DE19960096A1 - Particulate rinse aid and machine dishwashing detergent - Google Patents

Abstract

A particulate wetting agent, for machine dishwashing is disclosed, which comprises (a) 10 to 90 wt. % of one or several matrix materials, selected from polymers, which are solid at room temperature; (b) 90 to 10 wt. % of one or several active ingredients and (c) 0 to 10 wt. % of additional active ingredients and adjuncts. Said particulate wetting agent can be produced in supplied form, either as a solid rinsing agent for measuring out by the user, or as an additive component in a machine dishwashing agent.

Description

The present invention is in the field of automatic dishwashing detergents for the home standard dishwashers. It particularly relates to particulate mechanical Ge Dishwashing detergent (MGSM) containing rinse aid particles.

The automatic cleaning of dishes in domestic dishwashers usually includes se a pre-wash, a main wash and a rinse cycle by intermediate rinse be interrupted. With most machines, the pre-rinse cycle is very dirty zes dishes can be switched on, but is only selected in exceptional cases by the consumer, so that in Most machines have a main wash, an intermediate wash with pure water and a Rinse aid. The temperature of the main wash cycle varies depending on Machine type and program level selection between 40 and 65 ° C. In the rinse aid cycle, added a rinse aid to a dosing tank in the machine, which is usually used as the main contain non-ionic surfactants. Such rinse aids are in liquid form and are widely described in the prior art. Your job primarily consists of Kalkflec and to prevent deposits on the cleaned dishes. In addition to water and weakly shy With non-ionic surfactants, these rinse aids often also contain hydrotopes, pH adjusting agents such as Citro Nenoic acid or scale-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 you forget to fill the tank, glasses with limescale marks and Unsightly toppings. In the prior art, there are therefore some proposed solutions, one Integrate rinse aid into the detergent for machine dishwashing. This Lö Proposed solutions are tied to the offer form of the compact molded body.  

The European patent application EP-A-0 851 024 (Unilever) describes two-layer Rei detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer of acidifying agent and a continuous medium with a Contains melting point between 55 and 70 ° C and scale inhibitors. By melting up Continuous medium should delay the release of the acid (s) and scale inhibitor (s) and cause a rinse aid effect. Powdered automatic dishwashing detergent or Rinse aid systems containing surfactants are not mentioned in this document.

The older German patent application DE 198 51 426.3 (Henkel KGaA) describes a method for the production of multi-phase detergent tablets, in which a particle shaped premix is pressed into moldings which have a trough, which later with a separately prepared melt suspension or emulsion from a coating substance and one or more active substance (s) dispersed or suspended in it. Also the teaching of this document is tied to the "tablet" offer form. Powder detergent, which contain a "second phase", which be controlled release of ingredients achieve certain effects are not revealed.

The present invention was based on the object of the advantages of controlled release of ingredients, especially a rinse aid, also for powdery cleaning to make medium usable. Rather, an offer form should be provided that both separately as a rinse aid to be dosed by the consumer in a solid form and also as a admixture component can be used for powdered machine dishwashing detergents.

It has now been found that mixtures of a matrix material, active ingredients and optional other ingredients such as emulsifiers, colors and fragrances etc. after incorporation in transform a matrix into a particulate form that meets the above criteria enough.

The present invention relates to a particulate rinse aid for machine dishwashing

• a) 10 to 90 wt .-% of one or more matrix materials selected from at room temperature solid polymers,
• b) 90 to 10% by weight of one or more active substances and  
• c) 0 to 10% by weight of further active ingredients and auxiliaries

contains.

All substances which are solid at room temperature and which are considered as Matrix material for the active substances and any other active substances and auxiliaries present can serve substances and the release by a special solution kinetics of these substances in enable a rinse aid. The matrix materials are preferably meltable poly mers or polymer mixtures.

Polyurethanes have proven to be particularly suitable, preferably are meltable and / or soluble or swellable in water. The polyurethanes are becoming more common obtained by reacting polyols with a di- or polyisocyanate compound.

As polyol monomers are in particular dihydric and polyhydric alkyl alcohols having 2 to 22, preferably 6 to 22 carbon atoms, polyether polyols such as polyalkylene glycols, for. B. polyethylene glycol or polypropylene glycol, polyester polyols suitable. Crystallizing diols, in particular from the following group, are particularly suitable
Polyethylene glycol with a number average molecular weight of 200 to 40,000, in particular 1,500 to 15,000 and preferably 4,000 to 8,000,
Polytetrahydrofuran with a molecular weight of 200 to 4,000,
Copolymer of ethylene oxide and propylene oxide with a molecular weight of 200 to 40,000, preferably from 400 to 10,000, the copolymer expediently being a block copolymer of the PEG / PPG / PEG type with a PEG content of 10 to 80% and optionally
Polyester diol, in particular a polycaprolactone diol with a molecular weight of 200 to 50,000, in particular 200 to 5,000,
optionally at least one diol which is capable of ion formation, in particular the formation of carboxylate, sulfate or ammonium ions and
optionally at least one 3 or higher functional polyol such as glycerol and TMP and
optionally at least one hydrophobic diol, in particular from the group:
Polypropylene glycol with a molecular weight of 200 to 4000, in particular from 500 to 2000 and
Alkanediol with 1 to 100, in particular from 2 to 50, particularly preferably 5 to 30, carbon atoms.

Both aliphatic and aromatic isocyanates are suitable as the isocyanates. Examples of aliphatic isocyanates are linear alkyl diisocyanates, where the alkyl group can have a chain length of 4 to 12 carbon atoms. Examples of aromatic di- and polyisocyanates are ditolylene diisocyanates, xylylene diisocyanates, divinylalkane diisocyanates, naphthylene diisocyanates etc. Special examples of the aromatic diisocyanates are 4,4'-methylene di (phenyl isocyanate) (MDI), hexamethylene diisocyanate (HDI) , 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI), toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, naphthylene-1,5-diisocyanate, divinylmethane-4,4 ' isocyanate, tetramethylxylene III socyanate (TMXDI); 1,3-bis (1-isocyanato-1-methylethyl) benzene, hydrogenated MDI (H ₁₂ MDI), xylylene diisocyanate (XDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenyl methane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4- trimethylhexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1 , 4-diisocyanate, ethylene diisocyanate, bis-isocyanatoethyl ethyl phthalate, fer ner diisocyanates with reactive halogen atoms, such as 1-chloromethylphenyl-2,4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, 3,3-bis-chloromethyl ether -4,4'-diphenyl diisocyanate. Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexysulfide. Other important diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane and dimer fatty acid diisocyanate. Particularly suitable are: tetramethylene, hexamethylene, undecane, dodecamethylene, 2,2,4-trimethylhexane, 1,3-cyclohexane, 1,4-cyclohexane, 1,3- or 1,4-tetramethylxylene -, Isophorone, 4,4-dicyclohexylmethane and lysine ester diisocyanate.

The isocyanates can be polymers of one polyol monomer and one polyisocyanate monomer or copolymers of several polyol monomers and isocyanate monomers. An example of a suitable copolymer is a polyurethane that contains a polyethylene glycol and a C _12-18 alkyl diol and TMXDI as the isocyanate component as the polyol monomers.

The ratio of the isocyanate groups to the hydroxyl groups can be from 0.5 to 1.2: 1, in particular in particular vary from 0.7 to 1: 1.

The matrix materials are preferred in the particulate rinse aid according to the invention in an amount of 10 to 70% by weight, particularly preferably in an amount of 25 to 60% by weight, based on the finished particulate rinse aid.

Active substance (s)

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) so probably in solid as well as in liquid form.

The active substances contained in the rinse aid particles fulfill certain tasks. Through the Separation of certain substances or through the accelerated or delayed release The cleaning performance can be improved by adding additional substances. Active Substances that are preferably incorporated into the rinse aid particles are therefore such contents substances from washing and cleaning agents that are crucial to the washing or cleaning process involved.

Preferred rinse aid particles therefore contain one or more substances from the group as active substance Pen of surfactants, bleaching agents, bleach activator, corrosion inhibitors, scale inhibitors and / or cobuilders in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight and in particular from 10 to 20% by weight, based in each case on the particle weight. Fragrance Substances and enzymes can also be included as active substances, with the components übli are usually present in amounts of up to 2% by weight.

Rinse aid can be achieved by incorporating surfactants into the melted matrix material lerparticles produce the z. B. in a ready-made cleaning agent; that invented contains rinse aid particles according to the invention, at a predetermined time additional provides detergent substance. For example, according to the invention Produce rinse aid particles for automatic dishwashing that contain the additional surfactant release at temperatures, which household dishwashers only in rinse aid reach gear. In this way, additional surfactant is available in the rinse cycle  the drainage of the water accelerates and effectively prevents stains on the wash ware different. With a suitable amount of solidified melt suspension or emulsion in the rinse aid Particles can be dispensed with the use of additional rinse aid that is common today the.

In preferred rinse aid particles, the active substance (s) is / are selected from the Group of nonionic surfactants, especially 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 worked in is bleach. This can cause particles provides that release the bleach only when certain temperatures are reached ready-made cleaning agents, for example, which clean enzymatically in the pre-rinse cycle and only release the bleach in the main wash cycle. Also are detergents for the ma Fast dishwashing can be produced in such a way that additional bleach releases in the rinse cycle be set and so remove difficult stains, for example tea stains, more effectively.

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

Another class of compounds, which are preferred as active substances in the Invention The bleach activators are suitable as rinse aid particles. Also the important representatives from this group of substances are described below. As part of the The present invention preferred rinse aid particles contain bleaching acti as the active substance vators, in particular from the groups of polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (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 Ak active substance can be used. When fragrances are incorporated into the rinse aid particles  Detergents that release all or part of the perfume with a time delay. In this way, according to the invention, for example, cleaning agents for the mechanical Ge Dishwashers can be produced, in which the consumer, even after cleaning the dishes Opening the machine experienced the perfume note. This way the unwanted "Alkaline smell", which adheres to many automatic dishwashing detergents, can be eliminated.

Corrosion inhibitors can also be incorporated as active ingredients in the rinse aid particles, where in the case of substances familiar to the person skilled in the art. As a base inhi For example, bitor has a combination of enzyme (e.g. lipase) and lime soap disperser proven greed.

The particulate rinse aid according to the invention can be used to protect the particles Envelope materials may be coated. Through the selection of matrix materials and, if necessary, envelope sub punching, it is possible to set a temperature-independent release of the active ingredients.

The purpose of the coating substances is that the rinse aid particles last during transport or storage to protect against environmental influences. The coating substance should therefore have a high level of stability compared to shock loads occurring during packaging or transport point. The coating substance should either be at least partially elastic or at least have plastic properties in order to respond to an impact caused by elastic or to react plastic deformation and not to break. On the other hand, it's before if the coating substances contain the active substances during the rinse cycles, before the actual one Run off rinse aid, protect against premature release.

To the coating substances which are used in the rinse aid particles according to the invention, accordingly with regard to melting and solidification behavior and / or dissolving behavior different requirements.

In a preferred embodiment, so-called LCST polymers are used as coating substances used. These are substances that perform better at low temperatures Have solubility than at higher temperatures. They are also called substances with lower critical separation temperature. These substances are usually polymers. Each depending on the application conditions, the lower critical separation temperature should be between  Room temperature and the temperature of the heat treatment, for example between 20 ° C preferably 30 ° C and 100 ° C, in particular between 30 ° C and 50 ° C. The LCST Substances are preferably selected from alkylated and / or hydroxyalkylated polysac charides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide as well as blends of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropyl methyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), carboxy methyl methyl cellulose (CMMC), hydroxybutyl cellulose (HBC), hydroxybutyl methyl cellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), hydroxypropyl carboxy methylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulo se (MHEC), methylhydroxyethyl propyl cellulose (MHEPC), methyl cellulose (MC) and propyl cellulose (PC) and mixtures thereof, with carboxymethyl cellulose, methyl cellulose, methyl hy droxyethylcellulose and methylhydroxyproplcellulose as well as the alkali salts of the CMC and the slightly ethoxylated MC or mixtures of the above are preferred.

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethyl cellulose (CMC). Other polymers that have a lower critical segregation Show temperature in water and are also suitable are polymers of mono- or Di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks ken of the above (co) polymers. Polyethylene oxide or copoly are also suitable mere thereof, such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated ones Acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers of, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repetitive Unit in the natural protein elastin and certain alginates. Mixtures of these poly mers with salts or surfactants can also be used as LCST substances. By such additives or by the degree of crosslinking of the polymers, the LCST (lower crit separation temperature) are modified accordingly.  

In a further possible embodiment, enveloping substances are used, the one Have melting range (solidification range) in such a temperature range at which the active substances to be coated are not exposed to excessive thermal stress. Ande on the other hand, the melting range must be sufficiently high to be at least slightly increased Temperature still to provide effective protection for the enclosed active substances. The coating substances preferably have a melting point above 30 ° C.

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

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

The properties mentioned above are usually fulfilled by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificially derived substances that Usually melt above 40 ° C without decomposition and a little above the melting point are relatively low viscosity and non-stringy. They have a strong temperature dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, whale, lanolin (wool wax), or pretzel fat, mineral waxes such as Ceresin or Ozokerite (earth wax), or petrochemical waxes like petrolatum, paraffin waxes or Micro waxes.  

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

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Compounds made of are also usable as covering materials other classes of substances that meet the stated softening point requirements. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic waxes made from lower are also suitable Carboxylic acids and fatty alcohols, for example Dimyristyl Tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semi-synthetic are also Lower alcohol esters with fatty acids from native sources can be used. In this class of substances falls, for example, the Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Also Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) is according to the invention as Envelope material can be used.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are high molecular weight, water-insoluble Fatty alcohols usually with about 22 to 40 carbon atoms. The wax alcohols are coming for example in the form of wax esters of high molecular weight fatty acids (wax acids) as the main name component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1- Tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The wrapping of the Solid particles coated according to the invention can optionally also contain wool wax alcohols contain what is meant by triterpenoid and steroid alcohols, for example lanolin, that for example, is available under the trade name Argowax® (Pamentier & Co). Likewise can be used at least in part as part of the casing in the context of the present Invention of fatty acid glycerol esters or fatty acid alkanolamides but also if necessary water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

If detergents are used as coating substances, these preferably contain a predominant proportion Paraffin wax. This means that at least 50% by weight of the total coating substances contained, preferably more, consist of paraffin wax. Paraffin wax contents are particularly suitable (based on total coating substance) of about 60% by weight, about 70% by weight or about 80% by weight,  even higher proportions of, for example, more than 90% by weight are particularly preferred. In In a particular embodiment of the invention, the total amount used Shell substance made exclusively from paraffin wax.

Paraffin waxes show the other natural waxes mentioned within the scope of the present invention the advantage that in an alkaline detergent environment none Hydrolysis of the waxes takes place (as can be expected, for example, in the wax esters), because Paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially none Ingredients with a melting point of more than 70 ° C, particularly preferably of more than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the detergent fleet undesirable wax residues on the cleaning surfaces or the goods to be cleaned. Such wax residues result usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided become.

The content of the paraffin wax used is preferably at ambient temperature (in which Rule about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. Each The more solid wax components are present in a wax at room temperature, the more it is more useful in the context of the present invention. With increasing proportion of fixed Wax components increase the resilience of the rinse aid particles to impact or friction on other surfaces, which leads to a longer-lasting protection of the particles of active substances. High levels of oils or liquid wax components can weaken the particles lead, whereby pores are opened and the active ingredients mentioned above Be exposed to environmental influences.

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

The principle described above serves to delay the release of ingredients into one certain time in the cleaning cycle and should depend on the temperature of the cleaning cycle be independent. It can be used particularly advantageously when using in the main wash cycle lower temperature (for example 55 ° C) is rinsed, so that the active substance from the Rinse aid particles are only released in the rinse cycle at higher temperatures (approx. 70 ° C).

In a further preferred embodiment of the present invention, the Particulate rinse aid first coated with an LCST substance and then with a substance that has a melting range or melting point of 40 to 75 ° C.

If the second coating substance is a wax or a substance with wax-like Properties used, it is preferably made of one or more substances with one Melting range from 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25% by weight and in particular from 10 to 20% by weight, in each case based on the particle weight, selected.

By selecting matrix materials and, if necessary, coating substances, it is possible to create a temperature-independent release of the active ingredients can be set.

Auxiliaries

At exceptionally low temperatures, for example at temperatures below 0 ° C, the Break up rinse aid particles in the event of shock or friction. To stability at such low To improve temperatures, additives can optionally be added to the coating substances become. Suitable additives must mix completely with the molten wax must not significantly change the melting range of the coating substances, the To improve the elasticity of the casing at low temperatures, the permeability of the Wrapping in relation to water or moisture in general should not and must not be increased Do not increase the viscosity of the melt of the coating material to such an extent that processing is difficult or becomes impossible. Suitable additives that are essentially brittle To reduce paraffin existing coating at low temperatures, for example EVA Copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2- Ethyl hexyl acrylate.  

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

It can also be advantageous to add further additives to the coating substance, for example wise to prevent early withdrawal of the active substances. The antiab Settling agents, which are also referred to as floating agents, are from the prior art known for example from the manufacture of lacquer and printing inks. In order to transition from plasti solidification area to the solid sedimentation phenomena and concentration gradient avoiding the substances to be coated, for example, are surface-active Substances, waxes dispersed in solvents, montmorillonites, organically modified Bentonites, (hydrogenated) castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polya mide, metal stearates, calcium soaps or hydrophobized silicas. Other substances that the effects mentioned come from the groups of anti-floating agents and Thixotropic agents and can be used chemically as silicone oils (dimethylpolysiloxanes, methylphenyl polysiloxanes, polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, Polyamines, salts from long-chain polyamines and polycarboxylic acids, amine / amide-functional Polyester or amine / amide-functional polyacrylates are referred to.

Additives from the substance classes mentioned are commercially available in a wide variety true. Commercial products which are advantageous as part of the process according to the invention Aerosil® 200 (pyrogenic silica, De gussa), 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, Südchemie), Tixogel® VG, VP and VZ (Montmorillonite loaded with QAV, Südchemie), Disperbyk® 161 (Block copolymer, Byk-Chemie), Borchigen® ND (sulfo group-free ion exchanger, boron chers), Ser-Ad® FA 601 (servo), Solsperse® (aromatic ethoxylate, ICI), Surfynol® types (Air Products), Tamol® and Triton® types (Rohm), Texaphor®963, 3241 and 3250  (Polymers, Henkel), Rilanit® types (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 (Polyetsre polymer, Rheox) and the below different M-P-A® types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The auxiliaries mentioned can be used in the rinse aid particles according to the invention, depending on the order wrapping material and active substance are used in varying amounts. Usual one set concentrations for the above-mentioned anti-settling, anti-floating, thioxotropic and dispersants are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0 wt .-%, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the Total amount of coating substance and active substances.

Particulate rinse aid preferred in the context of the present invention contain others Auxiliaries from the group of anti-settling agents, floating agents, anti-floating agents, Thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5 wt .-%, and particularly preferably between 1.5 and 5 wt .-%, each be drew on the particle weight.

Especially in the production of mixtures from molten matrix materials and Ak Containing active substances that are liquid at the processing temperature, the use is speci eller emulsifiers advantageous. It has been shown that emulsifiers from the group in particular the fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are extremely good are suitable. Further details on the production of the rinse aid particles according to the invention fol gen below.

Under fatty alcohols the native fats or oils are converted to the corresponding ones Understand fatty acids (see below) available alcohols with 6 to 22 carbon atoms. This Depending on the origin of the fat or oil from which they are obtained, alcohols can be found in the Alkyl chain may be substituted or partially unsaturated.  

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

Emulsifiers can also be all from vegetable or animal oils and fats recovered fatty acids can be used. The fatty acids can be independent of their aggre state of matter saturated or mono- to polyunsaturated. Even with the unsaturated fatty acid ren are the solid species at room temperature before the liquid or pasty ones moves. Of course, not only "pure" fatty acids can be used, but also those technical fatty acid mixtures obtained from the splitting of fats and oils, these Mixtures are again clearly preferred from an economic point of view.

For example, individual emulsifiers in the context of the present invention Use species or mixtures of the following acids: caprylic acid, pelargonic acid, capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid, Behenic acid, lignoceric acid, cerotic acid, melissic acid, 10-undecenic acid, petroselinic acid, Petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and β- Eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course they are too Fatty acids with an odd number of carbon atoms can be used, for example undecanoic acid, tride canoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, Pentacosanoic acid, heptacosanoic acid.

In preferred rinse aid particles, the emulsifier (s) used are C _6-22 fatty acids, preferably C _8-22 fatty acids and in particular C _12-18 fatty acids, with particular preference given to the C _16-18 fatty acids.

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

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

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

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

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

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

The DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (e.g. Belsil® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHER (e.g. KF352A, Shin Etsu) are also in the context of the present invention as emulsifiers applicable.  

The emulsifiers can be used over a wide range. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight us in particular 5 to 10% by weight of the weight of the sum of wrapping materials and Active substances.

Particulate rinse aid preferred in the context of the present invention contain additional emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and / or Polyoxyalkylene siloxanes in amounts of 0.1 to 5% by weight, preferably 0.2 to 3.5% by weight %, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 to 1.25% by weight, each because of the particle weight.

The particulate rinse aid according to the invention can be produced in various ways. Another object of the present invention is also a method for the manufacture of particulate rinse aid, in which a melt is made

• a) 10 to 90 wt .-% of one or more matrix materials selected from at room temperature solid polymers, especially polyurethanes, with
• b) 90 to 10% by weight of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries, mixed and the mixture processed shaping.

In this process variant, a melt is first produced from the matrix materials then provides with the active ingredients and, where appropriate, active ingredients and adjuvants preferably in liquid or molten form, mixed. Then the Mixture processed to give shape.

Mixing the matrix materials with the active substances and the other active and auxiliary substances substances can be carried out in all usual mixing devices.

The shaping processing step for the mixture of matrix material and active substances as well as other active substances and auxiliary substances are also not subject to any procedural requirements restrictions, so that the expert can select from the methods familiar to him can. In tests by the applicant, methods have been found to be preferred in which  the shaping processing by granulating, compacting, pelleting, extruding or tableting.

Following the shaping processing, the particles produced can in themselves be coated in a known manner with the coating substances. Coating can be done by Immersion process or by spraying on melts or solutions of the coating substances consequences.

With regard to the ingredients that form particulate rinse aid in the process according to the invention lern can be processed, the same applies above. So procedures are preferred, in which the mixture produced as an active substance one or more substances from the Groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, base layers contains bitterns, cobuilders and / or fragrances. The active substances are usually in quantities from 10 to 90% by weight, preferably from 15 to 80% by weight and in particular from 20 to 65% by weight, each based on the mixture, before, the enzymes and fragrances usually in amounts of up to 2% by weight, based on the mixture.

The rinse aid particles according to the invention can be given directly to the consumer be so that he also doses them to the detergent as needed. Because of this additional dosing step would be in addition to the fixed form of supply and the addition in the same dispenser minimizes the advantages over liquid rinse aid. It is preferred therefore, the rinse aid particles of the particulate machine dishes according to the invention to add detergents.

Another object of the present invention is therefore also a particulate ma Fast dishwashing detergent containing builders and optionally other ingredients the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, Po polymers, dyes and fragrances, which is characterized in that it is an inventive particulate rinse aid in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular from 5 to 15% by weight, based in each case 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 in the rinse aid particles according to the invention be 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 especially zeolites, silicates, carbonates, organic cobuilders and - if not ecological There are concerns about their use - including the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} . H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 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 . yH ₂ O 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 release delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima during electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, where values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through 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 if such use should not be avoided for ecological reasons. 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.

Alkali metal phosphates is the general term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, in which one can 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 powders, which are very easily soluble in water, lose the 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 tri metaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^{- 3} , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Dinatrium hydrogen phosphate is produced 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 that have a density of 1.62 gcm ^{-3 as} a dode cahydrate and a melting point of 73-76 ° C (decomposition), as a 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 e.g. B. 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 stated 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 and the solution is dewatered 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 distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. For the latter in particular, a large number of names are used: melting or annealing phosphate, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 140 ° about 32 g of the water free of salt; after heating the solution at 100 ° for two hours, about 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the manufacture of pentasodium triphosphate, phosphoric acid is brought to the reaction 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 poly phosphates are widely used in the detergent and cleaning agent industry. Next exist 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 + 2KOH → 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 are used become. 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, adipin acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such an use is ecological is not objectionable for technical reasons, 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. In addition to their builder, the acids possess typically also have the property of an acidifying component and thus also serve for setting a lower and milder 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 of polyacrylic acid or polymethacrylic acid, for example those with a right latent 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 respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and in particular which preferably have 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 particularly suitable Copolymers of acrylic acid with maleic acid have proven to be net which are 50 to 90% by weight Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass on free acids, is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution be set. 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, as in for example, contain allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

Other preferred copolymers are those which use acrolein and acrylic acid as monomers right / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, which, in addition to cobuilder properties, frequently also have a bleaching stabilizer have a lizing effect.  

Other suitable builder substances are polyacetals, which are produced by the reaction of dialdehyde with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups indicate, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as Glu Conso and / or glucoheptonic acid obtained.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches nen. The hydrolysis can be carried out by customary, for example acid- or enzyme-catalyzed, processes be carried out. They are preferably hydrolysis products with medium Molar masses in the range from 400 to 500000 g / mol. Here is a polysaccharide with a dex trose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, preferably DE is a common measure of the reducing effect of a polysaccharide compared to Dextrose, which has a DE of 100. Both maltodextrins with one can be used DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

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

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Are also preferred in this context also glycerol disuccinates and glycerol trisuccinates. Appropriate A Quantities in zeolite-containing and / or silicate-containing formulations are 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 min at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acids groups included.  

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the hy Droxyalkanephosphonaten is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular Be interpretation as a cobuilder. It is preferably used as the sodium salt, with the disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As aminoalkane phosphonates come preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. You will before preferably in the form of neutral sodium salts, e.g. B. as the hexasodium salt EDTMP or as the hepta and octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. The aminoalkane phosphonates zen also has a pronounced heavy metal binding capacity. Accordingly, it can, in particular especially if the agents also contain bleach, aminoalkanephosphonates, in particular to use special DTPMP, or to use mixtures of the phosphonates mentioned.

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, bleaching agents important bleach activators, enzymes, polymers, and dyes and fragrances Detergent ingredients. 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 anionic, In contrast, cationic or amphoteric surfactants are of less importance. With special The automatic dishwashing agents according to the invention preferably contain nonionic surfactants, again it is preferred that a part, preferably a large part, of the total in the Detergent-containing surfactant is contained in the rinse aid particles. This is special of advantage, since in this way particulate dishwashing detergents can be provided develop their cleaning performance in the main wash cycle and the surfactant from the rinse aid particles first Release in the rinse aid. The presence of surfactants in the rinse aid of a machine Dishwashing has a positive effect on the gloss and the reduction of Limescale deposits.  

In particularly preferred embodiments of the present invention, the cleaning agent according to the invention contains nonionic surfactants, in particular nonionic 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 is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxoal alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of natural origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C. _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical 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, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

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

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 alkanolami de may be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.

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

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)

in 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 egg NEN aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, at for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.  

In addition to the pure nonionic surfactants, other substances from the Group of ionic surfactants, for example the anionic or cationic surfactants, in the Invention machine dishwashing detergents according to be included.

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

As a bleaching agent in the cleaning agents according to the invention for machine dishwashing substances that release chlorine or bromine can also be used. Among the appropriate ones Chlorine or bromine-releasing materials come, for example, from heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations like potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhy danthoin 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 described above possible ingredient of the rinse aid particles mentioned. Known bleach activators are verbin dungen containing one or more N- or O-acyl groups, such as substances from the class the anhydrides, the esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5- triazine DADHT and isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Are suitable Substances containing O and / or N-acyl groups with the number of carbon atoms mentioned and / or against also carry substituted benzoyl groups. Multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular their 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, esp special tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesul fonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and acetylated Sor bitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaace tyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted Acylacetals and acyllactams are also preferred. Combinations of con conventional bleach activators can be used.

In addition to the conventional bleach activators or in their place, so-called 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 as 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 iso nonanoyloxybenzenesulfonate (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 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the entire funds.

Bleach-enhancing transition metal complexes, in particular 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 Man Goose, 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 spe In some cases, more bleach activator can be used.

In the cleaning agents according to the invention, the enzymes in particular come from Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes me, 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. Particularly good are suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetic engineering modified variants obtained enzymatic active ingredients. Proteases are preferred of the subtilisin type, and in particular proteases obtained from Bacillus lentus set. Enzyme mixtures, for example of 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, ins special, however, protease and / or lipase-containing mixtures or mixtures with lipoly table-acting enzymes of particular interest. Examples of such lipolytically active Enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some Cases proved to be suitable. Suitable amylases include in particular alpha amylases, Iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or En zymgranulate can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% %.

Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention be set to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product. Individual perfumes can be used as perfume oils or fragrances connections, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone type, Alcohols and hydrocarbons can be used. Fragrance compounds of the type Esters are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate tat, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylme thylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear alkanals 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxy citronellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-isomethylionon and Me thylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenyls ethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as Lime and pinene. However, mixtures of different fragrances are preferably used det, which together create an appealing fragrance. Such perfume oils can also be natural Liche fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, Citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper beer oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.  

The fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers that detract from the adhesion of the Reinforcing perfumes on the laundry and by a slower fragrance release for long lasting the scent of the textiles. Cyclo, for example, have become such carrier materials dextrine has proven itself, the cyclodextrin-perfume complexes additionally with other auxiliaries fabrics can be coated. An incorporation of the fragrances into the Invention Moderate rinse aid particles are possible and lead to a scent impression when the machine is opened ne (see above).

In order to improve the aesthetic impression of the agents produced according to the invention, it can (or parts thereof) can be colored with suitable dyes. Preferred dyes whose Selection presents no difficulty for the expert, has a high storage stability and Insensitivity to the other ingredients of the agents and to light and none pronounced substantivity towards the substrates to be treated with the agents 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 in the area of the machine len dishwashing have a special meaning. The known substances can be used the state of the art. In general, silver protection agents can be selected from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylami notriazoles and the transition metal salts or complexes are used. Especially before benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaner form In addition, active chlorine-containing agents which corrode the silver surface frequently che can significantly reduce. In chlorine-free cleaners, oxygen and nitrogen-containing organic redox-active compounds, 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 and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred the transition metal salts selected from the group 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 the Corrosion can be used on the wash ware.

The composition of the rinse aid particles according to the invention is designed such that they are not in the main wash cycle (and also in optional pre-wash cycles) or only in the lower wash cycle orderly measure. This ensures that the active substances only in the rinse cycle are released and take effect here. In addition to this chemical packaging Depending on the type of dishwasher, physical assembly is required because with which the rinse aid particles are not pumped out when the water is changed in the machine and so that the rinse aid is no longer available. Household dishwashing Machines contain before the drain pump, which after the water or the cleaning solution pumps the individual cleaning cycles out of the machine, a strainer that clogs prevent the pump from dirt residues. If Ge is heavily contaminated by the consumer washed dishes, this strainer must be cleaned regularly, which is due to the light Accessibility and removability is easily possible. The clear according to the invention Dishwasher particles are now preferably designed in terms of their size and shape so that they Sieve insert of the dishwasher even after the cleaning cycle, d. H. after stress due to movement in the machine and the cleaning solution, do not happen. In this way ensures that there are rinse aid particles in the dishwasher in the rinse aid cycle which release the active substance (s) under the influence of the warmer water and bring the desired rinse aid effect. Before in the present invention Drawn particulate machine dishwashing detergents are characterized in that the part Chen-shaped rinse aid particle sizes between 1 and 40 mm, preferably between 1.5 and 25 mm and in particular between 2 and 20 mm.

In one embodiment of the present invention, the rinse aid particles become common powdery or granular machine dishwashing detergents.

In a further preferred embodiment, the rinse aid particles are used together the ingredients of the machine dishwashing detergent to form a combination product from Ge Dishwashing detergent and rinse aid processed. Such products are preferably so-called Shaped body, 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 shaped bodies and the rinse aid particles are produced separately provides and then connected to each other, the moldings can already for the Par have pre-made recesses. The connection can be done, for example, by simple Insert in the recess or glue the two fixed components.

In a further embodiment, the rinse aid particles or the premix for this are in a suitable tabletting device with the premix for the dishwashing detergent to form 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 that other particles can also have sizes that lie in the range mentioned, so that a total of a detergent is formulated, the large detergent and clear dishwasher particles. Especially when the rinse aid particles according to the invention are colored are, for example a red, blue, green or yellow color, it is for the Appearance of the product, d. H. of the entire cleaning agent is an advantage if the clear dishwasher particles are visibly larger than the matrix of the particles of the other ingredients of the Detergent. Here are particulate machine dishwashing detergents according to the invention preferred that (without taking into account the rinse aid particles) particle sizes between 200 and 3000 µm, preferably between 300 and 2500 µm and in particular between 400 and 2000 µm exhibit.

The visual appeal of such compositions can, in addition to the coloring of the rinse aid parts also through contrasting coloring of the powder matrix or through the shape of the rinse aid ler particles are increased. Since the manufacture of rinse aid particles is technically uncomplicated graceful procedures can be used, it is easily possible to include them in the to offer various forms. In addition to the particle shape, which is roughly spherical, For example, cylindrical or cube-shaped particles can be produced and used. Others too re geometric shapes can be realized. Special product designs can be found at for example, contain star-shaped rinse aid particles. Also discs or shapes that as Base area of plants and animal bodies, e.g. tree, flower, flower, sheep, fish etc. show can be easily produced. Interesting visual incentives can be created in this way  also by making the rinse aid particles in the form of a stylized glass, to visually underline the rinse aid effect in the product. The imagination are here no limits.

If the cleaning agents according to the invention are formulated as a powder mixture, then ins especially with very different sizes of rinse aid particles and detergent Matrix - on the one hand partial separation occurs when the package is shaken, the other on the one hand, the dosage can be different in two successive cleaning cycles, since the consumer does not always have the same amount of detergent and rinse aid particles dosed. Should be desired to technically always use the same amount per cleaning cycle can set this via the packaging of the agents according to the invention familiar to the person skilled in the art can be realized in bags made of water-soluble film. Also particulate machine ge Dishwashing detergent, in which a dosing unit is inserted into a bag made of water-soluble film welds are the subject of the present invention.

As a result, the consumer only has one bag which, for example, contains a detergent Contains powder and several optically prominent rinse aid particles in the dispenser Put in the 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. On Process for the production of powdered automatic dishwashing detergents, in which a powdered dishwasher detergent known per se with fiction appropriate rinse aid particles is mixed, is therefore another object of the present Invention.

The desired retention of the rinse aid particles in the machine described above Even when changing water, the rinse aid parts can be enlarged in addition to the above realized by reducing the holes in the sieve insert. That way to formulate dishwasher detergents that have a uniform mean particle size have which is smaller than, for example, 4 to 12 mm. For this purpose the a product in which the rinse aid particles also have smaller particle sizes insert that replaces or covers the insert in the machine. On  Another object of the present invention is therefore a kit-of-parts that a fiction appropriate powdered dishwashing detergent and a sieve insert for household items includes dishwashers.

As already mentioned, the combination of agent and sieve insert according to the invention allows Formulation of agents in which the rinse aid particles also have smaller particle sizes point. Kits-of-parts according to the invention, in which the particle 40154 00070 552 001000280000000200012000285914004300040 0002019960096 00004 40035el sizes of the machine Ge dishwashing detergent (taking into account the rinse aid particles) in the range from 400 to 2500 µm, are preferably from 500 to 1600 μm and in particular from 600 to 1200 μm at 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 kits according to the invention of-parts preferred, in which the mesh size or hole size of the sieve insert 1 to 4 mm and the rinse aid particles are larger than this mesh size or hole size of the you use.

The kit of parts according to the invention is not based on the specific shape of the sieve insert limits, in which this replaces or covers the insert in the machine. It is according to the invention also possible and preferred to include a sieve insert in the kit of parts, which has the shape of a basket, which in a known manner in the dishwasher - for example on the cutlery basket - can be hung. In this way, a sol appropriately designed sieve insert the dosing chamber, d. H. the consumer doses the inventions machine dishwashing detergent according to the invention directly into this sieve insert which is used in the cleaning and rinse aid acts in the manner described above.  

Since the consumer doesn't just fit particulate cleaners, the machine dishes rinsing uses, but also want to use moldings, these are another counter stood of the present invention. For this purpose, the melt can be made from the ingredients a) to c) formulate as a phase of a shaped body, for example the shape of a layer, a core shaped insert, etc.

Another object of the present invention is thus a multiphase cleaning agent shaped body for automatic dishwashing, containing builders and optionally further cleaning agent ingredients, in which at least one phase consists of

• a) 10 to 90 wt .-% of one or more matrix materials selected from at room temperature temperature-resistant polymers, especially polyurethanes,
• b) 90 to 10% by weight of one or more active substances, and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

consists.

The individual phases of the molded body can be within the scope of the present invention have different spatial shapes. The simplest possible implementation is in two- or multi-layer tablets, each layer of the shaped body representing a phase. However, it is also possible according to the invention to produce multi-phase molded articles in which a individual phases are in the form of inclusions in another phase (s). In addition to so-called "Ring-core tablets" are, for example, coated tablets or combinations of the embodiments mentioned possible. Examples of multi-phase moldings can be found in the illustrations of EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The The most widespread spatial form of multi-phase molded bodies is the two or more layered tablet. In the context of the present invention it is therefore preferred that the phases of the shaped body in the form of layers and the shaped body is 2-, 3- or 4-phase.

The moldings according to the invention can take on any geometric shape, ins special concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shapes are preferred. Also completely irregular bases such as arrow or Animal forms, trees, clouds, etc. can be realized. Assign the inventive  Shaped body corners and edges, they are preferably rounded. As an additional opti The differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

Instead of the layer structure, it is also possible to produce moldings which are the inventive ones Include detergent component in the form of other phases. It has proven itself here, Ba Manufacture sisformkörper, which have one or more cavity (s) and the melt from the ingredients a) to c) of the detergent component according to the invention in the Ka fill in and freeze there. This manufacturing process results in preferred multi-phase detergent tablets, which consist of a base tablet, which has a cavity, and consist of at least partially contained in the cavity.

The cavity in the pressed part of such shaped bodies according to the invention can be any Have shape. You can cut through the molded body, d. H. an opening at different be ten, for example on the top and bottom of the molded body, but it can also be a not be a cavity that extends through the entire molded body, the opening of which is only on one mold body side is visible. The shape of the cavity can also be freely selected within wide limits. For reasons of process economy, there are through holes, the openings of which mutually opposite surfaces of the molded body, and troughs with an opening proven on one side of the molded body. In preferred laundry detergent and cleaning product tablets the cavity is in the form of a through hole, the openings of which are opposed to two overlying molded surfaces. The shape of such a through hole can can be chosen freely, with molded bodies being preferred in which the through hole circle round, elliptical, triangular, rectangular, square, pentagonal, hexagonal, sevenec angular or octagonal horizontal sections. Completely irregular hole shapes such as arrow or animal forms, trees, clouds etc. can be realized. As with the moldings are in the case of square holes with rounded corners or edges or with abge rounded corners and chamfered edges preferred.

The geometric implementation forms mentioned above can be combined with one another as desired combine. Shaped bodies with a rectangular or square base and a circle can be made round holes as well as round shaped bodies with octagonal holes, where there are no limits to the variety of possible combinations. Because of  Process economics and aesthetic consumer perception are molded articles with holes particularly preferred in which the shaped body base area and the hole cross section are the same have geometric shape, for example shaped bodies with a square base area and central incorporated square hole. Ring moldings are particularly preferred, i. H. circular shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body on one Opening is reduced, mold bodies are obtained. Washing and Shaped detergent bodies in which the cavity has the shape of a trough are flat if preferred. As with the "hole moldings", the moldings according to the invention can also assume any geometric shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well as rhombohedri forms are preferred. Also completely irregular base areas like arrow or animal shapes, Trees, clouds, etc. can be realized. If the molding has corners and edges, see above they are preferably rounded. As an additional visual differentiation, there is a version Form with rounded corners and chamfered ("chamfered") edges preferred.

The shape of the trough can also be chosen freely, preference being given to moldings in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, zylin drical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octa cathedral, conical, pyramidal, ellipsoid, pentagonal, octagonal and octagonal prismatic as well as rhom can take a bohedral shape. Also completely irregular trough shapes like arrow or animal shapes, trees, clouds, etc. can be realized. As with the shaped bodies Troughs with rounded corners and edges or with rounded corners and chamfered can preferred.

In the case described above, the part at least partially contained in the cavity consists solely of the ingredients a) to c) of the rinse aid particles according to the invention. However, it is also possible to introduce carrier-based rinse aid particles into the cavity (s). For reasons of process economy, however, multiphase detergent tablets are preferred, in which the part contained in the cavity is made of

• a) 10 to 90 wt .-% of one or more matrix materials selected from at room temperature temperature-resistant polymers, especially polyurethanes,
• b) 90 to 10% by weight of one or more active substances, and
• c) 0 to 20% by weight of further active ingredients and auxiliaries

consists.

The size of the trough or through hole compared to the entire molded body depends on the intended use of the molded body. Depending on whether one Lesser or greater amount of detergent component should be included The size of the cavity vary. Washing and cleaning are independent of the intended use preferred moldings in which the volume ratio of the pressed part ("Ba sisformkörper ") to rinse aid up to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1.

In addition to the volume ratio mentioned, a mass ratio of the two parts can also occur are given, the two values relating to the densities of the base molding or the clear correlate dishwasher particles with each other. It is independent of the density of the individual parts Detergent tablets according to the invention are preferred, in which the weight ratio of base molding to pressed rinse aid particles up to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces, each of which is from the basic molding per or from the pressed rinse aid particles are visible. Here are washing or cleaning Preferred shaped tablets, in which the externally visible surface of the pressed Rinse aid particles 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular accounts for 4 to 10% of the total surface of the molded body.

The pressed rinse aid particles and the base molding are preferably optically underneath colored divisible. In addition to the optical differentiation, application technology can parts can be achieved through different solubilities of the different shaped body regions. Detergent tablets, in which the pressed rinse aid particles Solve faster than the base molding, are preferred according to the invention. By incorporation Certain components can, on the one hand, specifically target the solubility of the pressed rinse aid particles  accelerated, on the other hand, the release of certain ingredients from ver pressed rinse aid particles lead to advantages in the washing or cleaning process.

Of course, detergent tablets according to the invention are also be preferred, in which the pressed rinse aid particles dissolve later in the wash program than the Basic molded body. Performance benefits from this delayed release can be seen, for example thereby achieve that with the help of slowly soluble pressed rinse aid particles Aktivsub punch (s) are only released in later rinses. For example, with the maschi nell dishwashing can be achieved by slower dissolving pressed rinse aid particles, that further active substance (s) are / are available in the rinse cycle. By additional Substances such as nonionic surfactants, acidifying agents, soil release polymers, etc. can be so improve the rinse aid results. Incorporation of perfume is also possible without any problems Lich; due to its delayed release, the frequently occurring one in dishwashers "Lye smell" can be eliminated when opening the machine. The ingredients acidification agents, soil release polymers, etc. are on the pressed rinse aid part according to the invention celn related ingredients c).

In preferred embodiments of the present invention, the base molding has a high specific weight. Detergent tablets, which are characterized in that the base tablet has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 preferred according to the invention.

To facilitate the disintegration of highly compressed moldings, it is possible to disintegrate tools, so-called tablet disintegrants, to incorporate into them to reduce the disintegration times shorten. According to Römpp (9. Edition; Ld. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) understood auxiliaries for the rapid disintegration of tablets in water or gastric juice and release the pharmaceuticals in an absorbable form.

These substances, which are also called "explosives" due to their effect, enlarge their volume when water enters, whereby on the one hand the volume increases (swelling), the other on the other hand, a pressure can be generated by the release of gases, which the tablet in  lets smaller particles disintegrate. Well-known disintegration aids are, for example, Car bonat / citric acid systems, whereby other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and Starch and its derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each Weil based on the weight of the molded body. Contains only the basic molding disintegration auxiliaries, the information given relates only to the weight of the base molding. In the incorporation of disintegration aids in the cleaning according to the invention middle components count those as ingredient c).

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 wt .-% included. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegration agents based on cellulose, but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form Form, but before mixing into the premixes to be pressed into a transferred coarser form, for example granulated or compacted. Washing and cleaning medium shaped body, the disintegrant ent in granular or optionally cogranulated form ent hold, are in the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO 98/40463 (Henkel) be wrote. These writings are also more detailed information on the production of granulated, compact tated or cogranulated cellulose disintegrant. The particle sizes of such Disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The coarser ones mentioned above and described in more detail in the cited documents Disintegration aids based on cellulose are within the scope of the present invention preferably used as a disintegration aid and commercially, for example, under the Be drawing Arbocel® TF-30-HG available from Rettenmaier.

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial hydrolysis of celluloses obtained under such conditions that only the amorphous Attack areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve them completely but leave the crystalline areas (approx. 70%) undamaged. A subsequent desaggre gation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline Celluloses that have primary particle sizes of approx. 5 µm and, for example, to granules can be compacted with an average particle size of 200 µm.

Preferred detergent tablets contain in the context of the present invention additionally a disintegration aid, preferably a disintegration aid on cellulo sebasis, preferably in granular, cogranulated or compacted form, in quantities of 0.5 up to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the molded article.  

The detergent tablets according to the invention can moreover both in the base molded body as well as in the compressed rinse aid particles a gas-developing shower system contain. The gas evolving shower system can consist of a single substance, which at Contact with water releases a gas. Among these compounds is the magnesi in particular To name umperoxid, which releases oxygen on contact with water. Usually there is the gas-releasing bubble system, however, in turn consists of at least two components that react with each other to form gas. While here a multitude of systems think and is executable, which release nitrogen, oxygen or hydrogen, for example Bubble system used in the detergent tablets according to the invention Let you choose based on both economic and ecological considerations. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate such as an acidifying agent which is suitable from the alkali metal salts in aqueous solution Release carbon dioxide.

The alkali metal carbonates and bicarbonates are the sodium and potassium salts clearly preferred over the other salts for cost reasons. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates from washtech African interest may be preferred.

In preferred detergent tablets, 2 to 20% by weight are used as the shower system preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight an acidifying agent, based in each case on the entire molded body.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution, are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogenphos phate and other inorganic salts can be used. However, organic Acidi are preferred Fizierungsmittel used, the citric acid is a particularly preferred acidification is means. However, the other solid mono-, oligo- and Polycarboxylic acids. From this group tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organi Sulfonic acids such as sulfamic acid can also be used. Commercially available and  can also preferably be used as an acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt. %), Glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

Preferred in the context of the present invention are detergent tablets in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures of these are used.

The particulate detergents and / or detergent tablets can - like the detergent components according to the invention themselves - be packaged after manufacture, the use of certain packaging systems having proven particularly useful. Another aspect of the present invention is a combination of (a) particulate cleaning agent (s) according to the invention and / or (a) shaped detergent or cleaning product (s) according to the invention and one containing the cleaning agent and / or the detergent or cleaning product Packaging system, wherein the packaging system has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent component and / or detergent and / or detergent tablets (s) and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day, if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is also, for example, in the ASTM standard E-96- 53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the corresponding atmosphere, the container being closed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is closed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate within the scope of the present invention. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4). 100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), which means that if it cools further, it forms a precipitate in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in the laboratory chambers with humidity control depending on the device type to +/- 2% r. Adjust L. exactly. Also over saturated solutions of certain salts are formed in closed systems ner temperature constant and well-defined relative humidity, which on the Pha balance between water partial pressure, saturated solution and soil rest.

The combinations according to the invention can of course in turn in secondary packaging kung, such as cardboard boxes or trays, are packed, with the secondary packaging  no further requirements have to be made. The secondary packaging is that if possible, but not necessary.

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day.

The packaging system of the combination according to the invention encloses, depending on the design form of the invention a certain amount of rinse aid particles according to the invention, a be certain amount of a particulate detergent composition or one or more More detergent tablets. It is preferred according to the invention either to design the vain shaped body in such a way that it is an application unit for washing and cleaning Includes cleaning agent, and to pack this molded article individually, or the number of molded articles pern in a packaging unit, which in total comprises an application unit. With a nominal dosage of 80 g of detergent and cleaning agent, it is therefore according to the invention possible to manufacture a 80 g detergent tablet and individually to pack, but it is also possible according to the invention, two 40 g washing and rice Packing detergent tablets in a packaging in order to form an inventive Combination. This principle can of course be extended so that inventions According to the combinations also three, four, five or even more detergents and cleaning agents can contain molded articles in a packaging unit. Of course, two or more moldings in one package have different compositions. On this way it is possible to spatially separate certain components from each other in order to to avoid stability problems, for example.

The packaging system of the combination according to the invention can be of the most varied Materials exist and take on any external shape. For economic reasons and however, packaging systems are preferred for reasons of easier processing which the packaging material is light, easy to process and inexpensive is stig. In combinations preferred according to the invention, the packaging system consists of a sack or bag made of single-layer or laminated paper and / or plastic film.

The detergent tablets can be unsorted, i. H. as a loose fill, in a bag can be filled from the materials mentioned. But it is for aesthetic reasons  and preferred for sorting the combinations in secondary packaging, the washing and Fill detergent tablets individually or in groups in sacks or bags. For individual application units of the detergent tablets, which are in a sack or bag, the term "flow pack" has become common in technology. Such "flow packs" can then - again preferably sorted - optionally in Umverpac cations are packaged, which underlines the compact form of the molded body.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is caused by heat (hot fusion), adhesives or adhesive tapes be closed. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, as well as plastic films, which can optionally be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are specified, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Fig. 111 shown there also provides information on the water vapor permeability of the materials mentioned.

Combinations particularly preferred in the context of the present invention contain as Ver a sack or pouch made of single-layer or laminated plastic film a thickness of 10 to 200 microns, preferably from 20 to 100 microns and in particular from 25 to 50 µm.

Although it is possible to use wax-coated Pa in addition to the films or papers mentioned piere in the form of cardboard boxes as a packaging system for detergents and cleaning agents To use moldings, it is preferred in the context of the present invention if the Ver packaging system does not include boxes made of wax-coated paper. The term "Verpac In the context of the present invention, the identification system always identifies the primary ver Pack of the detergent component, detergent composition or molding per, d. H. the packaging, which is directly on the inside with the detergent component, Detergent composition or molded surface is in contact. An optional  Secondary packaging has no requirements, so that all the usual mate rialien and systems can be used.

As already mentioned above, the rinse aid particles contain detergents together settlements or detergent tablets of the combination according to the invention each according to their intended use, other ingredients of detergents and cleaning agents, especially riizing amounts. It is independent of the intended use of the agent or molded article preferred according to the invention that the agent or agents or detergents and cleaning agents moldings have a relative equilibrium moisture content of less than 30% at 35 ° C points / have.

The relative equilibrium moisture content of the detergent or detergent tablets per can be determined using common methods, whereby within the scope of the present The following procedure was chosen: A water-impermeable 1 liter Vessel with a lid, which has a closable opening for the introduction of samples has been infested with a total of 300 g detergent tablets and 24 h kept at a constant 23 ° C in order to maintain a uniform temperature of the vessel and the substance guarantee. The water vapor pressure in the space above the moldings can then be with a Hy grometer (Hygrotest 6100, Testoterm Ltd., England) can be determined. The water vapor pressure is now measured every 10 minutes, until two consecutive values no deviation show (equilibrium moisture). The above Hygrometer allows a direct display of the taken values in% relative humidity.

Embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations where the Packaging system has a microperforation can be preferred according to the invention realize.

As mentioned above, rinse aid particles, detergent compositions or detergent tablets for automatic dishwashing according to the invention Establish process. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, characterized in that one or more fiction appropriate particulate cleaning agent (s) and / or one or more of the invention  Detergent or detergent tablets insert the dosing chamber of the dishwasher and a rinsing program can run, in the course of which the metering chamber opens and the or the cleaning agent and / or the or the molded body are dissolved, another counter stood of the present invention.

The metering chamber can also be dispensed with in the cleaning process according to the invention and the rinse aid particles or detergent compositions according to the invention or insert the molded article (s) according to the invention into the cutlery basket, for example. Of course, the use of a dosing aid, for example one, is also here Basket, which is attached in the sink, easily possible. Accordingly, is a Cleaning process for cleaning dishes in a dishwasher, thereby ge indicates that one or more particulate cleaning (s) according to the invention agent and / or one or more detergent or cleaning agent form according to the invention body with or without dosing aid in the dishwasher's washing compartment and a washing pro can run in the course of which the cleaning agent (s) and / or the Moldings are dissolved, another object of the present invention.  

Examples Production Example 1

A polyurethane made from 0.2 mol of polyethylene glycol with one molecular was used as the matrix material weight of 6000, 0.14 mol of 12-hydroxystearyl alcohol and 0.37 mol of TMXDI, the one Melt viscosity according to Kegel-plate (Brookfield CAP 2000) of 91 Pas at 175 ° C set.

The polyurethane was commercially available with an alcohol alkoxylate (Polytergent SLF-18B-45; available from Olin Chemicals) in a weight ratio of 40:60 melted and then beaten.

Production Example 2

A polyurethane made from 0.2 mol of polyethylene glycol with one molecular was used as the matrix material weight of 6000, 0.412 mol of polytetrahydrofuran with a molecular wiping of 250 and 0.58 mol TMXDI, which has a melt viscosity according to the Kegel plate (Brookfield CAP 2000) 133.5 Pas at 150 ° C was used.

The polyurethane was commercially available with an alcohol alkoxylate (Polytergent SLF-18B-45; available from Olin Chemicals) in a weight ratio of 40:60 melted and then beaten. The particles obtained were washed with CULMINAL® MHPC 25 (cellulose derivative, manufacturer: Aqualon) coated.

Performance evaluation

To evaluate the rinse aid effect and the drying behavior, a commercially available one powder detergent for automatic dishwashing in a universal Cleaning program used. The program was carried out under the same conditions once without standard rinse aid (the dishwasher's storage tank is empty), with commercially available rinse aid (dosage of 3 ml of commercial rinse aid from the previous advice tank in the rinse aid) and once with the rinse aid particles according to the invention  Example 1 (addition of 3.3 g rinse aid particles to 20 g detergent, dosage before the main rinse gang). The storage tank was used when using the cleaning agents according to the invention for the standard rinse aid, of course, empty, d. H. the rinse aid is only on attributable to the rinse aid particles of the invention.

Test conditions

Dishwasher: Miele G 676
Detergent: 20 g, dosed in the main wash
Water hardness: 3 ° dH
Program: Universal 55 ° C (rinse aid temperature 65 ° C)
Dirt load: 100 g liquid dirt, dosed in the main wash cycle

composition

30% protein
30% strength
30% fat
10% water / emulsifier

The rinse aid effect (KSE) was assessed by visual inspection of the objects in a box, the walls of which are lined with black velvet, with the notes 0 to 8 were awarded; the top grade 8 refers to surfaces free of deposits and water droplets. Is the Note ≦ 4, the deposits and drops are clearly visible outside the box, d. H. she are perceived by the consumer as disturbing.  

The table shows that the agents according to the invention through the use of the inventive Rinse aid particles the rinse aid performance of the conventional combination of detergent and achieve or surpass rinse aid separately although fewer rinse aid (based on active substance) and the particles according to the invention in the main rinse are already in the machine, i.e. they are physically and chemically loaded. The trop Fen formation on the wash ware is only visible in the black box, outside the box brilliant shiny washware is observed.

Claims (26)

1. Containing particulate rinse aid for machine dishwashing

• a) 10 to 90% by weight of one or more matrix materials selected from polymers which are solid at room temperature,
• b) 90 to 10% by weight of one or more active substances and
• c) 0 to 10% by weight of further active ingredients and auxiliaries.

2. Particulate rinse aid according to claim 1, characterized in that it has the Ma trix material is selected from meltable and / or water-soluble or swellable Polyurethanes. 3. Particulate rinse aid according to one of claims 1 or 2, characterized in that that it contains one or more substances from the groups of surfactants, enzymes, Bleach, bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or Contains fragrances. 4. Particulate rinse aid according to one of claims 1 to 5, characterized in that it contains nonionic surfactants, preferably alkoxylated alcohols, as the active substance. 5. Particulate rinse aid according to one of claims 1 to 6, characterized in that as an active substance he bleach from the group of oxygen or halogen Bleach, especially containing chlorine bleach. 6. Particulate rinse aid according to one of claims 1 to 7, characterized in that that he as an active substance bleach activators, especially from the groups of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N- Acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n- Methyl morpholinium acetonitrile methyl sulfate (MMA) contains.   7. Particulate rinse aid according to one of claims 1 to 8, characterized in that that he has other auxiliaries from the group of anti-settling agents, suspending agents, anti-odors floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5% by weight, and particularly preferably between 1.5 and 5% by weight, each based on the particle weight. 8. Particulate rinse aid according to one of claims 1 to 9, characterized in that he also emulsifiers from the group of fatty alcohols, fatty acids, polyglyceri nests and / or polyoxyalkylene siloxanes in amounts of 0.1 to 5 wt .-%, preferably of 0.2 to 3.5% by weight, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 contains up to 1.25% by weight, based in each case on the particle weight. 9. Particulate rinse aid according to one of claims 1 to 8, characterized in that that it is coated with coating substances. 10. Particulate rinse aid according to one of claims 1 to 9, characterized in that that it contains one or more LCST polymers as the coating substance. 11. Particulate rinse aid according to one of claims 1 to 10, characterized in that that it contains one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20% by weight, based in each case on the particle weight. 12. A process for the production of particulate rinse aid, characterized in that a melt from

• a) 10 to 90 wt .-% of one or more matrix materials selected from polymers solid at room temperature, in particular polyurethanes, with
• b) 90 to 10% by weight of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries, mixed and the mixture processed to give shape.

13. The method according to claim 12, characterized in that the shaping processing by granulating, compacting, pelleting, extruding or tableting.   14. The method according to any one of claims 12 or 13, characterized in that the Ma trix material 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 to 50% by weight of the mixture. 15. Particulate machine dishwashing detergent containing builders and optional further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, Corrosion inhibitors, polymers, dyes and fragrances, characterized in that it a particulate rinse aid according to any one of claims 1 to 10 in amounts of 0.5 to 30% by weight, preferably from 1 to 25% by weight and in particular from 5 to 15% by weight, each because based on the entire mean. 16. Particulate dishwasher detergent according to claim 15, characterized indicates that the particulate rinse aid has particle sizes between 1 and 40 mm preferably between 1.5 and 25 mm and in particular between 2 and 20 mm. 17. Particulate dishwasher detergent according to one of claims 15 or 16, characterized in that it (without taking into account the rinse aid particles) particles sizes between 200 and 3000 microns, preferably between 300 and 2500 microns and in particular which has between 400 and 2000 µm. 18. Particulate dishwasher detergent according to one of claims 15 to 17, because characterized in that a dosing unit in a bag made of water-soluble film is welded in. 19. Multi-phase detergent tablets for automatic dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase consists of

• a) 10 to 90% by weight of one or more matrix materials selected from polymers which are solid at room temperature, in particular polyurethanes,
• b) 90 to 10% by weight of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

consists. 20. Multi-phase detergent tablet according to claim 19, characterized in that the phases have the form of layers and the shaped body is 2-, 3- or 4-phase. 21. Multi-phase detergent tablet according to claim 19, characterized in that it consists of a base molding which has a cavity and an at least partially part contained in the cavity. 22. Multi-phase detergent tablet according to claim 21, characterized in that the part contained in the cavity

• a) 10 to 90% by weight of one or more matrix materials selected from polymers which are solid at room temperature, in particular polyurethanes,
• b) 90 to 10% by weight of one or more active substances and
• c) 0 to 20% by weight of further active ingredients and auxiliaries,

consists. 23. Process for producing powdered dishwasher detergents with rinse aid fekt, characterized in that a known powdered mechanical Ge Dishwasher detergent is mixed with rinse aid particles according to one of claims 1 to 10. 24. Kit-of-parts, comprising a powdered dishwasher detergent according to one of the Claims 15 to 18 and a sieve insert for household dishwashers. 25. Kit-of-parts according to claim 24, characterized in that the particle sizes of the ma Fast dishwashing detergent (taking into account the rinse aid particles) in the area from 400 to 2500 µm, preferably from 500 to 1600 µm and in particular from 600 to 1200 µm. 26. Kit-of-parts according to one of claims 24 or 25, characterized in that the Ma width 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.