EP1299517B2 - Dishwasher agent with additional uses - Google Patents

Abstract

The invention relates to a cleaning agent for dishwashers comprising a first part (basic composition), which mainly acts during the main cleaning cycle of the dishwasher, and a second part, which mainly acts during the rinsing cycle of the dishwasher as a result a suitable coating. The second part contains one or several substances form the following group: detergency builders, acidifying agents, chelate complex builders or coating inhibiting polymers.

Description

The present invention relates to detergents, in particular controlled-release machine dishwashing detergents. In particular, the present invention relates to machine dishwashing detergents which have a system which allows a controlled release of at least one active ingredient in the cleaning process and at least one active ingredient in the post-treatment process. The invention also relates to a method for producing such machine dishwashing detergents. The invention also relates to cleaning methods using said machine dishwashing detergents.

For a long time, it has been customary to provide the user with detergent in the form of bulk-packaged goods and to leave it to the consumer, in use, to dose the detergent according to the application requirements, depending on the water hardness, the type, amount and / or Depending on the degree of contamination of the cleaning, the amount of cleaning fleet and other parameters.

In response to the consumer's desire to obtain cleaner detergents which are simpler and more convenient to dose, they have increasingly been provided in a form which eliminates the need for single case dosing: detergents were formulated in metered portions containing all the components required for a cleaning cycle. In the case of solid products, such portions have often been shaped into moldings (sometimes containing several phases) such as granules, beads, tablets ("tabs"), ashlars, briquettes, etc., which are dosed as a whole into the liquor. Liquid products were incorporated into water-soluble coatings which dissolve on contact with the aqueous liquor and release the contents into the liquor.

A disadvantage of these solutions is that all components that are needed in the course of a cleaning cycle, reach the same time in the aqueous liquor. Not only do problems of incompatibility of certain components of a cleaning agent with other components occur, but it also becomes impossible to meter targeted components into the fleet at a defined time.

In the prior art, ways have now been described in which individual detergent components can be metered specifically and at a defined time during use. Thus, for example, the temperature-controlled release of active ingredients is described which makes it possible to release active substances such as surfactants, bleaches, soil release polymers and the like either during the rinsing or cleaning cycle or even during the aftertreatment cycle, for example in the rinse cycle in automatic dishwashing. In the meantime, corresponding products with integrated rinse aid are commercially available.

These so-called "2in1" products lead to a simplification of handling and relieve the consumer of the burden of additional dosage of two different products (cleaner and rinse aid). Nevertheless, two metering operations are required to operate a domestic dishwasher at intervals because after a certain number of rinses the regenerating salt must be replenished in the water softening system of the machine. These water softening systems consist of ion exchange polymers which soften the hard water entering the machine and are regenerated by a rinsing with salt water following the washing program.

The present invention was based on the object to provide a product that must be dosed only once per application, without even after a higher number of rinsing cycles, the dosage of another product and thus a double dosing would be necessary. A product should be provided which, in addition to the "built-in rinse aid", eliminates the need to refill the regeneration brine tank, further simplifying handling. In doing so, the performance of the product should reach or exceed the performance level of conventional three-product dosing (salt-detergent rinse aid) or novel two-product dosing ("2in1" rinse-aid).

It has now been found that the addition of regenerating salt to household dishwashers is not necessary when compounds of certain classes of substances are introduced into the rinse cycle.

• a) einen ersten Teil (Basiszusammensetzung), der seine Wirkung im wesentlichen im Hauptreinigungsgang der Geschirrspülmaschine entfaltet; und
• b) einen zweiten Teil, der durch geeignete Beschichtung seine Wirkung im wesentlichen im Klarspülgang der Geschirrspülmaschine entfaltet,

bei denen der zweite Teil einen oder mehrere Stoffe aus der Gruppe der belagsinhibierenden Polymere nach Anspruch 1 enthält.The present invention relates to automatic dishwashing detergents comprising

• a) a first part (basic composition) which has an effect essentially in the main dishwashing cycle of the dishwasher; and
• b) a second part which, by means of a suitable coating, has its effect essentially in the rinse cycle of the dishwasher,

in which the second part contains one or more substances from the group of the surface-inhibiting polymers according to claim 1.

These substances, the use of which has hitherto not been described in the prior art rinse cycle, mean that rinse cycles, instead of softened water, can also be carried out with normally hard tap water without loss of power. The groups mentioned include substances, some of which are included of the present invention are particularly suitable. These are described below.

The most important ingredients of automatic dishwashing detergents are builders. In the second part of the machine dishwashing detergents according to the invention, it is possible for all builders customarily used in detergents to be present, in particular zeolites, silicates, carbonates, organic cobuilders and phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. 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 Na ₂ Si ₂ O ₅ .yH ₂ O are 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 are. 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 having 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, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. 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, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. 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 readily water-soluble powders which lose the water of crystallization on heating at 200 ° C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O _7), (at higher temperature in sodium trimetaphosphate Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light 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 goes on stronger heating in the diphosphate Na ₄ P ₂ O ₇ above. Disodium hydrogen phosphate is prepared by neutralization of 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 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.

Further suitable builders are carbonates, bicarbonates and the salts of oligocarboxylic acids, for example gluconates, succinates and in particular citrates. Detergents according to the invention, in which the second part comprises one or more builders from the group consisting of sodium carbonate, sodium hydrogencarbonate and trisodium citrate in amounts above 10% by weight, preferably above 15% by weight, more preferably above 20% by weight and in particular above 25% by weight, based in each case on the weight of the second part, are preferred according to the invention.

Acidifying agents are also suitable as an ingredient for the second part in the context of the present invention. Substances from this group can be used, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight). Particularly preferred cleaning agents according to the invention are characterized in that the second part comprises one or more acidifying agents from the group of citric acid, adipic acid, malic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid in amounts above 5% by weight, preferably above 10 Wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part.

Another possible group of ingredients for the second part are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, usually stretched verb are closed by complex formation over an ion to rings. The number of bound ligands depends on the coordination number of the central ion.

Typical and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also, complexing polymers, ie polymers that carry either in the main chain itself or side by side to this functional groups that can act as ligands and react with suitable metal atoms usually to form chelate complexes. are used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des zweiten Teils, enthält.In the context of the present invention, particular preference is given to cleaning agents in which the second part comprises one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of second part, contains.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) -glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

In the case of the scale-inhibiting polymers as the constituent of the second part, in particular cleaning agents according to the invention are characterized in that the second part comprises one or more scale-inhibiting polymers from the group of cationic homopolymers or copolymers, in particular hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallyl ammonium chloride and acrylamide, polymers having imino groups, polymers having quaternized ammonium alkyl methacrylate groups as monomer units, cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate and acrylamide, respectively; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary Ethyleniminpolymere and polyesters and polyamides with quaternary side groups in amounts above 5 wt .-%, preferably above 10 wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part contains.

• i) ungesättigten Carbonsäuren
• ii) Sulfonsäuregruppen-haltigen Monomeren
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

in Mengen oberhalb von 5 Gew.-%, vorzugsweise oberhalb von 10 Gew.-%, besonders bevorzugt oberhalb von 20 Gew.-% und insbesondere oberhalb von 25 Gew.-%, jeweils bezogen auf das Gewicht des zweiten Teils, enthält, bevorzugte Ausführungsformen der vorliegenden Erfindung.Another preferred ingredient for the second part are certain sulfonic acid group-containing copolymers. Thus, cleaning agents, the second part of one or more copolymers of

• i) unsaturated carboxylic acids
• ii) sulfonic acid group-containing monomers
• iii) optionally further ionic or nonionic monomers

in amounts above 5 wt .-%, preferably above 10 wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part, contains, preferred Embodiments of the present invention.

In the context of the present invention, unsaturated carboxylic acids of the formula I are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (I),

in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above, or -COOH or -COOR ⁴ wherein R ⁴ is a saturated or unsaturated, straight or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula I are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula II are preferred,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (II),

in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH _{2) n} - with n = 0 to 4, -COO- (CH _{2) k} - with k = 1 to 6, - C (O) -NH-C (CH _{3) 2} - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas IIa, IIb and / or IIc,

H ₂ C = CH-X-SO ₃ H (IIa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IIc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula IIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula IIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula IIb), allylsulfonic acid (X = CH ₂ in formula IIa), methallylsulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula IIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid (X = CH ₂ in formula IIb), styrenesulfonic acid (X = C ₆ H ₄ in formula IIa), vinylsulfonic acid (X not present in formula IIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Formula IIa), 3-Sul fopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula IIb), sulfomethacrylamide (X = -C (O) NH- in formula IIb), sulfomethylmethacrylamide (X = -C (O) NH-) CH ₂ - in formula IIb) and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers contained in the second part consist only of monomers of groups i) and ii).

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln IIa, IIb und/oder IIc:
  
          H₂C=CH-X-SO₃H     (IIa),
  
          H₂C=C(CH₃)-X-SO₃H     (IIb)
  
          HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H     (IIc),
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, - CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred cleaning agents comprise one or more copolymers in the second part

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas IIa, IIb and / or IIc:
  
  H ₂ C = CH-X-SO ₃ H (IIa),
  
  H ₂ C = C (CH ₃ ) -X-SO ₃ H (IIb)
  
  HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (IIc),
  
  in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , - CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The copolymers contained in the second part may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units, which are described below.

Thus, for example, an inventive RM is preferred, which is characterized in that in the second part, one or more copolymers are contained, the structural units of the formula III

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (III),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the second part of the cleaning agent according to the invention is also preferred and characterized in that one or more copolymers are used, the structural units of the formula IV

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IV)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. For example, cleaning agents according to the invention are preferred, the second part of which comprises one or more copolymers which contain structural units of the formula V

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (V)

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - are, are preferred, also a preferred embodiment of the present invention, just as cleaning agents are preferred, which are characterized in that the second part contains one or more copolymers, the structural units of the formula VI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (VI),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). One arrives in this way to inventively preferred cleaning agents, which are characterized in that one or more copolymers are contained in the second part, the structural units of the formula VII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH _{2) n} -, -NH-C (CH _{3) 2} - - with n = 0 to 4, is -O- (C ₆ H _4), or - NH-CH (CH ₂ CH ₃₎ - is, are preferred and to detergents, which are characterized in that the second part contains one or more copolymers, the structural units of the formula VIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (VIII),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH _{2) n} -, -NH-C (CH _{3) 2} - - with n = 0 to 4, is -O- (C ₆ H _4), or - NH-CH (CH ₂ CH ₃₎ - stands, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding cleaning agents, which are characterized in that the sulfonic acid groups are present in the copolymer partially or fully neutralized, are preferred according to the invention.

The monomer distribution in the copolymers according to the invention contained in the second part in copolymers containing only monomers from groups i) and ii), preferably each 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90 wt. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molecular weight of the polymers according to the invention contained in the second part can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In addition to the added benefit of being able to dispense with the dosage of regenerating salt, the products of the invention also make the additional dosage of a rinse aid superfluous. The clear rinse effect can be significantly improved if the detergents according to the invention contain surfactants, in particular nonionic surfactants. The surfactants may be present in the first part (of the "base composition") and be sent to the rinse cycle via caustic carryover or other phenomena, as well as being part of the second part which, due to the coating, essentially only unfolds its effect in the final rinse cycle of the dishwashing machine.

In the context of the present invention, cleaning agents are preferred in which the second part additionally contains 1 to 50% by weight, preferably 2.5 to 45% by weight and in particular 5 to 40% by weight of nonionic surfactant (s ), wherein the weights are based on the second part including coating.

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.

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 this nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular 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 (IX)

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 (X)

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

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. In particular, alcohol ethoxylates having 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.

Particular preference is given to detergents according to the invention which contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred detergents are characterized by having in the second part nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that these have a Viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred cleaning agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred cleaning agent according to the invention contains nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each of R ³ in the above formula may be different if x ≥ 2 is. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

If one summarizes the latter statements, detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Of course, the surfactants mentioned above may additionally be present in the first part of the cleaning agents according to the invention. Moreover, it is also possible that the second part is formulated surfactant-free and the aforementioned surfactants are all present in the first part (see below).

In addition to one or more substances from the groups of builders, Acidifizierungsmittel, chelate complexing agent or the coating-inhibiting polymers and optionally contained surfactants, the second part may contain other conventional ingredients of cleaning agents. In particular, a content of bleaching agents and / or bleach activators and / or bleach catalysts and / or enzymes and / or corrosion inhibitors (silver protectants) and / or dyes and / or fragrances in the second part can bring further performance advantages.

According to the invention, the second part has a suitable coating which causes the contents of the second part to be released substantially only in the final rinse cycle of the dishwasher and to exert their effect. Such a coating, which is often referred to as "coating" in German, usually has thicknesses of 10 to 1000 .mu.m, with layer thicknesses between 20 and 800 .mu.m, in particular between 50 and 400 .mu.m, being preferred within the scope of the present invention.

The coating can be uniformly composed, e.g. consist of a single substance, but it is also possible that multi-layer coatings are used, in the context of the present invention, two, three or four-layer coatings are preferred.

The coating protects the second part from premature dissolution in the main cleaning cycle and any intermediate rinsing. In the rinse cycle, the coating must be rapidly dissolved or otherwise destroyed to release the ingredients of the second part. In this case, several release mechanisms come into consideration that use altered properties of the coating materials as a function of varying external conditions. In this way prevailing conditions in the dishwasher, which are different in the main cleaning and rinse cycle, used to convert the second part in the rinse cycle. By changing the outer condition, the coating "switches" and releases the second part. As a "switch" offer temperature-controlled and / or enzyme-controlled and / or redox-controlled and / or electrolyte-controlled and / or pH-controlled systems.

Temperature-controlled systems may be, for example, to coat the second part with a substance that only above melts at a certain temperature and then washed away or becomes soluble above a certain temperature in the application medium. Such encapsulating substances, which will be described in detail below, are, for example, paraffins.
Another mechanism of temperature control can be realized with substances that dissolve better at low temperatures than at high. Such substances with a so-called "low critical solution temperature" are referred to as LCST substances or as substances with lower critical demixing temperature. In order to prevent these substances from dissolving when they first enter the machine (before the main cleaning cycle), they must be provided with a further coating which dissolves during the main cleaning cycle or is otherwise destroyed. At the hot temperatures of the scrubbing cycle, the LCST substance protects the second part while it dissolves at the low temperatures of the rinse cycle and releases the ingredients.

Cleaning agents preferred in the context of the present invention are therefore characterized in that the coating of the second part comprises an LCST polymer.

The cleaning agent can be used particularly advantageously in mechanical processes where the active ingredient is to be released in a rinse after the cleaning step. Examples are the mechanical cleaning of dishes both in the household and in the commercial sector. The packaging according to the invention, the active ingredients remain after a heat treatment in a liquid medium, eg. B. after the main rinse, at least partially unchanged and the active ingredient is released after cooling after the heat treatment, ie in the rinse cycle.

According to the preferred embodiment of the present invention, the second part is coated with an LCST substance. These substances are usually polymers. Depending on the conditions of use, the lower critical demixing 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. In this case, cleaning agents in which the lower critical demixing temperature of the LCST polymer is between 20 ° C and 90 ° C, are preferred.
An LCST polymer suitable in the context of the present invention is, for example, polyvinylcaprolactam (PVCap).
Further preferred cleaning agents are characterized in that the LCST polymer is selected from cellulose derivatives, mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylamides and / or acrylates or acrylic acids. The LCST substances are particularly preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances. Corresponding detergents which are characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, copolymers of the polyisopropylacrylamide and blends of these substances are preferred according to the invention.

Examples of alkylated and / or hydroxyalkylated polysaccharides are methylhydroxypropylmethylcellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose ( HBC), hydroxybutyl methylcellulose (HBMC), hydroxyethyl carboxymethyl cellulose (HEC), hydroxyethyl carboxymethyl cellulose (HEECMC), hydroxyethyl ethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), hydroxyethyl methyl cellulose (HEMC), methyl hydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose (MHEPC), methyl cellulose ( MC) and propylcellulose (PC) and mixtures thereof, with carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxyproplcellulose as well as the alkali metal salts of CMC and the slightly ethoxylated MC or mixtures of the foregoing being preferred.

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC). Other polymers which exhibit a lower critical demixing temperature in water and which 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 interconnected networks of the above (co) polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin, and certain alginates. Mixtures of these polymers with salts or surfactants can also be used as the LCST substance. By such additions or by the degree of crosslinking of the polymers, the LCST (lower critical demixing temperature) can be modified accordingly.

In a preferred embodiment of the present invention, the second part is coated with a further material which is soluble at a temperature above the lower separation temperature of the LCST substance or has a melting point above this temperature or a retarded solubility, ie above the lower separation temperature of LCST layer can be released. This layer serves to separate the mixture of active ingredient and LCST substance from water or other media that dissolve them before the heat treatment can protect. This additional layer should not be liquid at room temperature and preferably has a melting point or softening point at a temperature equal to or above the lower critical demixing temperature of the LCST polymer. The melting point of this layer is particularly preferably between the lower critical demixing temperature and the temperature of the heat treatment. In a particular embodiment of this embodiment, the LCST polymers and the further substance are mixed together and applied to the material to be encapsulated.

The further substance preferably has a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.

The above properties are usually met by so-called waxes. "Waxing" is understood to mean a number of natural or artificially produced substances which generally melt above 35 ° C. without decomposition and are already relatively low viscous and non-stringy just above the melting point. 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 the synthetic waxes.

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable as coating materials are compounds from other classes of substances which fulfill the stated requirements with regard to the softening point. 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), proved. Also suitable are synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea) Conversely, synthetic or partially synthetic esters of lower alcohols with fatty acids from natural sources can be used. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used as further substance.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating may optionally also contain wool wax alcohols, which are understood to mean triterpenoid and steroid alcohols, for example lanolin, which is obtainable, for example, under the trade name Argowax® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the coating in the context of the present invention.

Other suitable materials having a melting point above the LCST of the underlying coating material are saturated aliphatic hydrocarbons (paraffins).

Also suitable as coating materials are all water-soluble, water-dispersible and water-insoluble polymers which have a melting point which is above the lower critical demixing temperature of the LCST polymer used according to the invention or is soluble above this temperature. Suitable polymers are solid polyethyleneglycols, polyvinyl alcohols, polyacrylic acid and their derivatives at room temperature. Furthermore, gelatin has also proved to be suitable. Particular preference is given to using polyvinyl acetate (PVAc) as the material for protecting the LCST layer (topcoating).

Sometimes it may already be sufficient to protect the LCST polymer layer if it is shielded by a water-soluble coating of initially cold water. This water-soluble coating need only have a sufficiently delayed solubility, so that the layer is sufficiently stable for a long time. For this purpose, e.g. Polyalkylenglycole be used with preferably higher molecular weight.

The second part can be coated in a manner known per se with the LCST substance and / or the further material. Here, the substances can be sprayed, for example, as a melt or in the form of a solution or dispersion, or the mixture can be immersed in the melt, solution or dispersion or mixed with it in a suitable mixer. Coating in a fluidized bed apparatus is also possible. The spraying process is suitable for all production processes established in pharmacy and food technology of coated tablets, capsules and particles. The polymer suspension or solution is sprayed either batchwise in small portions, the particles are transported on a conveyor belt through a liquid curtain and then dried in air flow or sprayed continuously with simultaneous drying by the injected air flow in fluidized bed, fluidized bed or Flugschichtumhüllungsgeräten , The coating method is also conceivable if LCST polymers are added to the coating syrups in a sufficiently high concentration. The application of the second layer is analogous.

In a further preferred embodiment of the invention, the ingredients of the second part are released by an enzyme-controlled coating. In this case, enzymatically degradable (enzyme-sensitive) materials are used as coating material. The enzymes usually contained in cleaning agents cause, after a certain exposure time, a degradation of the enzyme-sensitive coating material and, consequently, a release of the active substance or detergents enclosed in the second part.

Suitable enzyme-sensitive materials are preferably cellulose derivatives, starch or starch derivatives, partially oxidized starch derivatives, glycerides, certain proteins and mixtures of these. Enzymes used in detergents are preferably proteases, amylases and / or lipases.

Agents according to the invention can be prepared in such a way that conventional solid detergents or components therefor, which are present as granules and / or agglomerates, as pellets, extrudates, tablets or in capsule form, are coated with the enzyme-sensitive material. If such enzyme-containing agents or components for cleaning agents are introduced into cleaning liquors together with conventional cleaning agents, the release of the enclosed active substances takes place only after the at least partial degradation of the enzyme-sensitive coating materials.

A further preferred embodiment of the invention is that a (redox system is used as the (physico -) - chemical switch, which causes a controlled drug release. As with the enzyme-controlled release of active substance, the redox materials can also be used as coating material, in particular of shaped articles, for example tablets, or capsules of active ingredients of cleaning agents, in the redox-controlled release of active substance. After a certain exposure time of redox-active components usually contained in cleaning agents, there is a chemical change of the redox-sensitive coating material and, consequently, a release of the active ingredient or detergents enclosed in the coated moldings, granules or capsules.

Particularly suitable as redox-sensitive materials are oxidation-sensitive organic and inorganic substances, including polymers. Particularly preferred is the use of polyvinylpyridine as a redox-sensitive material. As redox-active ingredients of cleaning agents are in particular oxidizing agents such as percarbonate and the like, especially in combination with bleach activators, especially tetraacetylethylenediamine (TAED) and other common bleach activators to call.

Solid compositions according to the invention can be prepared by coating conventional solid detergents or components therefor, which are present as granules and / or agglomerates, as pellets, extrudates, tablets or in capsule form, with the redox-sensitive material. If redox-sensitive materials containing agents or redox-sensitive materials containing components for cleaning agents are introduced together with conventional cleaning agents in cleaning liquors, the release of the entrapped active ingredients takes place only after the at least partial oxidative degradation of the redox-sensitive coating materials.

In the context of the present invention, a (physico-) chemical switch can be used, which causes an electrolyte-controlled drug release. Here, the difference in the electrolyte content between the cleaning cycle and the rinse cycle in automatic dishwashing can be exploited. A further preferred embodiment of the invention therefore relates to a cleaning agent in which the second part is coated with an electrolyte-sensitive substance, wherein the active substance (s) of the second part is released as a result of an occurring change in the electrolyte concentration.

• a) Cellulosederivate, z.B. Methylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose, Methylhydroxyethylcellulose, Carboxymethylcellulose mit verschiedenen Substitutionsgraden
• b) Polyvinylalkohole mit verschiedenen Verseifungsgraden und Molekulargewichten
• c) Polyelektrolyte z.B. Polyacrylate und besonders bevorzugt Polystyrolsulfonat

Such a coating with a material that dissolves better at low ionic strength than at high, hereinafter referred to as "electrolyte-sensitive material" releases the second part depending on the salinity in the application. As electrolyte-sensitive materials, the following classes of substance come into consideration:

• a) Cellulose derivatives, for example methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, carboxymethylcellulose with different degrees of substitution
• b) polyvinyl alcohols with different saponification degrees and molecular weights
• c) polyelectrolytes, for example polyacrylates, and particularly preferably polystyrenesulfonate

These materials have good solubility in pure water or at low ionic loading, but become difficult or insoluble in the presence of higher salt concentrations. The particular salt concentration required to make the substances insoluble, is different. Even with these "switches" it may be necessary to apply a second coating, which protects the first coating layer from dissolution by pure water at the beginning of the Cleaning program prevented.

Considering the process of machine dishwashing, during rinsing, the rinse liquor pH is about 10. Accordingly, the main commercially available dishwashing products on the market are alkaline. In particular, in the vast majority of machine dishwashers and their different cleaning programs, the rinsing liquor is pumped off after the cleaning cycle and replaced by fresh water. It comes, regardless of the temperature of the water, to a drop in the pH by about 1 to 2 pH units. The exact value of the pH drop depends on the amount of residual liquor left in the machine, which is around 2%.

In a further preferred embodiment of the present invention, therefore, it is possible to use a pH change to release active substances in a targeted manner.

In this embodiment of the invention, such (physico-) chemical switches are used as coating material for the second part, which undergo a change in the physicochemical properties when the pH of the application liquor changes. In particular, it is preferred that such substances be used as (physico) chemical switch, which have an increased solubility in water as a result of a change in the pH occurring in the application liquor. Alternatively or additionally, those switch substances are preferred which have a change, in particular a decrease in the diffusion density, with the corresponding change in the pH of the application liquor. In this case, means, in particular automatic dishwasher detergents, which contain a substance as a (physico-) chemical switch are advantageous, which, in the case of a change in pH occurring in the application liquor in the range from 11 to 6, preferably from 10 to 7, a change in their physical properties. experiences chemical properties and thereby preferably at a decreasing pH in the range of 10 to 7, in particular from 10 to 8, an increased solubility in water and / or a decrease in the diffusion density.

Suitable substances that can be used as such (physico) chemical switch are basic in nature and especially basic polymers and / or copolymers.

The principle of pH-dependent water solubility is generally based on protonation or deprotonation of functional side groups of the polymer molecules, as a result of which their charge state changes accordingly. The polymer must now be such that it dissolves in the stable charged state at a certain pH in water, in the uncharged state at another pH, however, precipitates. In the context of the present invention, it is preferred that the polymers used according to the invention have a lower water solubility at a higher pH than at lower pH values or even become insoluble in water at relatively high pH values.

Polymers with pH-dependent solubility are known in particular from pharmacy. Here, e.g. acid-insoluble polymers are used to give tablets an enteric-coated, but colonic-soluble, coating. Such acid-insoluble polymers are usually based on derivatives of polyacrylic acid, which is present in the acidic region in undissoziierter and thus insoluble form, in the alkaline range, but typically neutralized at pH 8 and goes as a polyanion in solution.

Also in the opposite case - soluble in the acidic range, insoluble in the alkaline range - examples are known in the art. These substances, in which the polymer molecules mostly carry amino-substituted side chains, are e.g. used for the preparation of gastric juice-soluble tablet coatings. They usually dissolve at pH values below 5. Polymers in which the solubility change from soluble to insoluble at higher pHs are not known in the pharmaceutical arts because these pHs are physiologically meaningless.

Particularly preferred suitable substances are basic (co) polymers which have amino groups or aminoalkyl groups. Comonomers may be, for example, conventional acrylates, methacrylates, maleinates or derivatives of these compounds. A particularly suitable aminoalkyl-methacrylate copolymer is sold by the company Röhm (Eudragit®).

In addition to the thermodynamic solubility, the dissolution kinetics of a filmed substance or the decrease in its mechanical stability may be important for the application. The solution kinetics of the switch substances used according to the invention is pH-dependent at room temperature down to the alkaline range, ie the films are significantly longer stable at pH 10 than at a pH of 8.5, although they are thermodynamically soluble at both pH values are.

In a further embodiment of the present invention, therefore, polymers are used whose water solubility varies between pH 6 to 7 and which are less soluble at higher pH than at lower pH. Suitable polymers contain, as already described above, basic groups, for example primary, secondary or tertiary amino groups, imino groups, amido groups or pyridine groups, generally those which have a quaternizable nitrogen atom. These are protonated at lower pHs, whereby the polymer is soluble. At higher pH, the molecule becomes uncharged and becomes insoluble. As a rule, the transition takes place - referred to below as the "switching point", depending on the pK _B value of the basic groups and their density along the polymer chain, in the range of acidic pH values. Subject of the present invention is therefore also a polymer in which the switching point is in a range between pH 6 and 7.

• Abhängig vom pK_B-Wert erfolgt im Bereich höherer pH-Werte nur noch eine sehr geringe pHabhängige Änderung des Ladungszustandes des Polymers in Lösung. Daher muß es gelingen, durch diese geringe Änderung des Ladungszustandes die Löslichkeit entscheidend zu beeinflussen. Das Polymer muß also genau eine solche Hydrophilie aufweisen, dass es in völlig ungeladenem Zustand unlöslich, jedoch bei einer bereits geringen Aufladung löslich wird.

This shift of the switching point succeeds in principle in the following way:

• Depending on the pK _B value, only a very small pH-dependent change in the charge state of the polymer in solution takes place in the region of higher pH values. Therefore, it must be possible to influence the solubility decisively by this slight change in the state of charge. The polymer must therefore have precisely such a hydrophilicity that it becomes insoluble in a completely uncharged state, but becomes soluble when already slightly charged.

• Copolymerisation eines Monomers mit basischer Funktion mit einem hydrophileren Monomer. Durch das Einbauverhältnis der jeweiligen Comonomeren wird der Schaltpunkt beeinflußt.
• Hydrophilierung des basische Gruppen tragenden Polymers durch eine polymeranaloge Umsetzung. Durch den Modifikationsgrad wird der Schaltpunkt beeinflusst.

Neben der einfachen Hydrophilierung ist es auch möglich, basische Funktionen verschiedener pK_B-Werte einzuführen. Durch das Verhältnis beider Gruppen und die resultierende Hydrophilie des Moleküls kann der Schaltpunkt beeinflusst werden.To adjust the hydrophilicity, the following methods can be used:

• Copolymerization of a monomer with a basic function with a more hydrophilic monomer. Due to the incorporation ratio of the respective comonomers, the switching point is influenced.
• Hydrophilization of the basic group-bearing polymer by a polymer-analogous reaction. The degree of modification influences the switching point.

In addition to simple hydrophilization, it is also possible to introduce basic functions of different pK _B values. Due to the ratio of both groups and the resulting hydrophilicity of the molecule, the switching point can be influenced.

A particularly preferred polymer of this class of substances is an N-oxidized polyvinylpyridine.

It is not necessary that the polymer of the coating of the second part completely dissolves at the appropriate pH conditions to release the drug. Rather, it suffices if, for example, the permeability of a polymer film changes, e.g. the penetration of water into the drug formulation is made possible. Thereby, a secondary effect, e.g. the activation of an effervescent system or the swelling of a water-swellable disintegrant, which are known in particular from the pharmaceutical industry, ensure the complete release of the active ingredient.

In a further preferred embodiment of the invention, so-called pH-shift boosters are used in addition to the above-mentioned switches. As a result, it can be prevented, at least to a large extent, that after the rinse cycle residues, which in particular consist of the pH-dependent, soluble substance itself, are found. For the purposes of this invention, suitable pH-shift boosters are all substances and formulations which are capable of controlling the extent of the pH shift either locally, i. in the immediate vicinity of the particular pH-shift-sensitive substance used, or also generalized, i. in the entire rinsing, to enlarge. These include all organic and / or inorganic water-soluble acids or acid-reacting salts, in particular at least one substance from the group of alkylbenzenesulfonic acids, alkylsulfuric acids, citric acid, oxalic acid and / or alkali metal hydrogensulfates.

The pH-shift booster can be incorporated into the cleaning agent. In a further embodiment of the invention, however, it is also possible to supply the pH-shift booster externally to the machine either after the end of the cleaning cycle or at the beginning of the rinse cycle or by a special delivery system (by coating with a slowly dissolving coating agent). or by diffusion from a matrix material.

As already mentioned, the coating of the second part of the cleaning agent according to the invention can also consist of several layers. In part, this is necessary to protect certain coating layers by a second layer during the main cleaning cycle (see above), but in some cases a sub-coating may be required to create a well-adhering and uniform surface for the functional coating. Of course, the combination of a Untercoatings with a functional coating and another protective layer is conceivable. In this embodiment, the second part has a three-layer coating. Detergents in which the coating of the second part consists of several coating layers, preferably of two or three coating layers, are preferred according to the invention.

The following is a description of preferred coating materials for undercoatings or for exterior coatings that may protect the "functional coating".

Preferred coating materials for an optional inner or outer coating layer are the polymers known from the prior art. In particular, cleaning agents are preferred in which the coating layer on the second part consists of a polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. With regard to the media into which cleaning agents are usually introduced, preference is given in particular to cleaning agents in which the outer coating layer on the second part consists of a water-soluble polymer.

Such preferred polymers may be of synthetic or natural origin. If polymers are used on a native or a fractional basis as a coating material, then the coating material is preferably selected from one or more substances from the group of carrageenan, guar, pectin, xanthan, cellulose and its derivatives, starch and its derivatives, and gelatin.

Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar built extract of North Atlantic, belonging to the Floridean red algae. The carrageenan precipitated from the algae's hot water extract is a colorless to sand-colored powder with molecular weights of 100,000-800,000 and a sulphate content of about 25%, which is very slightly soluble in warm water. Carrageenan has three main components: The yellow-forming f- fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (Agar, in contrast, contains 3,6-anhydro-α-L-galactose). The non-gelling I fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also denoted by Greek letters: α, β, γ, μ, ν, ξ, π, ω, χ. Also, the type of cations present (K, NH _4, Na, Mg, Ca) affects the solubility of the carrageenans. Semisynthetic products which contain only one type of ion and can also be used as coating materials in the context of the present invention are also called Carrag (h) eenates.

Guar, also known as guar flour, can be used as a coating material in the context of the present invention. It is an off-white powder that has been cultivated by milling the endosperm of the endemic species originally native to India and Pakistan, now also cultivated in other countries, for example in the southern United States the legume belonging to Guar bean (Cyamopsis tetragonobolus) is obtained. The main constituent of the guar is with up to about 85% by weight of the dry substance guar gum (guar gum, Cyamopsis gum); Secondary components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, ie a polysaccharide, the linear chain of which is unsubstituted (see formula XI) and substituted in the C6 position with a galactose residue (see formula (XII)) mannose units in α-D- (1 → 4 ) Link is established.

The ratio of XI: XII is about 2: 1; the XII units are not strictly alternating, contrary to initial assumptions, but are arranged in pairs or triplets in the polygalactomannan molecule. Data on the molecular weight of the guaran vary with values of about 2.2 × 10 ⁵ -2.2 × 10 ⁶ g / mol, depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to about 1350 -13,500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.

The pectins, which can also be used as coating material, are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-α-glycoside. connected galacturonic acid units whose acid groups are esterified to 20-80% with methanol, with a distinction between highly esterified (> 50%) and low-esterified pectins (<50%). The pectins have a leaflet structure and are thus in the middle of starch and cellulose molecules. Their macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin to 85% galacturonic acid. The molecular weights of the various pectins vary between 10,000 and 500,000. The structural properties are also highly dependent on the degree of polymerization; thus, e.g. dried pectins are asbestos-like fibers, whereas flax pectins are fine, granular powders.

The pectins are prepared by extraction with dilute acids mainly from the inner parts of citrus fruit peel, Obstresten or sugar beet pulp.

Xanthan gum can also be used according to the invention as an outer coating material for the second part. Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular mass of 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum. Xanthan can be described by the following formula:

The celluloses and their derivatives are also suitable as coating materials. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. As a coating material For the purposes of the present invention, it is also possible to use cellulose derivatives which are obtainable by cellulose-based polymer-analogous reactions. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and starch derivatives can also be used as coating materials.

Suitable nonionic organic coating materials 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 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

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

Even starch can be used as a coating material for the second part. Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight: about 20-30% straight-chain amylose (MW 50,000-150,000) and 70-80% branched-chain amylopectin (MW 300,000-2,000,000); Amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, entangled chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bond to a branch-like structure with about 1500-12000 molecules of glucose. In addition to pure starch, suitable coating materials in the context of the present invention are starch derivatives which are obtainable from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Among the proteins and modified proteins, gelatin as a coating material is of outstanding importance. Gelatin is a polypeptide (molecular weight: about 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
  • a1) Polyvinylpyrrolidone,
  • a2) Vinylpyrrolidon/Vinylester-Copolymere,
  • a3) Celluloseether.
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
  • b1) Alkylacrylamid/Acrylsäure-Copolymere
  • b2) Alkylacrylamid/Methacrylsäure-Copolymere
  • b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
  • b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
  • b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
  • b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
  • b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
  • b8) Copolymere aus
    • b8i) ungesättigten Carbonsäuren
    • b8ii) kationisch derivatisierten ungesättigten Carbonsäuren
    • b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
  • c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
  • c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
  • c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der
  • d1) Vinylacetat/Crotonsäure-Copolymere
  • d2) Vinylpyrrolidon/Vinylacrylat-Copolymere
  • d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
  • d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
  • d5) gepropften und vernetzten Copolymere aus der Copolymerisation von
    • d5i) mindesten einem Monomeren vom nicht-ionischen Typ,
    • d5ii) mindestens einem Monomeren vom ionischen Typ,
    • d5iii) von Polyethylenglycol und
    • d5iv) einem Vernetzter
  • d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
    • d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
    • d6ii) ungesättigte Carbonsäuren,
    • d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
  • d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
  • d8) Tetra- und Pentapolymere aus
    • d8i) Crotonsäure oder Allyloxyessigsäure
    • d8ii) Vinylacetat oder Vinylpropionat
    • d8iii) verzweigten Allyl- oder Methallylestern
    • d8iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
  • d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
  • d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der
  • e1) quaternierten Cellulose-Derivate
  • e2) Polysiloxane mit quaternären Gruppen
  • e3) kationischen Guar-Derivate
  • e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure
  • e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats
  • e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
  • e7) quaternierter Polyvinylalkohol
  • e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Other polymers which can be used as outer coating materials for the second part are synthetic polymers which are preferably water-swellable and / or water-soluble. Such sysnthetic based polymers can be "tailored" for the desired coating permeability during storage and dissolution of the coating layer in use. Particularly preferred cleaning agents according to the invention are characterized in that the outer coating material for the second part is selected from a polymer or polymer mixture, wherein the polymer or at least 50 wt .-% of the polymer mixture is selected from

• a) water-soluble nonionic polymers from the group of
  • a1) polyvinylpyrrolidones,
  • a2) vinylpyrrolidone / vinyl ester copolymers,
  • a3) cellulose ethers.
• b) water-soluble amphoteric polymers from the group of
  • b1) alkylacrylamide / acrylic acid copolymers
  • b2) alkylacrylamide / methacrylic acid copolymers
  • b3) alkylacrylamide / methylmethacrylic acid copolymers
  • b4) Alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • b5) Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • b6) Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • b7) Alkylacrylamide / Alkymethacrylate / Alkylaminoethylmethacrylate / Alkylmethacrylate Copolymers
  • b8) copolymers
    • b8i) unsaturated carboxylic acids
    • b8ii) cationically derivatized unsaturated carboxylic acids
    • b8iii) optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
  • c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts
  • c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts
  • c3) Methacroylethylbetaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
  • d1) vinyl acetate / crotonic acid copolymers
  • d2) vinylpyrrolidone / vinyl acrylate copolymers
  • d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
  • d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  • d5) grafted and crosslinked copolymers from the copolymerization of
    • d5i) at least one nonionic type monomer,
    • d5ii) at least one ionic-type monomer,
    • d5iii) of polyethylene glycol and
    • d5iv) a networked one
  • d6) copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
    • d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • d6ii) unsaturated carboxylic acids,
    • d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols
  • d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
  • d8) tetra- and pentapolymers from
    • d8i) crotonic acid or allyloxyacetic acid
    • d8ii) vinyl acetate or vinyl propionate
    • d8iii) branched allyl or methallyl esters
    • d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • d9) Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
  • d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid
• e) water-soluble cationic polymers from the group of
  • e1) quaternized cellulose derivatives
  • e2) polysiloxanes with quaternary groups
  • e3) cationic guar derivatives
  • e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
  • e5) Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate
  • e6) vinylpyrrolidone-methoimidazolinium chloride copolymers
  • e7) quaternized polyvinyl alcohol
  • e8) polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.

The outer coatings of the second part of the cleaning agents according to the invention may be made of any of the above-mentioned polymers, but it is also possible to use mixtures or multilayered layer structures of the polymers. The polymers are described in more detail below.

• Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol® (BASF) vertrieben werden. Polyvinylpyrrolidone sind bevorzugte nichtionische Polymere im Rahmen der Erfindung.
  Polyvinylpyrrolidone [Poly(1-vinyl-2-pyrrolidinone)], Kurzzeichen PVP, sind Polymere der allg. Formel (XIII)
  
  die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und - K-Wert-abhängig - Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).
• VinylpyrrolidonNinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol® (BASF) vertrieben werden. Luviskol® VA 64 und Luviskol® VA 73, jeweils VinylpyrrolidonNinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere.

Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are, for example:

• Polyvinylpyrrolidone, as sold for example under the name Luviskol® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the invention.
  Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (XIII)
  
  which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - K value-dependent - glass transition temperatures of 130-175 ° have. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• Vinylpyrrolidone-vinyl ester copolymers, for example as sold under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, in each case vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred nonionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of formula (XIV)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.

• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal® und Benecel® (AQUALON) vertrieben werden.

The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, Suspension polymerization, emulsion polymerization, bulk polymerization.). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (XIII) and (XIV)

• Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal® and Benecel® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (XI) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.Cellulose ethers can be described by the general formula (XV)

R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (XI) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, referred to as PVAL for short, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but in particular technically by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.

Commercially available PVAL (eg Mowiol® grades from Hoechst) come on the market as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (corresponding to molar masses of about 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.

The water-solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.

Further polymers which are suitable according to the invention are water-soluble amphopolymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO ^- - or -SO ₃ ^- groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers. Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoniumchlorid, as they are commercially available under the name Merquat®2001 N, according to the invention are particularly preferred amphopolymers. Further suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL).

• Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn® (NATIONAL STARCH), Luviset® (BASF) und Gafset® (GAF) im Handel sind.

According to the invention suitable anionic polymers include:

• Vinyl acetate / crotonic acid copolymers such as, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) are commercially available.

• Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold® strong (BASF) vertrieben werden.
• Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen

In addition to monomer units of the abovementioned formula (X), these polymers also have monomer units of the general formula (XVI):

[-CH (CH ₃ ) -CH (COOH) -] _n (XVI)

• Vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF).
• Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, which are sold, for example, under the name Ultrahold® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by subjecting the polyalkylene glycols to the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.

Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol corresponding to general formula XVII

H- (O-CH ₂ -CH ₂ ) _n -OH (XVII)

satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. For cosmetic ingredients, a different nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula V above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16. Commercially available are polyethylene glycols, for example, among the Trade names include Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trading name with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel XVIII.Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of the general formula XVIII

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula XVIII.

• gepropfte und vernetzte Copolymere aus der Copolymerisation von
  • i) mindesten einem Monomeren vom nicht-ionischen Typ,
  • ii) mindestens einem Monomeren vom ionischen Typ,
  • iii) von Polyethylenglycol und
  • iv) einem Vernetzter

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

• grafted and crosslinked copolymers from the copolymerization of
  • i) at least one nonionic type monomer,
  • ii) at least one ionic-type monomer,
  • iii) of polyethylene glycol and
  • iv) a networked person

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.

The nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.

The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.

• i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
• ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
• iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
• iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
  • durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden
  • Gruppen erhaltene Copolymere:
    • i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
    • ii) ungesättigte Carbonsäuren,
    • iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols

The grafted and crosslinked copolymers described above are preferably formed from:

• i) from 5 to 85% by weight of at least one nonionic type monomer,
• ii) from 3 to 80% by weight of at least one ionic-type monomer,
• iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).
  • by copolymerizing at least one monomer of each of the following three
  • Groups of obtained copolymers:
    • i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • ii) unsaturated carboxylic acids,
    • iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols

• Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester

Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S--.

• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and Monomer units of one or more allyl or methallyl esters of the formula XIX:

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

• Tetra- und Pentapolymere aus
  • i) Crotonsäure oder Allyloxyessigsäure
  • ii) Vinylacetat oder Vinylpropionat
  • iii) verzweigten Allyl- oder Methallylestern
  • iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure.

The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methallyletsre of the formula XIV.

• Tetra and pentapolymers from
  • i) crotonic acid or allyloxyacetic acid
  • ii) vinyl acetate or vinyl propionate
  • iii) branched allyl or methallyl esters
  • iv) vinyl ethers, Vinylesterrn or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid.

As outer coating materials for the second part, the anionic polymers are especially suitable for polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

Useful organic coating materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 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.

Also particularly preferred as coating materials 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 containing as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymeric coating materials 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 coating materials polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable coating materials are polyacetals, which can be obtained by reacting dialdehydes with polyol carboxylic 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, preferably usable as coating materials polymers are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to polymers which have a cationic group, irrespective of the pH of the composition (that is to say both the coating layer and the other detergent formulation). These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

• quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate.
• Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-aminomodifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydime-thylsiloxane, Quaternium-80),
• Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia®Guar und Jaguar® vertiebenen Produkte,
• Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich.
• Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat® angeboten werden.
• quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 und
• Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• quaternized cellulose derivatives, such as those commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• Polysiloxanes having quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxyl-amino modified silicone, also referred to as amodimethicones), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, in particular the products sold under the trade names Cosmedia®Guar and Jaguar®,
• Polymers Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755.
• Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those offered under the name Luviquat®.
• quaternized polyvinyl alcohol

as well as those under the designations

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 and
• Polyquaternium 27

known polymers with quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are designated according to the so-called INCI nomenclature, details of which can be found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, which are expressly incorporated herein by reference becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.

Also preferably used as coating materials are carbonic or dicarboxylic acids, or those having an even number of C atoms. Particularly preferred carboxylic or dicarboxylic acids are those having at least 4, preferably at least 6, more preferably at least 8 and especially those having 8 to 13 carbon atoms. Particularly preferred dicarboxylic acids are, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and mixtures thereof. But also tetradecanoic acid, Pentadecanoic acid and thapsic acid are suitable coating materials. Particularly preferred carboxylic acids are those having 12 to 22 carbon atoms, with those having 18 to 22 carbon atoms being particularly preferred. The use of the above-described disintegration aids is recommended especially in the case of acid coating layers, with typical use concentrations for the disintegration aids in the coating layers being 0.1 to 5% by weight, based on the coating layer.

The second part of the cleaning agents according to the invention may be present as granules and / or agglomerate, as pellets, extrudates, tablets or in capsule form, preference being given to embodiments which have a certain size as the second part. Cleaning agents according to the invention are preferred in which the second part has a diameter between 1 and 30 mm, preferably between 2.5 and 15 mm and in particular between 5 and 10 mm. Strictly speaking, the term "diameter" applies only to spherical second parts, since only these have a single diameter. If the second part is shaped differently - for example, cylindrical, ellipsoidal, cuboid or cube-shaped, etc., the above statement applies to the size (area) diameter.

As already mentioned, the second part can be produced by all current methods. In the context of the present invention preferred bodies having volumes between 0.1 and 10 cm ³ , preferably between 0.25 and 7.5 cm ³ and in particular between 0.5 and 5 cm ³ , the production by casting, by Sintering, by extrusion, by calendering or by tabletting preferred. With regard to the ingredients of the second part, particular preference is given to detergents in which the second part has been produced by a pressing process, in particular tableting.

Regardless of how the second coated part is made up, it can be combined with a first part of any design. The first part may be, for example, a detergent powder or present as a compact molding. Even liquid or gel-like first parts can be realized with an appropriate design, but because of the sedimentation and stability problem of the second parts in such a matrix but less preferred.

Before describing the possibilities for designing the first part and the finished cleaning agent from the two parts, a description of the ingredients that may be included in the first part follows. All of the substances listed below may also be wholly or partly part of the second part.

Builders have already been described above as a possible component of the second part. These are also contained in preferred embodiments of the present invention in the first part, wherein cleaning agents are preferred in which the first part builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95 wt .-%, particularly preferably from 10 to 90 wt .-% and in particular from 20 to 85 wt .-%, each based on the weight of the first part.

Cleaning agents according to the invention are particularly preferred in which the first part comprises phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, in particular from 30 to 70% by weight, based in each case on the weight of the first part.

In addition to the phosphates, especially the citrates are preferred builder substances. Thus, cleaning agents according to the invention in which the first part citrate (s), preferably sodium citrate, particularly preferably trisodium citrate dihydrate, in amounts of 10 to 60 wt .-%, preferably from 15 to 50 wt .-% and in particular from 20 to 40 Wt .-%, each based on the weight of the first part, also contains preferred embodiments of the present invention.

Nonionic surfactants have also been described in detail above. These may also be part of the first part, their amount in the first part usually in the range of 0.5 to 5 wt .-%, preferably between 1 and 2 wt .-%, is located. If formulations are to be provided where the first part provides for the "built-in rinse aid", higher surfactant contents are possible, see below for more information.

Cleaning agent according to one of Claims 1 to 17, characterized in that the first part comprises bleaching agents selected from the group consisting of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight. , preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the first part contains.

In addition to the builders, especially substances from the groups of surfactants (see above), 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.

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 (B) the aliphatic or substituted aliphatic peroxy acids 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, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-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.

Detergents according to the invention are preferred in which the first part comprises bleach activators from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate ( n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), in amounts of from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5 wt .-%, each based on the weight of the first part contains.

The said bleaching agents can also be introduced wholly or partly via the second part into the automatic dishwashing detergent according to the invention in order to achieve a "subsequent bleaching" in the rinse cycle.

Bleach activators which aid in the action of the bleaches can be both part of the first and second part. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the 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-methylsulfate (MMA), acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose and also acetylated, alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. 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 detergents. 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.

Other ingredients may also be part of the first or second part. Here are cleaning products preferably, in which the first part further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt. -% and in particular from 10 to 20 wt .-%, each based on the weight of the first part contains.

Further preferred cleaning agents are characterized in that the first part silver protectants from the group of the triazoles, the benzotriazoles, the Bisbenzotriazole, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the first part.

The corrosion inhibitors mentioned may be contained in the first or second part for the protection of the items to be washed or the machine, with silver protectants 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.

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 entanglements. 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. 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 may 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 perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols include 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 as are available from vegetable sources, eg 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 be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients. An incorporation of the fragrances in the second part is possible and leads to a fragrance impression when opening the machine, since the fragrances are released only in the final rinse cycle.

It is preferred to separate corrosion inhibitors from the bleaching agents, for example by containing substances of one group in the first part and those of the other group in the second part. Likewise, it is of course possible to design the first part of multi-phase and to separate the substances within the first part of each other.

Also, the separation of the bleach from other ingredients may be advantageous. Detergents according to the invention in which one part contains bleach while another contains enzymes are also preferred. Also preferred are detergents wherein one part contains bleach while another contains bleach activators. Again, it is of course possible to design the first part of multiphase and to separate the substances within the first part of each other.

As already mentioned, the first part can be provided both liquid, gelatinous or pasty as well as solid and, in particular, in powder form or in the form of a compact molding. In an order of increasing preference, detergents according to the invention are preferred in which the first part is a liquid, gelatinous or pasty machine dishwashing composition. Particularly preferred are detergents wherein the first part is a particulate automatic dishwashing composition.

Particularly preferred cleaning agents according to the invention are those in which the first part is a tablet-shaped machine dishwashing composition.

This tablet-like composition of the first part of the cleaning agent according to the invention is described by the term "base molding" and characterized in the context of the present invention, the moldings produced by known tabletting operations. In preferred embodiments of the present invention, the base molding is first prepared and the coated second part in a further step on or in this base molding introduced or introduced. The resulting product is hereinafter referred to by the generic term "shaped article" or "tablet".

The basic shaped body may take any geometric shape, in particular, concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five, seven and octagonal prismatic and rhombohedral shapes are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the base molding has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.

Preferred basic shaped bodies have a plurality of phases which enable a separation of incompatible ingredients. Thus, cleaning agents according to the invention are preferred, which are characterized in that the first part is a multiphase tablet, in particular a two-, three- or four-phase tablet, wherein it is preferred that the phases have the form of layers.

Such tablets can thereby be formulated into the finished cleaning agent according to the invention by containing the second coated part in the form of a further layer. Of course, the second part may also have a different shape, for example that of a hemisphere, which is glued to a surface of the base molding. Since it is best to coat spherical or ball-shaped bodies as closely as possible, it is preferable to adapt the shape of the first part to the preferred shape of the second part and to provide the first part with a cavity into which the second part is inserted and optionally fixed becomes. These cleaning agents, in which the coated second part has the form of a further layer, a core or a glued on or in the first part ("base tablet") body are preferred according to the invention, wherein cleaning agents are particularly preferred, in which the first part having a cavity (s) in which the second and optionally further parts are contained.

The shape of the cavity (s) can be freely selected within wide limits. For reasons of process economy, through holes whose openings are located on opposite surfaces of the moldings, and wells with an opening on a molded body side have proven. In preferred base moldings, the cavity has the shape of a through hole whose openings are located on two opposite mold body surfaces. The shape of such a through hole can be chosen freely, wherein moldings are preferred in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections. Even completely irregular hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized. As with the moldings, in the case of square holes, those with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The aforementioned geometric realization forms can be combined with each other as desired. Thus, moldings with a rectangular or square base and circular holes can be made as well as round moldings with octagonal holes, the variety of possible combinations are no limits. For reasons of process economy and aesthetic consumer sentiment, moldings with a hole are particularly preferred in which the mold body base area and the hole cross section have the same geometric shape, for example shaped bodies with a square base area and a centrally machined square hole. Particularly preferred are ring shaped bodies, i. circular shaped bodies with a circular hole.

If the o.g. Principle of the open at two opposite sides of the molding body holes is reduced to an opening, you get to Muldenformkörpern. Detergents according to the invention in which the cavity in the base molding has the shape of a trough are also preferred. As in the case of the "shaped perforated bodies", the shaped bodies can also assume any geometric shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic and rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped body has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.

The shape of the trough can be chosen freely, with moldings are preferred in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedrale, octahedral, conical, pyramidal, ellipsoidal , five-, seven- and octagonal-prismatic as well as rhombohedral form. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The size of the trough or the through hole compared to the entire shaped body depends on the desired use of the shaped body and the size of the second part to be inserted into the cavity. Depending on whether a smaller or larger amount of active substance should be included, the size of the cavity may vary. Regardless of the intended use, cleaning agents are preferred in which the volume ratio of base molding to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, more preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1 , is.

Similar statements can be made to the surface portions that make up the molded body with the cavity ("base moldings") or the opening area of the cavity on the overall surface of the molded body. Shaped bodies are preferred in which the area of the opening (s) of the cavity (s) constitutes 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the shaped body.

Of course, the present invention is not limited to combining a first part with only a second part. In particular, in the embodiment of the molded body with cavity, it is possible and preferred to provide a base molding having a plurality of cavities containing inserted further parts. These inserted further parts (hereinafter referred to as "cores") may all be "second parts" within the meaning of the present invention, i. have a suitable coating and contain the ingredients mentioned. But it is also possible that a shaped body is produced with, for example, two cavities ("basic shaped body" = first part), of which one cavity is filled with a "second part" in the sense of the present invention, while the second cavity contains another core, For example, an additional "rinse aid core" of losenverzögert ready-made surfactant or a fast-dissolving pre-rinse phase from dissolution accelerated ready-made enzyme and / or bleach. Corresponding cleaning agents, in which the first part has at least two cavities, one of which contains the second part, while the other includes a further, functionalized part, are preferred according to the invention.

As already mentioned, according to the invention it is also possible to provide shaped bodies which additionally contain a pre-rinsing phase. This embodiment can be realized in addition to the example of the three-part tablet with different solubility also by the form of the application: A base tablet comprising a "second part" according to the present invention can be provided with a notch. The consumer may then break off part of the tablet along the notch and place it in the cutlery basket while the remainder of the tablet is placed in the dosage box. The broken part, the composition of which may be the same as or different from the base tablet, unfolds its effect in the pre-rinse cycle, while the remainder via the metering chamber is only used in the main wash cycle. By choosing an outer coating over the functional coating, the "second part" for the purposes of the present invention may be both part of the broken part and of the other part of such a tablet.

Of course, the first and second parts (and optionally other parts) of the cleaning agent according to the invention need not necessarily be made up as a compact molding, even if this is preferred for handling reasons for the consumer. It is also possible, for example, a first and a second (and optionally other parts) separately prepared and packaged together in a bag of water-soluble film, which is placed by the consumer in the machine. Regardless of the type of packaging, the second part unfolds its effect essentially in the rinse cycle of the dishwasher by the coating.

As mentioned above, it is particularly preferred to provide agents that not only save the consumer the dosage of regenerating salt, but also already contain the rinse aid. This can be realized by incorporation of surfactant (s) in the second part (see above). Another way is to incorporate the surfactants into the first part, which advantageously is in solid form, i. is present as a powder or tablet.

Thus, cleaning agents according to the invention are preferred, which are characterized in that the content of the first part of nonionic surfactants from 5 to 25 wt .-%, each based on the first part. In means according to the invention of this embodiment, the amounts of surfactants remaining in the machine after the main rinse and the intermediate rinses cause an adequate run-off behavior in the rinse cycle, so that the water running off the items does not stain during drying. The rinse cycle does not need to be charged with additional intentionally added rinse aid when using these agents according to the invention.

The production of höhen surfactant-containing powder or granules can be done for example by conventional granulation. For this purpose, carrier materials are placed in a mixer and mixed with the / the surfactant (s) / granulated, which in the case of several surfactants used, these can be added either together or in succession. If subsequently finely divided material is added ("powdered"), the powder properties of the granules can be significantly improved again. As a powdering agent, the known substances of the prior art can be used, in the context of the present invention, in particular disilicates have proven to be particularly advantageous.
Also suitable are other finely divided substances, such as soda or phosphate, or overdried water glasses, ground ingredients of cleaning agents, etc ..

In the context of the present invention, it is particularly preferred to granulate carrier materials such as zeolites, sodium carbonate, sodium tripolyphosphate, maltodextrins, polyvinyl alcohols, starch and / or their derivatives, and also cellulose and / or their derivatives with the addition of the nonionic surfactants identified above as preferred and then in themselves known manner with a sodium silicate solution to spray in order to achieve at least partial coating of the granules. Instead of the silicate solution, it is also possible with advantage to use a solution of polyvinyl alcohol. The granules can be dried after production in a conventional manner (advantageously by fluidized bed drying) and optionally additionally "powdered" with finely divided substances such as zeolite and / or silicic acids. The high-surfactant-containing granules can then be prepared in a conventional manner with other components (bleach, enzymes, etc.) to detergents.

These powdered cleaning agents, the coated second parts can be added directly, so that a particulate inventive detergent results. The coated second parts in such machine dishwashing detergents according to the invention are prepared by their coating so that they do not dissolve or only to a minor extent in the main wash cycle (and also in optional pre-wash cycles). This ensures that the active substances are 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 coated second parts are not pumped out when changing the water in the machine and are thus 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 coated second parts in the cleaning agents according to the invention are now in terms of their size and shape preferably designed so that they the sieve insert of the dishwasher, even after the cleaning cycle, i. after exposure to movement in the machine and the cleaning solution, do not happen. In this way, it is ensured that coated in the final rinse cycle second parts are in the dishwasher, which release the active substance (s) under the action of the water flowing to the rinse cycle and bring the desired Klarspüleffekt. In the context of the present invention, preferred automatic dishwashing detergents are characterized in that the coated second parts have particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm.

In the dishwashing detergents according to the invention, the coated second parts 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 particles and coated second parts. In particular, when the coated second parts are colored, ie, for example, have a red, blue, green or yellow color, it is advantageous for the appearance of the product, ie the entire cleaning agent, if the coated second parts are visibly larger than the matrix of the particles of the remaining ingredients of the cleaning agent. Here, automatic dishwashing agents according to the invention are preferred which (without consideration of the coated second parts) 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 the coloration of the coated second parts, but also by contrasting coloring of the powder matrix or by the shape of the coated second parts. Since technically uncomplicated methods can be used in the production of the coated second parts, it is easily possible to offer these in a wide variety of forms. In addition to the particle shape, which has approximately spherical shape, for example, cylindrical or cube-shaped particles can be produced 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 optical incentives can be created in this way also by making the coated second parts 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 greatly varying sizes of coated second parts and detergent matrix, on the one hand when the package is shaken. On the other hand, the dosage may be different in two successive cleaning cycles, since the consumer is not always necessarily the same amount of detergent and coated second parts dosed. If it would be desirable to use a technically the same amount per cleaning cycle, this can be achieved by means of the packaging of the agents according to the invention in bags made of water-soluble film familiar to the person skilled in the art. Particulate machine dishwashing detergents in which a dosing unit is shrink-wrapped in a bag made 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 visually protruding coated second parts to insert in the dispenser of his dishwasher. This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.

The above-described desired restraint of the coated second parts in the machine even with water changes 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. 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 coated second parts 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 medium and sieve insert according to the invention allows the formulation of agents in which the coated second parts 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 coated second parts) 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 coated second parts 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 thus configured replaces the dosing chamber, i. 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.

The detergents according to the invention with a high surfactant content in the first part can also be prepared in the form of shaped bodies. In the simplest case, this is done by tableting the above-mentioned powdered detergent. In this case, the coated second part - as already described above - later be glued to the molding, or glued or inserted into a prepared cavity of the base molding.

However, it is preferred within the scope of the present invention, not the complete ones described above To powder-form detergent to a tablet to compress, but produce multi-phase base tablets with a surfactant-rich phase. In this way, incompatible active ingredients can be separated from one another in the at least two-phase base tablet. It is particularly preferred to compress the above-described high-surfactant-containing granules of carrier material, surfactant and optionally coating material and / or powdering agent to form a surfactant-rich molded body phase.

Preferred biphasic base tablets contain, for example, a phase containing up to 30, preferably up to 20 and especially up to 15% by weight of surfactants (based on phase) of phosphate, sodium carbonate, silicate and bleach, while a second phase contains enzymes, bleach activators , Silver protectants and dyes and up to 20, preferably up to 10 and in particular up to 5 wt .-% (based on the phase) of surfactant. Such biphasic moldings can then be joined to the coated second part and give inventive cleaning agents in tablet form.

The compression of such surfactant-rich powders into moldings can lead to technical difficulties, since these powders tend to agglomerate because of the high surfactant content and / or can be poorly free-flowing. In addition, under the compressive load of the pressing operation, the surfactant may be released ("squeezed") resulting in stamp caking. In order to solve such problems that may arise, there are common solutions from the prior art, in particular the use of rotating stamp has special significance.

Another effective measure is the use of plastic inserts or attachments in the tableting dies. Plastic attachments are in direct contact with the die wall during compression and are usually manufactured on polyamide. Plastic inserts are inserted into tabletting punches with faceted edges and reduce the risk of caking on the pressing surface.

Another possibility is to arrange the surfactant-rich premix in the middle of a three-layer tablet. In this case, the upper and lower layers can be formulated so that caking problems do not occur.

In summary, multiphase embodiments are preferred for a surfactant-rich base tablet, i. Cleaning agents, which are characterized in that the first part or at least one phase of a multiphase first part has a content of nonionic surfactants between 5 and 25 wt .-%, each based on the first part or on the phase of the first part ,

• A) Herstellung eines Körpers, der einen oder mehrere Stoffe aus der Gruppe der belagsinhibierenden Polymere nach Anspruch 1 enthält,
• B) Beschichtung des in Schritt A) hergestellten Körpers,
• C) Vereinigung des beschichteten Körpers mit einer Zusammensetzung, die ihre Wirkung im wesentlichen im Hauptreinigungsgang der Geschirrspülmaschine entfaltet

umfaßt.Another object of the present invention is a process for the preparation of dishwashing detergents comprising the steps

• A) Preparation of a body containing one or more substances from the group of the surface-inhibiting polymers according to claim 1,
• B) coating the body produced in step A),
• C) Combination of the coated body with a composition which has an effect essentially in the main dishwashing cycle of the dishwasher

includes.

In step A), the body referred to above as "second part" is prepared, which is coated in step B) and combined in step C) with a composition ("base composition" or "base molding") to form the finished cleaning agent according to the invention.

As already mentioned, the second part can be produced by casting, extruding, granulating, extruding, pelleting, sintering, foaming, etc. Particularly preferred as second parts are tabletted products which, because of their compact structure, can be coated particularly well with a suitable mold. Processes according to the invention in which the preparation in step A) is carried out by tableting are therefore particularly preferred.

The tableting of the "second part" in step A) is analogous to a tabletting of a base molding as an option for step C), wherein it has proven to be advantageous if the pre-mixture compressed into "second parts" or basic molded articles meets certain physical criteria. Preferred processes are characterized, for example, by the fact that particulate premixes to be compressed have a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

The particle size of the pre-mixture pressed into "second parts" or base moldings preferably also satisfies certain criteria: Processes in which particle-shaped premixes have particle sizes between 100 and 2000 .mu.m, preferably between 200 and 1800 .mu.m, more preferably between 400 and 1600 .mu.m and in particular between 600 and 1400μm, are preferred according to the invention. A further narrowed particle size in the premixes to be compressed can be adjusted to obtain advantageous molded body properties. In preferred variants for the process according to the invention, particulate premixes to be compressed have a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles is greater than 1600 μm or smaller than 200 μm. Here are narrower particle size distributions more preferred. Particularly advantageous process variants are characterized in that the particulate premixes to be compressed have a particle size distribution in which more than 30 wt .-%, preferably more than 40 wt .-% and in particular more than 50 wt .-% of the particles have a particle size between 600 and 1000 microns have.

When carrying out the tableting process, the preferred process according to the invention is not restricted to the fact that only a particulate premix is pressed into a shaped body. Rather, this process step - in particular in the production of base moldings, see above - can also be extended to the effect that one prepares in a conventional manner multilayer moldings by preparing two or more premixes which are pressed together. Here, the first-filled premix is slightly pre-pressed to get a smooth and parallel to the mold bottom extending top, and end-pressed after filling the second premix to the finished shaped body. In the case of three-layered or multi-layered shaped bodies, a further pre-compression takes place after each premix addition, before the shaped article is end-pressed after the last premix has been added. Preferably, the cavity described above in the base molding is a trough, so that preferred embodiments of the first method according to the invention are characterized in that multi-layered moldings having a trough, are prepared in a conventional manner by several different particulate premixes are pressed together.

The production of the moldings is carried out first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent Informbringen, in particular compression to tablets, wherein conventional methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix, some of the premix particles are also crushed, and even higher pressures cause sintering of the premix. With increasing pressing speed, so high throughput amounts, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of the tableting, the finished molded body is pushed out of the die by the lower punch and transported away by subsequent transfer devices. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.

The tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious increase or decrease of the stamp is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.

Concentric presses can be provided with two Füllschuhen to increase the throughput, with the production of a tablet only a semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low number of revolutions of the rotor
• Big filling shoes
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

It has also been shown that long pressing times are advantageous. These can be adjusted with pressure rails, several pressure rollers or low rotor speeds. Since the variations in the hardness of the tablet caused by the fluctuations of the pressing forces, systems should be applied, which limit the pressing force. Here, elastic punches, pneumatic compensators or resilient elements in the force path can be used. Also, the pressure roller can be made resilient.

Tableting machines suitable for the purposes of the present invention are obtainable, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ). Particularly suitable is, for example, the hydraulic double pressure press HPF 630 LAEIS, D. Tablettierwerkzeuge are for example from the company Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can - as already mentioned above - be made in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

But it is also possible that the various components are not pressed into a unitary tablet, but that moldings (in particular base moldings, see above) are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution. The layer structure of the moldings can be carried out both in a batch-like manner, whereby a dissolution process of the inner layer (s) takes place at the edges of the molded article already then, however, if the outer layers are not yet fully dissolved, complete envelopment of the inner layer (s) by the further outer layer (s) may be achieved, preventing the premature dissolution of internal components Layer (s) leads.

In a further preferred embodiment of the invention, a shaped body (in particular basic shaped body, see above) consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the stacked shaped body the Both outer layers and the shell-shaped body, the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to separate peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable $$\mathrm{\sigma }=\frac{2P}{\mathrm{\pi }\mathit{dt}}$$

Herein, σ is the diametrical fracture stress (DFS) in Pa, P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article, D is the molded article diameter in meters and t the height of the moldings.

The second step of the process of the invention comprises applying the coating. For this purpose, conventional methods of coating bodies can be used, in particular the immersion of the body in or the spraying of the body with a melt, solution or dispersion of said coating materials.

Since the immersion of detergent tablets in melts or solutions or dispersions leads to the desired thin coatings only with great technical effort, it is preferred in the present invention to spray solutions or dispersions of said coating materials on the moldings, wherein the solution or Dispersant evaporates and leaves a coating on the molding. In preferred processes according to the invention, an aqueous solution of one or more of the stated coating materials is sprayed onto the shaped bodies produced in step A), the aqueous solution, based in each case on the solution, being from 1 to 20% by weight, preferably from 2 to 15% by weight. % and in particular 4 to 10 wt .-% of one or more of said coating materials, optionally up to 20 wt .-%, preferably up to 10 wt .-% and in particular below 5 wt .-% of one or more water-miscible solvent and as the rest water, contains.

In order to shorten the drying time, further water-miscible volatile solvents can be added to the aqueous solution. These are in particular from the group of alcohols, with ethanol, n-propanol and iso-propanol being preferred. For reasons of cost, ethanol and isopropanol are particularly recommended.

The coating of anhydrous or low-water solutions may be advantageous for certain coating materials.

As already mentioned above, "subcoating" may be preferred for certain functional coatings in order to improve the adhesion of the coating. Also, protection of the functional coating by another "topcoat" may possibly provide benefits. For these reasons, methods according to the invention are preferred in which the coating in step B) comprises the application of one or more, preferably two or three coating layers.

As already mentioned, in particular functional coatings with temperature-inverse solution characteristics are preferred (see above). Thus, methods are also preferred in which the body produced in step A) is coated in step B) with an LCST polymer.

The composition with which the coated second part is made up for the cleaning agent according to the invention can take on any physical form, as described in detail above. In an order of increasing preference, preference is given to processes according to the invention in which the composition in step C) is a liquid, gelatinous or pasty composition. Particularly preferred are methods wherein the composition in step C) is a particulate composition. And particular preference is given to processes according to the invention which are characterized in that the composition in step C) is a tablet-like composition, details of tabletting and preferred embodiments of the "basic tablets" being found above.

It has already been pointed out that in particular an embodiment in which the base molding has one or more cavities, of which at least one contains the coated second part, are preferred. Thus, methods are also preferred in which the composition in step C) is a multi-phase detergent tablet having a cavity into which the coated body from step B) is glued or is pressed.

In these preferred methods, the second part may adhere to the first part only by the mold, but it is preferable to either press or glue into the first part for better transportation and handling stability, so that it is adhesively bonded thereto. Gluing is preferred over mechanical fastening by pressing, since the risk of destroying the coating of the second part is less. When gluing adhesion promoter is applied to one or more molding surfaces. This can be done in the above-mentioned method in which two moldings are joined together, either in the molded body with cavity or in the molding that fills the cavity. In preferred methods, adhesion promoters are introduced into the cavity of the molding.

This procedure is well feasible, in particular with hollow molded articles, since the metering of the adhesive can be achieved simply by dropping liquid adhesion promoters into the trough. Suitable dosing systems for large-scale dosing small amounts of liquid in cavities are well known to those skilled in the art.

Often it is technically easier to carry out the application of adhesion promoter on the cavity filling moldings. In such cases, processes are particularly preferred which are characterized in that the adhesion promoter is applied to one or more surfaces, preferably to one surface, of the coated second part.

This application of adhesion promoter to preferably one surface of the coated second part can be done in different ways. It is possible, for example, to wet the coated second part in the dipping process on one side with adhesive and then to place it in the cavity. This technique is technologically easy to implement, but involves the risk that adhesive contaminates the surface of the molding with cavity. The amount of adhesive can be controlled in this variant by varying the rheological properties of the adhesion promoter.

A further possibility, which is preferred in the context of the present invention, of applying adhesion promoters to preferably one surface of the coated second part consists of passing this dosing unit past adhesive dosing systems and subsequently placing it in the cavity. This is achieved by adhesion promoter dosing nozzles, impregnated with adhesion promoters brushes or nonwovens or by rolling. The latter method design is particularly easy to implement, since the coated second part has only a small contact surface to the roller. The bonding agent can be metered from the interior of the roll, but it is also possible to apply the bonding agent at a position which is remote from the point of contact of the roller with the coated second parts, on the roller. Methods in which the application of the adhesion promoter (s) takes place on a surface of the coated second part, preferably using adhesion promoter-transferring rolls, brushes or nonwovens, are therefore preferred.

The filling of the cavity (the coated second part) can fill the cavity completely, but it can also protrude from the cavity or fill it only partially, the imagination of the product developers are no limits. By varying the shape of the molded body with a continuous hole or trough, the shape of the trough or the hole and the shape of the coated second part, it is possible to produce a variety of shape body variations that differ visually from one another. Thus, for example, the circular ring shaped body described above can be filled with a circular hole with a form-fit cylinder. But it is also possible to use, for example, a ball, a square adjacent to the edges, a three-, five- or six-sided prism or another irregular shape. Depending on the effort that one wants to operate, it is also possible to realize octahedral, multi-capped prismatic or icosahedral forms for the coated second part.

Both in the case of the shaped perforated bodies and in the mold bodies, the adhesion of the coated second part in the cavity decreases with decreasing contact area. Maximum adhesion between the two moldings is achieved when the ring or mold body and the coated second part without gaps fit together form-fitting.

Completely analogously to the above-described preparation of two-phase moldings by the adhesion of two separately pressed moldings into one another, it is also possible to produce three-phase moldings. Either the adhesion of three separately produced moldings offers itself here, but it is also possible and preferred to produce a two-phase, for example, a two-layered tablet and to insert a further molded article on or into it.

The said principle can be extended accordingly to further multi-phase detergent tablets. Thus, for example, four-phase moldings can be produced by connecting two biphasic moldings to one another. Analogously, four-phase 3: 1 moldings can be produced. Of course, the two-phase molded bodies to be joined can also be produced in other ways. Thus, it is possible, for example, to produce a single-layer or multi-layer molded body, to fill the trough with an active substance (for example, as a melt, powder, granules, extrudate, flakes, etc.) and another one-, two- or three-phase molding to be applied to the molding. In this case, a wide variety of options can be varied, for example, a two-layer molded body, the trough is filled with a melt or a particulate mixture, wherein on the molded body side, which has the trough, another molded body is applied adherent. In this way, the trough is virtually the "core", since the filling is now enclosed on all sides. Completely identical can be moved with a molding which has a through hole ("ring molding") and because on both sides with a further molding "closed" is. Is essential to the invention in all these embodiments only that at least one phase is a coated second part in the context of the invention.

The above-mentioned possibilities of joining or joining of moldings can also be used to make the entire moldings or parts thereof more rapidly soluble. If, for example, two flat shaped bodies are glued together with adhesion promoter, then under the conditions of use a water access to the adhesive is possible only at the edges of the shaped body when the tablet is not yet loosened. Even when using readily water-soluble adhesion promoter, the compound can be practically solved only when a part of the overall molding is dissolved.

By targeted application of the primer can overcome the disadvantages mentioned. Thus, it is for example possible and preferred not to apply the bonding agent when joining two moldings with their flat surfaces on the connection surface, but only apply "primer points" at the contact edge or at the corners. These are exposed to the access of water when used immediately, so that the two moldings separate faster. If two cube-shaped moldings are joined together in this way, the adhesion promoter need not be applied on all four edges. It can rather contribute to even faster separation of the compound, apply only at the four corners adhesion promoter points. For even faster separation can be dispensed with individual adhesion promoter points, so that, for example, only two diagonally opposite contact corners are provided with adhesion promoter.

In summary, if a faster dissolution of the entire shaped body or of individual parts is desired, a rapid increase in surface area due to separation of the adhesive bond is optimal. This can be achieved or supported by selecting a favorable form of the adhesive bond. In such cases, line bonding is preferable to surface bonding, with dot bonding being particularly preferred.

In addition, the shape of the molded body parts to be joined with the adhesion promoter can also accelerate the dissolution. Here, moldings are preferred which are as free as possible against each other after dissolution of the bonding agent compound, so no toroidal moldings, but preferably basic body having "satellite shaped bodies" on their outer surfaces. There are hardly any limits to the multitude of geometric design possibilities. For procedural economic reasons, however, moldings which are orthorhombic, tetragonal or cubic are preferred. Shaped bodies with a circular base surface can only be glued along their lateral surface by means of correspondingly biconcave-shaped intermediate pieces, which in turn are more difficult to be tabletted. Nevertheless, the joining together of such moldings is possible according to the invention.

The cleaning agents according to the invention, in particular detergent tablets can be packaged after production, with the use of certain packaging systems has proven particularly effective because these packaging systems on the one hand increase the storage stability of the ingredients, in the case of moldings with cavities and inserted second part on the other hand, surprisingly, but also the long-term adhesion Significantly improve trough filling. A further subject of the present invention is therefore a combination of (a) cleaning agent according to the invention, in particular cleaning agent shaped body (s) and a packaging system containing the cleaning agent (s), the packaging system having 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 moisture content of 85%.

berechnen, wobei A die Fläche des zu testenden Materials in cm², x die Gewichtszunahme des Calciumchlorids in g und y die Expositionszeit in h bedeutet.The packaging system of the combination of detergent and cleaning composition shaped bodies (s) and packaging system has according to the invention has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system at 23 ° C and a relative Equilibrium moisture content of 85% is stored. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity"). The measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of the calcium chloride and the exposure time, the moisture vapor transmission rate decreases $$\mathit{FDDR}=\frac{24\cdot 10000}{A}\cdot \frac{x}{y}\left[G/m^2/24H\right]$$

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 moisture, often referred to as "relative humidity", in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C. 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 expressed in g / m ³ . For example, 1 m ^{3 of} air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor. The relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air at 17 ° contains 12 g / m ^{3 of} water vapor, then the relative humidity is (12 / 14.4) x 100 = 83%. If this air is cooled off, the saturation (100% RH) is reached at the so-called dew point (in the example: 14 °), ie, upon further cooling, a precipitate forms in the form of mist (dew). Hygrometers and psychrometers are used to quantify moisture.

The relative equilibrium moisture content of 85% at 23 ° C, for example, in laboratory chambers with moisture control depending on the device type to +/- 2% r.L. set exactly. Even saturated solutions of certain salts form constant and well-defined relative humidities in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the body of the soil.

The inventive combinations of detergent or detergent tablet (s) and packaging system can of course be in turn in secondary packaging, such as cardboard or trays, packed, with no secondary requirements on the secondary packaging must be made. The secondary packaging is therefore possible, but not necessary.

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

Depending on the embodiment of the invention, the packaging system of the combination according to the invention encloses a certain amount of cleaning agent or one or more detergent tablets. It is inventively preferred either to make a shaped body such that it comprises an application unit of the cleaning agent, and to pack this shaped body individually, or to pack the number of moldings in a packaging unit, which in sum comprises an application unit. With a desired dosage of 80 g of detergent, it is thus possible according to the invention to produce a 80 g detergent detergent body and pack individually, but it is also possible according to the invention to pack two 40 g detergent tablets in a package in order to arrive at a combination according to the invention. Of course, this principle can be extended so that combinations according to the invention can also contain three, four, five or even more detergent tablets in one packaging unit. Of course, two or more moldings in a package may have different compositions. In this way, it is possible to spatially separate certain components, for example to avoid stability problems.

The packaging system of the combination according to the invention may consist of a wide variety of materials and take on any external forms. For economic reasons and for reasons of easier processability, however, packaging systems are preferred in which the packaging material has a low weight, is easy to process and inexpensive. In inventively preferred combinations, the packaging system consists of a bag or sack of single-layer or laminated paper and / or plastic film.

The detergent tablets may be unsorted, i. as a loose filling, be filled in a bag of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent tablets individually or in a plurality of different sizes into sacks or bags. For individual application units of the detergent tablets, which are located in a bag or bag, the term "flow pack" has become common in the art. Such "flow packs" can then - again preferably sorted - optionally be packaged in outer packaging, which emphasizes the compact form of the molded article.

The preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become. Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded. Plastic films which can be used in the context of the present invention as a packaging system, for example, in Hans Domining House "The plastics and their properties", 3rd edition, VDI Verlag, Dusseldorf, 1988, page 193 . The figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.

In the context of the present invention particularly preferred combinations contain as packaging system a bag or bag of single-layer or laminated plastic film having a thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.

Although it is possible to use wax-coated papers in the form of cardboard as a packaging system for the detergent tablets in addition to the films mentioned above, it is preferred for the present invention if the packaging system does not comprise cardboard boxes of wax-coated paper. In the context of the present invention, the term "packaging system always characterizes the primary packaging of the cleaning agents or shaped bodies, ie the packaging which is in direct contact with the molded body surface on its inner side Materials and systems can be used.

As already mentioned above, the detergents or detergent tablets of the combination according to the invention contain, depending on their intended use, further ingredients of detergents in varying amounts. Regardless of the intended use of the moldings, it is preferred according to the invention that the cleaning agent or the detergent moldings have / have a relative equilibrium moisture content of less than 30% at 35.degree.

The relative equilibrium moisture content of the cleaning agents or detergent tablets can be determined by conventional methods, the following procedure being selected in the context of the present investigations: A water-impermeable 1-liter vessel with a lid which has a closable opening for the introduction of samples filled with a total of 300 g detergent or detergent tablets and held for 24 h at a constant 23 ° C to ensure a uniform temperature of the vessel and substance. The water vapor pressure in the space above the moldings can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two consecutive values show no deviation (equilibrium humidity). The above-mentioned hygrometer allows a direct display of the recorded values in% relative humidity.
Also preferred are embodiments of the combination according to the invention, in which the packaging system is reclosable. Combinations in which the packaging system has a microperforation can also be realized according to the invention with preference.

The compositions according to the invention can be used in all household dishwashing machines, with no limitations as regards the choice of program. The beneficial effects are achieved both in low temperature programs such as 45 ° C programs or glasses programs as well as in 50/55 ° C or 60/65 ° C programs.

A further subject of the present invention is therefore a method for cleaning dishes in a domestic dishwasher, in which a particulate automatic dishwashing agent according to the invention is introduced into the main cleaning cycle of the machine.

The introduction into the main cleaning gear can be done by filling the dosing with the powder, which is released by opening the dosing after a possible Vorreinigungsgang the powder in the machine. Alternatively, it is also possible to introduce the powder directly into the machine and in this way to release active substance in an optional pre-cleaning operation. Alternatively, it can be dispensed with a Vorreinigungsgang. Due to the composition according to the invention, no additional rinse aid needs to be metered in the rinse cycle. inventive methods in which the rinse cycle of the machine is carried out without the deliberate addition of further rinse aid, are therefore preferred.

The term "further rinse aid" includes liquid commercial rinse aid, which must be given by the consumer at intervals of several rinsing cycles in a reservoir of the machine and programmatically released from there. This deliberate addition of a rinse aid and the required for this second dosing at a distance of some rinsing cycles are not required by the use of the means according to the invention.

• a) Kontaktieren des verschmutzten Spülguts mit einer wäßrigen Reinigungsflotte aus Wasser und dem teilchenförmigen maschinellen Geschirrspülmittel, wobei das teilchenförmige maschinelle Geschirrspülmittel mindestens einen beschichteten zweiten Teil im Sinne der vorliegenden Erfindung enthält,
• b) Abpumpen der Reinigungsflotte und Kontaktieren des Spülguts mit einem Klarspülgang.

Another object of the present invention is a method of cleaning dishes in a domestic dishwasher using particulate automatic dishwashing detergent comprising the steps

• a) contacting the soiled items with an aqueous cleaning liquor of water and the particulate automatic dishwashing agent, wherein the particulate automatic dishwashing agent contains at least one coated second part according to the present invention,
• b) pumping out the cleaning liquor and contacting the items to be washed with a rinse cycle.

As already mentioned, the advantages of the present invention are achieved even if the main cleaning cycle and the rinse cycle are interrupted by intermediate rinsing. Therefore, preferred methods are characterized in that between the steps a) and b) one or more intermediate rinsing done.

Again, the additional intentional dosage of commercially available rinse aid is not required, so that methods are preferred in which in step b) no further rinse aid is intentionally added.

The mentioned methods for cleaning dishes also make the dosage of additional regenerating salt after several cleaning cycles superfluous. Of course, the cleaning methods are not tied to the offer form of the powdered cleaner, so that a method for cleaning dishes in a domestic dishwasher, in which a detergent tablet according to the invention is introduced into the main cleaning cycle of the machine, an embodiment of the present invention.

• a) Kontaktieren des verschmutzten Spülguts mit einer wäßrigen Reinigungsflotte aus Wasser und dem bzw. den Reinigungsmittelformkörper(n), wobei der bzw. die Reinigungsmittelformkörper mindestens einen beschichteten zweiten Teil im Sinne der vorliegenden Erfindung enthält,
• b) Abpumpen der Reinigungsflotte und Kontaktieren des Spülguts mit einem Klarspülgang.

ein weiterer Gegenstand der vorliegenden Erfindung.Last but not least, there is also a method for cleaning dishes in a domestic dishwasher using one or more detergent tablets comprising the steps

• a) contacting the soiled items with an aqueous cleaning liquor of water and the detergent tablet (s), wherein the detergent tablet or bodies contains at least one coated second part according to the present invention,
• b) pumping out the cleaning liquor and contacting the items to be washed with a rinse cycle.

Another object of the present invention.

Claims (36)

1. Cleaning agents for automatic dishwashing, comprising

   a) a first part (base composition), which substantially performs its action in the main cleaning cycle of the dishwashing machine; and

   b) a second part which, thanks to a suitable coating, substantially performs its action in the rinse cycle of the dishwashing machine,

   characterised in that the second part contains one or more substances from the group of deposition-inhibiting polymers, wherein the deposition-inhibiting polymer(s) is/are selected from the group of cationic homo- or copolymers, in particular hydroxypropyltrimethylammonium guar; copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, polymers comprising quaternised ammonium alkyl methacrylate groups as monomer units, cationic polymers of monomers such as trialkylammonium alkyl (meth)acrylate or -acrylamide; dialkyldiallyldiammonium salts; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular derivatives of guar, cellulose and starch; polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups.
2. Cleaning agents according to claim 1, characterised in that the second part contains one or more chelate complexing agents in quantities of above 0.1 wt.%, preferably of above 0.5 wt.%, particularly preferably of above 1 wt.% and in particular of above 2.5 wt.%, in each case relative to the weight of the second part.
3. Cleaning agents according to either one of claim 1 or claim 2, characterised in that the second part contains the deposition-inhibiting polymer(s) in quantities of above 5 wt.%, preferably of above 10 wt.%, particularly preferably of above 20 wt.% and in particular of above 25 wt.%, in each case relative to the weight of the second part.
4. Cleaning agents according to any one of claims 1 to 3, characterised in that the second part contains one or more copolymers prepared from i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionogenic monomers in quantities of above 5 wt.%, preferably of above 10 wt.%, particularly preferably of above 20 wt.% and in particular of above 25 wt.%, in each case relative to the weight of the second part.
5. Cleaning agents according to any one of claims 1 to 4, characterised in that the second part additionally contains 1 to 50 wt.%, preferably 2.5 to 45 wt.% and in particular 5 to 40 wt.% of nonionic surfactant(s).
6. Cleaning agents according to any one of claims 1 to 5, characterised in that the coating of the second part comprises an LCST (low critical solution temperature) polymer.
7. Cleaning agents according to claim 6, characterised in that the LCST polymer is selected from cellulose derivatives, mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylamides and/or acrylates or acrylic acids.
8. Cleaning agents according to either one of claim 6 or claim 7, characterised in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
9. Cleaning agents according to any one of claims 6 to 8, characterised in that the lower critical segregation temperature of the LCST polymer is between 20°C and 90°C.
10. Cleaning agents according to any one of claims 1 to 9, characterised in that the coating of the second part consists of a plurality of coating layers, preferably of two or three coating layers.
11. Cleaning agents according to any one of claims 1 to 10, characterised in that the second part has been produced by a pressing operation, in particular tabletting.
12. Cleaning agents according to any one of claims 1 to 11, characterised in that the second part has a diameter of between 1 and 30 mm, preferably of between 2.5 and 15 mm and in particular of between 5 and 10 mm.
13. Cleaning agents according to any one of claims 1 to 12, characterised in that the first part contains builders in quantities of 1 to 100 wt.%, preferably of 5 to 95 wt.%, particularly preferably of 10 to 90 wt.% and in particular of 20 to 85 wt.%, in each case relative to the weight of the first part.
14. Cleaning agents according to any one of claims 1 to 13, characterised in that the first part contains phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities of 20 to 80 wt.%, preferably of 25 to 75 wt.% and in particular of 30 to 70 wt.%, in each case relative to the weight of the first part.
15. Cleaning agents according to any one of claims 1 to 14, characterised in that the first part contains citrate(s), preferably sodium citrate, particularly preferably trisodium citrate dihydrate, in quantities of 10 to 60 wt.%, preferably of 15 to 50 wt.% and in particular of 20 to 40 wt.%, in each case relative to the weight of the first part.
16. Cleaning agents according to any one of claims 1 to 15, characterised in that the first part contains bleaching agents from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with sodium perborate and sodium percarbonate being particularly preferred, in quantities of 2 to 25 wt.%, preferably of 5 to 20 wt.% and in particular of 10 to 15 wt.%, in each case relative to the weight of the first part.
17. Cleaning agents according to any one of claims 1 to 16, characterised in that the first part contains bleach activators from the groups of 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) and n-methylmorpholinium-acetonitrile-methyl sulfate (MMA), in quantities of 0.25 to 15 wt.%, preferably of 0.5 to 10 wt.% and in particular of 1 to 5 wt.%, in each case relative to the weight of the first part.
18. Cleaning agents according to any one of claims 1 to 17, characterised in that the first part contains silver protection agents from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, particularly preferably benzotriazole and/or alkylaminotriazole, in quantities of 0.01 to 5 wt.%, preferably of 0.05 to 4 wt.% and in particular of 0.5 to 3 wt.%, in each case relative to the weight of the first part.
19. Cleaning agents according to any one of claims 1 to 18, characterised in that the first part furthermore contains one or more substances from the groups of enzymes, corrosion inhibitors, deposition inhibitors, cobuilders, dyes and/or scents in total quantities of 6 to 30 wt.%, preferably of 7.5 to 25 wt.% and in particular of 10 to 20 wt.%, in each case relative to the weight of the first part.
20. Cleaning agents according to any one of claims 1 to 19, characterised in that the first part is a composition in liquid, gel or paste form for automatic dishwashing.
21. Cleaning agents according to any one of claims 1 to 19, characterised in that the first part is a particulate composition for automatic dishwashing.
22. Cleaning agents according to any one of claims 1 to 19, characterised in that the first part is a composition in tablet form for automatic dishwashing.
23. Cleaning agents according to claim 22, characterised in that the first part is a multiphasic tablet, in particular a di-, tri- or tetraphasic tablet, wherein it is preferred for the phases to have the form of layers.
24. Cleaning agents according to either one of claim 22 or claim 23, characterised in that the coated second part has the form of a further layer, a core or a body adhesively bonded on or in the first part ("base tablet").
25. Cleaning agents according to any one of claims 22 to 24, characterised in that the first part comprises a cavity or cavities containing the second and optionally further parts.
26. Cleaning agents according to claim 25, characterised in that the first part comprises at least two cavities, one of which contains the second part, while the other contains a further, functionalised part.
27. Cleaning agents according to any one of claims 1 to 26, characterised in that the nonionic surfactant content of the first part amounts to 5 to 25 wt.%, in each case relative to the first part.
28. Cleaning agents according to any one of claims 22 to 26, characterised in that the first part or at least one phase of a multiphasic first part has a nonionic surfactant content of between 5 and 25 wt.%, in each case relative to the first part or the phase of the first part.
29. A method for producing cleaning agents for automatic dishwashing, characterised by the steps

    A) producing a body which contains one or more substances from the group of deposition-inhibiting polymers, wherein the deposition-inhibiting polymer(s) is/are selected from the group of cationic homo- or copolymers, in particular hydroxypropyltrimethylammonium guar; copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, polymers comprising quaternised ammonium alkyl methacrylate groups as monomer units, cationic polymers of monomers such as trialkylammonium alkyl (meth)acrylate or -acrylamide; dialkyldiallyldiammonium salts; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular derivatives of guar, cellulose and starch; polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups.

    B) coating the body produced in step A),

    C) combining the coated body with a composition which substantially performs its action in the main cleaning cycle of dishwashing machine.
30. A method according to claim 29, characterised in that production in step (a) is carried out by tabletting.
31. A method according to either one of claim 29 or claim 30, characterised in that coating in step B) comprises the application of one or more, preferably of two or three, coating layers.
32. A method according to any one of claims 29 to 31, characterised in that the body produced in step A) is coated in step B) with an LCST polymer.
33. A method according to any one of claims 29 to 32, characterised in that the composition in step C) is a composition in liquid, gel or paste form.
34. A method according to any one of claims 29 to 32, characterised in that the composition in step C) is a particulate composition.
35. A method according to any one of claims 29 to 32, characterised in that the composition in step C) is a composition in tablet form.
36. A method according to claim 35, characterised in that the composition in step C) is a multiphasic cleaning agent tablet which comprises a cavity, into which the coated body from step B) is adhesively bonded or pressed.