EP1103599A1 - Particle form rinse aid and dishwasher detergent composition - Google Patents

Abstract

Particulate rinse aid comprises 5-95 wt.% active component(s) and 95-5 wt.% carrier and/or binder and is compressed so that the materials are released at a predetermined time (frame). Particulate rinse aid comprises 5-95 wt.% active component(s), 95-5 wt.% carrier and/or binder and 0-10 wt.% aids and is compressed so that the materials are released at a predetermined time (frame). Independent claims are included for the production of the above aid by mixing and compressing the components, a particulate dishwashing detergent containing 0.5-30, especially 2-15 wt.% of the above rinse aid and a kit comprising this detergent and a strainer.

Description

The present invention relates to particulate rinse aid for machine dishwashing, containing 95 to 5% by weight of one or more carrier materials and / or binders, and, 5 to 95% by weight of one or more active substances, and 0 to 10% by weight of another Active ingredients and auxiliaries, a process for its production and particulate mechanical Dishwashing detergent (MGSM) containing the rinse aid particles.

The automatic cleaning of dishes in domestic dishwashers usually includes a pre-rinse, a main rinse and a rinse cycle that of intermediate rinse to be interrupted. On most machines, the pre-rinse cycle is for heavily soiled crockery can be switched on, but is only used by the consumer in exceptional cases selected so that in most machines a main rinse cycle, an intermediate rinse cycle with pure water and a rinse aid. The temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection. In the rinse cycle, rinse aid is added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your task consists primarily of preventing limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often contain also hydrotopes, pH regulators such as citric acid or deposit-inhibiting polymers.

The storage tank in the dishwasher must be rinse-aid at regular intervals be filled, whereby one filling is sufficient for 10 to 50 rinse cycles, depending on the machine type. If the refilling of the tank is forgotten, glasses in particular are worn out Limescale and deposits unsightly. There are therefore some proposed solutions in the prior art, a rinse aid in the detergent for machine dishwashing to integrate. These proposed solutions are based on the offer form of the compact Molded body bound.

For example, European patent application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agents and a continuous medium with a melting point between 55 and 70 ° C. and scale inhibitors contains. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) should be released with a delay and cause a rinse aid effect. Powdered machine dishwashing detergents or surfactant-containing rinse aid systems are not mentioned in this document.

The present invention was based on the object of the advantages of controlled release of ingredients, especially a rinse aid, both for powder detergents as well as for granules and detergent tablets. Here should avoid complex procedural steps such as coating or multiple coating can be. Rather, an offer form should be provided that is both separate as a solid form of rinse aid to be dosed by the consumer as well as an admixing component can be used for powdered machine dishwashing detergents.

It has now been found that mixtures of carrier materials, active ingredients and optional other ingredients, such as enzymes, colors and fragrances etc. as well as suitable carrier materials and / or binders can be compressed such that the active substances as well as the further ingredients at a predetermined time or during a predetermined Period will be released.

a) 5 bis 95 Gew.-% eines oder mehrerer Aktivstoffe,

b) 95 bis 5 Gew.-% eines oder mehrerer Trägermaterialien und/oder Bindemittel, sowie

c) 0 bis 10 Gew.-% weiterer Wirk- und Hilfsstoffe enthält,

dadurch gekennzeichnet, dass
die Komponenten a und b und ggf. c derart verdichtet sind, dass die Aktivstoffe der Komponente a und ggf. die weiteren Inhaltsstoffe der Komponente c zu einem vorbestimmten Zeitpunkt oder während eines vorbestimmten Zeitraumes im Reinigungsprozeß freigesetzt werden. The present invention relates to a particulate rinse aid for machine dishwashing

a) 5 to 95% by weight of one or more active substances,

b) 95 to 5% by weight of one or more carrier materials and / or binders, and

c) contains 0 to 10% by weight of further active ingredients and auxiliaries,

characterized in that
components a and b and possibly c are compressed in such a way that the active ingredients of component a and possibly the further ingredients of component c are released at a predetermined point in time or during a predetermined period in the cleaning process.

The delayed release of the active ingredients and possibly other ingredients to a predetermined one Time or during a predetermined period in the cleaning process takes place in the particulate rinse aid according to the invention by adjusting the strength the molded body and depending on the amount and type of the respective components, especially the binder.

A usual process sequence in automatic dishwashing is that after the actual one The dishes are cleaned and then a so-called rinse cycle is carried out becomes. The particles according to the invention can be compressed in such a way that the compressed ones Particles in the main rinse cycle remain largely unchanged or only soften, swell or only erode on the surface and disintegrate in the subsequent rinse cycle and the active substances, how to release the rinse aid and any other substances. The one described here The delayed release process can also be referred to as "retarded decay" become.

The active substances to be incorporated into the rinse aid particles according to the invention can be used in the Processing temperature (i.e. the temperature at which the particles are produced) both in solid and in liquid form.

The active substances contained in the rinse aid particles fulfill certain tasks. Through the Separation of certain substances or by the accelerated or delayed time Release of additional substances can improve cleaning performance. Active substances, which are preferably incorporated into the rinse aid particles are therefore such ingredients of detergents and cleaning agents that are crucial to the washing or cleaning process involved.

In preferred rinse aid particles there are therefore one or more substances from the active substances Groups of surfactants, bleaches, bleach activators, corrosion inhibitors, scale inhibitors and / or cobuilders in amounts of 5 to 95% by weight, preferably 10 to 70% by weight and in particular from 10 to 60% by weight, based in each case on the particle weight.

In a particularly preferred embodiment of the present invention, the is or the active substance (s) selected from the group of nonionic surfactants, in particular of the alkoxylated alcohols. These substances are described in detail below.

Another class of active substances, which are particularly advantageous in the invention Having rinse aid particles incorporated is bleach. Also are detergents can be produced for automatic dishwashing in such a way that additional rinse aid Bleach is released and so difficult stains, such as tea stains more effectively be removed.

In preferred particulate rinse aid particles, the active substance (s) is / are selected from the group of oxygen or halogen bleaches, in particular the Chlorine bleach. These substances are also described in detail below.

Another class of compounds, which are preferred as active substances in the invention Rinse aid particles can be used are the bleach activators. The important representatives from this group of substances are also described below. in the Rinse aid particles preferred within the scope of the present invention contain as active substance Bleach activators, especially from the groups of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA).

Fragrances can also be used as active substances in the rinse aid particles according to the invention incorporate. All fragrances described in detail below can be used as Active substance can be used. When fragrances are incorporated into the rinse aid particles This results in cleaning agents that release all or part of the perfume with a time delay. In this way, for example, cleaning agents for the machine are according to the invention Dishwashing can be produced, in which the consumer even after cleaning the dishes experienced the perfume note when opening the machine. In this way, the eliminates the undesirable "alkaline smell" that adheres to many automatic dishwashing detergents become.

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

The carrier materials and / or binders of component b) can be made from all of the State-of-the-art materials can be selected for the production of compacted Particles are suitable. It is obvious to a person skilled in the art that they are simultaneously as a carrier for the active substances and also as a binder in the particles according to the invention can work.

Suitable carrier materials b) are all substances which are solid at room temperature, which have sufficient absorption capacity for the active substance (s). One can also select substances that have an additional effect, whereby builders especially offer. For example, substances from the group of solid detergent and detergent ingredients can be used, preferably the zeolites, Bentonites, silicates, carbonates, hydrogen carbonates, sulfates, phosphates, and synthetic Polymers, e.g. cross-linked polycarboxylates, polyvinyl alcohols, and at room temperature solid organic polycarboxylic acids. Also natural or semi-synthetic polymers such as starch derivatives and cellulose derivatives can be used

The preferred carrier materials mentioned are described in detail below.

A large number of binders known from pharmacy are used as binders Tablets in question. They differ in their hydrophilicity / hydrophobicity, their solubility and resulting from their binding effect under the influence of the washing liquor. In particular can substances from the group of polyalkylene glycols and polyoxyalkylene glycols different molecular weight can be used. Have proven themselves Higher molecular weight polyethylene glycols that are solid at room temperature. Besides other substances are also suitable, e.g. Waxes, paraffins, fatty acid salts (soaps), in particular Stearates; Fatty acids and fatty alcohols, fatty acid esters, cellulose derivatives, hydrocolloids, Mono-, oligo-, or polysaccharides and polymer compounds (e.g. polyacrylates) and resins.

The rinse aid particles according to the invention can contain further active ingredients as further ingredients Contain auxiliaries, such as. B. enzymes, colors and fragrances etc.

The particulate rinse aid according to the invention can be produced in various ways.

a) 5 bis 95 Gew.-% eines oder mehrerer Aktivstoffe,

b) 95 bis 5 Gew.-% eines oder mehrerer Trägermaterialien und/oder Bindemittel, sowie

d) 0 bis 10 Gew.-% weiterer Wirk- und Hilfsstoffe,

worin ein Gemisch aus den Komponenten a und b und ggf. c hergestellt wird und das Gemisch derart verdichtet wird, dass die Aktivstoffe der Komponente a und ggf. die weiteren Inhaltsstoffe der Komponente c zu einem vorbestimmten Zeitpunkt oder während eines vorbestimmten Zeitraumes im Reinigungsgang freigesetzt werden.Another object of the present invention is a process for producing telcheniform rinse aid containing

a) 5 to 95% by weight of one or more active substances,

b) 95 to 5% by weight of one or more carrier materials and / or binders, and

d) 0 to 10% by weight of further active ingredients and auxiliaries,

wherein a mixture of components a and b and optionally c is produced and the mixture is compressed in such a way that the active ingredients of component a and possibly the further ingredients of component c are released at a predetermined point in time or during a predetermined period in the cleaning cycle .

Regarding the ingredients used in the method according to the invention and the inventive Rinse aid particles are processed, the same applies as above.

The statements made above also apply to the active substances. As active ingredients are preferred one or more substances from the groups of surfactants including rinse aid surfactants, Bleach, bleach activator, corrosion inhibitors, scale inhibitors and / or cobuilders contain.

To carry out the method, a mixture, preferably one, is preferably first used Melt mixture of the ingredients including any other active and Excipients manufactured. In the event that the active ingredients of component a) or active ingredients and h-substances are in liquid form, they can first be placed on suitable carrier materials applied and mixed with binder if necessary. Then the obtained one Mixture compressed according to the invention. Compression can be done in a manner known per se Way. In a preferred embodiment, the compression in a tablet press or carried out in an extruder. The compression in a tablet press is particularly preferred, all common press types can be used, e.g. hydraulic Presses, eccentric presses or rotary presses. Another possible compression method represents processing in roller presses.

In a further embodiment of the present invention, the active substances are initially applied to a carrier in a manner known per se and then, if appropriate in the presence compressed by further components and / or binders. Applying the Active substances on the carrier material can be carried out in all usual mixing devices become.

The rinse aid particles according to the invention can be given directly to the consumer so that he also doses them to the cleaning agent as required. Because of this additional dosing step, however, would be in addition to the fixed form of supply and the addition in the same dosing compartment the advantages over liquid rinse aid minimized. It is therefore preferred that the rinse aid particles according to the invention are particulate to combine with automatic dishwashing detergents.

Another object of the present invention is therefore also a particulate mechanical Dishwashing detergent containing builders and optionally other ingredients the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, Polymers, dyes and fragrances, and a particulate rinse aid according to the invention in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular of 2 to 15 wt .-%, based on the total average.

The ingredients of automatic dishwashing detergents are described below. To the Some of these can also be used as active substances or carrier materials in the inventive Rinse aid particles are included.

The most important ingredients in automatic dishwashing detergents are builders. In the Detergents according to the invention for machine dishwashing can all be used builders usually used in detergents and cleaning agents, in particular, zeolites, silicates, carbonates, organic cobuilders, the phosphates. The Builders mentioned below are all as carrier materials for the inventive Rinse aid particles are suitable, as already explained above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} . H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. 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 disilicates are Na ₂ Si ₂ O ₅ . yH2O preferred.

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O. (1-n) K ₂ O. Al ₂ O ₃ . (2 - 2.5) SiO ₂ . (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible. Among the variety of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm-3, melting point 60 °) and as a monohydrate (density 2.04 gcm-3). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt with a density of 2.33 gcm-3, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water .

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. 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 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% 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 tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the dishwasher detergents according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates be used. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use for ecological reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower pH value of detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass from 500 to 70,000 g / mol.

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid, 50 to 90 % By weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances, for example polyaspartic acids or their salts and derivatives.
Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is a polysaccharide with a dextrose equivalent (DE) in the range from 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 are usable Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly special Meaning as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As aminoalkane phosphonates come preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as a hexasodium salt the EDTMP or as the hepta and octa sodium salt of DTPMP. As Builder from the phosphonate class is preferably HEDP. The aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly it can be preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

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

In addition to the builders, there are in particular substances from the groups of surfactants Bleach, bleach activators, enzymes, polymers, colors and fragrances important ingredients of detergents. Important representatives from the substance classes mentioned are described below.

Usually only surfactants are used in automatic dishwashing detergents low-foaming nonionic surfactants are used. Representatives from the groups of In contrast, anionic, cationic or amphoteric surfactants have a lower level Meaning, but are not excluded. The contain with particular preference Machine dishwashing detergents according to the invention are nonionic surfactants it is preferred that a part,, of the total surfactant contained in the cleaning agents in 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 rinse cycle release. 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 surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly 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 containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C ₁₂ _ ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (III),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] 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 rest.

[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, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In addition to the pure nonionic surfactants, other substances can of course also be used from the group of ionic surfactants, for example anionic or cationic surfactants, in the machine dishwashing detergents according to the invention may be included. You can do this be contained both in the basic detergent and in the rinse aid particles. In particular may contain alkyl sulfates in the rinse aid particles.

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

As a bleach in the cleaning agents according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable. The bleaches mentioned can also be used to achieve "post-bleaching" in the rinse cycle wholly or partly via the rinse aid particles according to the invention in the inventive machine dishwashing detergent.

Bleach activators that support the action of the bleach have already been mentioned above mentioned as a possible ingredient of the rinse aid particles. Known bleach activators are Compounds containing one or more N or O acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 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 as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives , in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated gluc amine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts are incorporated into the rinse aid particles. With these fabrics are bleach-enhancing transition metal salts or transition metal 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 as well Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

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

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group 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, the manganese sulfate are in conventional amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in In special cases, more bleach activator can be used.

Enzymes in particular come from the cleaning agents according to the invention the classes of hydrolases such as proteases, esterases, lipases or lipolytic Enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help remove soiling such as protein, fat or starch Stains on. Oxidoreductases can also be used for bleaching. Bacterial strains or fungi such as Bacillus subtilis or Bacillus are particularly suitable licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well their genetically modified variants obtained enzymatic active ingredients. Preferably are proteases of the subtilisin type and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures are, for example, from Protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the consumer, in addition to performance, a visually and sensorially "typical and unmistakable" To provide product. Individual as perfume oils or fragrances Fragrance compounds, e.g. synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether Aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together have an appealing fragrance produce. Perfume oils of this type can also contain natural fragrance mixtures such as these are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, Lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, Galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can also be incorporated into the rinse aid particles according to the invention, which leads to a scent 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 thereof) are dyed with suitable dyes. Preferred dyes, the selection of which is no problem for the person skilled in the art has a high storage stability and insensitivity to the other ingredients of the agents and to light as well as no pronounced substantivity towards those to be treated with the agents Substrates such as glass, ceramics or plastic dishes so as not to stain them.

The cleaning agents according to the invention can protect the dishes or the machine Contain corrosion inhibitors, especially silver protection agents in the area of automatic dishwashing have a special meaning. The known ones can be used State of the art substances. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, Aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used become. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in detergent formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners organic and redox-active compounds containing oxygen and nitrogen, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, Gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, the are 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 to prevent corrosion on the wash ware become.

The composition of the rinse aid particles according to the invention is designed such that that they are not in the main wash cycle (and also in optional pre-wash cycles) or only in a subordinate one Dimensions disintegrate. This ensures that the active substances largely are only released in the rinse aid cycle and develop their effect here. In addition to this chemical Depending on the type of dishwasher, assembly is a physical one Packaging required so that the rinse aid particles when changing the water in the machine are not drained and are therefore no longer available for the rinse aid. Domestic dishwashers contain in front of the drain pump, which the Water or the cleaning solution after the individual cleaning cycles from the machine pumps, a strainer that prevents the pump from becoming clogged with dirt should. If heavily soiled dishes are washed by the consumer, this must be used be cleaned regularly, which is due to the easy accessibility and removability is easily possible. The rinse aid particles according to the invention are now regarding their size and shape preferably designed so that they are the sieve insert of the dishwasher even after the cleaning cycle, i.e. 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 aid, the active substance (s) release and bring the desired rinse aid effect. As part of the present Particulate rinse aid particles preferred according to the invention are characterized in that that the particulate rinse aid preferably has particle sizes between 2 and 30 mm between 2.5 and 25 mm and in particular between 3 and 20 mm.

In one embodiment of the present invention, the rinse aid particles become common powdered or granular machine dishwashing agents added.

In a further preferred embodiment, the rinse aid particles become common with the ingredients of machine dishwashing detergents to form a combination product Dishwasher detergent and rinse aid processed. Such products are preferably so-called Shaped bodies, also referred to as tablets in the prior art.

The combination products can be produced in a manner known per se. In a In one possible embodiment, the moldings and the rinse aid particles are produced separately and then connected to each other, the moldings can already be used for the particles have prefabricated recesses. The connection can, for example, by simply insert into the recess or glue the two fixed components.

In a further embodiment, the rinse aid particles or the premix for this in a suitable tabletting device with the premix for the dishwashing liquid Molded bodies processed.

In the dishwashing detergents according to the invention, the rinse aid particles with the above protruding sizes from the matrix of the other particulate ingredients, the other particles can also have sizes in the range mentioned so that overall a cleaning agent is formulated that consists of large cleaning agent and rinse aid particles. Especially when the invention Rinse aid particles are colored, for example a red, blue, green or yellow Color, it is for the appearance of the product, i.e. of the entire detergent an advantage if the rinse aid particles are visibly larger than the matrix the particles of the other ingredients in the detergent. Here are inventive particulate machine dishwashing detergent preferred (without taking into account the Rinse aid particles) particle sizes between 200 and 3000 pm, preferably between 300 and 2500 pm and in particular between 400 and 2000 microns.

The optical appeal of such compositions can, in addition to the coloring of the rinse aid particles also by contrasting coloring of the powder matrix or by the shape of the Rinse aid particles are increased. Because in the manufacture of rinse aid particles on technical uncomplicated procedures can be resorted to, it is easily possible to use these in to offer a wide variety of shapes. In addition to the cylindrical particle shape, for example approximately spherical or cube-shaped rinse aid particles can be produced and used. Other geometric shapes can also be realized. Special product designs can contain star-shaped rinse aid particles, for example. Also Disks or shapes that form the base of plants and animal bodies, for example trees, Show flower, blossom, sheep, fish, etc. can be easily produced. Interesting optical Incentives can also be created in this way by having the rinse aid particles in the form of a stylized glass to visually add the rinse aid effect to the product underline. There are no limits to your imagination.

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

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

The cleaning agents according to the invention can be produced in a manner known per se. A process for producing powdered dishwasher detergents with a rinse aid effect, in which a powdered dishwasher detergent known per se with inventive Rinse aid particles are mixed is therefore another subject of present invention.

The desired retention of the rinse aid particles in the machine described above in the case of water changes, in addition to the above-mentioned enlargement Realize rinse aid particles by reducing the holes in the sieve insert. On this way you can formulate automatic dishwashing detergents that have a uniform medium Have particle size which is smaller than, for example, 4 to 12 mm. To do this the product according to the invention, in which the rinse aid particles also have smaller particle sizes have a sieve insert added to the insert in the machine replaced or covers. Another object of the present invention is therefore a kit-of-parts, which is an inventive powdered dishwashing detergent and includes a sieve insert for household dishwashers.

As already mentioned, the combination of agent and sieve insert according to the invention allows the formulation of agents in which the rinse aid particles also have smaller particle sizes exhibit. Kits-of-parts according to the invention, in which the particle sizes of the machine Dishwashing detergent (taking into account the rinse aid particles) in the range from 400 to 2500 µm, preferably from 500 to 1600 µm and in particular from 600 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 according to the invention kits-of-parts are preferred in which the mesh size or hole size of the sieve insert 1 is up 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 restricted to the specific shape of the sieve insert, where it replaces or covers the insert in the machine. It it is also possible and preferred according to the invention to include a sieve insert in the kit of parts, which has the shape of a basket, which is in a known manner in the dishwasher - for example on the cutlery basket - can be hung. In this way A sieve insert designed in this way replaces the dosing chamber, i.e. the consumer doses the dishwasher detergent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.

Examples:

The carrier material was incorporated into the melted rinse aid until the resulting compound had a granular structure. The additive was then incorporated and the mixture was pressed into compacts using a hydraulic press.
The composition of the mixture (% by weight, based on the mixture) is given in the table below: Polypore ¹ E200 20th - Water glass - 36 Poly Tergent SLF-18B-45 ² 47 37 PEG 35000 33 27

The mass of the compacts can be between 0.5 g and 2 g. The pressing force is so chosen that the compacts in the 65 ° C program of a dishwasher at the end of the rinse cycle have crumbled.

In the present example, the compacts were placed in a cylindrical trough in the ordinary MGSM cleaning tabs used.

To show that the tablet according to the invention has a sufficient amount of rinse aid transported in the rinse aid was carried out in a 65 ° C rinsing test with the inventive Tablet measured the surface tension of the rinse aid. It was receive a value of 28 mN / m, i.e. the maximum possible with the surfactant used Lowering of surface tension

Claims (21)

Containing particulate rinse aid for automatic dishwashing a) 5 to 95% by weight of one or more active substances, b) 95 to 5% by weight of one or more carrier materials and / or binders, and c) 0 to 10% by weight of further active ingredients and auxiliaries, characterized in that
components a, b and possibly c are compressed in such a way that the active ingredients of component a and possibly the further ingredients of component c are released at a predetermined point in time or during a predetermined period in the cleaning process. Particulate rinse aid according to claim 1, characterized in that it contains surfactants, bleaches, bleach activators, corrosion inhibitors, scale inhibitors and / or builders in amounts of 5 to 95% by weight, preferably 10 to 70% by weight and in particular 10 up to 60 wt .-%, based in each case on the particle weight. Particulate rinse aid according to claims 1 or 2, characterized in that it contains surfactants, preferably nonionic surfactants, in an amount of up to 95% by weight, preferably from 7.5 to 70% by weight and in particular from 10 to 60% by weight. %, each based on the particle weight. Particulate rinse aid according to claim 3, characterized in that the surfactants are nonionic surfactants, preferably alkoxylated alcohols. Particulate rinse aid according to one of claims 1 to 4, characterized in that it contains bleaching agents from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, as the active substance. Particulate rinse aid according to one of claims 1 to 5, characterized in that it contains bleach activators as active substance, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), of acylated phenolsulfonates , in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA). Particulate rinse aid according to one of claims 1 to 6, characterized in that the binders include polyethylene glycols, paraffins, waxes, polymeric compounds (eg polyacrylates), hydrocolloids (eg galactomannan, cellulose ethers), mono-, oligo- or polysaccharides and / or resins . Particulate rinse aid according to one of claims 1 to 7, characterized in that it contains, as carrier materials, substances selected from zeolites, bentonites, silicates, carbonates, hydrogen carbonates, sulfates, phosphates, synthetic polymers, such as crosslinked polycarboxylates, polyvinyl alcohols, the polycarboxylic acids which are solid at room temperature or natural or contains semi-synthetic polymers such as starch or cellulose derivatives. Process for making particulate rinse aid containing a) 5 to 95% by weight of one or more active substances, b) 95 to 5% by weight of one or more carrier materials and / or binders, and c) contains 0 to 10% by weight of further active ingredients and auxiliaries, characterized in that
components a and b and possibly c are compressed in such a way that the active ingredients of component a and possibly the other ingredients of component c are released at a predetermined point in time or during a predetermined period in the cleaning cycle. A method according to claim 9, characterized in that the particles are compacted in a press or by extrusion. Method according to one of claims 9 or 10, characterized in that components a) are applied to component b and then optionally compressed with the addition of further substances. Method according to one of claims 9 to 11, characterized in that the mixture to be compressed as an active ingredient one or more substances from the groups of surfactants, bleaching agents, bleach activator, corrosion inhibitors, scale inhibitors and / or cobuilders in amounts of 5 to 80 wt .-% , preferably from 10 to 70 wt .-% and in particular from 10 to 60 wt .-%, each based on the particle weight. Particulate machine dishwashing detergent, containing builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, colorants and fragrances, characterized in that it contains a particulate rinse aid according to one of claims 1 to 10 in amounts of 0 , 5 to 30 wt .-%, preferably from 1 to 25 wt .-% and in particular from 2 to 15 wt .-%, each based on the total agent. Particulate dishwasher detergent according to claim 13, characterized in that the particulate rinse aid has particle sizes between 1 and 30 mm, preferably between 1.5 and 25 mm and in particular between 2 and 20 mm. Particulate machine dishwashing detergent according to one of claims 13 or 14, characterized in that (without taking into account the rinse aid particles) it has particle sizes between 200 and 3000 µm, preferably between 300 and 2500 µm and in particular between 400 and 2000 µm. Particulate machine dishwashing detergent according to one of claims 15 to 17, characterized in that it contains the rinse aid particles according to one of claims 1 to 8 in a mixture with the other ingredients customary for machine dishwashing detergents. Particulate machine dishwashing detergent according to one of claims 15 to 17, characterized in that it is a shaped body which contains the rinse aid particles according to one of claims 1 to 8 and ingredients customary for machine dishwashing detergents. Particulate machine dishwashing detergent according to one of claims 15 to 17, characterized in that a dosing unit is packaged in a bag made of water-soluble film. Kit-of-parts, comprising a powdered automatic dishwashing agent according to one of claims 15 to 18 and a sieve insert for household dishwashers. Kit-of-parts according to claim 20, characterized in that the particle size of the machine Dishwashing detergent (taking into account the rinse aid particles) in the area from 400 to 2500 μm, preferably from 500 to 1600 pm and in particular from 600 to 1200 µm. Kit of parts according to one of claims 20 or 21, characterized in that the Mesh size or hole size of the sieve insert is 1 to 4 mm and the rinse aid particles are larger than this mesh size or hole size of the sieve insert.