DE19918457A1 - Particulate enzyme preparation for use in dishwashing machines, comprising encapsulating material containing dispersed liquid enzyme preparation, and optionally carrier - Google Patents

Abstract

Controlled release particulate enzyme preparations for use in dishwashing machines, based on a dispersion of a liquid enzyme preparation in an encapsulating material. Particulate enzyme preparation for use in dishwashing machines comprises: (a) 5-99.5 wt. % of one or more encapsulating substances with a melting point of above 30 deg C; (b) 0.5-60 wt. % one or more liquid enzyme preparations dispersed in the encapsulating substance(s); (c) 0-5 wt. % other active ingredients and assistants; and (d) 0-90 wt. % one or more carrier materials.

Description

The present invention is in the field of enzyme-containing washing and Cleaning supplies. It particularly affects performance-enhanced multi-component Detergents, which are divided into several different ingredients Benefits in cleaning activity can be achieved. Such detergents include in particular powdery or granular cleaning agents for mechanical Wash the dishes.

Detergents for automatic dishwashing are currently called powdery or granular products, offered as tablets or as liquid products, each Offer form technical and aesthetic advantages but also has disadvantages. The The largest part of the market is owned by the compact detergent tablets enjoy increasing popularity among consumers because of the simple dosage. The Offer form "tablet" also enables different combinations Areas of the shaped body certain ingredients only under defined conditions in the Release the washing or cleaning cycle in order to improve cleaning success. In addition to the core / shell Tablets and ring / core tablets, in particular multilayered molded articles, which are offered today for many areas of washing and cleaning or hygiene become.  

The aspect of "controlled release" of ingredients, like to translate as "controlled release" called, was and is also in the field of washing and Cleaning agents worked intensively, so that this also a variety of Publications exist. In the field of washing and cleaning active Powdered products is the controlled release of certain ingredients through Coating individual particles can be realized, which is technically complex and costly is.

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes one Process for the production of multi-phase detergent tablets, at which a particulate premix is pressed into shaped bodies which are a depression have the later with a separately prepared melt suspension or emulsion from a coating substance and one or more dispersed or suspended in it Active substance (s) is filled. In this document, paraffins or Polyethylene glycols called, as active substances come enzymes, bleach, Bleach activators, surfactants, corrosion inhibitors, scale inhibitors, cobuilders and / or Fragrances into consideration. Liquid enzyme preparations are not described in this document mentioned. The teaching of this document is also tied to the "tablet" offer. Powdered cleaners containing a "second phase", which is controlled by Release of ingredients to achieve certain effects are not disclosed.

The older German patent application DE 199 14 364.1 (Henkel KGaA) describes Rinse aid particles to achieve a rinse aid effect in household dishes dishwashers containing 30 to 90% by weight of one or more carrier materials, 5 to 40 % By weight of one or more coating substances 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 further active substances and contain auxiliary substances. The rinse aid particles are advantageous through Press agglomeration process and are suitable for incorporation in powder detergents. According to the teaching of this, the envelope materials should Be achieved that the rinse aid particles are significant only in the rinse cycle dissolve and survive the main wash cycle undamaged and without active ingredient release. An accelerated and longer-lasting release of active substances is in this Scripture not taught.  

Automatic dishwashing detergent that has a rinse aid effect Household dishwashers are also used in older German ones Patent application DE 199 14 363.3 (Henkel KGaA). This powdery Detergents contain rinse aid particles, which in turn contain 20 to 80% by weight or several coating substances 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 further active ingredients Contain auxiliaries. The rinse aid particles are preferably used in amounts of 0.5 to 30% by weight incorporated into the agents according to the invention. Even after teaching this Scripture should be achieved that the rinse aid particles only in the rinse aid significantly dissolve and the main wash cycle is undamaged and without active ingredient release survive. An accelerated and longer-lasting release of active substances will not taught in this script either.

The present invention was based on the object, the advantages of controlled Release of ingredients can also be used for powdered cleaning agents do. This should involve complex process steps such as coating or Multiple coatings can be dispensed with. The particulate to be provided Cleaning agents should in particular with regard to storage stability and Performance of enzymes to be superior to conventional means.

It has now been found that particulate cleaning agents are suitable for mechanical Dishwashing with the desired properties in a flexible and simple way can be produced if you have liquid enzyme preparations with coating substances and optional Carriers and / or other ingredients processed to melt dispersions, which then processed to form and into particulate machine dishwashing detergents be incorporated.

The present invention relates on the one hand to particulate enzyme particles for machine dishwashing, which

• a) 5 to 99.5% by weight of one or more coating substances with a melting point above 30 ° C,  
• b) 0.5 to 60% by weight of one or more dispersed in the coating substance (s) liquid enzyme preparation (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

contain.

In the context of the present invention, commercially available liquid Enzyme preparations, if necessary with the addition of carrier materials and others Auxiliaries and / or active ingredients embedded in a matrix of shell material (s) and form Enzyme particles. On the one hand, this matrix makes the enzymes faster and on the other hand surprisingly released over a longer period of time, so that rapid and continuous release of the enzymes is achieved. The maximum of Enzyme activity is due to the procedure according to the invention in the cleaning cycle reached much earlier, and enzyme activity remains throughout Cleaning cycle at a higher level.

The enzyme particles according to the invention can be formulated to contain carrier material, the release kinetics being influenced by the type and amount of the carrier material can. The most important aspect of the use of carrier materials lies in the Increasing the bulk density of the enzyme particles. Should particles with higher Bulk weights are produced, the use of higher amounts of carrier materials he wishes.

All substances which are solid at room temperature are suitable as carrier substances a). Usually you will select fabrics that add an additional one in the cleaning cycle Developing an effect, with builders being particularly suitable. In preferred Particulate enzyme particles are substances from the group of the carrier materials water-soluble detergent and cleaning agent ingredients, preferably the carbonates, Hydrogen carbonates, sulfates, phosphates and the organic solid at room temperature Oligocarboxylic acids in amounts of 10 to 85% by weight, preferably 20 to 80% by weight and in particular from 30 to 75% by weight, in each case based on the particle weight, contain.

The preferred carriers mentioned are described in detail below.  

The enzyme particles according to the invention can also be produced with or without carrier material. Such particulate enzyme particles according to the invention then preferably contain

• a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more Envelope (s) with a melting point above 30 ° C
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30 % By weight and in particular 5 to 25% by weight of one or more in the Envelope substance (s) dispersed liquid enzyme preparation (s) as well
• c) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10 % By weight and in particular 0 to 5% by weight of optionally further carrier materials, Auxiliaries and / or active ingredients.

In the enzyme particles according to the invention, in addition to those that can be used optionally Carrier materials and other auxiliaries are mandatory coating substances and liquid Enzyme preparations included. Preferred coating substances have a melting range from 45 ° C to 75 ° C. Due to this melting range, the usual Cleaning programs in dishwashers an advantageous enzyme release guaranteed. It is advantageous in the context of the present invention if the Envelope is water soluble.

Particular preference is given to particulate enzyme particles in which the coating substance Region at least one substance from the group of polyethylene glycols (PEG) and / or Contains polypropylene glycols (PPG), with polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred.

Particulate enzyme particles, the only ones, are particularly preferred here Contain envelope substance propylene glycols (PPG) and / or polyethylene glycols (PEG).

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula I

are sufficient, where n can take values between 10 and 2000. Preferred PPG show Molar masses between 1000 and 10,000, corresponding to values of n between 17 and approx. 170, on.

Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula II

H- (O-CH ₂ -CH ₂ ) _n -OH (II)

are sufficient, where n can have values between 20 and approx. 1000. The above Preferred molecular weight ranges mentioned correspond to preferred ones Ranges of the value n in formula II from approx. 30 to approx. 820 (exactly: from 34 to 818), particularly preferably from about 40 to about 150 (exactly: from 45 to 136) and in particular from approx. 70 to approx. 120 (exactly: from 68 to 113).

In addition to the essential components, the enzyme particles according to the invention can Wrapping material and liquid enzyme preparation contain further active ingredients and / or auxiliary substances, for example those from the groups of anti-settling agents, suspending agents, Anti-floating agents, thixotropic agents and dispersing agents. So certain can enzyme particles according to the invention further auxiliaries from the group of anti-settling agents, Suspending agents, anti - floating agents, thixotropic agents and dispersing agents in Amounts from 0.5 to 8.0% by weight, preferably from 1.0 to 5.0% by weight, and in particular from 1.5 to 3.0% by weight, based in each case on the weight of the enzyme particles.

The region also contains emulsifiers from the group of fatty alcohols, fatty acids, Polyglycerol esters and / or polyoxyalkylene siloxanes in amounts of 1 to 20% by weight, preferably from 2 to 15% by weight, and particularly preferably from 2.5 to 10% by weight, in each case based on the weight of the enzyme particles, is possible according to the invention.  

However, preferred enzyme particles are characterized in that they are in addition to the / the Wrapping material (a) and the components of the liquid enzyme preparations as well as optional Carrier materials contain no other ingredients.

The most commonly used enzymes in detergents and cleaning agents include Lipases, cellulases, amylases and proteases. Beyond that too Hemicellulases, peroxidases and pectinases used in special products. In Detergents for automatic dishwashing are in particular proteases, Amylases and lipases of importance. Usually the enzymes are used in powder products in a granulated and encapsulated form and the Detergent added in this form. In water-based liquid cleaning agents would partially dissolve these granulated and encapsulated enzymes, which is why in generally the use of liquid enzyme concentrates is preferred. Such Liquid enzyme concentrates are either homogeneously based on one basis Propylene glycol / water or heterogeneous as a slurry, or they are in microencapsulated Structure before. The use of liquid enzyme products in solid detergents is not described so far.

Preferred liquid proteases are e.g. B. Savinase® L, Durazym® L, Esperase® L, and Everlase® from Novo Nordisk, Optimase® L, Purafect® L, Purafect® OX L, Properase® L from Genencor International, and BLAP® L from Biozym Ges.m.b.H.

Preferred amylases are Termamyl® L, Duramyl® L, and BAN® from Novo Nordisk, Maxamyl® WL and Purafect® HPAm L from Genencor International.

Preferred lipases are Lipolase® L, Lipolase® ultra L and Lipoprime® L from Novo Nordisk and Lipomax® L from Genencor International.

As slurries or microencapsulated liquid products such. B. Products like those with SL or LCC designated products from Novo Nordisk are used. The above commercially available liquid enzyme preparations contain, for example, 20 to 90% by weight Propylene glycol or mixtures of propylene glycol and water. As part of the Enzyme particles preferred in the present invention are characterized in that they one or more liquid amylase preparations and / or one or more liquid Protease preparations included.  

The enzyme particles according to the invention can be prepared in different ways, the processes for producing the enzyme particles differing slightly depending on whether the enzyme particles contain carrier materials or not. Another object of the present invention is a method for producing particulate enzyme particles, in which a melt dispersion is made

• a) 5 to 99.5% by weight of one or more coating substances with a melting point above 30 ° C,
• b) 0.5 to 60% by weight of one or more dispersed in the coating substance (s) liquid enzyme preparation (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,

molded in the solidification area of the melt or on one or more Applying carrier materials and processing the mixture shaping.

First, a melt dispersion of the enzyme particle ingredients (description see above). This can either be processed directly to shape or on a or several carrier materials are applied, after which the shaping Processing is done.

The shaping processing step for the melt dispersion or the mixture The melt and carrier material are not subject to any procedural restrictions, so that the expert can also choose from the methods familiar to him. At Trials by the applicant have been found to be preferred in which the shaping processing by granulating, compacting, pelleting, extruding or tableting. The granules, compactates, pellets, Prills, extrudates, pearls, scales, flakes, tablets etc. can then be powdered or granular machine dishwashing detergents. The particle size the enzyme particles can be adapted to the particle size of the "base powder". Particle sizes of are preferred in the context of the present invention Enzyme particles between 200 and 2000 microns, preferably between 400 and 1800 microns and in particular between 600 and 1600 microns, with at least 90 wt .-% of each Particles are within the ranges mentioned.  

In the process variant for the production of carrier material-containing enzyme particles First, a melt dispersion is prepared that contains other active ingredients and auxiliary substances can. This is placed on a carrier material and mixed with it Base material processed to give shape. The application of the melt suspension or -emulsion on the carrier material can be in all usual mixing devices be performed. This method variant according to the invention comprises the application of melts from coating substances and liquid enzyme preparations Carrier materials. In principle, the melt and carrier (s) can be used in varying amounts be contained in the resulting enzyme particles. Preferred methods are thereby characterized in that a mixture of 5 to 50 wt .-%, preferably 10 to 45 wt .-%, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of one Melt dispersion and 50 to 95 wt .-%, preferably 55 to 90 wt .-%, particularly preferably 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) is processed to give shape.

In both production processes mentioned for the enzyme particles according to the invention Process variants are preferred in which the coating substance, 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 to 50% by weight of the Makes up melt dispersion.

As already mentioned in the description of the enzyme particles according to the invention, are especially suitable polyethylene glycols as coating substances. Are analog The method according to the invention is preferred in which the melt dispersion is used as the coating substance Polyethylene glycols with molecular weights between 1500 and 36,000, preferably those with Molar masses from 2000 to 6000 and in particular those with molar masses from 3000 to 5000, contains.

Regarding the ingredients used in the method according to the invention and the enzyme particles according to the invention are processed, applies analogously to the above Executed. The melt suspension or emulsion to be produced is preferably sufficient certain criteria, which have also been described above.  

In principle, the enzyme particles according to the invention can be sent directly to the consumer Hand be given so that he also needs the cleaning agent added in order to achieve a higher cleaning performance with heavily soiled dishes achieve. Because of this additional dosing step, the route described is often not desired by the consumer. It is therefore preferred that Enzyme particles according to the invention particulate machine dishwashing detergents to mix.

Another object of the present invention is therefore also a particulate machine dishwashing detergent which contains builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, colorants and fragrances and additionally particulate enzyme particles which

• a) 5 to 99.5% by weight of one or more coating substances with a melting point above 30 ° C,
• b) 0.5 to 60% by weight of one or more dispersed in the coating substance (s) liquid enzyme preparation (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries.
• d) 0 to 90% by weight of one or more carrier materials,

each based on the weight of the enzyme particles.

As already stated for the enzyme particles according to the invention, the composition of the enzyme particles is preferably within a narrow range, so that particulate machine dishwashing detergents are also preferred, in which the particulate enzyme particles consist of

• a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more Envelope (s) with a melting point above 30 ° C
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30 % By weight and in particular 5 to 25% by weight of one or more in the Envelope substance (s) dispersed liquid enzyme preparation (s) as well
• c) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10 % By weight and in particular 0 to 5% by weight of optionally further carrier materials, Auxiliaries and / or active ingredients

consist.

The ingredients of automatic dishwashing detergents are described below. Some of these can also be used as carrier materials in the inventive Enzyme particles may be included.

The most important ingredients in automatic dishwashing detergents are builders. In the cleaning agents according to the invention for machine dishwashing all builders commonly used in detergents and cleaning agents be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and as an important builder in machine dishwashing detergents, also phosphates. The The builders mentioned below are all used as carrier materials for the enzyme particles according to the invention suitable, as already explained above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.  

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO4, is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , 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 being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also 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 can be used according to the invention.

The particulate machine dishwashing detergents according to the invention are preferably characterized in that they contain builders in amounts of 20 to 80 % By weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, each based on the weight of the agent.  

As organic cobuilders in the machine according to the invention Dishwashing detergents, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances will described below.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect Typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have proven particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The amount of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar Derivatives included.

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.  

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder Properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which have a DE of 100 owns. Both maltodexirins with a DE between 3 and 20 can be used and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

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. Such oxidized dextrins and processes for their preparation 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 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine N, N'-disuccinate (EDDS) preferably in the form of its sodium or magnesium salts used. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups. Such cobuilders will described for example in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa- DTPMP sodium salt used. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it can, in particular if the agents also contain bleach, aminoalkanephosphonates are preferred, use in particular DTPMP, or mixtures of the phosphonates mentioned use.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.  

In addition to the builders, there are in particular substances from the groups of surfactants Bleach, bleach activators, corrosion inhibitors and color and Fragrances important ingredients of detergents. Important representatives from the substance classes are described below.

In addition to the builders, there are in particular substances from the groups of surfactants Bleaching agents, bleach activators, enzymes, polymers as well as color and Fragrances important ingredients of detergents. Preferred particulate Machine dishwashing detergents therefore continue to contain one or more substances the groups of bleaching agents, bleach activators, bleach catalysts, surfactants, Corrosion inhibitors, polymers, dyes and fragrances, pH adjusting agents and the enzymes. Important representatives from the substance classes mentioned are described below.

Usually only surfactants are used in automatic dishwashing detergents low-foaming nonionic surfactants are used. Representatives from the groups of By contrast, anionic, cationic or amphoteric surfactants are of less importance. The detergent tablets according to the invention particularly preferably contain machine dishwashing non-ionic surfactants.

In particularly preferred embodiments of the present invention, the detergent tablets according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred eth oxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (III),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually 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 polyhydroxy fatty acid amides also includes compounds of the formula (IV)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[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 can then, for example, according to the teaching of the international application WO-A-95/07331 by implementation with  Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In addition to the pure nonionic surfactants, other substances can of course also be used from the group of ionic surfactants, for example anionic or cationic surfactants the machine dishwashing detergents according to the invention may be included.

Particulate mechanical preferred in the context of the present invention Dishwashing detergents contain surfactant (s), preferably nonionic surfactant (s), in Amounts from 0.5 to 10% by weight, preferably from 0.75 to 7.5% by weight and in particular from 1.0 to 5% by weight, based in each case on the total agent.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides, such as. B. Dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic peroxycapene (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysoxybralic acid, diperoxic acid, diperacid acid, diperoxy acid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleach in the cleaning agents according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches are usually used in machine dishwashing detergents in amounts of 1 up to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, each based on the agent used. In the context of the present invention the proportions mentioned refer to the weight of the base powder, d. H. of Detergent without the addition of the enzyme particles according to the invention.

Bleach activators that support the action of the bleach can also Be part of the base powder. Known bleach activators are compounds that are one or contain more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2- dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Substances which contain O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Are preferred multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran,  n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and those from the German Patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams also preferably used. Combinations of conventional bleach activators can be used. The bleach activators are made in machine Dishwashing agents usually in amounts of 0.1 to 20 wt .-%, preferably 0.25 up to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the aforementioned relate Quantities based on the weight of the base molding.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts are incorporated into the base powder. With these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu Complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight based on the total agent used.

Bleach-enhancing transition metal complexes, especially with 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, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total Means used. But in special cases, more bleach activator can be used become.

Of course, the base powder can also contain enzymes, so that a conventional enzyme release and action is achieved by the Enzyme release and action supported by the enzyme particles of the invention becomes. Such cleaning agents have a "booster enzyme effect". The in Basic powder optionally used enzymes are preferably commercially available solid Enzyme preparations.

Enzymes in the base powders come in particular from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help remove stains such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching become. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis. Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic derived from their genetically modified variants Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones  Amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight. Preferred in the context of the present invention Cleaning agents are characterized in that the base powder protease and / or Contains amylase.

Because the cleaning agents according to the invention can contain the enzyme (s) in two fundamentally different areas, cleaning agents with a very precisely defined enzyme release and action can be provided. The table below gives an overview of possible enzyme distributions in cleaning agents according to the invention:

Dyes and fragrances can be used in the dishwasher detergents according to the invention added both in the base powder and in the enzyme particles according to the invention to improve the aesthetic impression of the resulting products and the In addition to performance, consumers are visually and sensory "typical and to provide a distinctive "product. As perfume oils or fragrances individual fragrance compounds, e.g. B. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl  phenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear Alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, among the Hydrocarbons mainly belong to the terpenes like limonene and pinene.

However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also contain natural fragrance mixtures as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, Linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention , but it can also be advantageous to apply the fragrances to carriers.

In order to improve the aesthetic impression of the agents according to the invention, they can (or parts thereof) can be colored with suitable dyes. Preferred dyes, the selection of which is no problem for the expert has a high degree Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards those with the means too treating substrates such as glass, ceramics or plastic dishes to avoid them stain.

The cleaning agents according to the invention can be used in particular in the base powder Protect the dishes or the machine contain corrosion inhibitors, whereby especially silver protection agents in the area of automatic dishwashing Have meaning. The known substances of the prior art can be used. In general, silver protection agents selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred to  benzotriazole and / or alkylaminotriazole are used. One finds in In addition, detergent formulations frequently contain active chlorine-containing agents Can significantly reduce corroding of the silver surface. In chlorine-free cleaners oxygen and nitrogenous organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives thereof Connection classes. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred the transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

When used in dishwashing detergents, the enzyme particles according to the invention have clear advantages over previous products. Another object of the present invention is therefore the use of particulate enzyme particles

• a) 5 to 99.5% by weight of one or more coating substances with a melting point above 30 ° C,
• b) 0.5 to 60% by weight of one or more dispersed in the coating substance (s) liquid enzyme preparation (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

in particulate detergents for automatic dishwashing.

In particular, the use of in polyethylene glycols with molecular weights from 1500 to 36,000, preferably from 2,000 to 6,000 and in particular from 3,000 to 5,000 dispersed enzymes in detergents for automatic dishwashing is included prefers.

The enzyme particles according to the invention release - as the examples below show, the enzymes release faster and longer-lasting than previously customary cleaning agents. Another object of the present invention is therefore the use of particulate enzyme particles

• a) 5 to 99.5% by weight of one or more coating substances with a melting point above 30 ° C,
• b) 0.5 to 60% by weight of one or more dispersed in the coating substance (s) liquid enzyme preparation (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

for the quick and long-lasting release of enzymes from detergents, which contain these enzyme particles.  

Examples

Spherical particles with a diameter between 500 and 700 µm were produced from melt dispersions of the composition given in the table below:

These enzyme particles were admixed as "boosters" of powdered automatic dishwashing detergents with the following composition:

Here, the protease-containing cleaning agent 1 with the enzyme particles 1 mixed, whereby 24 g of powder were mixed with 1 g of enzyme particles. It became analog Protease-free cleaning agent 2 mixed with the enzyme particles 1.

The cleaning performance of the powders which contained the enzyme particles according to the invention was assessed against the non-additive cleaning agent powders 1 and 2 (comparative examples V1 and V2). Dirty dishes were used in a 55 ° C program with 16 ° d water hardness in the main wash in a Miele G 590 with a universal program, each using 25 g of detergent. The table below shows the cleaning performance of the individual powders on different protease-sensitive soils. It should be noted that the detergent powder 2 is protease-free, while the detergent powder 1 contains protease. The inventive powder E1 (protease-containing cleaning agent 1 with the enzyme particles 1) contains the protease both in the powder and in the enzyme particles, while the powder E2 according to the invention contains the protease only in the enzyme particles. The cleaning performance of the agents on the soiling was carried out visually by experts and graded, with the rating "0" meaning no cleaning on a scale of 0-10 and "10" meaning complete removal of the stains. The results of the cleaning tests are summarized in the table below. For better clarity, a content of protease in the base powder is marked with "B", a content of protease in enzyme particles with "P".

To further clarify the "booster effect" of the enzyme core, the cleaning agent powders V1 and E1 were compared in a 40 ° C program:

The results show that the sole presence of protease in the Enzyme particles according to the invention with certain stains one More dosage of protease in the base powder is on par (comparison E2-V1). Will the Protease used both in powder and in enzyme particles, the Cleaning performance on all soiling, even with low-temperature programs improve significantly.  

Analogous effects can be shown on soils sensitive to amylase. For this purpose, the detergent powder 2 was mixed with the enzyme particles 2 (E3) and the performance against unadditized detergent powder 2 (V3) was compared.

Here, too, it can be seen that the cleaning performance on all stains also Low temperature programs can be significantly improved if the amylase both in Detergent powder is also used in enzyme particles.

Release kinetics

In an experiment for enzyme release, the protease-containing base powder 1 (V4) was compared with a protease-free base powder 2 which contained the analogous amount of protease in the form of the enzyme particle 1 according to the invention of the above composition (85% PEG, 15% protease) ( E4). Both agents were subjected to a main wash in a dishwasher, the enzyme activity being measured as a function of time. The results are shown in the table below:

The table shows that the agent according to the invention already has the maximum activity 6.75 minutes reached, while the comparative example takes 10 minutes. In addition, the enzyme activity in the cleaning liquor remains throughout Main wash at a high level, while in the comparative example it was shortly after the maximum drops drastically.

Claims (20)

1. Containing particulate enzyme particles for automatic dishwashing

• a) 5 to 99.5% by weight of one or more coating substances 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 substance (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

2. Particulate enzyme particles according to claim 1, characterized in that they are as Carrier materials Fabrics from the group of water-soluble washing and Detergent ingredients, preferably the carbonates, hydrogen carbonates, Sulfates, phosphates and the organic oligocarboxylic acids that are solid at room temperature in amounts of 10 to 85% by weight, preferably 20 to 80% by weight and in particular from 30 to 75% by weight, in each case based on the particle weight, contain. 3. Particulate enzyme particles according to claim 1, characterized in that they

• a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more coating substance (s) which has a melting point above 30 ° C.
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight of one or more in the coating substance (s) ( dispersed liquid enzyme preparation (s) and
• c) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight and in particular 0 to 5% by weight optionally of further carrier materials, auxiliaries and / or active ingredients

contain. 4. Particulate enzyme particles according to one of claims 1 to 3, characterized characterized in that the coating substance a) has a melting range of 45 ° C to 75 ° C having. 5. Particulate enzyme particles according to one of claims 1 to 4, characterized characterized in that the coating substance a) at least one substance from the group of Contains polyethylene glycols (PEG) and / or polypropylene glycols (PPG), where Polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with Molar masses from 2000 to 6000 are particularly preferred and those with molar masses of 3000 to 5000 are particularly preferred. 6. Particulate enzyme particles according to one of claims 1 to 5, characterized characterized in that they contain one or more liquid amylase preparations and / or contain one or more liquid protease preparations. 7. Particulate enzyme particles according to one of claims 1 to 6, characterized characterized in that they contain other auxiliary substances from the group of anti-settling agents, Suspension medium. Anti - floating agents, thixotropic agents and dispersing agents in Amounts from 0.5 to 8.0% by weight, preferably from 1.0 to 5.0% by weight, and in particular from 1.5 to 3.0% by weight, in each case based on the weight of the Enzyme particles. 8. Particulate enzyme particles according to one of claims 1 to 7, characterized characterized in that they additionally contain emulsifiers from the group of fatty alcohols, Fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in amounts of 1 to 20 % By weight, preferably from 2 to 15% by weight, and particularly preferably from 2.5 to 10 % By weight, based in each case on the weight of the enzyme particles. 9. A process for the production of particulate enzyme particles, characterized in that a melt dispersion

• a) 5 to 99.5% by weight of one or more coating substances 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 substance (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,

processed in the solidification area of the melt or applied to one or more carrier materials and the mixture processed in a shape. 10. The method according to claim 9, characterized in that the shaping Processing by granulating, compacting, pelleting, extruding or Tableting takes place. 11. The method according to any one of claims 9 or 10, characterized in that the Envelope, 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 accounts for up to 50% by weight of the melt dispersion. 12. The method according to any one of claims 9 to 11, characterized in that a Mixture of 5 to 50 wt .-%, preferably 10 to 45 wt .-%, particularly preferred 15 to 40% by weight and in particular 20 to 35% by weight of a melt dispersion and 50 up to 95% by weight, preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight % and in particular 65 to 80 wt .-% carrier material (ien) processed shaping becomes. 13. The method according to any one of claims 9 to 12, characterized in that the Enamel dispersion as a coating substance polyethylene glycols with molecular weights between 1500 and 36,000, preferably those with molecular weights from 2000 to 6000 and in particular contains those with molecular weights from 3000 to 5000. 14. Particulate dishwasher detergent, containing builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, characterized in that it contains particulate enzyme particles which

• a) 5 to 99.5% by weight of one or more coating substances 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 substance (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

each based on the weight of the enzyme particles. 15. Particulate dishwasher detergent according to claim 14, characterized in that the particulate enzyme particles

• a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more coating substance (s) which has a melting point above 30 ° C.
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight of one or more in the coating substance (s) ( dispersed liquid enzyme preparation (s) and
• c) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight and in particular 0 to 5% by weight optionally of further carrier materials, auxiliaries and / or active ingredients

consist. 16. Particulate dishwasher detergent according to one of claims 14 or 15, characterized in that there are builders in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the agent. 17. Particulate dishwasher detergent according to one of claims 14 to 16, characterized in that it also contains one or more substances from the Groups of bleaching agents, bleach activators, bleaching catalysts, surfactants, Corrosion inhibitors, polymers, dyes and fragrances, pH adjusting agents and the enzymes contains. 18. Use of particulate enzyme particles

• a) 5 to 99.5% by weight of one or more coating substances 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 substance (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

in particulate detergents for automatic dishwashing. 19. Use of in polyethylene glycols with molecular weights from 1500 to 36,000, preferably from 2000 to 6000 and in particular from 3000 to 5000 dispersed Enzymes in detergents for automatic dishwashing. 20. Use of particulate enzyme particles

• a) 5 to 99.5% by weight of one or more coating substances 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 substance (s) and
• c) 0 to 5% by weight of further active ingredients and auxiliaries,
• d) 0 to 90% by weight of one or more carrier materials,

for the quick and long-lasting release of enzymes from detergents containing these enzyme particles.