase - Amylase + Protease - Amylase + Lipase - Protease + Lipase - Amylase + Protease +

Lipase Amylase Amylase Protease Amylase Amylase + Protease Amylase Amylase Protease Protease Protease Amylase + Protease Protease Amylase Amylase + Protease Protease Amylase + Protease Amylase + Protease Amylase + Protease Lipase Amylase Amylase + Lipase Amylase Protease + Lipase Amylase Amylase + Protease + Amylase Lipase Lipase Protease Amylase + Lipase Protease Protease + Lipase Protease Amylase + Protease + Protease Lipase Lipase Amylase + Protease Amylase + Lipase Amylase + Protease Protease + Lipase Amylase + Protease amylase + Protease+ Lipase~ Amylase + Protease Dyes and perfumes may be added to the dishwasher detergents according to the invention both in the basic powder and in the enzyme particles according to the invention in order to improve the aesthetic impression created by the products and to provide the consumer not only with the required performance but also with a visually and sensorially "typical and unmistakable" product. Suitable perfume oils or perfumes include individual perfume compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume compounds of the ester type are, for example, benzyl acetate, 5 phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals 10 containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetal-dehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, a-isomethyl ionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol and the hydrocarbons include, 15 above all, the terpenes, such as limonene and pinene. However, mixtures of various perfumes which together produce an attractive perfume note are preferably used. Perfume oils such as these may also contain natural perfume mixtures obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary 20 oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
The perfumes may be directly incorporated in the detergents 25 according to the invention, although it can also be of advantage to apply the perfumes to supports.
In order to improve their aesthetic impression, the detergents according to the invention (or parts thereof) may be colored with suitable dyes. Preferred dyes, which are not difficult for the expert to choose, have 30 high stability in storage, are not affected by the other ingredients of the detergents or by light and do not have any pronounced substantivity for the substrates treated with the detergents, such as glass, ceramics or plastic tableware, so as not to color them.
To protect the tableware or the machine itself, the detergents according to the invention may contain corrosion inhibitors, especially in the basic powder, silver protectors being particularly important for dishwashing machines. Known corrosion inhibitors may be used. Above all, silver protectors selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes may generally be used. Benzotriazole and/or alkylaminotriazole is/are particularly preferred. In addition, dishwashing formulations often contain corrosion inhibitors containing active chlorine which are capable of distinctly reducing the corrosion of silver surfaces.
Chlorine-free dishwashing detergents contain in particular oxygen- and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxy-hydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives of these compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used.
Of these, the transition metal salts selected from the group of manganese and/or cobalt salts and/or complexes are preferred, cobalt(ammine) complexes, cobalt(acetate) complexes, cobalt(carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate being particularly preferred. Zinc compounds may also be used to prevent corrosion of tableware.
The enzyme particles according to the invention have clear advantages over conventional products when used in dishwasher detergents. Accordingly, the present invention also relates to the use of enzyme particles of a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials in particulate dishwasher detergents.
The use of enzymes dispersed in polyethylene glycols with molecular weights of 1500 to 36,000, preferably in the range from 2000 to 6000 and more preferably in the range from 3000 to 5000 in dishwasher detergents is particularly preferred.
As the following Examples show, the enzyme particles according to the invention release the enzymes more quickly and for longer periods than conventional detergents. Accordingly, the present invention also relates to the use of enzyme particles of a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparations) dispersed in the coating materials) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials for the rapid and long-lasting release of enzymes from detergents containing these enzyme particles.
Specific embodiments of the present invention are described in the following examples which are not to be construed as limiting.
Examples Spherical particles between 500 and 700 Nm in diameter were prepared by prilling from melt dispersions with the composition shown in the following Table:

Enzyme particles Enzyme particles Protease (BLAP~ S 260 15.0 -LD) Amylase (Termamyl~ 300 - 15.0 L) PEG 4000 85.0 85.0 These enzyme particles were incorporated as "boosters" in powder form dishwasher detergents with the following composition:
Detergent powder Detergent powder Protease-containingProtease-free Sodium carbonate 16.5 18.0 Sodium tripolyphosphate50.0 50.0 Sodium disilicate 5.0 5.0 Polycarboxylate 5.0 5.0 HEDP* 1.0 1.0 Sodium perborate 10.0 10.0 Tetraacetyl ethylenediamine2.0 2.0 C~2 fatty alcohol + 2.0 2.0 Protease (BLAP~ 200 1.5 -S) Amylase (Duramyl~ 60 2.0 2.0 T) Balance** 5.0 5.0 * Hydroxyethane-1,1-diphosphonicacid, tetrasodium salt ** Perfume, dye, salts, binder The protease-containing detergent 1 was mixed with the enzyme particles 1, 24 g powder being mixed with 1 g enzyme particles. The protease-free detergent 2 was similarly mixed with the enzyme particles 1.
The cleaning performance of the powders containing the enzyme particles according to the invention was evaluated against the additive-free detergent powders 1 and 2 (Comparison Examples C1 and C2). To this end, soiled tableware was cleaned in the main wash cycle of a 55°C
program (water hardness 16°d) of a Miele G 590 with universal program, the detergent being used in a quantity of 25 g. The following Table shows the cleaning performance of the individual powders against various protease-sensitive soils. It is pointed out in this connection that detergent powder 2 is protease-free while detergent powder 1 contains protease.
Powder E1 according to the invention (protease-containing detergent 1 with the enzyme particles 1 ) contains the protease both in the powder and in the enzyme particles whereas powder E2 according to the invention contains the protease in the enzyme particles only. The cleaning performance of the detergents against the soils was visually evaluated by experts and scored on a scale of 0 to 10 where a score of "0" signifies no cleaning while a score of "10" signifies complete removal of the stains. The results of the cleaning tests are set out in the following Table. In the interests of clarity, the presence of protease in the basic powder is indicated by the letter "B"
while the presence of protease in enzyme particles is indicated by the letter "P".
Protease in B + p B
p Minced meat on glass (burnt-on)9.0 - 8.0 -Minced meat on china (dried-on)10.0 - 9.0 -Egg yolk (dried-on) 10.0 8.0 8.9 1.0 Egg/milk (dried-on) 10.0 10.0 10.0 1.0 In order further to illustrate the "booster effect" of the enzyme core, detergent powders C1 and E1 were compared in a 40°C program:

Minced meat on glass (burnt-on)5.2 6.0 Minced meat on china (dried-on)5.7 6.5 Egg yolk (dried-on) 3.2 5.8 Egg/milk (dried-on) 5.0 8.8 The results show that the presence of protease on its own in the enzyme particles according to the invention is equivalent to a multiple dose of protease in the basic powder against certain soils (comparison E2-C1).
If the protease is used both in the powder and in enzyme particles, cleaning performance against all soils can be distinctly improved, even in low-temperature programs.
Effectiveness against amylase-sensitive soils can be similarly demonstrated. To this end, detergent powder 2 was mixed with the enzyme particles 2 (E3) and compared for performance with additive-free detergent powder 2 (C3).

Oat flakes (dried-on)7.2 8.2 8.4 9.5 Rice starch (dried-on)2.8 - 8.3 -Starch mix (dried-on)5.7 10.0 9.1 10.0 Spaghetti 7.0 - 7.6 -It can again be seen that cleaning performance against all soils is distinctly improved, even in low-temperature programs, where amylase is used both in the detergent powder and in enzyme particles.
Release kinetics In an enzyme release test, the protease-containing basic powder 1 (C4) was compared with a protease-free basic powder 2 which contained the same quantity of protease in the form of the enzyme particles 1 according to the invention with the composition mentioned above (85%
PEG, 15% protease) (E4). Both detergents were subjected to the main wash cycle of a dishwashing machine, enzyme activity being measured as a function of time. The results are set out in the following Table:
Time [mins.j 2.5 5 6.75 7.5 10 15 20 25 Protease activity 2 5 10 25 100 60 10 6 Protease activity 0 60 100 80 70 70 66 50 The Table shows that the detergent according to the invention reaches its maximum activity after only 6.75 minutes while the comparison detergent takes 10 minutes. In addition, enzyme activity in the wash liquor remains at a high level throughout the main wash cycle whereas, in the Comparison Example, it falls dramatically only shortly after the maximum.

Claims (61)

1. Enzyme particles for dishwashing machines containing a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials.

2. Enzyme particles as claimed in claim 1, containing water-soluble detergent ingredients as carrier materials in quantities of 10 to 85% by weight based on the weight of the particles.

3. Enzyme particles as claimed in claim 2, wherein said water-soluble detergent ingredients are selected from the group consisting of carbonates, hydrogen carbonates, sulfates, phosphates and organic oligocarboxylic acids that are solid at room temperature.

4. Enzyme particles as claimed in any of claims 2 or 3, wherein said carrier materials are present in quantities of 20 to 80% by weight.

5. Enzyme particles as claimed in any of claims 2 to 4, wherein said carrier materials are present in quantities of 30 to 75% by weight.

6. Enzyme particles as claimed in any of claims 1 to 5, containing a) 40 to 99.5% by weight of one or more coating material(s) with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 20% by weight, optionally, of other carrier materials, auxiliaries and/or active substances.

7. Enzyme particles as claimed in claim 6, containing 50 to 97.5% by weight of one or more coating material(s) with a melting point above 30°C.

8. Enzyme particles as claimed in any of claims 6 to 7, containing 60 to 95% by weight of one or more coating material(s) with a melting point above 30°C.

9. Enzyme particles as claimed in any of claims 6 to 8, containing 70 to 90% by weight of one or more coating material(s) with a melting point above 30°C.

10. Enzyme particles as claimed in any of claims 6 to 9, containing 1 to 40% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s).

11. Enzyme particles as claimed in any of claims 6 to 10, containing 2.5 to 30% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s).

12. Enzyme particles as claimed in any of claims 6 to 11, containing 5 to 25% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s).

13. Enzyme particles as claimed in any of claims 6 to 12, containing 0 to 15% by weight of other carrier materials, auxiliaries and/or active substances.

14. Enzyme particles as claimed in any of claims 6 to 13, containing 0 to 10% by weight of other carrier materials, auxiliaries and/or active substances.

15. Enzyme particles as claimed in any of claims 6 to 14, containing 0 to 5% by weight of other carrier materials, auxiliaries and/or active substances.

16. Enzyme particles as claimed in any of claims 1 to 15, wherein the coating material a) has a melting range of 45°C to 75°C.

17. Enzyme particles as claimed in any of claims 1 to 16, wherein the coating material a) contains at least one substance selected from the group consisting of polyethylene glycols (PEGs) with a molecular weight in the range of 1500 to 36,000 and/or polypropylene glycols (PPGs).

18. Enzyme particles as claimed in claim 17, wherein the PEGs have a molecular weight in the range of 2000 to 6000.

19. Enzyme particles as claimed in any of claims 17 to 18, wherein the PEGs have a molecular weight in the range of 3000 to 5000.

20. Enzyme particles as claimed in any of claims 1 to 19, containing one or more liquid amylase preparations and/or one or more liquid protease preparations.

21. Enzyme particles as claimed in any of claims 1 to 20, containing further auxiliaries from the group of anti-sedimenting agents, anti-settling agents, anti-floating agents, thixotropicizing agents and dispersants in quantities of 0.5 to 8.0% by weight based on the weight of the enzyme particles.

22. Enzyme particles as claimed in claim 21, wherein said auxiliaries are present in quantities of 1.0 to 5.0% by weight.

23. Enzyme particles as claimed in claim 22, wherein said auxiliaries are present in quantities of 1.5 to 3.0% by weight.

24. Enzyme particles as claimed in any of claims 1 to 23, additionally containing emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and/or polyoxyalkylene siloxanes in quantities of 1 to 20% by weight based on the weight of the enzyme particles.

25. Enzyme particles as claimed in claim 24, wherein said emulsifiers are present in quantities of 2 to 15% by weight.

26. Enzyme particles as claimed in claim 25, wherein said emulsifiers are present in quantities of 2.5 to 10% by weight.

27. A process for the production of enzyme particles, wherein a melt dispersion of a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 5% by weight of other active substances and auxiliaries is processed by forming/shaping in the solidification range of the melt or is applied to one or more carrier materials and the mixture is processed by forming/shaping.

28. A process as claimed in claim 27, wherein the forming/ shaping process step is carried out by granulation, compacting, pelleting, extrusion or tabletting.

29. A process as claimed in any of claims 27 to 28, wherein the coating material makes up 25 to 85% by weight of the melt dispersion.

30. A process as claimed in claim 29, wherein the coating material makes up 30 to 70% by weight of the melt dispersion.

31. A process as claimed in claim 30, wherein the coating material makes up 40 to 50% by weight of the melt dispersion.

32. A process as claimed in any of claims 27 to 31, wherein a mixture of to 50% by weight of a melt dispersion and 50 to 95% by weight of carrier material(s) is processed by forming/shaping.

33. A process as claimed in claim 32, wherein a melt dispersion of 10 to 45% by weight is processed.

34. A process as claimed in claim 33, wherein a melt dispersion of 15 to 40% by weight is processed.

35. A process as claimed in claim 34, wherein a melt dispersion of 20 to 35% by weight is processed.

36. A process as claimed in any of claims 32 to 35, wherein 55 to 90%
by weight of carrier material(s) is processed.

37. A process as claimed in claim 36, wherein 60 to 85% by weight of carrier material(s) is processed.

38. A process as claimed in claim 37, wherein 65 to 80% by weight of carrier material(s) is processed.

39. A process as claimed in any of claims 27 to 38, wherein the melt dispersion contains polyethylene glycols with molecular weights of 1500 to 36,000 as the coating material.

40. A process as claimed in claim 39, wherein the melt dispersion

41 contains polyethylene glycols with molecular weights of 2000 to 6000 as the coating material.
41. A process as claimed in claim 40, wherein the melt dispersion contains polyethylene glycols with molecular weights of 3000 to 5000 as the coating material.

42. A particulate dishwasher detergent containing builders and optionally other ingredients selected from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and perfumes, characterized in that it contains enzyme particles which contain a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials, based on the weight of the enzyme particles.

43. A particulate dishwasher detergent as claimed in claim 42, wherein the enzyme particles consist of a) 40 to 99.5% by weight of one or more coating material(s) with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 20% by weight optionally of other carrier materials, auxiliaries and/or active substances.

44. A particulate dishwasher detergent as claimed in claim 43, wherein the enzyme particles consist of 50 to 97.5% of one or more coating material(s) with a melting point above 30°C.

45. A particulate dishwasher detergent as claimed in claim 44, wherein the enzyme particles consist of 60 to 95% of one or more coating material(s) with a melting point above 30°C.

46. A particulate dishwasher detergent as claimed in claim 45, wherein the enzyme particles consist of 70 to 90% of one or more coating material(s) with a melting point above 30°C.

47. A particulate dishwasher detergent as claimed in claim 43, wherein the enzyme particles consist of 1 to 40% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s).

48. A particulate dishwasher detergent as claimed in claim 47, wherein the enzyme particles consist of 2.5 to 30% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s).

49. A particulate dishwasher detergent as claimed in claim 48, wherein the enzyme particles consist of 5 to 25% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s).

50. A particulate dishwasher detergent as claimed in claim 43, wherein the enzyme particles consist of 0 to 15% by weight optionally of other carrier materials, auxiliaries and/or active substances.

51. A particulate dishwasher detergent as claimed in claim 50, wherein the enzyme particles consist of 0 to 10% by weight optionally of other carrier materials, auxiliaries and/or active substances.

52. A particulate dishwasher detergent as claimed in claim 51, wherein the enzyme particles consist of 0 to 5% by weight optionally of other carrier materials, auxiliaries and/or active substances.

53. A particulate dishwasher detergent as claimed in any of claims 43 to 52, containing builders in quantities of 20 to 80% by weight based on the weight of the detergent.

54. A particulate dishwasher detergent as claimed in claim 53, wherein said builders are present in quantities of 25 to 75% by weight.

55. A particulate dishwasher detergent as claimed in claim 54, wherein said builders are present in quantities of 30 to 70% by weight.

56. A particulate dishwasher detergent as claimed in any of claims 43 to 55, additionally containing one or more substances from the groups of bleaching agents, bleach activators, bleach catalysts, surfactants, corrosion inhibitors, polymers, dyes and perfumes, pH regulators and enzymes.

57. The use of enzyme particles of a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials, in particulate dishwasher detergents.

58. The use of enzymes dispersed in polyethylene glycols with molecular weights of 1500 to 36,000 in dishwasher detergents.

59. The use as claimed in claim 58, wherein said polyethylene glycols have molecular weights in the range of 2000 to 6000.

60. The use as claimed in claim 59, wherein said polyethylene glycols have molecular weights in the range of 3000 to 5000.

61. The use of enzyme particles of a) 5 to 99.5% by weight of one or more coating materials with a melting point above 30°C, b) 0.5 to 60% by weight of one or more liquid enzyme preparation(s) dispersed in the coating material(s) and c) 0 to 5% by weight of other active substances and auxiliaries, d) 0 to 90% by weight of one or more carrier materials, for the rapid and long-lasting release of enzymes from detergents containing these enzyme particles.