EP1103599B1 - Particle form rinse aid and dishwasher detergent composition - Google Patents

Abstract

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

Description

The present invention relates to particulate rinse aid for machine dishwashing containing from 95 to 5% by weight of one or more carrier materials and / or binders, and from 5 to 95% by weight of one or more active agents, and from 0 to 10% by weight of others Active ingredients and excipients, a process for its preparation and particulate machine dishwashing detergents (MGSM) containing the rinse aid particles.

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

The storage tank in the dishwasher must be filled with rinse aid at regular intervals, with a filling sufficient for 10 to 50 rinses, depending on the machine type. If the filling of the tank is forgotten, then glasses in particular by lime stains and coverings become unsightly. In the prior art, therefore, there are some solutions proposed to integrate a rinse aid in the detergent for machine dishwashing. These proposed solutions are tied to the offer form of the compact molded article.

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

International patent application WO 00/60047 A1 (Henkel KGaA) discloses particle-type rinse aids based on water-insoluble, high-temperature, temperature-controlled carrier materials.

It is an object of the present invention to make use of the advantages of the controlled release of ingredients, in particular a clear rinse effect, both for pulverulent detergents and for granules and cleaner moldings. It should be possible to dispense with expensive process steps such as coating or multiple coating. Instead, a supply form should be provided which can be used both separately as a rinse aid to be dosed by the consumer in solid form and as an admixing component for powdered automatic dishwashing detergents.

It has now been found that mixtures of carrier materials, active ingredients and optionally other ingredients such as enzymes, dyes and fragrances, etc., and suitable carrier materials and / or binders can be compressed in such a way that the active ingredients and the other ingredients at a predetermined time or released during a predetermined period of time.

• a) 5 bis 95 Gew.-% eines oder mehrerer Aktivstoffe, wobei mindestens einer der Aktivstoffe ein Tensid ist
• b) 95 bis 5 Gew.-% eines oder mehrerer Trägermaterialien aus der Gruppe der Zeolithe, Bentonite, Silicate, Carbonate, Hydrogencarbonate, Sulfate, Phosphate, quervernetzten Polycarboxylaten, Polyvinylalkohole, den bei Raumtemperatur festen Polycarbonsäuren oder Stärke- oder Cellulosederivate und eines oder mehrerer Bindemittel aus der Gruppe Polyethylenglykole, Polyacrylate, Galaktomannan, Celluloseether, Mono-, Oligo- oder Polysaccharide und/oder Harze , sowie
• c) 0 bis 10 Gew.-% weiterer Wirk- und Hilfsstoffe,
  dadurch gekennzeichnet, dass die Komponenten a, b und ggf. c derart verdichtet sind, dass die Aktivstoffe der Komponente a und ggf. die weiteren Inhaltsstoffe der Komponente c zu einem vorbestimmten Zeitpunkt oder während eines vorgegebenen Zeitraums im Reinigungsvorgang freigesetzt werden.

The present invention is a particulate rinse aid for automatic dishwashing containing

• a) 5 to 95 wt .-% of one or more active ingredients, wherein at least one of the active ingredients is a surfactant
• b) 95 to 5 wt .-% of one or more support materials from the group of zeolites, bentonites, silicates, carbonates, bicarbonates, sulfates, phosphates, crosslinked polycarboxylates, polyvinyl alcohols, solid at room temperature polycarboxylic acids or starch or cellulose derivatives and one or more Binders from the group of polyethylene glycols, polyacrylates, galactomannan, cellulose ethers, mono-, oligo- or polysaccharides and / or resins, and
• c) 0 to 10% by weight of further active ingredients and auxiliaries,
  characterized in that the components a, b and optionally c are compressed such that the active ingredients of the component a and optionally the further ingredients of the component c are released at a predetermined time or during a predetermined period in the cleaning process.

The delayed release of the active ingredients and optionally further ingredients at a predetermined time or during a predetermined period in the cleaning process takes place in the particulate rinse aid according to the invention by adjusting the strength of the moldings and depending on the amount and nature of the respective components, in particular binder.

A common procedure in automatic dishwashing is that after the actual cleaning the dishes are rinsed and finally a so-called. Rinse cycle is performed. The particles according to the invention can be compressed in such a way that the compacted particles remain largely unchanged in the main rinse or only soften, swell or erode only superficially and disintegrate in the subsequent rinse and release the active substances, such as the rinse aid and optionally further substances. The sustained-release method described herein may also be referred to as "delayed-release".

The actives to be incorporated into the rinse aid particles of the present invention may be in both solid and liquid form at the processing temperature (i.e., at the temperature at which the particles are being made).

The active substances contained in the rinse aid particles fulfill certain tasks. By separating certain substances or by the temporally accelerated or delayed release of additional substances, the cleaning performance can be improved. Active substances which are preferably incorporated into the rinse aid particles are therefore those ingredients of detergents and cleaning agents which are crucially involved in the washing or cleaning process.

In preferred rinse aid particles are therefore as active substances one or more substances from the groups of surfactants, bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors and / or co-builders in amounts of 5 to 95 wt .-%, preferably from 10 to 70 wt .-% and in particular from 10 to 60 wt .-%, each based on the particle weight.

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

Another class of active substances which can be incorporated with particular advantage into the rinse aid particles according to the invention are bleaching agents. Also, automatic dishwashing detergents can be prepared so that additional bleaching agent is released in the rinse cycle and so difficult stains, for example tea stains, are removed more effectively.

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

Another class of compounds which can preferably be used as active substances in the rinse aid particles according to the invention are the bleach activators. Also the important representatives from this group of substances are described below. In the context of the present invention, preferred rinse aid particles contain bleach activators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or as active substance Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

As active substances, fragrances can also be incorporated into the rinse aid particles according to the invention. All fragrances described in detail below can be used as the active substance. Incorporation of fragrance into the rinse aid particles results in detergents that release all or part of the perfume with a time delay. In this way, according to the invention, for example, detergents for automatic dishwashing can be produced, in which the consumer experiences the perfume note even after completion of the dishwashing process when the machine is opened. In this way, the unwanted "Alkaligeruch", which adheres to many automatic dishwashing detergents, can be eliminated.

Corrosion inhibitors can also be incorporated into the rinse aid particles as active substance, it being possible to resort to the substances familiar to the person skilled in the art. As a scale inhibitor, for example, a combination of enzyme (e.g., lipase) and lime soap dispersant has been found to be useful.

As support materials are zeolites, bentonites, silicates, carbonates, bicarbonates, sulfates, phosphates, as well as synthetic polymers, such as. cross-linked polycarboxylates, polyvinyl alcohols, and solid organic polycarboxylic acids used at room temperature. Natural or semi-synthetic polymers such as starch derivatives and cellulose derivatives can also be used.

The said preferred support materials are described in detail below.

Suitable binders are a multiplicity of pharmaceutically known binders for tablets. They differ in their hydrophilicity / hydrophobicity, their solubility and, as a result, their binding effect under the influence of the rinsing liquor. In particular, substances from the group of polyalkylene glycols and polyoxyalkylene glycols of different molecular weight can be used. Polyethylene glycols of higher molecular weight, which are solid at room temperature, have proven particularly useful. Also suitable are other substances, such as polyacrylates, mono-, oligo- or polysaccharides and resins.

As further ingredients, the rinse aid particles of the invention may contain other active ingredients and adjuvants, such as. As enzymes, dyes and fragrances, etc.

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

• a) 5 bis 95 Gew.-% eines oder mehrerer Aktivstoffe, wobei mindestens einer der Aktivstoffe ein Tensid ist
• b) 95 bis 5 Gew.-% eines oder mehrerer Trägermaterialien aus der Gruppe der Zeolithe, Bentonite, Silicate, Carbonate, Hydrogencarbonate, Sulfate, Phosphate, quervernetzten Polycarboxylaten, Polyvinylalkohole, den bei Raumtemperatur festen Polycarbonsäuren oder natürliche oder halbsynthetische Polymere wie Stärke- oder Cellulosederivare und/oder Bindemittel aus der Gruppe Polyethylenglykole, Polyacrylate, Galaktomannan, Celluloseether, Mono-, Oligo- oder Polysaccharide und/oder Harze, sowie
• c) 0 bis 10 Gew.-% weiterer Wirk- und Hilfsstoffe enthält,

dadurch gekennzeichnet, dass die Komponenten a und b und ggf. c derart verdichtet sind, dass die Aktivstoffe der Komponente a und ggf. die weiteren Inhaltsstoffe der Komponente c zu einem vorbestimmten Zeitpunkt oder während eines vorbestimmten Zeitraumes im Reinigungsgang freigesetzt werden.Another object of the present invention is a process for the preparation of particulate rinse aid containing

• a) 5 to 95 wt .-% of one or more active ingredients, wherein at least one of the active ingredients is a surfactant
• b) 95 to 5 wt .-% of one or more support materials from the group of zeolites, bentonites, silicates, carbonates, bicarbonates, sulfates, phosphates, crosslinked polycarboxylates, polyvinyl alcohols, solid at room temperature polycarboxylic acids or natural or semisynthetic polymers such as starch or Cellulosederivare and / or binders from the group of polyethylene glycols, polyacrylates, galactomannan, cellulose ethers, mono-, oligo- or polysaccharides and / or resins, as well as
• c) 0 to 10 wt .-% of other active ingredients and excipients,

characterized in that the components a and b and optionally c are compressed such that the active ingredients of the component a and optionally the other ingredients of the component c are released at a predetermined time or during a predetermined period in the cleaning cycle.

With regard to the ingredients used in the process according to the invention and processed into the rinse aid particles according to the invention, the same applies as stated above.

Also with regard to the active substances, the above applies. Active substances which are preferably contained are one or more substances from the groups of the surfactants, including rinse aid surfactants, bleaches, bleach activators, corrosion inhibitors, coating inhibitors and / or cobuilders.

To carry out the process, it is preferable to first prepare a mixture, if appropriate a melt mixture of the ingredients, including any other active ingredients and auxiliaries which may be present. In the event that the active ingredients of component a) or active ingredients and ingredients are in liquid form, they can first be applied to suitable carrier materials and, if necessary, mixed with a binder. Subsequently, the resulting mixture is compacted according to the invention. The compression can be done in a conventional manner. In a preferred embodiment, the compaction is carried out in a tablet press or in an extruder. Compression in a tablet press is particularly preferred, all common types of presses can be used, e.g. hydraulic presses, eccentric presses or rotary presses. Another possible compression method is the processing in roller presses.

In a further embodiment of the present invention, the active substances are first applied in a manner known per se to a carrier and then, if appropriate, compressed in the presence of further components and / or binders. The application of the active substances to the support material can be carried out in all conventional mixing devices. draulic presses, eccentric presses or rotary presses. Another possible compression method is the processing in roller presses.

In a further embodiment of the present invention, the active substances are first applied in a manner known per se to a carrier and then, if appropriate, compressed in the presence of further components and / or binders. The application of the active substances to the support material can be carried out in all conventional mixing devices.

The rinse aid particles according to the invention can be given to the consumer directly to the hand, so that they additionally added to the detergent as needed. Because of this additional metering step, however, the advantages over liquid rinse aids would be minimized except for the solid dosage form and the addition to the same dosing compartment. It is therefore preferred to combine the rinse aid particulate according to the invention particulate with automatic dishwashing detergents.

Another object of the present invention is therefore also a particulate machine dishwashing detergent containing builders and optionally further ingredients from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, and a particulate rinse aid according to the invention in amounts of 0 , 5 to 30 wt .-%, preferably from 1 to 25 wt .-% and in particular from 2 to 15 wt .-%, each based on the total agent.

The ingredients of the automatic dishwashing detergents are described below. In some cases, these may also be present as active substances or carrier materials in the rinse aid particles according to the invention.

The most important ingredients of automatic dishwashing detergents are builders. In the machine dishwashing detergents according to the invention, it is possible for all builders customarily used in detergents and cleaners to be present, in particular zeolites, silicates, carbonates, organic cobuilders, the phosphates. The builders mentioned below are all suitable as support materials for the rinse aid particles according to the invention, as has already been explained above.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} . H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH2O is preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried 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. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

nNa 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, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, it is also possible to use the generally known phosphates as builders. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the 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 soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2P04, is a white salt with a density of 2.33 gcm-3, has a melting point of 253 ° [decomposition with formation of potassium polyphosphate (KPO _{3) x]} and is readily soluble in water ,

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is made by neutralization of phosphoric acid with soda solution prepared using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

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

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

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches 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 with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

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

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

As organic cobuilders, it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

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

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

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

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

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

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

In addition to the builders, especially substances from the groups of surfactants, bleaching agents, bleach activators, enzymes, polymers and dyes and fragrances are important ingredients of detergents. Important representatives from the mentioned substance classes are described below.

As surfactants, only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance, but are not excluded. The automatic dishwasher detergents according to the invention particularly preferably comprise nonionic surfactants, wherein it is again preferred that a part of the total amount of surfactant contained in the detergents is contained in the rinse aid particles. This is particularly advantageous, since in this way particulate dishwashing agents can be provided which unfold their cleaning performance in the main wash cycle and release the surfactant from the rinse aid particles only in the final rinse cycle. The presence of surfactants in the rinse cycle of a machine dishwashing process 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 alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols 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 of these, 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 means which, for a particular product, may be an integer or a fractional number. 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, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

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

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

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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In addition to the pure nonionic surfactants, it is of course also possible for other substances from the group of ionic surfactants, for example the anionic or cationic surfactants, to be present in the automatic dishwasher detergents according to the invention. These may be contained both in the basic detergent and in the rinse aid particles. In particular, alkyl sulphates may be present in the rinse aid particles.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. 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-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , 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, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. The said bleaching agents can also be introduced wholly or partly via the rinse aid particles according to the invention into the automatic dishwashing detergent according to the invention in order to achieve a "subsequent bleaching" in the final rinse cycle.

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

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives , in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated Gluc amine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the rinse aid particles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.

Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or Mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. To the Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5 wt.%, Preferably 0.5 to about 4.5 wt.%.

Dyes and fragrances can be added to the machine dishwasher detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, α-isomethylionone and methylcedryl ketone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The fragrances can also be incorporated into the rinse aid particles according to the invention, which leads to a fragrance impression when the machine is opened (see above).

In order to improve the aesthetics of the compositions made according to the invention, it may (or parts thereof) be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.

The detergents according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, 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. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

The rinse aid particles according to the invention are designed in such a way that they do not disintegrate in the main rinse cycle (and also in optional pre-rinse cycles) or only to a lesser extent. This ensures that the active substances are largely released only in the rinse cycle and unfold their effect here. Depending on the type of dishwasher, physical packing is required in addition to this chemical preparation, so that the rinse aid particles are not pumped out when changing the water in the machine and thus are no longer available to the rinse cycle. Domestic dishwashers contain before the drain pump, which pumps the water or the cleaning solution after each cleaning cycles out of the machine, a strainer, which is to prevent clogging of the pump by dirt residues. If the consumer rinsed heavily contaminated dishes, so this screen insert must be cleaned regularly, which is easily possible due to the easy accessibility and removability. The rinse aid particles according to the invention are now preferably designed with respect to their size and shape so that they do not pass through the sieve insert of the dishwasher even after the cleaning cycle, ie after loading by movement in the machine and the cleaning solution. In this way it is ensured that in the rinse cycle rinse aid particles are in the dishwasher, release the active substance (s) and bring the desired Klarspüleffekt. Particulate rinse aid particles which are preferred in the context of the present invention are characterized in that the particulate rinse aid has particle sizes between 2 and 30 mm, preferably between 2.5 and 25 mm and in particular between 3 and 20 mm.

In one embodiment of the present invention, the rinse aid particles are admixed to conventional powdered or granular machine dishwashing compositions.

In a further preferred embodiment, the rinse aid particles are processed together with the ingredients of the dishwasher detergents to a combination product of dishwashing detergent and rinse aid. Such products are preferably so-called shaped bodies, which are also referred to as tablets in the prior art.

The preparation of the combination products can be done in a conventional manner. In one possible embodiment, the shaped bodies and the rinse aid particles are produced separately and then connected to one another, in which case the shaped bodies can already have prefabricated recesses for the particles. The connection can be made for example by simply inserting into the recess or bonding the two fixed components.

In a further embodiment, the rinse aid particles or the premix therefor are processed in a suitable tabletting device with the premix for the dishwashing detergent to give moldings.

In the dishwasher detergents according to the invention, the rinse aid particles having the above-mentioned sizes may protrude from the matrix of the other particulate ingredients, but the other particles may likewise have sizes which are in the stated range, so that overall a detergent is formulated which consists of large detergent and cleaning agents Rinse aid particles. In particular, when the rinse aid particles according to the invention are dyed, that is, for example, have a red, blue, green or yellow color, it is for the appearance of the product, i. the entire cleaning agent advantageous if the rinse aid particles are visibly larger than the matrix of the particles of the remaining ingredients of the cleaning agent. Particulate automatic dishwasher detergents according to the invention are preferred here which (without consideration of the rinse aid particles) have particle sizes between 200 and 3000 μm, preferably between 300 and 2500 μm and in particular between 400 and 2000 μm.

The optical appeal of such compositions can be increased not only by coloring the rinse aid particles but also by contrasting the powder matrix or by the shape of the rinse aid particles. Since it is possible to resort to technically uncomplicated methods in the production of the rinse aid particles, it is easily possible to offer these in a wide variety of forms. In addition to the cylindrical particle shape, for example, approximately spherical or cube-shaped rinse aid particles can be prepared and used. Other geometric shapes can be realized. Specific product embodiments may include, for example, star shaped rinse aid particles. Slices or forms that show as a base plant and animal body, such as tree, flower, flower, sheep, fish, etc., are easy to produce. Interesting visual incentives can be created in this way by making the rinse aid particles in the form of a stylized glass to underline the Klarspüleffekt also in the product visually. The imagination knows no bounds.

If the cleaning agents according to the invention are formulated as a powder mixture, partial segregation may occur, in particular in the case of very different sizes of rinse aid particles and detergent matrix, on the one hand with shake loading of the package, on the other hand, the dosage may be different in two successive cleaning cycles, since the consumer is not always compelling the same amount of detergent and rinse aid particles dosed. Should it be desired to use a technically the same amount per cleaning cycle, this can be done using the packaging familiar to the person skilled in the art agents according to the invention are realized in bags of water-soluble film. Particulate machine dishwashing detergents in which a dosing unit is packaged in a bag of water-soluble film are also the subject of the present invention.

As a result, the consumer has only one bag containing, for example, a detergent powder and a plurality of optically prominent rinse aid particles to insert in the dosing of his dishwasher. This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.

The cleaning agents according to the invention can be prepared in a manner known per se. A method for producing powdered automatic dishwashing detergents with a clear rinse effect, in which a powdered machine dishwashing detergent which is known per se is mixed with rinse aid particles according to the invention, is therefore a further subject of the present invention.

The above-described desired restraint of the rinse aid particles in the machine even when changing water can be realized in addition to the above-mentioned increase in the rinse aid particles by reducing the size of the holes in the sieve insert. In this way one can formulate automatic dishwashing detergents which have a uniform average particle size which is smaller than, for example, 4 to 12 mm. For this purpose, the product according to the invention, in which also the rinse aid particles have smaller particle sizes, is added to a sieve insert which replaces or covers the insert located in the machine. Another object of the present invention is therefore a kit-of-parts comprising a powdered machine dishwashing detergent according to the invention and a sieve insert for household dishwashers.

As already mentioned, the combination of agent and sieve insert according to the invention allows the formulation of agents in which the rinse aid particles also have smaller particle sizes. Kits-of-parts according to the invention in which the particle sizes of the automatic dishwashing detergent (taking into account the rinse aid particles) are in the range from 400 to 2500 .mu.m, preferably from 500 to 1600 .mu.m and in particular from 600 to 1200 .mu.m, are preferred.

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

The kit-of-parts according to the invention is not limited to the particular shape of the sieve insert, in which this substitutes or covers the insert located in the machine. It is also possible and preferred according to the invention to add a sieve insert to the kit-of-parts which has the shape of a basket which can be hung in the dishwasher in a known manner, for example on the cutlery basket. In this way, a sieve insert configured in this way replaces the dosing chamber, ie the consumer doses the machine dishwashing detergent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.

Examples:

The support material was incorporated into the molten rinse aid surfactant until the resulting compound had a granular structure. Subsequently, the additive was incorporated and the mixture was pressed with a hydraulic press into compacts.
The composition of the mixture (wt .-%, based on the mixture) is given in the table below: 1 2 Polypore ¹ E200 20 - water glass - 36 Poly Tergent SLF-18B-45 ² 47 37 PEG 35000 33 27 1 support, allyl methacrylate crosspolymer (available from Chemdal Corp., USA) 2 Alcohol alkoxylate from Olin Chemicals, softening point 25-45 ° C.

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

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

In order to demonstrate that the tablet according to the invention transports a sufficient amount of rinse aid surfactant into the rinse cycle, the surface tension of the rinse aid was measured in a 65 ° C. rinse test with the tablet according to the invention. A value of 28 mN / m was obtained, ie the maximum possible lowering of the surface tension with the surfactant used

Claims (19)

1. Particulate rinse aid for machine dishwashing, comprising

   a) 5 to 95% by weight of one or more active substances, at least one of the active substances being a surfactant,

   b) 95 to 5% by weight of one or more carrier materials from the group of the zeolites, bentonites, silicates, carbonates, hydrogen carbonates, sulphates, phosphates, crosslinked polycarboxylates, polyvinyl alcohols, the polycarboxylic acids or starch or cellulose derivatives which are solid at room temperature and one or more binders from the group of polyethylene glycols, polyacrylates, galactomannan, cellulose ethers, mono-, oligo- or polysaccharides and/or resins, and

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

   
   characterized in that

   - components a, b and, where appropriate, c are compacted such that the active substances of component a and, where appropriate, the further ingredients of component c are released at a predetermined time or during a predefined period in the cleaning cycle.
2. Particulate rinse aid according to Claim 1, characterized in that it comprises, as active substances, surfactants, bleaches, bleach activators, corrosion inhibitors, scale inhibitors and/or builders in amounts of 5 to 95% by weight, preferably of 10 to 70% by weight and in particular of 10 to 60% by weight, based in each case on the particle weight.
3. Particulate rinse aid according to Claim 1 or 2, characterized in that it comprises, as an active substance, surfactants, preferably nonionic surfactants, in an amount up to 95% by weight, preferably of 7.5 to 70% by weight and in particular of 10 to 60% by weight, based in each case on the particle weight.
4. Particulate rinse aid according to Claim 3, characterized in that the surfactants present are nonionic surfactants, preferably alkoxylated alcohols.
5. Particulate rinse aid according to one of Claims 1 to 4, characterized in that it comprises, as an active substance, bleaches from the group of the oxygen or halogen bleaches, especially of the chlorine bleaches.
6. Particulate rinse aid according to one of Claims 1 to 5, characterized in that it comprises, as an active substance, bleach activators, especially from the groups of the polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), of the N-acylimides, especially N-nonanoylsuccinimide (NSOI), of the acylated phenolsulphonates, especially n-nonanoyl- or isononanoyloxybenzenesulphonate (n- or iso-NOBS), n-methylmorpholinioacetonitrile methylsulphate (MMA) .
7. Process for producing particulate rinse aids comprising

   a) 5 to 95% by weight of one or more active substances, at least one of the active substances being a surfactant,

   b) 95 to 5% by weight of one or more carrier materials from the group of the zeolites, bentonites, silicates, carbonates, hydrogen carbonates, sulphates, phosphates, crosslinked polycarboxylates, polyvinyl alcohols, the polycarboxylic acids or natural or semisynthetic polymers such as starch or cellulose derivatives which are solid at room temperature and one or more binders from the group of polyethylene glycols, polyacrylates, galactomannan, cellulose ethers, mono-, oligo- or polysaccharides and/or resins, and

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

   
   characterized in that

   - components a and b and, where appropriate, c are compacted such that the active substances of component a and, where appropriate, the further ingredients of component c are released at a predetermined time or during a predefined period in the cleaning cycle.
8. Process according to Claim 7, characterized in that the particles are compacted in a press or by extrusion.
9. Process according to one of Claims 7 or 8, characterized in that components a) are applied to component b) and subsequently compacted, if appropriate with addition of further substances.
10. Process according to one of Claims 7 to 9, characterized in that the mixture to be compacted comprises, as an active substance, one or more substances from the groups of the bleaches, bleach activators, corrosion inhibitors, scale inhibitors and/or cobuilders in amounts of 5 to 80% by weight, preferably of 10 to 70% by weight and in particular of 10 to 60% by weight, based in each case on the particle weight.
11. Particulate machine dishwasher detergent comprising builders and optionally further ingredients from the groups of the surfactants, enzymes, bleaches, bleach activators, corrosion inhibitors, polymers, dyes and fragrances, characterized in that it comprises a particulate rinse aid according to one of Claims 1 to 6 in amounts of 0.5 to 30% by weight, preferably of 1 to 25% by weight and in particular of 2 to 15% by weight, based in each case on overall composition.
12. Particulate machine dishwasher detergent according to Claim 11, characterized in that the particulate rinse aid has particle sizes between 2 and 30 mm, preferably between 2.5 and 25 mm and in particular between 3 and 20 mm.
13. Particulate machine dishwasher detergent according to one of Claims 11 or 12, characterized in that it has, without taking account of the rinse aid particles, particle sizes between 0.2 and 3 mm, preferably between 0.3 and 2.5 mm and in particular between 0.4 and 2 mm.
14. Particulate machine dishwasher detergent according to one of Claims 11 to 13, characterized in that it comprises the rinse aid particles according to one of Claims 1 to 8 in a mixture with the further ingredients customary for machine dishwasher detergents.
15. Particulate machine dishwasher detergent according to one of Claims 11 to 14, characterized in that it is a tablet which comprises the rinse aid particles according to one of Claims 1 to 8 and ingredients customary for machine dishwasher detergents.
16. Particulate machine dishwasher detergent according to one of Claims 11 to 15, characterized in that one metering unit is present packaged in a sachet composed of water-soluble film.
17. Kit of parts comprising a pulverulent machine dishwasher detergent according to one of Claims 11 to 16 and a sieve insert for domestic machine dishwashers.
18. Kit of parts according to Claim 17, characterized in that the particle size of the machine dishwasher detergent, taking account of the rinse aid particles, is in the range of 0.4 to 2.5 mm, preferably of 0.5 to 1.6 mm and in particular of 0.6 to 1.2 mm.
19. Kit of parts according to one of Claims 17 or 18, characterized in that the mesh width or hole size of the sieve insert is 1 to 4 mm and the rinse aid particles are larger than this mesh width or hole size of the sieve insert.