CA2303578A1

CA2303578A1 - Dishwasher detergent containing particulate rinse aid

Info

Publication number: CA2303578A1
Application number: CA 2303578
Authority: CA
Inventors: Thomas Holderbaum; Bernd Richter; Christian Nitsch; Juergen Haerer; Oliver Kurth; Markus Semrau; Thomas Gassenmeier
Original assignee: Individual
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-03-30
Filing date: 2000-03-30
Publication date: 2000-09-30
Also published as: DE19914363A1; AU3430500A; WO2000060046A1

Abstract

Dishwasher detergents which produce a clear rinse effect in domestic dishwashers contain rinse aid particles which in turn contain 20 to 80% by weight of one or more coating materials with a melting point above 30°C, 20 to 80% by weight of one or more active substances and 0 to 20%
by weight of other auxiliaries and additives. The rinse aid particles are preferably incorporated in the detergents according to the invention in quantities of 0.5 to 30% by weight.

Description

Dishwasher Detergent Containing Particulate Rinse Aid Field of the Invention This invention relates generally to dishwasher detergents for domestic dishwashing machines and, more particularly, to particulate rinse aids for use in such detergents.
Background of the Invention The cleaning of tableware in domestic dishwashing machines normally comprises a prerinse cycle, a main wash cycle and a final rinse cycle which are interrupted by intermediate rinse cycles. With most machines, the prerinse cycle can be selected for heavily soiled tableware, but is only selected by the consumer in exceptional cases so that, in most machines, a main wash cycle, an intermediate rinse cycle with clean water and a final rinse cycle are carried out. The temperature of the main wash cycle varies between 40 and 65°C, according to the type of machine and the program selected. In the final rinse cycle, rinse aids which normally contain nonionic surfactants as their main constituent are added from a dosing tank. These rinse aids are liquids and are widely described in the prior art. Their principal function is to prevent lime stains and films on the cleaned tableware. Besides water and low-foaming nonionic surfactants, many rinse aids often contain hydrotropes, pH regulators, such as citric acid, or film-inhibiting polymers.
The storage tank in the dishwashing machine has to be filled with rinse aid at regular intervals, one filling being enough for 10 to 50 rinse cycles according to the type of machine. If the consumer forgets to fill the tank, glasses in particular are spoiled by lime stains and films. Accordingly, some proposals have been put forward in the prior art with a view to integrating a rinse aid in dishwasher detergents. These proposed solutions are confined to tablets.
Thus, European patent application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets of which the first layer contains peroxy bleaching agent, builder and enzyme while the second layer contains an acidifying agent, a continuous medium with a melting point of 55 to 70°C and film inhibitors. The high-melting continuous medium is said to release the acids) and film inhibitors) with delay and to develop a clear rinse effect. Powder-form dishwasher detergents or surfactant-containing rinse aid systems are not mentioned in this document.
Earlier German patent application DE 198 51 426.3 (Henkel KGaA) describes a process for the production of multiphase detergent tablets in which a particulate premix is compressed to form tablets with a cavity which is subsequently filled with a separately prepared melt suspension or emulsion of a coating material and one or more active substances) dispersed or suspended therein. The teaching of this document also confined to tablets. Powder-form detergents containing a second phase which produce certain effects through the controlled release of ingredients are not disclosed.
Earlier German patent application DE 198 17 964.2 (Henkel KGaA) describes a process for the production of coated solid particles in which the materials to be coated are dispersed in a melt of a substantially water-insoluble material (coating) which is solid at room temperature and which has a plastic solidification range, the dispersion is cooled and optionally further processed, the materials to be coated being liquid at the solidifica-tion temperature of the coating material and one or more emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and polyoxy-alkylene siloxanes being added to the melt. The use of these compositions in dishwasher detergents is also disclosed in the document in question.
The problem addressed by the present invention was to enable the advantages afforded by the controlled release of ingredients, more particularly a clear rinse effect, to be made available to powder-form detergents without any need for complicated process steps, such as single or multiple coating. Instead, the invention set out to provide a supply form which could be used both separately in solid form as a rinse aid to be dosed by the consumer and as an additivelmixing component for powder-form dishwasher detergents. The proposed solutions known from the prior art would be extended to a complete detergent with a clear-rinse effect, i.e.
would not be confined to tablets.
Summary of the Invention It has now been found that melt dispersions or emulsions of coating materials with melting points above 30°C, active substances and optionally other ingredients, such as emulsifiers, dyes and perfumes, etc., can be processed by shaping and made up in such a way that dishwasher detergents with a clear rinse effect are obtained.
The present invention provides in one aspect a particulate rinse aid comprising a) 20 to 80% by weight of one or more coating materials with a melting point above 30°C, b) 20 to 80% by weight of one or more active substances and c) 0 to 20% by weight of other active substances and auxiliaries, based on the weight of the particulate rinse aid.
The present invention relates to a particulate dishwashing detergent containing builders and optionally other ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and perfumes, characterized in that it additionally contains a particulate rinse aid which contains a) 20 to 80% by weight of one or more coating materials with a melting point above 30°C, b) 20 to 80% by weight of one or more active substances and c) 0 to 20% by weight of other active substances and auxiliaries, based on the weight of the particulate rinse aid.

Detailed Description of the Invention The rinse aid particles may be used in varying quantities according to the detergents to which they are added and the strength of the required effect. Preferred dishwasher detergents contain the particulate rinse aid in quantities of 0.5 to 30% by weight, preferably in quantities of 1 to 25% by weight and more preferably in quantities of 5 to 15% by weight, based on the detergent as a whole.
The coating materials used in the rinse aid particles are expected to satisfy various requirements which relate on the one hand to the melting or solidification behavior of the coating and, on the other hand, to the material properties of the coating in the solidified state, i.e in the rinse aid particle.
Since the rinse aid particles are intended to be permanently protected against outside influences during transportation and storage, the coating material must show high stability to the impacts occurring, for example, during packaging or transportation. Accordingly, the coating should have either at least partly elastic or at least plastic properties in order to react to impact without breaking by elastic or plastic deformation. The coating material should have a melting range (solidification range) at temperatures at which the active substances to be coated are not exposed to significant thermal stressing. On the other hand, however, the melting range must be high enough still to afford the encapsulated particles effective protection at at least slightly elevated temperatures. According to the invention, the coating materials have a melting point above 30°C.
It has been found to be of advantage if the coating material does not have a sharply defined melting point, as would normally be the case with pure crystalline substances, but rather a melting range possibly covering several degrees Celsius.
The coating material preferably has a melting range of about 45°C
to about 75°C. This means in the present case that the melting range lies within the temperature range mentioned and does not denote the width of the melting range. The width of the melting range is preferably at least 1 °C
and more preferably about 2 to about 3°C.
The properties mentioned above are generally exhibited by so-called waxes. "Waxes" in the context of the present invention are understood to 5 be any of a number of natural or synthetic substances which generally melt above 40°C without decomposing and, even just above their melting point, are of relatively low viscosity and non-stringing. Their consistency and solubility are dependent to a large extent on temperature.
Waxes are divided into three groups according to their origin, namely: natural waxes, chemically modified waxes and synthetic waxes.
The natural waxes include, for example, vegetable waxes, such as candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax or montan wax, animal waxes, such as bees wax, shellac wax, spermaceti, lanolin (wool wax) or uropygial fat, mineral waxes, such as ceresine or ozocerite (earth wax), or petrochemical waxes, such as petrolatum, paraffin waxes or microwaxes.
The chemically modified waxes include, for example, hard waxes, such as montan ester waxes, sassol waxes or hydrogenated jojoba waxes.
Synthetic waxes are generally understood to be polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes which satisfy the above-mentioned softening point requirements may also be used as coating materials. For example, higher esters of phthalic acid, more particularly the dicyclohexyl phthalate commercially available under the name of Unimoll~ 66 (Bayer AG), have proved to be suitable synthetic compounds. Synthetic waxes of lower carboxylic acids and fatty alcohols, for example the dimyristyl tartrate commercially available under the name of Cosmacol~ ETLP (Condea), are also suitable. Conversely, synthetic or partly synthetic esters of lower alcohols with fatty acids from native sources may also be used. This class of substances includes, for example, Tegin~

90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example Schellack-KPS-Dreiring-SP (Kalkhoff GmbH), may also be used as a coating material in accordance with the invention.
In the context of the invention, the waxes also include, for example, the so-called wax alcohols. Wax alcohols are relatively high molecular weight water-insoluble fatty alcohols generally containing about 22 to 40 carbon atoms. The wax alcohols are used as a principal constituent of many natural waxes, for example in the form of wax esters of relatively high molecular weight fatty acids (wax acids). Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the solid particles coated in accordance with the invention may also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example the lanolin obtainable, for example, under the name of Argowax~ (Pamentier & Co.). According to the invention, fatty acid glycerol esters or fatty acid alkanolamides and also water-insoluble or substantially water-insoluble polyalkylene glycol compounds may also be used at least partly as a constituent of the coating.
In one preferred embodiment, the coating material present in the rinse aid particles used in accordance with the invention predominantly contains paraffin wax. In other words, at least 50% by weight of the total of coating materials present and preferably more consists of paraffin wax.
Paraffin wax contents (based on total coating material) of about 60% by weight, about 70% by weight or about 80% by weight are particularly suitable, even higher contents of, for example, more than 90% by weight being particularly preferred. In one particular embodiment of the invention, the total quantity of coating material used consists entirely of paraffin wax.
So far as the present invention is concerned, paraffin waxes have the advantage over the other natural waxes mentioned that the waxes do not undergo hydrolysis in an alkaline detergent environment (as might be expected, for example, in the case of the wax esters), because a paraffin wax does not contain any hydrolyzable groups.
Paraffin waxes consist principally of alkanes and small amounts of iso- and cycloalkanes. The paraffin to be used in accordance with the invention preferably contains virtually no constituents with a melting point above 70°C and, more preferably, above 60°C. If the temperature in the cleaning solution falls below this melting temperature, high-melting alkanes in the paraffin can leave unwanted wax residues behind on the surfaces to be cleaned or the ware to be cleaned. Wax residues such as these generally leave the cleaned surface with an unattractive appearance and should therefore be avoided.
Preferred dishwasher detergents are characterized in that the particulate rinse aid contains one or more substances with a melting range of 40°C to 75°C in quantities of 25 to 70% by weight, preferably in quantities of 30 to 60% by weight and more preferably in quantities of 40 to 50% by weight, based on the weight of the particulate rinse aid, as coating material.
Particularly preferred coating materials are paraffin waxes so that particularly preferred dishwasher detergents are characterized in that the particulate rinse aid contains at least one paraffin wax with a melting range of 50°C to 50°C as coating material.
The paraffin wax used preferably has a high content of alkanes, isoalkanes and cycloalkanes solid at ambient temperature (generally about 10 to about 30°C). The higher the percentage of solid wax constituents present in a wax at room temperature, the more useful that wax is for the purposes of the present invention. The higher the percentage of solid wax constituents, the greater the resistance of the coating to impact or friction with other surfaces, which leads to longer lasting protection of the coated solid particles. Large percentages of oils or liquid wax constituents can weaken the paticles so that pores are opened and the active substances are thus exposed to the outside influences mentioned.

Besides paraffin as principal constituent, the coating material may also contain one or more of the waxes or wax-like substances mentioned above. Basically, the composition of the mixture forming the coating material should be such that the rinse aid particles are at least substantially insoluble in water. Their solubility in water should not exceed about 10 mg/l at a temperature of about 30°C and should preferably be below 5 mgll.
At all events, the coating should have very low solubility in water, even in water at elevated temperature, in order largely to avoid the coated active substances being released independently of temperature.
The principle described above facilitates the delayed release of ingredients at a certain time in the wash cycle of a dishwasher and may be applied with particular advantage when the main wash cycle is carried out at a relatively low temperature (for example 55°C), so that the active substance is only released from the rinse aid particles in the final rinse cycle at relatively high temperatures (ca. 70°C).
Active substance(s):
The active substances to be incorporated in the rinse aid particles may be present both in solid and in liquid form at the processing temperature (i.e. at the temperature at which the particles are produced).
The active substances present in the rinse aid particles perform certain functions. Cleaning performance can be improved through the separation of certain substances or through the accelerated or delayed release of additional substances. Accordingly, active substances preferably incorporated in the rinse aid particles are ingredients of detergents which are crucially involved in the washing or cleaning process.
In preferred dishwasher detergents, the particulate rinse aid contains one or more substances from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors, co-builders and/or perfumes in quantities of 25 to 70% by weight, preferably 30 to 60% by weight and more preferably 40 to 50% by weight, based on the weight of the particles.
By incorporating surfactants in molten coating material, it is possible to prepare a melt suspension or emulsion which provides additional detersive substance at a predetermined time in the final rinse aid particles or in the final detergent containing rinse aid particles in accordance with the invention. For example, it is possible in this way to produce dishwasher detergents which only release the additional surfactant from the rinse aid particles according to the invention at temperatures which domestic dishwashers only reach in the final rinse cycle. In this way, additional detergent is available in the final rinse cycle to accelerate drainage of the water and thus effectively to prevent stains on the tableware. Thus, with a suitable quantity of solidified melt suspension or emulsion in the rinse aid particles, there is no longer any need to use the additional rinse aid typically encountered today.
Accordingly, in preferred diswasher detergents, the particulate rinse aid contains nonionic surfactants, preferably alkoxylated alcohols, as active substance. These substance are described in detail hereinafter.
Another class of active substances which may be incorporated with particular advantage in the rinse aid particles are bleaching agents. In their case, detergents can be produced which only release the bleaching agent on reaching certain temperatures, for example fully compounded detergents which clean enzymatically in the prerinse cycle and only release the bleaching agent in the main wash cycle. Dishwasher detergents can also be produced in such a way that additional bleaching agents are released in the final rinse cycle so that difficult stains, for example tea stains, are more effectively removed.
In preferred dishwasher detergents, the particulate rinse aid contains bleaching agents selected from the group of oxygen or halogen bleaching agents, more particularly chlorine bleaching agents, as active substance.

These substances are also described in detail hereinafter.
Another class of compounds which may preferably be used as active substances in the rinse aid particles according to the invention are bleach activators. The important representatives of this group are also described 5 in detail hereinafter. Preferred dishwasher detergents according to the invention are characterized in that the particulate rinse aid contains bleach activators, more particularly from the groups of polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), N-acyl imides, more particularly N-nonanoyl succinimide (NOSI), acylated 10 phenol sulfonates, more particularly n-nonanoyl or isononanoyl-oxybenzenesulfonate (n- or iso-NOBS), n-methyl morpholinium acetonitrile methyl sulfate (MMA), as active substance.
Perfumes may also be incorporated as active substances in the rinse aid particles to be used in accordance with the invention. All the perfumes described in detail hereinafter may be used as active substance.
Where perfumes are incorporated in the rinse aid particles, detergents according to the invention which release all or part of the perfume with delay are obtained. According to the invention, it is possible in this way for example to produce dishwasher detergents where the consumer experiences the perfume note even after the machine has been opened on completion of the program. In this way, the unwanted "alkali smell"
characteristic of many dishwasher detergents can be eliminated.
Corrosion inhibitors may also be introduced as active substance into the rinse aid particles, any of the corrosion inhibitors familiar to the expert being suitable. A combination of enzyme (for example lipase) and lime soap dispersant, for example, has been successfully used as a scale inhibitor.
Auxiliaries:
At extremely low temperatures, for example at temperatures below 0°C, the rinse aid particles can disintegrate under impact or friction.
In order to improve stability at temperatures as low as these, additives may optionally be incorporated in the coating materials. Suitable additives must be completely miscible with the molten wax, should not significantly alter the melting range of the coating materials, should improve the elasticity of the coating at low temperatures, should generally not increase the permeability of the coating to water or moisture and should not increase the viscosity of the molten coating material to such an extent as to make processing difficult or even impossible. Suitable additives which reduce the brittleness of a coating consisting essentially of paraffin at low temperatures are, for example, EVA copolymers, hydrogenated resin acid methyl esters, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.
Another useful additive where paraffin is used as the coating is a surfactant, for example a C~Z_~8 fatty alcohol sulfate, used in a small quantity. This additive improves the wetting of the material to be encapsulated by the coating. In one advantageous embodiment, it is added in a quantity of about <5% by weight and preferably < about 2% by weight based on the coating material. In many cases, the effect of adding an additive can be to promote the coating of even those active substances which, without the additive, would generally form a viscous plastic mass of paraffin and partly dissolved active substance after melting of the coating material.
It can also be of advantage to incorporate other additives in the coating material, for example to prevent premature sedimentation of the active substances. This is particularly advisable in the production of the rinse aid particles according to the invention without carrier materials.
Suitable antisedimenting agents, which are also known as antisettling agents, are known from the prior art, for example from the production of paints and printing inks. Sedimentation phenomena and concentration gradients of the substances to be coated during the transition from the plastic solidification range to the solid can be counteracted, for example, by interfacially active substances, waxes dispersed in solvents, montmoril-lonites, organically modified bentonites, (hydrogenated) castor oil derivatives, soya lecithin, ethyl cellulose, low molecular weight polyamides, metal stearates, calcium soaps or hydrophobicized silicas. Other sub-stances which have the effects mentioned belong inter alia to the groups of antifloating agents and thixotropicizing agents and, chemically, may be classed as silicone oils (dimethyl polysiloxanes, methylphenyl polysiloxanes, polyether-modified methylalkyl polysiloxanes), oligomeric titanates and silanes, polyamines, salts of long-chain polyamines and polycarboxylic acids, amine/amide-functional polyesters and aminelamide-functional polyacrylates.
Additives from the classes mentioned above are commercially available in large numbers. Commercial products which may advantage-ously be used as additives in the process according to the invention are, for example, Aerosil~ 200 (pyrogenic silica, 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 smectite, Sudchemie), Tixogel~ VG, VP and VZ (QUAT-charged montmorillonite, Sudchemie), Disperbyk~ 161 (block copolymer, Byk-Chemie), Borchigen~
ND (sulfo-group-free ion exchanger, Borchers), Ser-Ad~ FA 601 (Servo), Solsperse~ (aromatic ethoxylate, ICI), Surfynol~ types (Air Products), Tamol~ and Triton~ types (Rohm & Haas), Texaphor~ 963, 3241 and 3250 (polymers, Henkel), Rilanit~ types (Henkel), 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 additives mentioned may be used in varying quantities in the rinse aid particles, according to the coating material and the active substance. The antisettling agents, antifloating agents and thixotropicizing agents and dispersants mentioned above are typically used in concentrations of 0.5 to 8.0% by weight, preferably in concentrations of 1.0 to 5.0% by weight and more preferably in concentrations of 1.5 to 3.0% by weight, based on the total quantity of coating material and active substances.
According to the invention, preferred dishwasher detergents are characterized in that the particulate rinse aid contains further auxiliaries from the group of antisedimenting agents, antisettling agents, antifloating agents, thixotropicizing agents and dispersion aids in quantities of 0.5 to 9% by weight, preferably in quantities of 1 to 7.5% by weight and more preferably in quantities of 1.5 to 5% by weight, based on the weight of the particulate rinse aid.
Particularly in the production of melt suspensions or emulsions containing additives which are liquid at the processing temperature, it is of advantage to use special emulsifiers. It has been found that, above all, emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are particularly suitable.
In the context of the invention, fatty alcohols are understood to be the Cs_22 alcohols obtainable from native fats or oils via the corresponding fatty acids (see below). Depending on the origin of the fat or oil from which they are obtained, these alcohols may be substituted or locally unsaturated in the alkyl chain.
Accordingly, Cs_22 fatty alcohols, preferably C8_22 fatty alcohols, more preferably C~2_~a fatty alcohols and most preferably Cps-~a fatty alcohols are used as emulsifiers in the rinse aid particles according to the invention.
Other suitable emulsifiers are any fatty acids obtained from vegetable or animal oils and fats. Irrespective of their aggregate state, the fatty acids may be saturated or mono- to polyunsaturated. With the unsaturated fatty acids also, the species solid at room temperature are preferred to the liquid or paste-form species. It is of course possible to use not only "pure" fatty acids, but also the technical fatty acid mixtures obtained in the hydrolysis of fats and oils, these mixtures being distinctly preferred from the economic point of view.
For example, individual species or mixtures of the following acids may be used as emulsifiers in accordance with the present invention:
caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-oleic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, 10-undecenoic acid, petroselic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, a- and ~i-elaeostearic acid, gadoleic acid, erucic acid, brassidic acid.
It is of course also possible to use the fatty acids with an odd number of carbon atoms, for example undecanoic acid, tridecanoic acid, pentadeca-noic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.
C6_22 fatty acids, preferably C$_22 fatty acids, more preferably C~2_~$
fatty acids and most preferably C,6_~$ fatty acids are used as emulsifiers) in preferred rinse aid particles.
According to the invention, particularly preferred emulsifiers are polyglycerol esters, more particularly esters of fatty acids with poly-glycerols. These preferred polyglycerol esters may be represented by general formula I:
R' HO-(CH2-CH-CHz-O]"-H (I) in which the substituents R' in each glycerol unit independently of one another represent hydrogen or a fatty acyl group containing 8 to 22 and preferably 12 to 18 carbon atoms and n is a number of 2 to 15 and preferably 3 to 10.
These polyglycerol esters are known and commercially available, more especially with degrees of polymerization n of 2, 3, 4, 6 and 10.
5 Since substances of the type mentioned are also widely used in cosmetic formulations, some of them are also classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, 5~n Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997). For example, this cosmetic dictionarylhandbook contains 10 information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLY-CERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLY-CERYL-10-DECALINOLEATE, POLYGLYCERYL-10-DECAOLEATE, POLYGLYCERYL-10-DECASTEARATE, POLYGLYCERYL-2-DIISO-STEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLYGLYCERYL-10-15 DISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLYGLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLEATE, POLYGLYCERYL-10-DIOLE-ATE, POLYGLYCERYL-3-DISTEARATE, POLYGLYCERYL-6-DISTEAR-ATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10-HEPTA-OLEATE, POLYGLYCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL-10-HEPTASTEARATE, POLYGLYCERYL-6-HEXAOLEATE, POLYGLY-CERYL-2-ISOSTEARATE, POLYGLYCERYL-4-ISOSTEARATE, POLY-GLYCERYL-6-ISOSTEARATE, POLYGLYCERYL-10-LAURATE, POLY-GLYCERYLMETHACRYLATE, POLYGLYCERYL-10-MYRISTATE, POLY-GLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE, POLYGLYCERYL-4-OLEATE, POLYGLYCERYL-6-OLEATE, POLYGLYCERYL-8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLYGLYCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTA-STEARATE, POLYGLYCERYL-10-PENTASTEARATE, POLYGLYCERYL-2-SESQUIISOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYCERYL-2-STEARATE, POLYGLYCERYL-3-STEARATE, POLY-GLYCERYL-4-STEARATE, POLYGLYCERYL-8-STEARATE, POLYGLY-CERYL-10-STEARATE, POLYGLYCERYL-2-TETRAISOSTEARATE, POLYGLYCERYL-10-TETRAOLEATE, POLYGLYCERYL-2-TETRA-STEARATE, POLYGLYCERYL-2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLEATE, POLYGLYCERYL-6-TRISTEARATE. The commercially obtainable products of various manufacturers which are classified under the above-mentioned keywords in the dictionarylhandbook mentioned above may advantageously be used as emulsifiers in process step b) according to the invention.
Another group of emulsifiers which may be used in the rinse aid particles according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide. These polyalkylene siloxanes may be represented by general formula II:
R' R' R' H 3C-S i-O-[S i-O] ~-S i-C H 3 ( I I ) R' R' R' in which the substituents R' independently of one another represent -CH3 or a polyoxyethylene or polyoxypropylene group -[CH(R2)-CH2-O]xH group, R2 represents -H or -CH3, x is a number of 1 to 100, preferably 2 to 20 and more particularly below 10 and n is the degree of polymerization of the silicone.
The polyoxyalkylene siloxanes mentioned may also be etherified or esterified at the free OH groups of the polyoxyethylene or polyoxypropylene side chains. The unetherified and unesterified polymer of dimethyl siloxane with polyoxyethylene andlor polyoxypropylene is known under the INCI
nomenclature as DIMETHICONE COPOLYOL and is commercially available under the names of Abil~ B (Goldschmidt), Alkasil~ (Rhone-Poulenc), Silwet~ (Union Carbide) or Belsil~ DMC 6031.
The DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil~ DMC 6032, 6033 and 6035, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHER (for example KF352A, Sin Etsu) may also be used as emulsifiers in accordance with the invention.
In the same way as the coating materials and the substances to be coated, the emulsifiers may be used over a widely varying range.
Emulsifiers of the type mentioned normally make up 1 to 25% by weight, preferably 2 to 20% by weight and more preferably 5 to 10% by weight of the sum of coating materials and active substances.
According to the invention, preferred dishwasher detergents are characterized in that the particulate rinse aid additionally contains emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters andlor polyoxyalkylene siloxanes in quantities of 0.1 to 5% by weight, preferably in quantities of 0.2 to 3.5% by weight, more preferably in quantities of 0.5 to 2% by weight and most preferably in quantities of 0.75 to 1.25% by weight, based on the weight of the particles.
The particulate rinse aids used in accordance with the invention can be produced in various ways, cf. in particular earlier German patent application DE 198 17 964.2. In a particularly preferred embodiment, the melt suspension or emulsion is converted into particles by pelleting or prilling.
The ingredients of the dishwasher detergents according to the invention are described in the following. Some of them may also be present as active substances in the rinse aid particles.
The most important ingredients of dishwasher detergents are builders. The dishwasher detergents according to the invention may contain any of the builders typically present in laundry and dishwasher detergents, i.e. in particular zeolites, silicates, carbonates, organic cobuilders and - providing there are no ecological objections to their use -also the phosphates.
Suitable crystalline layered sodium silicates correspond to the general formula NaMSiXO~+~Y H20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layered silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both ~- and 8-sodium disilicates Na2Si205y H20 are particularly preferred, ~-sodium disilicate being obtainable, for example, by the process described in International patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to encompass "X-ray amorphous". In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-44 00 024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing bound water used in accordance with the invention is preferably zeolite A andlor zeolite P.
Zeolite MAP~ (Crosfield) is a particularly preferred P-type zeolite.
However, zeolite X and mixtures of A, X andlor P are also suitable.
According to the invention, it is preferred to use, for example, a commercially obtainable co-crystallizate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under the name of VEGOBOND AX~ and which may be described by the following formula:
nNa20 ~ (1-n)K20 ' AI2O3 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20.
Suitable zeolites have a mean particle size of less than 10 m (volume distribution, as measured by the Coulter Counter Method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of bound water.
The generally known phosphates may of course also be used as builders providing their use should not be avoided on ecological grounds.
Among the large number of commercially available phosphates, alkali metal phosphates have the greatest importance in the detergent industry, pentasodium triphosphate and pentapotassium triphosphate (sodium and potassium tripolyphosphate) being particularly preferred.
"Alkali metal phosphates" is the collective term for the alkali metal (more particularly sodium and potassium) salts of the various phosphoric acids, including metaphosphoric acids (HP03)~ and orthophosphoric acid (H3P04) and representatives of higher molecular weight. The phosphates combine several advantages: they act as alkalinity sources, prevent lime deposits on machine parts and lime incrustations in fabrics and, in addition, contribute towards the cleaning effect.
Sodium dihydrogen phosphate (NaH2P04) exists as the dihydrate 5 (density 1.91 gcm3, melting point 60°) and as the monohydrate (density 2.04 gcm3). Both salts are white readily water-soluble powders which, on heating, lose the water of crystallization and, at 200°, are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na2H2P207) and, at higher temperatures, into sodium trimetaphosphate (Na3P309) and 10 Maddrell's salt (see below). NaH2P04 shows an acidic reaction. It is formed by adjusting phosphoric acid with sodium hydroxide to a pH value of 4.5 and spraying the resulting "mash". Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2P04, is a white salt with a density of 2.33 gcm~3, has a melting 15 point of 253° [decomposition with formation of potassium polyphosphate (KP03)X] and is readily soluble in water.
Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP04, is a colorless, readily water-soluble crystalline salt. It exists in water-free form and with 2 moles (density 2.066 gcm3, water loss at 95°), 7 20 moles (density 1.68 gcm3, melting point 48° with loss of 5 H20) and moles of water (density 1.52 gcm3, melting point 35° with loss of 5 H20), becomes water-free at 100° and, on fairly intensive heating, is converted into the diphosphate Na4P207. Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenol-phthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HP04, is an amorphous white salt which is readily soluble in water.
Trisodium phosphate, tertiary sodium phosphate, Na3P04, consists of colorless crystals which have a density of 1.62 gcm3 and a melting point of 73-76° (decomposition) as the dodecahydrate, a melting point of 100° as the decahydrate (corresponding to 19-20% P205) and a density of 2.536 gcm~3 in water-free form (corresponding to 39-40% P205). Trisodium phosphate is readily soluble in water through an alkaline reaction and is prepared by concentrating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH by evaporation. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3P04, is a white deliquescent granular powder with a density of 2.56 gcm3, has a melting of 1340° and is readily soluble in water through an alkaline reaction. It is formed, for example, when Thomas slag is heated with coal and potassium sulfate.
Despite their higher price, the more readily soluble and therefore highly effective potassium phosphates are often preferred to corresponding sodium compounds in the detergent industry.
Tetrasodium diphosphate (sodium pyrophosphate), Na4P207, exists in water-free form (density 2.534 gcm3, melting point 988°, a figure of 880°
has also been mentioned) and as the decahydrate (density 1.815 - 1.836 gcm3, melting point 94° with loss of water). Both substances are colorless crystals which dissolve in water through an alkaline reaction. Na4P207 is formed when disodium phosphate is heated to >200° or by reacting phosphoric acid with soda in a stoichiometric ratio and spray-drying the solution. The decahydrate complexes heavy metal salts and hardness salts and, hence, reduces the hardness of water. Potassium diphosphate (potassium pyrophosphate), K4P207, exists in the form of the trihydrate and is a colorless hygroscopic powder with a density of 2.33 gcm3 which is soluble in water, the pH value of a 1 % solution at 25° being 10.4.
Relatively high molecular weight sodium and potassium phosphates are formed by condensation of NaH2P04 or KH2P04. They may be divided into cyclic types, namely the sodium and potassium metaphosphates, and chain types, the sodium and potassium polyphosphates. The chain types in particular are known by various different names: fused or calcined phosphates, Graham's salt, Kurrol's salt and Maddrell's salt. All higher sodium and potassium phosphates are known collectively as condensed phosphates.
The industrially important pentasodium triphosphate, Na5P30~o (sodium tripolyphosphate), is a non-hygroscopic white water-soluble salt which crystallizes without water or with 6 H20 and which has the general formula Na0-[P(O)(ONa)-O]n-Na where n = 3. Around 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, around 20 g at 60° and around 32 g at 100°. After heating of the solution for 2 hours to 100°, around 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide in a stoichiometric ratio and the solution is spray-dried. Similarly to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K5P30~o (potassium tripolyphosphate), is marketed for example in the form of a 50% by weight solution (> 23% P205, 25% K20).
The potassium polyphosphates are widely used in the detergent industry.
Sodium potassium tripolyphosphates, which may also be used in accordance with the invention, also exist. They are formed for example when sodium trimetaphosphate is hydrolyzed with KOH:
(NaP03)3 + 2 KOH -~ Na3K2P3O~o + H20 According to the invention, they may be used in exactly the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures thereof. Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate may also be used in accordance with the invention.

If the detergents according to the invention contain phosphates, they are normally used in quantities of 50 to 85% by weight. Phosphate-free detergents normally contain builder combinations of zeoliye and polycarboxylate andlor of carbonate, hydrogen carbonate, citrate and polymeric polycarboxylates. The polycarboxylates, which are often also referred to as cobuilders, are described in the following.
Organic cobuilders suitable for use in the dishwasher detergents according to the invention are, in particular, polycarboxylateslpolycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described in the following.
Useful organic builders are, for example, the polycarboxylic acids usable, for example, in the form of their sodium salts, polycarboxylic acids in this context being understood to be carboxylic acids which bear more than one acid function. Examples of such carboxylic acids are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), providing their use is not ecologically unsafe, and mixtures thereof.
Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
The acids per se may also be used. Besides their builder effect, the acids also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value in detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates such as, for example, the alkali metal salts of polyacrylic or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric polycarboxylates are weight-average molecular weights MW of the particular acid form which, basically, were determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which provides realistic molecular weight values by virtue of its structural similarity to the polymers investigated. These values differ distinctly from the molecular weights measured against polystyrene sulfonic acids as standard. The molecular weights measured against polystyrene sulfonic acids are generally higher than the molecular weights mentioned in this specification.
Particularly suitable polymers are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 glmole. By virtue of their superior solubility, preferred representatives of this group are the short-chain polyacrylates which have molecular weights of 2,000 to 10,000 glmole and, more particularly, 3,000 to 5,000 glmole.
Also suitable are copolymeric polycarboxylates, particularly those of acrylic acid with methacrylic acid and those of acrylic acid or methacrylic acid with malefic acid. Acrylic acidlmaleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have proved to be particularly suitable. Their relative molecular weights, based on the free acids, are generally in the range from 2,000 to 70,000 glmole, preferably in the range from 20,000 to 50,000 glmole and more preferably in the range from 30,000 to 40,000 glmole.
The (co)polymeric polycarboxylates may be used either in powder form or in the form of an aqueous solution. The content of (co)polymeric polycarboxylates in the detergent is preferably from 0.5 to 20% by weight and more preferably from 3 to 10% by weight.
In order to improve solubility in water, the polymers may also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as monomer.
Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those which contain salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers.
5 Other preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acidlacrylic acid salts or acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts 10 or precursors thereof. Particular preference is attributed to polyaspartic acids or salts and derivatives thereof which, according to German patent application DE-A-195 40 086, are also said to have a bleach-stabilizing effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by 15 reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least three hydroxyl groups. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-aldehyde and mixtures thereof and from polyol carboxylic acids, such as gluconic acid andlor glucoheptonic acid.
20 Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates which may be obtained by partial hydrolysis of starches. The hydrolysis may be carried out by standard methods, for example acid- or enzyme-catalyzed methods. The end products are preferably hydrolysis products with average molecular weights of 400 to 25 500,000 glmol. A polysaccharide with a dextrose equivalent (DE) of 0.5 to 40 and, more particularly, 2 to 30 is preferred, the DE being an accepted measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20 and dry glucose sirups with a DE of 20 to 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights of 2,000 to 30,000 glmole may be used.
The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Dextrins thus oxidized and processes for their production are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and from International patent applications WO 92118542, WO 93108251, WO 93116110, WO 94128030, WO 95107303, WO 95112619 and WO 95120608. An oxidized oligosaccharide corresponding to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C6 of the saccharide ring can be particularly advantageous.
Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this connection. The quantities used in zeolite-containing and/or silicate-containing formulations are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids and salts thereof which may optionally be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxy group and at most two acid groups. Co-builders such as these are described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the phosphonates, more particularly hydroxyalkane and aminoalkane phos-phonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used in the form of a sodium salt, the disodium salt showing a neutral reaction and the tetrasodium salt an alkaline ration (pH 9).
Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP and as the hepta- and octasodium salt of DTPMP. Within the class of phosphonates, HEDP is preferably used as builder. The aminoalkane phosphonates also show a pronounced heavy metal binding capacity. Accordingly, it can be of advantage, particularly where the detergents also contain bleaching agents, to use aminoalkane phosphonates, more especially DTPMP, or mixtures of the phosphonates mentioned.
In addition, any compounds capable of forming complexes with alkaline earth metal ions may be used as co-builders.
Besides the builders, substances from the groups of surfactants, bleaching agents, bleach activators, enzymes, polymers and dyes and perfumes are particularly important ingredients of detergents. Important representatives of the classes of substances mentioned are described in the following.
Normally, the only surfactants used in dishwasher detergents are low-foaming nonionic surfactants. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are far less important.
In one particularly preferred embodiment, the dishwasher detergents according to the invention contain nonionic surfactants. In another preferred embodiment, part of the total surfactant present in the detergents, preferably a large part, is present in the rinse aid particles. This is of particular advantage because particulate dishwasher detergents which develop their cleaning effect in the main wash cycle and only release the surfactant from the rinse aid particles in the final rinse cycle can be made available in this way. The presence of surfactants in the final rinse cycle of a dishwasher program has a positive effect on sparkle and the reduction of lime deposits.

In particularly preferred embodiments of the present invention, the detergent according to the invention contains nonionic surfactants, more particularly nonionic surfactants from the group of alkoxylated alcohols.
Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C~2_~4 alcohols containing 3 EO or 4 EO, C9_~~ alcohol containing 7 EO, C~3-~5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~2_~a alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2-~a alcohol containing 3 EO and C~2_~8 alcohol containing 5 EO. The degrees of ethoxylation mentioned represent statistical mean values which, for a special product, can be a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used, examples including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Suitable other nonionic surfactants are alkyl glycosides with the general formula RO(G)X where R is a primary, linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is a number of 1 to 10 and preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more especially the fatty acid methyl esters which are described, for example, in Japanese patent application JP 581217598 or which are preferably produced by the process described in International patent application WO-A-90113533.
Nonionic surfactants of the amine oxide type, for example N-coconutalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxy-ethylamine oxide, and the fatty acid alkanolamide type are also suitable.
The quantity in which these nonionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, more preferably, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides corresponding to formula (III):
R' R-CO-N-[Z] (III) in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms, R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds corresponding to formula (IV):
R'-O-R2 5 R-CO-N-[Z] (IV) in which R is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and RZ is a linear, branched or cyclic alkyl 10 group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms, C~~ alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-alkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of that group.
15 [Z) is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst, for 20 example in accordance with the teaching of International patent application WO-A-95!07331.
Besides the pure nonionic surfactants, other substances from the group of ionic surfactants, for example anionic or cationic surfactants, may of course also be present in the dishwasher detergents according to the 25 invention.
Among the compounds yielding H202 in water which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhy-30 drates and H202-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane dioic acid. Detergents according to the invention may also contain bleaching agents from the group of organic bleaches may also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide for example. Other typical organic bleaching agents are the peroxy acids, of which alkyl peroxy acids and aryl peroxy acids are particularly mentioned as examples. Preferred representatives are (a) peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, s-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxy-caproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuc-cinates and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, 2-decyldiperoxy-butane-1,4-dioic acid, N,N-terephthaloyl-di(6-aminopercaproic acid).
Other suitable bleaching agents in the dishwasher detergents according to the invention are chlorine- and bromine-releasing substances.
Suitable chlorine- or bromine-releasing materials are, for example, heterocyclic N-bromamides and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) andlor salts thereof with cations, such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethyl hydantoin, are also suitable.
The bleaching agents mentioned may also be partly or completely introduced into the dishwasher detergents according to the invention through the rinse aid particles to obtained a "post-bleaching" effect in the final rinse cycle.
Bleach activators which support the effect of the bleaching agents were mentioned earlier on as a possible ingredient of the rinse aid particles. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, irnides and acylated imidazoles or oximes. Examples are tetraacetyl ethylenediamine TAED, tetraacetyl methylenediamine TAMD an tetraacetyl hexylenediamine TAHD and also pentaacetyl glucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
The bleach activators used may be compounds which form aliphatic peroxocarboxylic acids preferably containing 1 to 10 carbon atoms and, more particularly, 2 to 4 carbon atoms andlor optionally substituted perbenzoic acid under perhydrolysis conditions. Suitable bleach activators are substances which carry O- andlor N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups.
Preferred bleach activators are polyacylated alkylenediamines, more especially tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, more especially tetraacetyl glycoluril (TAGU), N-acyl imides, more especially N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more especially phthalic anhydride, acylated polyhydric alcohols, more especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 and also acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, more especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose and acetylated, optionally N-alkylated, glucamine and gluconolactone, andlor N-acylated lactams, for example N-benzoyl caprolactam. Hydrophilically substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators may also be used.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleach catalysts may also be incorporated in the rinse aid particles. These substances are transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-ammine complexes may also be used as bleach catalysts.
Bleach activators from the group of polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), N-acyl imides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl morpholinium acetonitrile methyl sulfate (MMA) are preferably used, preferably in quantities of up to 10% by weight, more preferably in quantities of 0.1 % by weight to 8% by weight, most preferably in quantities of 2 to 8% by weight and, with particular advantage, in quantities of 2 to 6% by weight, based on the detergent as a whole.
Bleach-boosting transition metal complexes, more particularly containing the central atoms Mn, Fe, Co, Cu, Mo, V, Ti andlor Ru, preferably selected from the group of manganese andlor cobalt salts andlor complexes, more preferably the cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate, are also present in typical quantities, preferably in a quantity of up to 5% by weight, more preferably in a quantity of 0.0025% by weight to 1 % by weight and most preferably in a quantity of 0.01 % by weight to 0.25% by weight, based on the detergent as a whole.

In special cases, however, more bleach activator may even be used.
Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures thereof. All these hydrolases contribute to the removal of stains, such as protein-containing, fat-containing or starch-containing stains. Oxidoreductases may also be used for bleaching.
Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens and from genetically modified variants are particularly suitable. Proteases of the subtilisin type are preferably used, proteases obtained from Bacillus lentus being particularly preferred. Of particular interest in this regard are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease- andlor lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also been successfully used in some cases. Suitable amylases include in particular - a mylases, isoamylases, pullanases and pectinases.
The enzymes may be adsorbed to supports andlor encapsulated in shell-forming substances to protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme granules may be, for example, from about 0.1 to 5% by weight and is preferably from 0.5 to about 4.5% by weight.
Dyes and perfumes may be added to the dishwasher detergents according to the invention to improve the aesthetic impression created by the products and to provide the consumer not only with the required washing performance but also with a visually and sensorially "typical and unmistakable" product. Suitable perfume oils or perfumes include individual perfume compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume com-pounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl 5 carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetal-10 dehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, a-isomethyl ionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol and the hydrocarbons include, above all, the terpenes, such as limonene and pinene. However, mixtures 15 of various perfumes which together produce an attractive perfume note are preferably used. Perfume oils such as these may also contain natural fragrance mixtures obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime 20 blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
The perfumes may be directly incorporated in the detergents according to the invention, although it can also be of advantage to apply 25 the perfumes to supports which strengthen the adherence of the perfume to the washing and which provide the textiles with a long-lasting fragrance through a slower release of the perfume. Suitable support materials are, for example, cyclodextrins, the cyclodextrin/perfume complexes optionally being coated with other auxiliaries. The perfumes may also be 30 incorporated in the rinse aids which creates an impression of perfume on opening of the dishwasher (see above).
In order to improve their aesthetic impression, the detergents produced in accordance with the invention may be colored with suitable dyes. Preferred dyes, which are not difficult for the expert to choose, have high stability in storage, are not affected by the other ingredients of the detergents or by light and do not have any pronounced substantivity for the substrates treated with the detergents, such as glass, ceramics or plastic tableware, so as not to color them.
To protect the tableware or the machine itself, the detergents according to the invention may contain corrosion inhibitors, silver protectors being particularly important for dishwashing machines. Known corrosion inhibitors may be used. Above all, silver protectors selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkyl-aminotriazoles and the transition metal salts or complexes may generally be used. Benzotriazole andlor alkylaminotriazole islare particularly preferred. In addition, dishwashing formulations often contain corrosion inhibitors containing active chlorine which are capable of distinctly reducing the corrosion of silver surfaces. Chlorine-free dishwashing detergents contain in particular oxygen- and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloro-glucinol, pyrogallol and derivatives of these compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Of these, the transition metal salts selected from the group of manganese andlor cobalt salts andlor complexes are preferred, cobalt(ammine) complexes, cobalt(acetate) complexes, cobalt(carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate being particularly preferred. Zinc compounds may also be used to prevent corrosion of tableware.
The composition of the rinse aid particles in the dishwasher detergents according to the invention is such that they dissolve to only a limited extent, if at all, in the main wash cycle (and even in optional prerinse cycles). In this way, the active substances are only released and develop their effect in the final rinse cycle. Besides this chemical make-up, the rinse aid particles also require a physical make-up, depending on the type of dishwasher, to ensure that they are not pumped off whenever the water is changed in the machine so that they would no longer be available to the final rinse cycle. In conventional domestic dishwashers, the solution pump, which pumps the water or rather the cleaning solution from the machine after the individual cleaning cycles, is preceded by a filter insert which is supposed to prevent the pump from becoming blocked by residual soil.
Where heavily soiled tableware is cleaned by the consumer, this filter insert has to be cleaned at regular intervals which is easy to do by virtue of its ready accessibility and removability. Now, the rinse aid particles in the detergents according to the invention preferably have such a shape and size that they are unable to pass through the filter insert of the dishwasher, even after the wash cycle, i.e. after stressing by movement in the machine and by the cleaning solution. This ensures that rinse aid particles are present in the final rinse cycle of the dishwasher, releasing the active substances) and developing the required clear rinse effect under the influence of the relatively warm water. According to the invention, preferred dishwasher detergents are characterized in that the particulate rinse aid has particle sizes of 1 to 20 mm, preferably in the range from 1.5 to 15 mm and more preferably in the range from 2 to 12 mm.
In the dishwasher detergents according to the invention, the rinse aid particles with the dimensions mentioned above can project from the matrix of the other particulate ingredients, although the other particles can also have sizes in the range mentioned above so that, overall, a detergent consisting of large detergent and rinse aid particles is formulated.
Particularly in cases where the rinse aid particles according to the invention are colored, i.e. for example are red, blue, green or yellow in color, it is of advantage so far as the appearance of the product, i.e. the detergent as a whole, is concerned if the rinse aid particles are visibly larger than the matrix of the particles of the other ingredients of the detergent. In this case, preferred dishwasher detergents according to the invention are characterized in that they have particle sizes (disregarding the rinse aid particles) of 200 to 3000 Nm, preferably in the range from 300 to 2500 Nm and more preferably in the range from 400 to 2000 Nm.
Besides coloring the rinse aid particles, the visual appeal of such compositions can also be enhanced by contrasting coloring of the powder matrix or by the shape of the rinse aid particles. Since the rinse aid particles can be produced by technically uncomplicated processes, they may readily be produced in various forms. Besides the particle form, which is substantially spherical, cylindrical or cubic particles, for example, can be produced and used. In special product designs, the rinse aid particles may be present for example in the form of small stars. Disks or forms where the bottom surface is in the shape of a plant or animal, for example a tree, flower, blossom, sheep, fish, etc., are also easy to produce. In this way, interesting visual stimuli can also be created by making the rinse aid particles in the form of a stylized glass so that the clear rinse effect can also be visually emphasized in the product. There are no limits in this regard to the imaginativeness of the product developer.
If the detergents according to the invention are formulated as a powder mixture, it is possible on the one hand for partial separation to occur whenever the pack is shaken, particularly where the rinse aid particles and the detergent matrix differ considerably in size, and on the other hand for the dosage to be different in two successive cleaning cycles because the consumer does not always necessarily dose exactly the same amount of detergent and rinse aid particles. Should it be desired always to use exactly the same quantity per cleaning cycle, this may be achieved by packing the detergents according to the invention in bags of a water-soluble film, as well-known to the expert. Accordingly, the present invention also relates to particulate dishwashing detergents where a dosage unit is sealed by welding in a bag of water-soluble film.
In this way, the consumer merely has to place a bag containing, for example, a detergent powder and several visually prominent rinse aid particles in the dispensing compartment of hislher dishwashing machine.
Accordingly, this embodiment of the present invention is a visually attractive alternative to conventional detergent tablets.
The detergents according to the invention may be produced by known methods. Accordingly, the present invention also relates to a process for the production of powder-form dishwasher detergents with a clear-rinse effect, characterized in that a powder-form dishwasher detergent known per se is mixed with rinse aid particles of a) 20 to 80% by weight of one or more coating materials with a melting point above 30°C, b) 20 to 80% by weight of one or more active substances and c) 0 to 20% by weight of other auxiliaries and additives, based on the weight of the particulate rinse aid.
Besides increasing the size of the rinse aid particles, as mentioned above, the desired retention of the rinse aid particles in the machine; even when the water is changed, described in the foregoing can also be achieved by reducing the size of the holes in the filter insert. In this way, it is possible to formulate dishwasher detergents with a uniform mean particle size which is smaller than, for example, 4 to 12 mm. To this end, a filter insert which replaces or covers the insert present in the machine is added to the product according to the invention where the rinse aid particles are also relatively small in size. Accordingly, the present invention also relates to a kit-of-parts which comprises a powder-form dishwasher detergent according to the invention and a filter insert for domestic dishwashers.
As already mentioned, the combination according to the invention of detergent and filter insert enables detergents in which the rinse aid 5 particles also have relatively small particle sizes to be formulated. Kits-of-parts according to the invention where the particle sizes of the dishwasher detergent (taking the rinse aid particles into account) are in the range from 400 to 2500 Nm, preferably in the range from 500 to 1600 Nm and more preferably in the range from 600 to 1200 pm are preferred.
10 In order to prevent blockage of the filter insert by residual soil, the mesh width or hole diameter of the insert should not be too small.
Accordingly, preferred kits-of-parts according to the invention are charac-terized in that the mesh width or hole diameter of the filter insert is between 1 and 4 mm and the rinse aid particles are larger than this mesh width or 15 hole diameter of the filter insert.
The kit-of-parts according to the invention is not confined to the particular shape of the filter insert where it replaces or covers the insert present in the machine. According to the invention, it is also possible and preferred to include in the kit-of-parts a filter insert which is in the form of a 20 basket which can be suspended in known manner in the dishwasher, for example from the cutlery basket. In this way, a filter insert of this design replaces the dispensing compartment, i.e. the consumer doses the dishwasher detergent according to the invention directly into the filter insert which acts in the manner described above during the wash and final rinse 25 cycles.
The subject of the present invention is illustrated in the accompanying drawings. Figures 1 and 2 show dishwasher detergents according to the invention where the matrix of detergent particles has mean particle sizes of 600 Nm while the rinse aid particles used in accordance 30 with the invention in the detergent have mean particle sizes of 8 mm. In the interests of a visually attractive contrast, in Fig. 1 the rinse aid particles are blue in color while the basic powder is white and additionally contains red color specks, i.e. red colored particles with the same particle size. In Fig. 2, the colors red and blue have been interchanged, i.e. the basic powder is white and has blue color specks while the rinse aid particles are red.
Figures 3 and 4 show detergents according to the invention where the detergent particles, i.e. the "basic powder", have a larger mean particle size. In this case, the powder matrix has mean particle sizes of 1800 Nm while the rinse aid particles present in the detergent in accordance with the invention again have mean particle sizes of 8 mm. The particles are colored similarly to Figs. 1 and 2, i.e. in Fig. 3 the rinse aid particles are colored blue while the basic powder is white and additionally contains red color specks. In Fig. 4, the colors red and blue are again interchanged, i.e.
the basic powder is white and has blue specks while the rinse aid particles are red.
Figures 5, 6 and 7 show a dishwasher detergent according to the invention where the rinse aid particles have a mean particle size of the same order as that of the basic powder. Corresponding detergents are eminently suitable for use in the kit-of-parts according to the invention. In this case, the powder matrix has mean particle sizes of 1800 Nm while the rinse aid particles present in the detergent also has mean particle sizes of 1800 Nm. In Fig. 5, the rinse aid particles are red in color while the basic powder is white. In Fig. 6, the rinse aid particles are blue in color.
Finally, Fig. 7 shows a detergent according to the invention in which both red and also blue rinse aid particles are present. Alternatively, color specks may 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 designed to be processed to form rinse aid particles either directly or after application to a carrier material was prepared.
Process step a~prelaaration of the melt emulsion A melt emulsion SE 1 of which the composition (% by weight, based on the melt) is shown in the following Table was prepared by heating the coating material and stirring in the active substances and optional auxiliaries:

Paraffin 57-60C 49.5 Poly Tergent SLF-18B-45* 45.0 Dye 0.5 Polyglycerol-12-hydroxystearate 5.0 * Alcohol alkoxylate produced by Olin Chemicals, softening point 25-45°C
This melt emulsion may be directly prilled or pelleted to form rinse aid particles with the composition indicated above.
The invention may be varied in any number of ways as would be apparent to a person skilled in the art and all obvious equivalents and the like are meant to fall within the scope of this description and claims. The description is meant to serve as a guide to interpret the claims and not to limit them unnecessarily.

Claims

1. A particulate rinse aid comprising a) 20 to 80% by weight of one or more coating materials with a melting point above 30°C, b) 20 to 80% by weight of one or more active substances and c) 0 to 20% by weight of other active substances and auxiliaries, based on the weight of the particulate rinse aid.

2. A particulate rinse aid as claimed in claim 1, comprising one or more substances with a melting range of 40°C to 75°C as coating material in quantities of 25 to 70% by weight, based on the weight of the particulate rinse aid.

3. A particulate rinse aid as claimed in claim 2, wherein the coating material is present in quantities of 30 to 60% by weight, based on the weight of the particulate rinse aid.

4. A particulate rinse aid as claimed in claim 2, wherein the coating material is present in quantities of 40 to 50% by weight, based on the weight of the particulate rinse aid.

5. A particulate rinse aid as claimed in any one of claims 1 to 4, wherein the particulate rinse aid contains at least one paraffin wax with a melting range of 50°C to 60°C as coating material.

6. A particulate rinse aid as claimed in any of claims 1 to 5, wherein the particulate rinse aid contains one or more substances selected from surfactants, enzymes, bleaching agents, bleach activator, corrosion inhibitors, film inhibitors, co-builders and/or perfumes as active substance in quantities of 25 to 70% by weight, based on the weight of the particles.

7. A particulate rinse aid as claimed in claim 6, wherein the one or more substances are present in quantities of 30 to 60% by weight, based on the weight of particles.

8. A particulate rinse aid as claimed in claim 6, wherein the one or more substances are present in quantities of 40 to 50% by weight, based on the weight of particles.

9. A particulate rinse aid as claimed in claims 1 to 8, wherein the particulate rinse aid contains nonionic surfactants, as active substance.

10. A particulate rinse aid as claimed in claim 9, wherein the nonionic surfactants are alkoxylated alcohols.

11. A particulate rinse aid as claimed in any of claims 1 to 10, wherein the particulate rinse aid contains bleaching agents from the group of oxygen or halogen bleaching agents, as active substance.

12. A particulate rinse aid as claimed in claim 11, wherein the bleaching agent is selected from chlorine bleaching agents.

13. A particulate rinse aid as claimed in any of claims 1 to 12, wherein the particulate rinse aid contains bleach activators, as active substance.

14. A particulate rinse aid as claimed in claim 13 wherein the bleach activator is selected from polyacylated alkylenediamines, N-acyl imides and acylated phenol sulfonates as active substance.

15. A particulate rinse aid as claimed in claim 14 wherein the bleach activator is tetraacetyl ethylenediamine (TAED), or is N-nonanoyl succinimide (NOSI), n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n-or iso- NOBS), n-methyl morpholinium acetonitrile methyl sulfate (MMA) as active substance.

16. A particulate rinse aid as claimed in any of claims 1 to 15, wherein the particulate rinse aid contains other auxiliaries from the group of antisedimenting agents, antisettling agents, antifloating agents, thixotropicizing agents and dispersants in quantities of 0.5 to 9% by weight, based on the weight of the particulate rinse aid.

17. A particulate rinse aid as claimed in claim 16, wherein the other auxiliaries are present in quantities of 1 to 7.5% by weight, based on the weight of the particulate rinse aid.

18. A particulate rinse aid as claimed in claim 17, wherein the other auxiliaries are present in quantities of 1.5 to 5% by weight, based on the weight of the particulate rinse aid.

19. A particulate rinse aid as claimed in any of claims 1 to 18, wherein the particulate rinse aid additionally contains emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and/or polyoxyalkylene siloxanes in quantities of 0.1 to 5% by weight, based on the weight of the particulate rinse aid.

20. A particulate rinse aid as claimed in claim 19 wherein the emulsifiers are present in quantities of 0.2 to 3.5% by weight, based on the weight of the particulate rinse aid.

21. A particulate rinse aid as claimed in claim 20 wherein the emulsifiers are present in quantities of 0.5 to 2% by weight, based on the weight of the particulate rinse aid.

22. A particulate rinse aid as claimed in claim 21 wherein the emulsifiers are present in quantities of 0.75 to 1.25% by weight, based on the weight of the particulate rinse aid.

23. A particulate rinse aid as claimed in any of claims 1 to 22, wherein the particulate rinse aid has particle sizes of 1 to 20 mm.

24. A particulate rinse aid as claimed in claim 23 wherein the particle sizes are in the range of from 1.5 to 15mm.

25. A particulate rinse aid as claimed in claim 24 wherein the particle sizes are in the range of from 2 to 12mm.

26. A dishwasher detergent comprising builders and optionally other ingredients selected from surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and perfumes and containing a particulate rinse aid as claimed in any one of claims 1 to 25.

27. A dishwasher detergent as claimed in claim 26 wherein the particulate rinse aid is present in quantities of 0.5 to 30% by weight based on the detergent as a whole.

28. A dishwasher detergent as claimed in claim 27 wherein the particulate rinse aid is present in quantities of 1 to 25% by weight based on the detergent as a whole.

29. A dishwasher detergent as claimed in claim 28 wherein the particulate rinse aid is present in quantities of 5 to 15% by weight based on the detergent as a whole.

30. A dishwasher detergent as claimed in anyone of claims 26 to 29 for use as a machine dish washing detergent.

31. A dishwasher detergent as claimed in any of claims 26 to 30, wherein it has particle sizes (disregarding the rinse aid particles) of 200 to 3000 µm.

32. A dishwasher detergent as claimed in claim 31, wherein the particle sizes are in the range of 300 to 2500 µm.

33. A dishwasher detergent as claimed in claim 32, wherein the particle sizes are in the range of 400 to 2000 µm.

34. A dishwasher detergent as claimed in any of claims 26 to 33, wherein the detergent comprises dosage units and each dosage unit is sealed by welding in a bag of water-soluble film.

35. A process for the production of powder-form dishwasher detergents having a clear rinse effect, characterized in that a powder-form dishwasher detergent is mixed with rinse aid particles of a composition comprising a) 20 to 80% by weight of one or more coating materials with a melting point above 30°C, b) 20 to 80% by weight of one or more active substances and c) 0 to 20% by weight of other active substances and auxiliaries, based on the weight of the particulate rinse aid.

36. A kit-of-parts comprising a powder-form dishwasher detergent as claimed in any of claims 26 to 34 and a filter insert for domestic dishwashing machines.

37. A kit-of parts as claimed in claim 36, wherein the particle sizes of the dishwasher detergent (taking into account the rinse aid particles) are in the range from 400 to 2500 µm.

38. A kit-of-parts as claimed in claim 37 wherein the particles are in the range of from 500 to 1600 µm.

39. A kit-of-parts as claimed in claim 38 wherein the particles are in the range of from 600 to 1200 µm.

40. A kit-of-parts as claimed in claims 36, 37, 38 or 39, wherein the mesh width or hole diameter of the filter insert is 1 to 4 mm and the rinse aid particles are larger than this mesh width or hole diameter of the filter insert.