DE19914363A1 - Dishwasher detergent, which includes a particulate rinsing agent comprising coating substances such as paraffin wax, removing the need for separate addition of a rinsing agent - Google Patents

Abstract

A particulate rinsing agent, which comprises one or more coating substances with a melting point above 30 deg C, one or more active agents, and other auxiliaries, is included in a particulate dishwasher detergent which contains builders and optionally other components. Particulate dishwasher detergent, which contains builders and optionally other components (selected from surfactants, enzymes, bleaches, bleach activators, corrosion inhibitors, polymers, dyes and perfumes), comprises a particulate rinsing agent comprising: (a) 20-80 wt.% of one or more coating substances with a melting point above 30 deg C; (b) 20-80 wt.% of one or more active agents; and (c) 0-20 wt.% of other auxiliaries.

Description

The present invention is in the field of automatic dishwashing detergents household dishwashers. It particularly concerns particulate ma rapid dishwashing detergent (MGSM) containing rinse aid particles.

The mechanical cleaning of dishes in household dishwashers includes übli a pre-rinse, a main rinse and a rinse cycle, which are from Zwi rinse cycles are interrupted. Most machines have the pre-rinse cycle can be switched on for heavily soiled dishes, but is only used in exceptional cases by the Ver user selected, so that in most machines a main wash, an intermediate rinse clean water and a rinse cycle. The temperature of the The main wash cycle varies depending on the machine type and program level selection 40 and 65 ° C. In the rinse cycle, a dosing tank in the machine turns into rinse aid agents added, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely used in the prior art wrote. Your job is primarily to keep limescale and deposits on the ge to prevent cleaned dishes. In addition to water and low-foaming non-ionic surfactants these rinse aids often also contain hydrotropes, pH adjusting agents such as citric acid or be lag-inhibiting polymers.

The storage tank in the dishwasher must be clear at regular intervals dishwasher can be filled, with one filling for 10 to 50 rinse cycles depending on the machine type  sufficient. If the refilling of the tank is forgotten, glasses in particular unsightly due to limescale and deposits. There are therefore some in the prior art Proposed solutions, a rinse aid in the detergent for machine wash to integrate dishwashing. These proposed solutions are based on the offer form of the kom compact molded body bound.

For example, the European patent application EP-A-0 851 024 (Unilever) describes two-layered Detergent tablets, the first layer of peroxy bleach, builder and enzyme contains while the second layer of acidifying agent and a continuous medium with a melting point between 55 ° and 70 ° C and coating inhibitors. By the high-melting continuous medium should the acid (s) and deposit inhibitor (s) are released with a delay and produce a rinse aid effect. Powdered machi Normal dishwashing detergents or surfactant-containing rinse aid systems are not described in this document mentioned.

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a Ver drive to the production of multi-phase detergent tablets, in which a particulate premix is pressed to form bodies which have a trough sen, which later with a separately prepared melt suspension or emulsion from a Envelope and one or more active dispersed or suspended in it substances) is filled. The teaching of this writing is also based on the "tablet" bound. Powdered cleaners containing a "second phase", which by kon controlled release of ingredients achieve certain effects, are not open beard.

The older German patent application DE 198 17 964.2 (Henkel KGaA) describes one Process for the production of coated solid particles, in which the substances to be coated in the melt of a largely water-insoluble substance that is solid at room temperature (Envelope), which has a plastic solidification area, which are dispersed Cooled dispersion and, if necessary, further processed, the to be wrapped the substances are liquid at the softening temperature of the coating agent and the  Melt one or more emulsifiers from the group of fatty alcohols, fatty acids, buttocks lyglycerol esters and the polyoxyalkylene siloxanes are added. The use of the This agent in automatic dishwashing agents is also disclosed there.

The present invention was based on the object, the advantages of controlled clearance setting of ingredients, especially a rinse aid, also for powdered rice make use of cleaning agents. Here, complex procedural steps such as Coating or multiple coating can be dispensed with. Rather, an offer should bot form are provided, both separately and to be dosed by the consumer Rinse aid in solid form as well as an additive component to powdered machine len dishwashing detergents can be used. The solutions known from the prior art Suggestions should be expanded to include a complete detergent with a rinse aid effect that is not bound to the "tablet" offer form.

It has now been found that melt dispersions or emulsions are made from enveloping substance zen with melting points above 30 ° C, active ingredients and optional additional content Process substances such as emulsifiers, dyes and fragrances, etc. to give a shape Allow to machine that dishwashing detergent with rinse aid results.

The present invention relates to a particulate machine dishwashing detergent containing builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, which additionally contains a particulate rinse aid

• a) 20 to 80 wt .-% of one or more coating substances with a melt point above 30 ° C,
• b) 20 to 80 wt .-% of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

each based on the weight of the particulate rinse aid.  

The particulate rinse aid particles can be used in varying amounts the, depending on what agents they are mixed in and how strong the desired Effect should occur. Preferred automatic dishwashing detergents contain the particles shaped rinse aid in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight % and in particular from 5 to 15 wt .-%, each based on the total average.

The coating substances that are used in the rinse aid particles are - different requirements, on the one hand the melting or Solidification behavior, but also the material properties of the coating in the solidified state, d. H. in the rinse aid particle. Because the rinse aid particles Transport or storage should be permanently protected against environmental influences the coating substance has a high stability compared to, for example, packaging or Shock loads occurring during transport. The coating substance should either have at least partially elastic or at least plastic properties in order to to react to an occurring shock load through elastic or plastic deformation and not to break. The coating substance should have a melting range (solidification range) have such a temperature range in which the active substances to be coated are none exposed to excessive thermal stress. On the other hand, the melting range however, be sufficiently high to have another at least slightly elevated temperature to provide effective protection for the enclosed active substances. According to the invention the coating substances have a melting point above 30 ° C.

It has proven to be advantageous if the coating substance does not have a sharply defined one Melting point shows how it usually occurs with pure, crystalline substances, but may have a melting range spanning several degrees Celsius.

The coating substance preferably has a melting range which is between approximately 45 ° C. and is about 75 ° C. In the present case, this means that the melting range within the specified temperature interval occurs and does not denote the width of the Melting range. The width of the melting range is preferably at least 1 ° C. preferably about 2 ° to about 3 ° C.  

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances, which usually melt above 40 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Connections can also be used as covering materials from other classes of substances which meet the requirements mentioned with regard to the Meet softening point. Suitable synthetic compounds have been found for example higher esters of phthalic acid, especially dicyclohexyl phthalate, the is commercially available under the name Unimoll® 66 (Bayer AG). Suitable are also synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example Dimyristyl Tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semi-synthetic esters from lower are also Alcohols with fatty acids from native sources can be used. It falls into this class of substances for example the Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Also  Shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH) is according to the invention can be used as a covering material.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols, for example, come in the form of wax esters of higher molecular weight Fatty acids (wax acids) as the main component of many natural waxes. examples for Wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or Melissyl alcohol. The coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, for example lanolin, means that, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least in part can be used as part of the envelope within the scope of the present invention Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble ones or only slightly water-soluble polyalkylene glycol compounds.

Preferably contains the rinse aid particles used in the invention Shell substance in the majority of paraffin wax. That is, at least 50% by weight of the total contained substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total coating substance) of approximately are particularly suitable 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher proportions of for example, more than 90% by weight are particularly preferred. In a special one Embodiment of the invention consists of the total amount of the coating substance used made exclusively from paraffin wax.

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline Detergent environment no hydrolysis of the waxes takes place (as for example is to be expected in the wax esters), since paraffin wax has no hydrolyzable groups contains.  

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can Undershoot of this melting temperature in the detergent fleet is not desirable Wax residues on the surfaces to be cleaned or on the goods to be cleaned leave. Such wax residues usually lead to an unsightly appearance cleaned surface and should therefore be avoided.

Preferred machine dishwashing detergents are characterized in that the particles shaped rinse aid as an enveloping substance one or more substances with a melting range from 40 ° C to 75 ° C in amounts of 25 to 70% by weight, preferably from 30 to 60% by weight % and in particular from 40 to 50 wt .-%, each based on the weight of the particle shaped rinse aid.

Particularly preferred coating substances are paraffin waxes, so that particularly preferred machine dishwashing detergents are characterized in that the particulate At least one paraffin wax with a melting range of Contains 50 ° C to 60 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 ° to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components in a wax at room temperature are present, the more useful it is within the scope of the present invention. With The increasing proportion of solid wax components increases the resilience of the Rinse aid particles against bumps or friction on other surfaces, resulting in a longer-lasting protection of particles leads to active substances. High levels of oils or liquids Wax components can weaken the particles, causing pores be opened and the active substances to the environmental influences mentioned at the beginning get abandoned.  

In addition to paraffin as the main constituent, the coating substance can also have one or more of the above mentioned waxes or wax-like substances. Basically, that should be the Envelope forming mixture should be such that the rinse aid particles at least are largely insoluble in water. The solubility in water should be at a temperature of about 30 ° C do not exceed about 10 mg / l and are preferably below 5 mg / l.

In any case, however, the coating should have the lowest possible water solubility, also in Water with elevated temperature, have a temperature-independent release of the Avoid active substances as much as possible.

The principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be particularly advantageous use if in the main wash cycle at a lower temperature (e.g. 55 ° C) is rinsed so that the active substance from the rinse aid particles only in the rinse aid higher temperatures (approx. 70 ° C) is released.

Active substance (s)

The active ingredients to be incorporated into the rinse aid particles can be processed temperature (i.e. at the temperature at which the particles are produced) both in both solid and liquid.

The active substances contained in the rinse aid particles fulfill certain tasks. Through the separation of certain substances or through the accelerated or Delayed release of additional substances can reduce cleaning performance be improved. Active substances that are preferably incorporated into the rinse aid particles are therefore ingredients of detergents and cleaning agents that are decisive on Washing or cleaning process are involved.

In preferred automatic dishwashing detergents, the particulate rinse aid contains as One or more substances from the groups of surfactants, enzymes, bleaches, Bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances  in amounts of 25 to 70% by weight, preferably 30 to 60% by weight and in particular from 40 to 50% by weight, based in each case on the particle weight.

By incorporating surfactants into the melted shell material, one can Prepare melt suspension or emulsion, which in the finished rinse aid particle or in the ready-made cleaning agent; the rinse aid particle according to the invention ent holds, at a predetermined time, additional detergent-active substance poses. For example, cleaning agents according to the invention for the machine dishwashing which produce the additional surfactant from the rinse aid Only release particles at normal household dishwashers only reach in the rinse aid. In this way there is additional surfactant in the rinse aid available, which accelerates the drainage of the water and so stains on the rinse well prevented effectively. With a suitable amount of solidified melt suspension or -emulsion in the rinse aid particles can thus be added to the use customary today rinse aid can be dispensed with.

In preferred automatic dishwashing detergents, therefore, contains the particulate clear Dishwasher as active substance, nonionic surfactants, preferably alkoxylated alcohols. This Substances are described in detail below.

Another class of active substances that are particularly beneficial in rinse aid Allowing particles to be incorporated are bleaching agents. Here, cleaning agents can be used are set, which releases the bleach only when certain temperatures are reached zen, for example ready-made detergents, the enzyma in the pre-rinse cycle Clean the table and only release the bleach in the main wash cycle. Also are Reini agents for machine dishwashing so that in the rinse aid additional bleach are released and so difficult stains, such as tea remove stains more effectively.

In preferred automatic dishwashing detergents, the particulate rinse aid contains as Active substance bleach from the group of oxygen or halogen bleach,  especially chlorine bleach. These substances are also explained below Lich described.

Another class of compounds that are preferred as active substances in the inventions Bleach activators can be used in accordance with the invention. The important representatives from this group of substances are also described below. in the Machine dishwashing detergents preferred in the context of the present invention are present characterized in that the particulate rinse aid as an active substance bleaching acti vators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, especially N- Nonanoyl succinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium- Acetonitrile methyl sulfate (MMA) contains.

Fragrances can also be used as active substances in the clears used according to the invention Work in the dishwasher particles. All fragrances described in detail below can be used as an active substance. When fragrances are incorporated into the rinse aid particles result in cleaning agents according to the invention which cover the entire or release some of the perfume with a time delay. In this way, fiction are can be produced according to, for example, cleaning agents for automatic dishwashing, at those of the consumer even after the dishes have been cleaned when the machine is opened experienced the perfume note. In this way, the unwanted "alkaline smell" of many machine dishwashing detergent, be eliminated.

Corrosion inhibitors can also be incorporated into the rinse aid particles as an active ingredient, the substances familiar to the person skilled in the art can be used. As Base inhibitor has, for example, a combination of enzyme (e.g. lipase) and Lime soap dispersant proven.  

Auxiliaries

At exceptionally low temperatures, for example at temperatures below 0 ° C, the rinse aid particle can break under impact or friction. To ensure stability Such coating temperatures can possibly improve the coating substances Additives are added. Suitable additives must be completely with the Allow melted wax to mix, the melting range of the coating substances Do not change significantly, the elasticity of the sheathing at low temperatures improve the permeability of the casing to water or moisture generally do not increase and must not increase the viscosity of the melt of the shell material increase to the extent that processing becomes difficult or even impossible. Suitable Additives that reduce the brittleness of an envelope consisting essentially of paraffin Lowering at low temperatures are, for example, EVA copolymers, hydrogenated resin Acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

Another useful additive when using paraffin as a coating is the addition of a small amount of a surfactant, for example a C _12-18 fatty alcohol sulfate. This addition results in a better wetting of the material to be embedded through the covering. It is advantageous to add the additive in an amount of about <5% by weight, preferably <about 2% by weight, based on the coating substance. The addition of an additive can in many cases lead to the fact that active substances can also be encased which, without the addition of an additive, generally form a tough, plastic body made of paraffin and partially dissolved active substance after the encapsulation material has melted.

It can also be advantageous to add further additives to the coating substance in order to to prevent early withdrawal of the active substances. This is particularly so advisable in the preparation of the rinse aid particles according to the invention without carriers. The anti-settling agents that can be used for this purpose, which are also known as floating agents, are from the state of the art, for example from paint and printing ink production, known. To sediments during the transition from plastic solidification area to solid tion phenomena and concentration differences of the substances to be coated avoid, there are, for example, surface-active substances, dis  pergified waxes, montmorillonite, organically modified bentonite, (hydrogenated) castor oil oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, metal stearates, cal cium soaps or hydrophobicized silicas. Other substances that have the effects mentioned cause come from the groups of anti-floating agents and thixotropic agents and can be used chemically as silicone oils (dimethylpolysiloxanes, methylphenylpolysiloxanes, Polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyami ne, salts of long-chain polyamines and polycarboxylic acids, amine / amide-functional Polyester or amine / amide-functional polyacrylates are referred to.

Additives from the classes of substances mentioned are commercially extremely diverse available. Commercial products that are advantageous in the context of the method according to the invention Aerosil® 200 (pyrogenic pebbles acid, Degussa), Bentone® SD-1, SD-2, 34, 52 and 57 (Bentonite, Rheox), Bentone® SD-3, 27 and 38 (hectorite, Rheox), Tixogel® EZ 100 or VP-A (organically modified Smec tit, Südchemie), Tixogel® VG, VP and VZ (montmorillonite loaded with QAV, Südche mie), Disperbyk® 161 (block copolymer, Byk-Chemie), Borchigen® ND (sulfo-free er ion exchanger, Borchers), Ser-Ad® FA 601 (servo), Solsperse® (aromatic Ethoxylate, ICI), Surfynol® types (Air Products), Tamol® and Triton® types (Rohm), Texaphor®963, 3241 and 3250 (polymers, Henkel), Rilanit® types (Hen kel), Thixcin® E and R (castor oil derivatives, Rheox), Thixatrol® ST and GST (castor oil Derivatives, Rheox), Thixatrol® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol® 289 (polyester polymer, Rheox) and the various M-P-A® Types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The aids mentioned can be in the rinse aid particles depending on the wrapping material and active substance can be used in varying amounts. Usual concentration of use tions for the aforementioned anti-settling, anti-floating, thioxotropic and Dispersants are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0 wt .-%, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the total amount of coating substance and active substances.  

Machine dishwashing detergents preferred in the context of the present invention are characterized in that the particulate rinse aid from the auxiliary Group of anti-settling, suspended, anti-floating, thixotropic and Dispersing aids in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5 Wt .-%, and particularly preferably between 1.5 and 5 wt .-%, each based on the Weight of particulate rinse aid.

Especially in the production of melt suspensions or emulsions that are active Containing substances that are liquid at the processing temperature, the use is speci eller emulsifiers advantageous. It has been shown that in particular emulsifiers from the Group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are extremely suitable.

Under fatty alcohols the native fats or oils are converted to the corresponding ones Understand fatty acids (see below) available alcohols with 6 to 22 carbon atoms. These alcohols can vary depending on the origin of the fat or oil from which they are obtained are substituted or unsaturated in places in the alkyl chain.

The emulsifiers used in the rinse aid particles according to the invention are therefore preferably C _6-22 fatty alcohols, preferably C _8-22 fatty alcohols and in particular C _12-18 fatty alcohols, with particular preference given to the C _16-18 fatty alcohols.

All of vegetable or animal oils and fats can also be used as emulsifiers obtained fatty acids are used. The fatty acids can be independent of theirs Physical state saturated or mono- to polyunsaturated. Even with the unsown saturated fatty acids are the solid at room temperature compared to the liquid or pasty preferred. Of course, not only "pure" fatty acids can be used but also the technical fat obtained from the splitting of fats and oils acid mixtures, these mixtures again clearly ahead from an economic point of view are moving.  

For example, emulsifiers can be used in the context of the present invention use individual species or mixtures of the following acids: caprylic acid, pelargonic acid, approx pric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, Arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, 10- Undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, Linolaidic acid, α- and β-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, the fatty acids with an odd number of carbon atoms are also used bar, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, no nadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

C _6-22 fatty acids, preferably C _8-22 fatty acids and in particular C _12-18 fatty acids, with particular preference for C _16-18 fatty acids, are used as emulsifier (s) in preferred kiar rinsing agent particles.

Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula I.

in which R ¹ in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.

These polyglycerol esters are known in particular with the degrees of polymerization n 2, 3, 4, 6 and 10 and are commercially available. As materials of the type mentioned can also be found in cosmetic formulations widespread, some of these substances are classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997). This standard cosmetic work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY- GLYCERYL-10-DECAOLETELARY POLYGLYTE GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY- GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLYATELY POLYGLY DISTEARATE, POLYGLYCERYL-6 DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10- HEPTAOLEATE, POLY-GYLCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL- 10-HEPTASTEARATE, POLYGLYXERYLYARTE-6 4-ISOSTEARATE, POLY-GLYCERYL-6- ISOSTEARATE, POLY-GLYCERYL-10-LAURATE, POLY- LYCERYLMETHACRYLATE, POLYGLYCERYL-10-MYRISTATE, POLYGLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE 6-OLEATE, POLYGLYCERYL-8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, P OLYGLYCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL-10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI- IOSOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYARARATE-POLYGLYCARATE POLYGLYCERYL-8-STEARATE, POLYGLYCERYL-10-STEARATE, POLY- GLYCERYL-2-TETRAISOSTEARATE, POLYGLYCERYL-10-TETRAOLEATE, POLYGLYCERYL-2-TETRASTEARATE, POLYGLYCERYL-2-TRIISOLYTE-TRYISOLATE The commercially available products from different manufacturers, which are classified under the abovementioned keywords in the work mentioned, can advantageously be used as emulsifiers in process step b) according to the invention.

Another group of emulsifiers which can be used in the rinse aid particles according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula II

in which each radical R ¹ independently of one another for -CH ₃ or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ² for -H or -CH ₃ , x for a number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be attached to the free OH groups of the Polyoxyethylene or polyoxypropylene side chains are etherified or esterified. The Unetherified and unesterified polymer from dimethylsiloxane with polyoxyethylene and / or In the INCI nomenclature, polyoxypropylene is called DIMETHICONE COPOLYOL designated and is under the trade names Abil® B (Goldschmidt), Alkasil® (Rhône- Poulenc), Silwet® (Union Carbide) or Belsil® DMC 6031 commercially available.

The DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHERS (e.g. KF352A, Shin Etsu) are also considered within the scope of the present invention Emulsifiers can be used.

The same applies to the emulsifiers as to the wrapping materials and enveloping substances that they are used over a wide range can. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight,  preferably 2 to 20 wt .-% and in particular 5 to 10 wt .-% of the weight of the sum from wrapping materials and active substances.

Machine dishwashing detergents preferred in the context of the present invention are characterized in that the particulate rinse aid additionally emulsifiers the group of fatty alcohols, fatty acids, polyglycerol esters and / or polyoxyalkylene silox ane in amounts of 0.1 to 5% by weight, preferably 0.2 to 3.5% by weight, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 to 1.25% by weight, in each case be referred to the weight of the particulate rinse aid.

The particulate rinse aid used according to the invention can be different create a way. In particular, this can refer to the explanations in the older one be referred to patent claims DE 198 17 964.2. The melt suspension or Emulsion is particularly preferred in this case by pastilling or prilling into the particles transferred shape.

The ingredients of the automatic dishwashing detergents according to the invention are as follows described below. Some of these can also be used as active substances in the rinse aid parties 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 can be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - also the phosphates. 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-0164 5144. 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 the 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 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, compaction / 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 in such a way that the products have microcrystalline ranges 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 the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

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 (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta S. pA 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 we 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 buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.

Alkali metal phosphates is the general term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, in which one can differentiate 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 lime deposits on machine parts or lime incrustations in fabrics 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 that lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P2O ₇ ) at 200 ° C, and 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 arises 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 PO ₄ , 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 water-free 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 and} has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when he heats of 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 dehydrating 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 of the 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 distinguish 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:
Melting or annealing 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 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of crystalline water; 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 cattle 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% strength 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 tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

If the detergents according to the invention contain phosphates, these become nasty Usually used in amounts of 50 to 85 wt .-%. Phosphate-free agents contain Lichlich combinations of builders made of zeolite and polycarboxylate and / or car bonate, hydrogen carbonate, citrate and polymeric polycarboxylates. The polycarboxylates, often referred to as cobuilders, are described below.

As organic cobuilders in the dishwasher according to the invention agents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, As Paraginic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. These classes of substances are described below.

Usable organic builders are, for example, those in the form of their sodium salt ze usable polycarboxylic acids, such polycarboxylic acids among polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve  thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, 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.

In the context 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), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. 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, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 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 a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 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 content of (co) polymeric polycarboxylates in the agent is before 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 ten.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

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. Polyas are particularly preferred paraginic acids or their salts and derivatives, of which in the German patent application dung DE-A-195 40 086 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained 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 a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe 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 30,000 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 and 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 are known. 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.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi  contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from 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). Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

In addition to the builders, there are in particular substances from the groups of surfactants Bleach, bleach activators, enzymes, polymers, as well as color and fragrance important ingredients of detergents. Important representatives from the above Substance classes are described below.

Usually only surfactants are used in automatic dishwashing detergents low-foaming nonionic surfactants are used. Representatives from the groups of In contrast, anionic, cationic or amphoteric surfactants have a lower level Importance. The machine tools according to the invention contain with particular preference Dishwashing detergent non-ionic surfactants, it being again preferred that a part,  preferably a large part of the total surfactant contained in the cleaning agents contains the rinse aid particles. This is particularly beneficial because this way Particulate dishwashing detergents can be provided in the main wash Develop cleaning performance and the surfactant from the rinse aid particles only in the Release rinse aid. The presence of surfactants in the rinse aid of a machine Dishwashing has a positive effect on the gloss and the reduction of Limescale deposits.

In particularly preferred embodiments of the present invention, the cleaning agent according to the invention contains nonionic surfactants, in particular nonionic ten side 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 has a methyl or linear branching in the 2-position may be 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 ethoxylated 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 mean values, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates 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, carbon 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 preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa Tent application JP 581217598 are described or which preferably according to the in ternational patent application WO-A-90/13533 who produced the.

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 alka nolamides may be suitable. The amount of these nonionic surfactants is before 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 the RCO stands for an aliphatic acyl radical having 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 the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being 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 international application WO-A-95/07331 by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy 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.  

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. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as per benzoates, 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-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, s-phthalimidthanoic acid poperoxycaproic acid [ ], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxyacid-1,4-diperoxybutylthylacidoxydiperoxyacid, -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 mentioned can also be used to achieve "post-bleaching" in rinse aid fully or partially via the rinse aid particles in the machine according to the invention len dishwashing detergent.  

Bleach activators that support the action of the bleach have already been added mentioned above as a possible ingredient of the rinse aid particles. Known bleach activators are compounds that contain one or more N- or O-acyl groups, such as Substan zen from the class of anhydrides, esters, imides and acylated imidazoles or Oximes. Examples are tetraacetylethylene diamine TAED, tetraacetyl methylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1.5- Diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated tria Zinderivate, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acy gelled Glycolurile, in particular tetraacetylglycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol as their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acety gelled, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and Acyl lactams are also preferred. Combinations of conventional ones Bleach activators can be used.  

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

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 to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, bezo on the entire medium.

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 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and be 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 the.

Enzymes in particular come from the cleaning agents according to the invention from the classes of hydrolases such as proteases, esterases, lipases or lipolytic acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases help to remove stains such as protein,  greasy or starchy stains. Oxidoreductases can also be used for bleaching be used. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and en derived from their genetically modified variants active enzymatic agents. Proteases of the subtilisin type and in particular are preferred their proleases, which are obtained from Bacillus lentus, are used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or li poly-acting enzymes or from protease, amylase and. Lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes, in particular special however protease and / or lipase-containing mixtures or mixtures with lipo enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also have peroxidases or oxidases proved to be suitable in some cases. Suitable amylases include in particular special 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.

Dyes and fragrances can be used in the dishwasher detergents according to the invention can be added to improve the aesthetic impression of the resulting products and to the consumer, in addition to the performance, a visually and sensory "typical and unmatched interchangeable "product. As perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Smell Substances of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p tert-Butylcyclohexylacetate, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylace tat, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl lether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronel  lal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeo nal, to the ketones z. B. the Jonone, α-isomethylionone and methylcedryl ketone to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and ter pineol, the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such parflime oils can also be used naturally che fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention be, but it can also be advantageous to apply the fragrances to carriers that the Increase the adhesion of the perfume to the laundry and by a slower fragrance release the long-lasting fragrance of the textiles. As such have backing materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes can also be coated with other auxiliaries. Also an inconsistency Ration of the fragrances in the rinse aid particles is possible and leads to a fragrance impression when opening the machine (see above).

In order to improve the aesthetic impression of the agents produced according to the invention, it (or parts of it) can be colored with suitable dyes. Preferred Dye, the selection of which is not difficult for the person skilled in the art, has one high storage stability and insensitivity to the other ingredients of Mit tel and against light and no pronounced substantivity towards those with the means substrates to be treated, such as glass, ceramics or plastic dishes, to avoid them stain.

The cleaning agents according to the invention can protect the items to be washed or the Ma schine corrosion inhibitors contain, especially silver protection in the area of  automatic dishwashing have a special meaning. The be knew substances of the prior art. In general, silver protection in particular medium selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, Aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes be set. Benzotriazole and / or alkylami are particularly preferably to be used notriazole. In addition, active chlorine is often found in cleaner formulations Means that can significantly reduce the corroding of the silver surface. In chlorine free Cleaners are especially oxygen and nitrogenous organic redox-active Compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hy droxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of this verb classes. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred here the transition metal salts selected from the group consisting of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware.

The rinse aid particles in the automatic dishwashing detergents according to the invention are designed in such a way that it can be found in the main wash cycle (and also in optional pre-rinse cycles) or only to a minor extent. Hereby it is achieved that the active substances are only released in the rinse aid and here take effect. In addition to this chemical packaging, depending on the type Dishwashers require a physical assembly, so that the clear dishwasher particles are not pumped out when changing water in the machine and thus the rinse aid is no longer available. Household dishwashing Machines contain in front of the drain pump, which contains the water or the cleaning solution pumps out of the machine after the individual cleaning cycles To prevent the pump from becoming blocked by dirt residues. Becomes strong from the consumer soiled dishes, this strainer must be cleaned regularly, which is easily possible due to the easy accessibility and removability.  

The rinse aid particles in the cleaning agents according to the invention are now relevant their size and shape preferably designed so that they use the sieve of the dishes dishwasher even after the cleaning cycle, d. H. after exercise due to movement Machine and the cleaning solution, do not happen. This ensures that there are rinse aid particles in the dishwasher in the rinse cycle, which release the active substance (s) under the influence of the warmer water and the ge desired rinse aid. Preferred in the context of the present invention automatic dishwashing detergents are characterized in that the particulate Rinse aid particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm.

In the dishwashing detergents according to the invention, the rinse aid particles can be mixed with the above sizes mentioned from the matrix of the other particulate ingredients protrude, but the other particles can also have sizes that mentioned Range, so that a total of a detergent is formulated, which consists of large Detergent and rinse aid particles. Especially when the fiction moderate rinse aid particles, for example a red, blue, green or have yellow color, it is for the appearance of the product, i. H. of the total detergent is an advantage if the rinse aid particles are visibly larger than that Matrix of the particles of the other ingredients of the cleaning agent. Here are invented machine dishwashing detergent according to the invention preferred, which (without taking into account the Rinse aid particles) particle sizes between 200 and 3000 microns, preferably between Have 300 and 2500 microns and in particular between 400 and 2000 microns.

The visual appeal of such compositions can be in addition to the color of the rinse aid particles also by contrasting coloring of the powder matrix or by the shape of the Rinse aid particles are increased. Since the manufacture of rinse aid particles relies on tech nically uncomplicated procedures can be used, it is easily possible to offer them in various forms. In addition to the particle shape, which approx hernd spherical shape are, for example, cylindrical or cube-shaped particles can be manufactured and used. Other geometric shapes can also be realized. Spec  All product designs can, for example, have star-shaped rinse aid particles contain. Also disks or shapes that form the base of plants and carcasses for example show tree, flower, blossom, sheep, fish etc., can be easily produced. Interesting visual incentives can also be created in this way by: which produces rinse aid particles in the form of a stylized glass to achieve the rinse aid effect also to emphasize optically in the product. There are no limits to your imagination puts.

If the cleaning agents according to the invention are formulated as a powder mixture, it can - especially in the case of very different sizes of rinse aid particles and detergent agent matrix - on the one hand partial separation when the package is shaken occur, on the other hand, the dosage in two successive cleaning cycles be different because the consumer does not always necessarily have the same amount of cleaning medium and rinse aid particles dosed. Should be desired, technically always the same To use the amount per cleaning cycle, this can be done using the Ver Pack of the agents according to the invention in bags made of water-soluble film who realized the. Also particulate machine dishwashing detergents in which a dosing unit is in a bag made of water-soluble film is welded in, are the subject of this invention.

As a result, the consumer has only one bag, for example a cleaning contains medium powder and several optically prominent rinse aid particles in the dosage to put in his dishwasher. This embodiment of the present Invention is therefore a visually appealing alternative to conventional cleaning agents tablet tablets.

The cleaning agents according to the invention can be produced in a manner known per se. A method for producing powdered machine dishwashing detergent with rinse aid effect, in which a known powdered machine dishwashing agent with rinse aid particles.

• a) 20 to 80 wt .-% of one or more coating substances with a melting point above 30 ° C,
• b) 20 to 80 wt .-% of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

is based in each case on the weight of the particulate rinse aid therefore another object of the present invention.

The desired retention of the rinse aid particles in the Ma The machine can also be used for water changes in addition to the above-mentioned enlargement Realize rinse aid particles by reducing the holes in the sieve insert. In this way you can formulate automatic dishwashing detergents that are uniform have average particle size which is smaller than, for example, 4 to 12 mm. For this purpose, the product according to the invention, in which the rinse aid particles are also clogged have larger particle sizes, a sieve insert is added, which be in the machine sensitive use replaced or covering. Another subject of the present inven Therefore, manure is a kit-of-parts that contains a powdered machine according to the invention Dishwashing detergent and a sieve insert for household dishwashers.

As already mentioned, the combination of agent and sieve according to the invention allows set the formulation of funds in which the rinse aid particles are less have sizes. Kits-of-parts according to the invention, in which the particle sizes of the automatic dishwashing detergent (taking into account the rinse aid particles) in the Be range from 400 to 2500 µm, preferably from 500 to 1600 µm and in particular from 600 up to 1200 µm are preferred.

In order to prevent clogging of the enclosed sieve insert due to dirt residues the mesh size or hole size should not be chosen too small. Here are fictional according kits-of-parts preferred, in which the mesh size or hole size of the sieve rate is 1 to 4 mm and the rinse aid particles are larger than this mesh size or hole size of the sieve insert.  

The kit of parts according to the invention is not based on the specific shape of the sieve insert limited, in which this replaces or covers the insert in the machine. According to the invention, it is also possible and preferred for the kit of parts to have a sieve insert enclose, which has the shape of a basket that in a known manner in the Ge dishwasher - for example on the cutlery basket - can be hung. On in this way a sieve insert designed in this way replaces the dosing chamber, d. H. the Consumers meter the machine dishwashing detergent according to the invention directly into this Sieve salt, in the cleaning and rinse cycle in the manner described above works.

The object of the present invention is further illustrated by the accompanying figure. Fig. 1 and Fig. 2 show detergent according to the invention for the ma ski nelle dishwashing, in which the matrix of detergent particles middle part chengrößen having microns by 600, while the OF INVENTION contained in the cleaning agent have rinse agent dung used according to the average particle sizes mm 8. In Fig. 1, the rinse aid particles are colored blue for visually appealing contrasting, while the base powder is white and additionally has red colored spots, ie red colored particles of the same particle size. In Fig. 2, the colors are red and blue interchanged, ie the base powder is white and has blue speckled particles, while the rinse aid particles are red.

In FIGS. 3 and 4, detergent according to the invention are shown in which the detergent particles, ie, the "base powder" a larger average particle size has. The powder matrix here has average particle sizes of 1,800 μm, while the rinse aid particles contained according to the invention in turn have average particle sizes of 8 mm. The particles were colored analogously to FIGS. 1 and 2, ie in FIG. 3 the rinse aid particles are colored blue, while the base powder is white and additionally has red colored spots. In Fig. 4, the colors red and blue are in turn interchanged, ie the base powder is white and has blue speckle particles, while the rinse aid particles are red.

The Fig. 5, 6 and 7 illustrate an inventive cleaning compositions for machine dishwashing, in which the rinse aid particles having a mean particle size which is of the same order of magnitude as that of the base powder. Such cleaning agents are extremely suitable for use in the kit-of-parts according to the invention. The powder matrix here has average particle sizes of 1800 μm, while the rinse aid particles according to the invention contained in the detergent also have average particle sizes of 1800 μm. In FIG. 5, the rinse agent are colored red, currency rend the base powder is white. In FIG. 6, the rinse agent are colored blue. Fig. 7 shows an inventive cleaning agent in which both red and blue colored rinse aid available. Alternatively, sprinkles of color can of course also be used, for example as a replacement for the red or blue rinse aid particles in FIG. 7.

Examples

A melt emulsion was prepared which was applied either directly or after application a carrier material can be shaped to form rinse aid particles.

Process step a) Preparation of the melt emulsion

By heating the casing material and stirring in the active substances and optional auxiliaries, a melt emulsion SE 1 was produced, the composition (% by weight, based on the melt) of which is given in the table below:

This melt emulsion can be fed directly to a prilling or pastillation, which results in rinse aid particles of the specified composition.

Claims (17)

1. Particulate machine dishwashing detergent containing builders and optional additional ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, characterized in that it contains a particulate rinse aid which

• a) 20 to 80% by weight of one or more coating substances with a melting point above 30 ° C.,
• b) 20 to 80 wt .-% of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

each based on the weight of the particulate rinse aid. 2. Automatic dishwasher detergent according to claim 1, characterized in that it is the particulate rinse aid in amounts of 0.5 to 30% by weight, preferably 1 up to 25% by weight and in particular from 5 to 15% by weight, in each case based on the total Means, contains. 3. Automatic dishwasher detergent according to one of claims 1 or 2, characterized records that the particulate rinse aid as an enveloping substance one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 25 to 70 wt .-% before preferably from 30 to 60 wt .-% and in particular from 40 to 50 wt .-%, each be referred to the weight of the particulate rinse aid. 4. Automatic dishwasher detergent according to one of claims 1 to 3, characterized records that the particulate rinse aid as a coating substance at least one paraffin contains wax with a melting range of 50 ° C to 60 ° C. 5. Automatic dishwasher detergent according to one of claims 1 to 4, characterized records that the particulate rinse aid as an active ingredient one or more substances  from the groups of surfactants, enzymes, bleach, bleach activator, corrosion inhibitor Bitters, scale inhibitors, cobuilders and / or fragrances in amounts of 25 to 70 % By weight, preferably from 30 to 60% by weight and in particular from 40 to 50% by weight, each based on the particle weight. 6. Automatic dishwasher detergent according to one of claims 1 to 5, characterized indicates that the particulate rinse aid as an active substance is nonionic surfactants, preferably alkoxylated alcohols. 7. Automatic dishwasher detergent according to one of claims 1 to 6, characterized records that the particulate rinse aid as an active substance bleach from the Group of oxygen or halogen bleaches, especially chlorine bleaches, contains. 8. Automatic dishwasher detergent according to one of claims 1 to 7, characterized records that the particulate rinse aid as an active substance bleach activators, ins particularly from the groups of polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), the N-acylimide, especially N- Nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl Morpholinium acetonitrile methyl sulfate (MMA) contains. 9. Automatic dishwasher detergent according to one of claims 1 to 8, characterized records that the particulate rinse aid further excipients from the group of Anti-settling agents, floating agents, anti-floating agents, anti-swell agents and dis Pergierhilfsmittel in amounts of 0.5 to 9 wt .-%, preferably between 1 and 7.5 % By weight, and particularly preferably between 1, 5 and 5% by weight, in each case based on the weight of the particulate rinse aid. 10. Automatic dishwasher detergent according to one of claims 1 to 9, characterized records that the particulate rinse aid also emulsifiers from the group  of fatty alcohols, fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in Amounts from 0.1 to 5 wt .-%, preferably from 0.2 to 3.5 wt .-%, particularly be preferably from 0.5 to 2 wt .-% and in particular from 0.75 to 1.25 wt .-%, each be referred to the weight of the particulate rinse aid. 11. Automatic dishwashing detergent according to one of claims 1 to 10, characterized indicates that the particulate rinse aid has particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm points. 12. Automatic dishwasher detergent according to one of claims 1 to 11, characterized records that it (without taking into account the rinse aid particles) particle sizes between rule 200 and 3000 microns, preferably between 300 and 2500 microns and in particular has between 400 and 2000 microns. 13. Automatic dishwasher detergent according to one of claims 1 to 12, characterized records that a dosing unit in a bag made of water-soluble film welds present. 14. A process for the production of powdered machine dishwashing detergents with a clear rinsing effect, characterized in that a known powdery ma machine dishwashing agent with rinse aid particles

• a) 20 to 80% by weight of one or more coating substances with a melting point above 30 ° C.,
• b) 20 to 80 wt .-% of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

each based on the weight of the particulate rinse aid, is mixed. 15. Kit-of-parts, comprising a powdered automatic dishwashing detergent according to ei nem of claims 1 to 13 and a sieve insert for household dishwashers nen. 16. Kit-of-parts according to claim 15, characterized in that the particle sizes of the automatic dishwashing detergent (taking into account the rinse aid particles) in the Range from 400 to 2500 microns, preferably from 500 to 1600 microns and in particular from 600 to 1200 µm. 17. Kit-of-parts according to one of claims 15 or 16, characterized in that the Mesh size or hole size of the sieve insert is 1 to 4 mm and the rinse aid ler particles are larger than this mesh size or hole size of the sieve insert.