EP1299517B1 - 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 cleaning agents, in particular machine dishwashing detergents with controlled release of active substance. In particular, the present invention relates to machine dishwashing detergents, which have a system that provides a controlled release of at least one Active ingredient in the cleaning process and at least one active ingredient in the post-treatment process allowed. 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 was common for consumers to use detergent in the form of bulk-packed goods to provide it to the consumer when using the detergent according to the application requirements, which depends on the hardness of the water, the type, amount and / or the degree of soiling of the cleaning, the amount of cleaning fleet and also depending on other parameters.

In view of the desire of the consumer, easier and more convenient metered detergent These were increasingly provided in a form that was case-by-case dependent Dosing is superfluous: detergents were in measured portions formulated containing all components required for a cleaning cycle. at solid products such portions often became (sometimes containing several phases) Shaped bodies such as granules, beads, tablets ("tabs"), ashlars, briquettes, etc., as Whole be dosed into the fleet. Liquid products were dissolved in water-soluble coatings introduced, which dissolve upon contact with the aqueous liquor and release the contents in the liquor.

A disadvantage of these solutions is that all components in the course of a cleaning cycle be needed, at the same time get into the aqueous liquor. This not only problems of Incompatibility of certain components of a cleaning agent with other components, but it also becomes impossible to target specific components at a defined time to dose into the fleet.

In the prior art, ways have now been described on which individual detergent components targeted and dosed at a defined time during use can. For example, the temperature-controlled release of active substances is described. which enables active ingredients such as surfactants, bleaches, soil release polymers and the like either in the rinsing or cleaning cycle or even in the aftertreatment course, for example in the rinse cycle when machine dishwashing, release. Meanwhile are appropriate Products with integrated rinse aid commercially available.

These so-called "2in1" products lead to a simplification of handling and take the consumer the load of the additional dosage of two different products (cleaner and rinse aid). Nevertheless, to operate a household dishwasher at intervals two Dosiervorgänge required because after a certain number of rinses the Regenerating salt in the water softening system of the machine must be refilled. These water softening systems consist of ion exchanger polymers, which the machine tapered Hard water soften and after flushing with a rinse with Salt water to be regenerated.

The present invention was based on the object to provide a product that per Application must be dosed only once, without even after a higher number of Rinsing cycles the dosage of another product and thus a double dosing necessary would. A product should be provided which in addition to the "built-in rinse aid" makes the filling of the regeneration salt tank superfluous and thus the handling further simplified. The performance of the product should be at the same level of performance Three-product dosing (salt-detergent-rinse aid) or novel two-product dosing Reach or surpass ("2in1" Cleaner Rinse Aid).

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

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 Gerüststoffe, Acidifizierungsmittel, Chelatkomplexbildner oder 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 builders, acidifiers, chelating agents or the scale-inhibiting polymers according to claim 1.

These substances, their use in the final rinse cycle in the prior art not yet described was, cause rinse cycles instead of softened water with normal hard tap water can be performed without loss of power. The groups mentioned include Substances, some of which are particularly suitable in the context of the present invention are. These are described below.

The most important ingredients of automatic dishwashing detergents are builders. In the second Part of the automatic dishwashing detergents according to the invention can thereby all builders commonly used in detergents may be included, in particular So 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 possible, unless such use should be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (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, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . 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 according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are 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 contains one or more builders from the group of sodium carbonate, Sodium bicarbonate and trisodium citrate in amounts above 10 wt .-%, preferably above 15 wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part contains preferred according to the invention.

Acidifying agents are also within the scope of the present invention as an ingredient for the second part suitable. Substances from this group are, for example, boric acid and alkali metal hydrogen sulfates, Alkali metal dihydrogen phosphates and other inorganic salts. Preferably, however, organic Acidifizierungsmittel be used, the citric acid a particularly preferred acidifying agent. In addition, but especially the other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well as Polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and as Acidifizierungsmittel in the context of the present invention also Sokalan® DCS (trademark of BASF), a mixture of succinic acid, can preferably be used (max 31 wt%), glutaric acid (max 50 wt%) and adipic acid (max 33 wt%). Especially preferred cleaning agents according to the invention are characterized in that the second Part of one or more Acidifizierungsmittel from the group citric acid, adipic acid, malic acid, Fumaric acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid in quantities above 5 wt .-%, preferably above 10 wt .-%, more preferably above of 20 wt .-% and in particular above 25 wt .-%, each based on the weight of second part, contains.

Another possible group of ingredients for the second part are the chelating agents Chelate complexing agents are substances that form cyclic compounds with metal ions, wherein a single ligand occupies more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched verb. By complexation closed for a while over a lon. The number of bound ligands depends on the Coordination number of the central lone.

Common and preferred chelate complex images within the scope of the present invention are for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complexing polymers, ie polymers which are either in the Main chain or self-supporting to this functional groups that act as ligands can and with suitable metal atoms usually to form chelate complexes react,. are used according to the invention. The polymer-bound ligands of the resulting Metal complexes can come from just one macromolecule or different ones Belong to polymer chains. The latter leads to the networking of the material, provided that the complex-forming Polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, Hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. T. very specific. Activities towards ions of different metals. Many base polymers too commercially significant complexing polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Also natural polymers like cellulose, Starch or chitin are complexing polymers. In addition, these may be due to polymer analogues Transformations are provided with additional 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.

As polycarboxylic acids a), in the context of this patent application, carboxylic acids, including monocarboxylic acids, are used. understood, in which the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the group of nitrogen-containing polycarboxylic acids, especially EDTA, are preferred. In the invention required alkaline pH values of the treatment solutions, these Komplexbilner are at least partially as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts become. In the case of use as salts are alkali, ammonium or alkylammonium salts, especially sodium salts, preferred.

In the case of the scale-inhibiting polymers as an ingredient of the second part, in particular cleaning agents preferred, which are characterized in that the second part one or more coating-inhibiting polymers from the group of cationic homo- or copolymers, in particular Hydroxypropyl guar; Copolymers of aminoethyl methacrylate and Acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, Polymers containing monomer units as quaternized Ammoniumalkylmethacrylatgruppen cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; 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 Ethylenimine polymers and polyesters and polyamides with quaternary side groups in quantities above 5 wt .-%, preferably above 10 wt .-%, more preferably above of 20 wt .-% and in particular above 25 wt .-%, each based on the weight of 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 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 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.

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 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 H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H 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.

As further ionic or nonionic monomers are in particular ethylenically unsaturated Compounds considered. The content is preferably that used according to the invention Polymers of monomers of group iii) less than 20 wt .-%, 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 H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H 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 H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H 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, the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives of the group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units on, 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 - 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 - 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 - 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 - 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 - 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 ) - 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 - 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.

In the polymers, the sulfonic acid groups can be completely or partially in neutralized form, i.e. that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be exchanged. Appropriate detergents characterized are that the sulfonic acid groups in the copolymer partially or fully neutralized, are according to the invention prefers.

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

In the case of terpolymers, particular preference is given to those which contain from 20 to 85% by weight of monomer Group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer 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 do without the dosage of Regeneriersalz make the products of the invention also unnecessary the additional dosage of a rinse aid. The rinse effect can be significantly improved if the detergents of the invention Surfactants, especially nonionic surfactants. The surfactants can do this both in the first part (of the "basic composition") and above caustic carryover or other phenomena enter the rinse cycle, as well as part of the second Be part of the effect of the coating essentially only in the final rinse of the Dishwasher unfolds.

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

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 alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 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-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable. The amount of these nonionic surfactants is preferably no longer than that of the ethoxylated fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.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 prepared by reaction with fatty acid methyl esters in Presence of an alkoxide as a catalyst in the desired Polyhydroxyfettsäureamide converted become.

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 are a nonionic surfactant contained, which has a melting point above room temperature. Accordingly, preferred Cleaning agent characterized in that in the second part it contains nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.

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

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

In a preferred embodiment of the present invention, this is nonionic surfactants with a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction from a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms with, preferably at least 12 mol, more preferably at least 15 mol, in particular at least 20 mol 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 bis to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols additionally having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferably more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 Wt .-% 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 bis to 15% by weight of the total molecular weight of the nonionic surfactant.

Further particularly preferably used nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 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 can be used with particular preference are, for example available 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 R ³ in the above formula may be different if x ≥ 2. 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 above-mentioned surfactants can additionally in the first part of the invention Detergent may be included. It is also possible that the second part is formulated surfactant-free and the above surfactants all in the first part present (see below).

In addition to one or more substances from the groups of builders, acidifiers, Chelating agents or the scale-inhibiting polymers and optional surfactants the second part may contain other common ingredients of detergents. Especially 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 more performance advantages.

According to the invention, the second part has a suitable coating which causes the ingredients of the second part essentially released only in the final rinse cycle of the dishwasher become effective. Such a coating, new German often as "coating" denotes, depending on the selected material usually strengths of 10 to 1000 on, with layer thicknesses between 20 and 800 .mu.m, in particular between 50 and 400 .mu.m in Within the scope of the present invention, preference is given.

The coating can be uniformly composed, e.g. from a single substance However, it is also possible that multi-layer coatings are used, wherein 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 rinses. In the rinse cycle, the coating must be dissolved quickly or otherwise destroyed to release the ingredients of the second part. Come here several release mechanisms into consideration, the changed properties of the coating materials use as a function of varying external conditions. This way will be in Dishwasher prevailing conditions in the main cleaning and rinse cycle are different, used to transfer the second part in the rinse cycle. By Changing the outer condition "switches" the coating and releases the second part. When "Switches" are 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 melts only above 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.

Detergents 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 should be released in a rinse after the cleaning step. Examples are Mechanical cleaning of dishes both in the household and in the commercial sector. By the packaging according to the invention remain the active ingredients after a heat treatment in a liquid medium, e.g. B. after the main rinse, at least partially unchanged and the Active substance is only after cooling after the heat treatment, ie in the rinse, released.

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), hydroxypropyl cellulose (HPC), Methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose (PC) and their Mixtures, wherein carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxypropellulose and the alkali salts of CMC and the slightly ethoxylated MC or mixtures the above are preferred.

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC). Other polymers that have a lower critical segregation 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 intertwined 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 like 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 LCST substance. By such additives or by the Degree of crosslinking of the polymers may correspond to the LCST (lower critical demixing temperature) be modified.

In a preferred embodiment of the present invention, the second part is provided with a coated further material, which at a temperature above the lower separation temperature the LCST substance is soluble or a melting point above this temperature or has a retarded solubility, ie above the lower separation temperature of LCST layer can be released. This layer serves to mix the active ingredient and LCST substance from water or other media that dissolve before heat treatment can protect. This additional layer should not be liquid at room temperature and has preferably a melting point or softening point at a temperature equal to or is above the lower critical demixing temperature of the LCST polymer. Especially the melting point of this layer is 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 is located. That means in the present case that the melting range within the specified Temperature interval occurs and does not denote the width of the melting range.

The above properties are usually met by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificial substances, usually Melt over 35 ° C without decomposition and just above the melting point are relatively low-viscosity and non-stringy. They are strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three Groups of natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.

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

Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood. Also usable as coating materials are compounds from others Classes of substances meeting the said softening point requirements. When suitable synthetic compounds are, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG) available, proved. Also suitable are synthetically produced waxes from lower Carboxylic acids and fatty alcohols, for example dimyristyl tartrate, sold under the name Cosmacol® Conversely, synthetic or partially synthetic esters are also available lower alcohols can be used with fatty acids from natural sources. Falls into this class For example, the Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Also shellac, For example, shellac KPS three-ring SP (Kalkhoff GmbH) can be used as another substance.

Likewise to the waxes in the context of the present invention are, for example, the Calculated so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms. The waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as Main ingredient of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), Cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating can optionally also containing wool wax alcohols, including triterpenoid and steroidal alcohols, For example, lanolin, which, for example, under the trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as part of the coating For the purposes of the present invention, it is possible to use fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble Polyalkylene glycol.

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

Suitable coating materials are also all water-soluble, water-dispersible and water-insoluble polymers having a melting point above the lower one critical demixing temperature of the inventively used LCST polymer is or are soluble above this temperature. Suitable polymers are solid polyethyleneglycols at room temperature, Polyvinyl alcohols, polyacrylic acid and their derivatives. Furthermore, has also Gelatin proved suitable. Particularly preferred is polyvinyl acetate (PVAc) as a material for Protection of the LCST layer ("topcoating") used.

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

The second part can in known manner with the LCST substance and / or the other Material to be coated. Here, the substances may be e.g. as a melt or in the form of a Solution or dispersion can be sprayed on, or the mixture can be melted, solution or dispersion or immersed in a suitable mixer. That too Coating in a fluidized bed apparatus is possible. In the spray process, all in the Pharmacy and food technology established processes for the production of coated Tablets, capsules and particles. The polymer suspension or solution is either discontinuous sprayed in small portions, the particles being e.g. through on a conveyor belt transported a liquid curtain and then dried in a stream of air or continuously with simultaneous drying by the injected air stream in fluidized bed, Fluid bed or air-layer cladding sprinkles. Also conceivable is the coating process, when LCST polymers are added in sufficiently high concentrations to the coating syrups. The application of the second layer is analogous.

In a further preferred embodiment of the invention, the ingredients of the second Partly released by an enzyme-controlled coating. Here are enzymatically degradable (enzyme-sensitive) materials used as a coating material. Usually in detergents contained enzymes cause after a certain exposure time degradation of the enzyme-sensitive coating material and, consequently, a release of the or in the second part included active ingredients of the detergents.

As enzyme-sensitive materials are preferably cellulose derivatives, starch or starch derivatives, partially oxidized starch derivatives, glycerides, certain proteins and mixtures thereof in Consideration. As enzymes in detergents preferably proteases, amylases and / or Used lipases.

Inventive agents can be prepared so that conventional solid detergent or components thereof, which are in the form of granules and / or agglomerates, pellets, extrudates, Tablets or in capsule form are coated with the enzyme-sensitive material. If such enzyme-containing detergent components or components together with introduced conventional cleaning agents in cleaning liquors, the release of the included active ingredients only after the at least partial degradation of the enzyme-sensitive coating materials.

A further preferred embodiment of the invention is that as (physico -) - chemical Switch, which causes a controlled drug release, a redox system used becomes. As with the enzyme-controlled drug release can also be used in the redox-controlled Drug release the redox materials as coating material in particular of Molded articles, for example tablets, or capsules of active ingredients of cleaning agents used become. After a certain exposure time of usually contained in cleaning agents redox-active components there is a chemical change of the redox-sensitive Coating material and concomitant release of the or in the coated Molded bodies, granules or capsules included active ingredients of the detergents.

As redoxsensitive materials are particularly 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 detergents are in particular oxidizing agents such as percarbonate and the like, in particular in Combination with bleach activators, especially tetraacetylethylenediamine (TAED) and other common Bleach activators, to name a few.

Solid agents according to the invention can be prepared in such a way that conventional solid detergents or components thereof, which are in the form of granules and / or agglomerates, pellets, extrudates, Tablets or in capsule form, be coated with the redox-sensitive material. Become redoxsensitive materials containing agents or redox-sensitive materials containing Components for cleaning agents together with conventional cleaning agents in cleaning fleets introduced, the release of the trapped drugs 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 also be used which causes an electrolyte-controlled drug release. Here can be the difference in the electrolyte content between the cleaning cycle and the rinse cycle in automatic dishwashing be exploited. A further preferred embodiment of the invention relates therefore, a detergent in which the second part is coated with an electrolyte-sensitive substance is, wherein the / the active substance (s) of the second part as a result of an occurring change in the Electrolyte concentration is / are released.

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 ion load, but become difficult or insoluble in the presence of higher salt concentrations. The respectively required salt concentration to make the substances insoluble, is different. Even with these "switches" it may be necessary to apply a second coating, which is the first coating layer before dissolution by pure water at the beginning of the cleaning program prevented.

Looking at the process of machine dishwashing, it is during cleaning the pH of the rinsing liquor at about 10. Accordingly, the main ones available on the market Products for machine dishwashing containing alkali. In particular, in the vast majority Most of the automatic dishwashers and their different cleaning programs the rinsing liquor pumped off after the cleaning cycle and fresh water replaced. 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 is hereby in the Machine remaining residual amount dependent, which is about 2%.

In a further preferred embodiment of the present invention, therefore, a pH change be used to selectively release active ingredients.

In this embodiment of the invention, such (physico-) chemical switch as Coating material used for the second part, which in the event of a change in the pH the application fleet undergoes a change in physicochemical properties. Especially It is preferred that such substances used as (physico) chemical switch which, as a result of a change in the pH occurring in the have increased solubility in water. Alternatively or additionally, such switch substances which, when the corresponding change in the pH of the in particular have a decrease in the diffusion density. Advantageously, there are means in particular automatic dishwashing detergents containing a substance as a (physico-) chemical switch contained in a change in the pH of the application in the range from 11 to 6, preferably from 10 to 7, a change in their physicochemical properties undergoes 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 having.

Suitable substances which can be used as such (physico-) chemical switches, are basic in nature and especially basic polymers and / or copolymers.

The principle of pH-dependent water solubility is usually based on protonation or Deprotonation of functional side groups of the polymer molecules, resulting in their charge state changes accordingly. The polymer must now be such that it is in the at a certain pH stable charged state dissolves in water, in the uncharged state at a different pH, on the other hand, fails. It is part of the present invention preferred that the polymers used in this invention at a higher pH have lower water solubility than at lower pHs or even at higher pHs become water insoluble.

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

Also for the opposite case - soluble in the acidic range, insoluble in the alkaline range - are known in the art examples. These substances in which the polymer molecules mostly amino-substituted side chains, e.g. for the preparation of gastric juice-soluble tablet coatings used. They usually dissolve at pH values below 5. Polymers in which the Solubility change from soluble to insoluble at higher pH values occurs from pharmacy not known because these pH values have no physiological significance.

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

For the application, but in addition to the thermodynamic solubility and the dissolution kinetics a filmed substance or the decrease of its mechanical stability of importance be. The solution kinetics of the switch substances used according to the invention is at room temperature pH-dependent to the alkaline range, i.e., the films are significantly longer at pH 10 are stable than at pH 8.5 although they are thermodynamic at both pH levels are soluble.

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. The present invention therefore furthermore relates to a polymer in which the switching point lies 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 in the corresponding pH conditions to release the drug completely dissolves. Rather, it is enough For example, if the permeability of a polymer film changes and e.g. the penetration of water in the drug formulation is made possible. This can be 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 pharmacy, for the complete release of the active ingredient to care.

In a further preferred embodiment of the invention, in addition to the above Switches so-called pH-shift boosters used. This can, at least in the vast majority Measures are prevented that after the rinse cycle residues, in particular from the pH-dependent soluble substance itself, can be found. Suitable pH-shift boosters For the purposes of this invention, all substances and formulations that are capable of this invention are the extent of the pH shift either locally, i. in the immediate vicinity of each used pH-shift-sensitive substance, or else generalized, i. throughout the rinse, too enlarge. These include all organic and / or inorganic water-soluble acids or acidic salts, in particular at least one substance from the group of alkylbenzenesulfonic acids, Alkyl sulfuric acids, citric acid, oxalic acid and / or alkali metal hydrogen sulfates.

The pH-shift booster can be incorporated into the cleaning agent. In a further embodiment However, it is also possible to use the pH shift booster either after the end of the Cleaning cycle or at the beginning of the rinse cycle externally fed to the machine 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 also consist of several layers. In part, this is necessary to certain Coating layers during the main cleaning cycle by a second layer to protect (see above), but sometimes a sub-coating may be required to make a well-adherent and to create a uniform surface for the functional coating. Of course, that too Combination of undercoating with a functional coating and another protective layer conceivable. In this embodiment, the second part has a three-layer coating. Cleaning supplies, in which the coating of the second part of several coating layers, preferably consists 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 outer coatings, protect the "functional coating" if necessary.

Preferred coating materials for an optional inner or outer coating layer are the known in the art polymers. In particular, cleaning agents are preferred in the coating layer on the second part of a polymer with 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, in the detergents Usually be introduced, in particular cleaning agents are preferred 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. Become Polymers on native or partnative basis used as coating material, so is the coating material preferably selected from one or more substances from the group 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 10000 and 500000. The structural properties are also strongly influenced by Degree of polymerization dependent; thus, e.g. the fruit pectins in asbestos dried condition Fibers, whereas flax pectins are fine, granular powders.

The pectins become by extraction with diluted acids predominantly from the internal portions made of citrus fruit peel, Obstresten or sugar beet cuttings.

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. Cellulosic coating materials which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. 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 be used as coating materials.

Suitable nonionic organic coating materials are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed. Preferably, they are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Useful 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 having higher molecular weights in the range of 2000 to 30,000 g / mol.

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

Even starch can be used as a coating material for the second part. Strength is a homoglycan, wherein the glucose units are linked α-glycosidically. Strength is made up of two components composed of about 20-30% straight-chain amylose 50,000-150,000) and 70-80% branched-chain amylopectin (M.W., about 300,000-2,000,000), In addition, small amounts of lipids, phosphoric acid and cations are still included. While the amylose due to binding in the 1,4-position long, helical, entangled Forms chains with about 300-1200 glucose molecules, the chain branches in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1500-12000 molecules of glucose. In addition to pure starch are used as coating materials in the The present invention also starch derivatives by polymer-analogous reactions are available from starch, suitable. Such chemically modified starches include For example, products of esterifications or etherifications in which hydroxy-hydrogen atoms were substituted. But also strengths in which the hydroxy groups against functional groups that are not bound by an oxygen atom have been replaced can be as starch derivatives use. For example, fall into the group of starch derivatives Alkali starches, carboxymethyl starch (CMS), starch esters and ethers and amino acids.

Among the proteins and modified proteins, gelatin as a coating material has an excellent Importance. Gelatine is a polypeptide (molecular weight: about 15,000-> 250,000 g / mol), the predominantly by hydrolysis of the collagen contained in the skin and bones of animals under acidic conditions or alkaline conditions. The amino acid composition of gelatin corresponds largely to that of the collagen from which it was obtained, and varies in dependence from its provenance. The use of gelatin as a 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 stable at room temperature Water to more than 2.5 wt .-% are soluble.

The outer coatings of the second part of the cleaning agent according to the invention can thereby may be made of any of the above-mentioned polymers, but it can also mixtures or multilayered layer structures of the polymers are used. The polymers will be 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 (e.g., Mowiol® grades from Hoechst) come as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (corresponding to molecular weights about 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. So you are partially hydrolyzed polyvinyl acetates with a residual content Acetyl groups of about 1-2 or 11-13 mol%.

The water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Reduce 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, Represents methacrylic acid and its 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. Furthermore suitable Zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, referred to under the name Amersette® (AMERCHOL) are commercially available.

• 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

• 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 obtained by polymerization in the heat in a homogeneous phase characterized in that the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence stirred by radical generator.

Examples of suitable vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those containing aliphatic alcohols 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 available, 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 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, under the trade name 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 trade 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, on.

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

The nonionic monomers can equally be of very different types, among these, particularly preferred are crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, Acrylic acid and methacrylic acid are contained in the graft polyamides.

As crosslinkers are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose with 2 to 5 allyl groups per molecule 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 comprise 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 are offered in the anionic polymers in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, Polyacetals and dextrins, which are described below.

Useful organic coating materials are, for example, in the form of their sodium salts also usable in free form polycarboxylic acids. Polymeric polycarboxylates are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 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, this group may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their 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 30,000 to 40,000 g / mol.

Particularly preferred as coating materials are biodegradable polymers more than two different monomer units, for example those which are salts as monomers of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymeric coating materials are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, as further preferred coating materials are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives.

Further suitable coating materials are polyacetals which are obtained by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

Further, preferably usable as coating materials polymers are cationic polymers. Under The cationic polymers are the permanent cationic polymers are preferred. As "permanent cationic "according to the invention refers to such polymers which are independent of pH value of the agent (that is to say both the coating layer and the other detergent tablet) have a cationic group. These are usually polymers that are 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 as well 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 carboxylic or dicarboxylic acids, or those with even number of carbon atoms. Particularly preferred carboxylic or dicarboxylic acids are those having at least 4, preferably at least 6, more preferably with at least 8 and especially those having 8 to 13 carbon atoms. Especially 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. Especially preferred Carboxylic acids are those having 12 to 22 carbon atoms, those having 18 to 22 carbon atoms are particularly preferred. The use of disintegration aids described above is particularly recommended for acid coating layers, with conventional use concentrations for the disintegration aids in the coating layers at 0.1 to 5 wt .-%, based on the coating layer lie.

The second part of the cleaning agents according to the invention may be in the form of granules and / or agglomerates, as a pellet, extrudate, tablet or in capsule form, wherein as a second part embodiments preferred are those which have a certain size. Here are cleaning agents according to the invention 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. The term "Diameter" is strictly speaking only for spherical second parts, since only these have a single diameter. Is the second part shaped differently - for example cylindrical, ellipsoidal, cuboid or cube-shaped etc., the above statement applies to the Sizes (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 can be combined. For example, the first part may be a detergent powder be present or as a compact shaped body. Also liquid or gel-like first Parts can be realized with appropriate design, because of the sedimentation and stability problem but less preferred in the second parts in such a matrix.

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

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

In this case, particular preference is given to cleaning agents according to the invention, in which the first part Phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, 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 contains.

In addition to the phosphates, especially the citrates are preferred builder substances. So are inventive Detergents in which the first part citrate (s), preferably sodium citrate, particularly preferably trisodium citrate dihydrate, in amounts of from 10 to 60% by weight, 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 can also be part of the first part, with their amount in the first part usually in the range from 0.5 to 5 wt .-%, preferably between 1 and 2 wt .-%, is. Should formulations provided that the first part provides for the "built-in rinse aid", so are higher Tenside levels possible, see below for more information.

Cleaning agent according to one of claims 1 to 17, characterized in that the first part Bleaching agents from the group of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in quantities from 2 to 25 wt .-%, 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 are in particular substances from the groups of surfactants (see above), the Bleaching agents, bleach activators, enzymes, polymers and dyes and perfumes 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 alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent in the automatic dishwashing detergents according to the invention It is also possible to use chlorine or bromine-releasing substances. Among the suitable Chloro or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Cleaning agents according to the invention in which the first part is bleach activators are preferred the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the 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-methyl sulfate (MMA), in amounts of from 0.25 to 15% by weight, preferably from 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the Weight of the first part contains.

The bleaching agents mentioned can also be used to achieve a "after-bleaching" in the final rinse cycle or partially via the second part in the machine dishwashing detergent according to the invention be introduced.

Bleach activators which aid in the action of the bleaches can be both part of the first as well as the second part. Known bleach activators are compounds which have a or more N- or O-acyl groups, such as substances from the class of anhydrides, the ester, 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, compounds which under perhydrolysis conditions can be aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted Wear benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid 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 acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used.

In addition to or in place of the conventional bleach activators, so-called Bleaching catalysts are incorporated into the detergents. These substances are it is bleach-enhancing transition metal salts or transition metal complexes such For example, Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes are useful as bleach catalysts.

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

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

Other ingredients may also be part of the first or second part. Here are cleaning products preferred in which the first part further comprises one or more substances from the groups the 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 of 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 triazoles, benzotriazoles, bisbenzotriazoles, 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 of 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the first Partly contains.

The corrosion inhibitors mentioned can be used to protect the items to be washed or the machine first or second part, wherein in the field of automatic dishwashing silver protectants have a special meaning. Can be used, the known substances of the State of the art. In general, especially silver protectants can be selected from the group triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. You will find in cleaner formulations beyond often active chlorine-containing agents that can significantly 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, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, Gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are frequently used. Preference is given here to the transition metal salts selected are from the group of manganese and / or cobalt salts and / or complexes, especially preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Likewise Zinc compounds are used to prevent corrosion on the items to be washed.

As enzymes in the detergents according to the invention, in particular those from the Classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of said enzymes in question. All these hydrolases contribute to the removal of stains such as protein, fat or starch containing impurities at. For bleaching and oxidoreductases can be used. Especially suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as from their genetically modified Variants obtained enzymatic agents. Preferably, subtilisin type proteases and in particular proteases derived from Bacillus lentus. there are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting Enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of special interest. Examples of such lipolytic enzymes are 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 encapsulating substances to them to protect against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules may, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% be.

Dyes and fragrances can be added to the automatic dishwasher detergents according to the invention to improve the aesthetic impression of the resulting products and to the consumer in addition to performance, a visually and sensory "typical and unmistakable" product to provide. As perfume oils or perfumes, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons are used. Fragrance compounds of the ester type are known e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 carbon atoms, citral, citronellal, Citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, too ketones e.g. the ionones, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes such as limes and pinene. However, mixtures are preferred various fragrances used, which together create an appealing scent. Such perfume oils may also contain natural perfume mixtures as they come from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muscat, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the detergents according to the invention, it However, it may also be advantageous to apply the fragrances to carriers that the adhesion of the perfume intensify on the laundry and through a slower release of fragrance for long-lasting Fragrance of the textiles provide. Examples of such carrier materials are cyclodextrins proven, wherein the cyclodextrin-perfume complexes additionally coated with other excipients can be. It is also possible to incorporate the fragrances into the second part and leads to a fragrance impression when opening the machine, since the fragrances only in the rinse cycle be released.

It is preferred to separate corrosion inhibitors from the bleaching agents, for example by Substances of one group are included 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 the Separate substances within the first part of each other.

Also, the separation of the bleach from other ingredients may be advantageous. invention Detergents in which one part contains bleach while another enzyme contains are also preferred. Likewise preferred are cleaning agents in which a part Contains bleach while another contains bleach activators. Again, it goes without saying possible to design the first part multiphase and the substances within the first part separate from each other.

As already mentioned, the first part can be both liquid, gel or pasty as well as firm and be provided in particular powdered or in the form of a compact molded body. In an order of increasing preference, cleaning agents according to the invention are preferred, in which the first part of a liquid, gel or pasty composition for automatic dishwashing. Particularly preferred are cleaning agents in which 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 automatic 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 is within the scope of the present invention Invention the moldings produced by tableting known per se. In In preferred embodiments of the present invention, the base molding is first produced and the coated second part in a further step on or in this base molding on or introduced. The resulting product is hereinafter referred to as the generic term "Shaped body" or "tablet".

The base molding may take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal forms, trees, clouds etc. can be realized. If the base molding has corners and edges, these are preferably rounded. As additional optical differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

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

Such tablets can thereby be made up into the finished cleaning agent according to the invention by containing the second coated part in the form of another layer. Of course, the second part may also have a different shape, for example the one Hemisphere which is glued to a surface of the base molding. As is spherical or the spherical shape as possible to coat the best possible body, it is preferred that Adapt the shape of the first part to the preferred shape of the second part and the first part to be provided with a cavity into which the second part is inserted and optionally fixed. These Detergents in which the coated second part takes the form of another layer, one Kerns or one on or in the first part ("base tablet") glued body are According to the invention preferred, wherein cleaning agents are particularly preferred in which the First part (a) cavity (s), in / those of the second and optionally further parts are included.

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

The aforementioned geometric realization forms can be arbitrarily with each other combine. Thus, shaped bodies with rectangular or square base and circular Holes are made as well as round shaped bodies with octagonal holes, where There are no limits to the variety of possible combinations. For the sake of procedural economy and aesthetic consumer sentiment are specially shaped with hole preferred in which the mold base body and the hole cross section of the same geometric Have shape, for example, shaped body with square base and centrally incorporated square hole. Particularly preferred are ring shaped bodies, i. circular Shaped body with a circular hole.

If the o.g. Principle of the open at two opposite sides of the molding body holes on a Opening is reduced, 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 with the "perforated tablets", the shaped bodies can also be any in this embodiment assume geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, seven and octagonal prismatic and rhombohedral forms are preferred. Also completely irregular Base areas 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 is an embodiment with rounded corners and bevelled ones ("chamfered") edges preferred.

The shape of the trough can be chosen freely, wherein moldings are preferred in which at least one well a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral Can take shape. Also completely irregular trough shapes like arrow or animal forms, Trees, clouds etc. can be realized. As with the moldings are wells with rounded corners and edges or with rounded corners and chamfered edges preferred.

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

Similar statements can be made to the surface portions of the molding with the Cavity ("base molding") or the opening area of the cavity on the entire surface of the Make out shaped bodies. Here, moldings are preferred in which the area of the opening (s) the cavity (s) 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 molding.

Of course, the present invention is not limited to a first part with only to combine a second part. In particular, in the embodiment of the shaped body With cavity, it is possible and preferred to provide a basic shaped body which has several Having cavities containing inserted additional parts. These inserted further parts (hereinafter referred to as "cores") may be all "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 produced with, for example, two cavities is ("basic molding" = first part), of which a cavity with a "second part" in the sense of 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 containing the second part while the other contains another functionalized part includes 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-rinse phase. Can realize this embodiment in addition to the mentioned example of the three-part tablet with different solubilities also by the Form of application: A base tablet containing a "second part" for the purposes of the present invention can be provided with a notch. The consumer can then go along the notch break off part of the tablet and place in the cutlery basket while the rest of the tablet is introduced into the dosing box. The broken part, whose composition is the same which may be different from or different from the base tablet, unfolds its effect in the pre-rinse cycle, while the rest via the metering chamber only in the main wash cycle is used. By the choice of an outer coating over the functional coating may be the "second part" in the sense the present invention both part of the broken part and the other Part of such a tablet.

Of course, first and second part (and optionally other parts) of the invention Detergents are not necessarily 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 possibly additional parts) separately and together in a bag of water-soluble film packaged by the consumer into the machine. Regardless of the type of packaging unfolds the second part by the coating its effect essentially in the rinse cycle the dishwasher.

As mentioned above, it is particularly preferred to provide means to the consumer not only save the dosage of regenerating salt, but also the rinse aid already included. This can be realized by incorporation of surfactant (s) in the second part (see above). Another way is to incorporate the surfactants in the first part, which advantageously 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 5 to 25 wt .-%, each based on the first part, amounts to. In means of this embodiment according to the invention causes after the Main rinse and the intermediate rinses in the machine remaining amounts of surfactants an adequate drainage behavior in the rinse cycle, so that the effluent from the wash water during Dry leaves no stains. The rinse requires when using this invention Means not to be fed with additional intentionally added rinse aid.

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 ..

It is particularly preferred in the context of the present invention, support materials such as zeolites, Sodium carbonate, sodium tripolyphosphate, maltodextrins, polyvinyl alcohols, starch and / or their derivatives and cellulose and / or their derivatives with the addition of the above preferred Granulated labeled nonionic surfactants and then in a conventional manner with to spray a sodium silicate solution to at least partial coating of the granule particles to reach. Instead of the silicate solution may advantageously be a solution of polyvinyl alcohol be used. The granules can after production in per se known Be dried (advantageously by fluidized bed drying) and optionally in addition be "powdered" with finely divided substances such as zeolite and / or silica. The high-surfactant-containing Granules can then in a conventional manner with other components (Bleaching agents, enzymes, etc.) are processed into detergents.

These powdered detergents can be added directly to the coated second parts so that a particulate detergent according to the invention results. The coated ones second parts in such automatic dishwashing detergents according to the invention made by their coating so that they are in the main rinse (and also in optional Pre-rinse cycles) not or only to a lesser extent dissolve. This ensures that the Active substances are released only in the rinse cycle and unfold their effect here. Next Depending on the type of dishwasher, this chemical preparation is a physical one Assembly required so that the coated second parts when changing water in the Machine can not be pumped out and thus no longer available to the rinse cycle. Household standard dishwashers contain before the drain pump, which is the water or the cleaning solution pumps out of the machine after each cleaning cycle, one Sieve insert to prevent clogging of the pump by dirt residue. Is from the consumer rinsed heavily contaminated dishes, so this sieve 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 with regard to their size and shape preferably designed so that they the sieve insert of the dishwasher even after the cleaning cycle, i. after loading by movement in the machine and the cleaning solution, do not happen. In this way it is ensured that the rinse cycle coated second parts are in the dishwasher, which under the action of the water flowing to the rinse cycle liberate the active substance (s) and the bring desired Klarspüleffekt. In the context of the present invention preferred machine Dishwashing detergents are characterized in that the coated second parts are 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 compositions according to the invention, the coated second parts with the protrude above sizes from the matrix of other particulate ingredients, but the other particles may also have sizes that in the stated range lie so that a total of a detergent is formulated, consisting of large detergent particles and coated second parts. In particular, when the coated second Parts are colored, for example, have a red, blue, green or yellow color, it is for the appearance of the product, i. the entire cleaning agent of advantage, when the coated second parts are visibly larger than the matrix of the remainder particles Ingredients of the cleaning agent. Here are automatic dishwashing detergents according to the invention preferably, the (excluding the coated second parts) particle sizes between 200 and 3000 microns, preferably between 300 and 2500 microns and in particular between 400 and 2000 microns have.

The optical appeal of such compositions may be beyond the coloring of the coated second parts also by contrasting coloring of the powder matrix or by the shape of the coated second parts can be increased. As in the production of the coated second parts It is easily possible to use technically straightforward procedures to offer these in different forms. In addition to the particle shape, the approximately spherical shape For example, cylindrical or cube-shaped particles can be produced and used. Other geometric shapes can be realized. Special product designs For example, they may contain star-shaped rinse aid particles. Also discs or Forms that are used as a base plant and animal body, for example tree, flower, flower, sheep, Fish, etc. show, are easy to produce. Interesting optical incentives can be applied to this Way also by creating the coated second parts in the form of a stylized Produced glass to underline the Klarspüleffekt also in the product visually. The imagination There are no limits here.

If the cleaning agents according to the invention are formulated as a powder mixture, then - in particular for widely differing sizes of coated second parts and detergent matrix - On the one hand when Rüttelbelastung the package a partial segregation occur, on the other hand the dosage may be different in two consecutive cleanings, because the consumer does not always have the same amount of detergent and coated second Parts dosed. Should be desired, technically an equal amount per cleaning cycle can use this, the familiar to the expert packaging of the invention Means be implemented in bags made of water-soluble film. Also particulate machine Dishwashing detergents in which a dosing unit is sealed in a bag of water-soluble film is present, are the subject of the present invention.

As a result, the consumer has only one bag, for example, a detergent powder and a plurality of optically protruding coated second parts, into the dispensing compartment his dishwasher insert. This embodiment of the present invention is therefore a visually 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 except the above-mentioned increase in the rinse aid particles also realize by a reduction of the holes in the sieve insert. In this way One can formulate automatic dishwashing detergents which have a uniform average particle size which is smaller than, for example, 4 to 12 mm. For this purpose, the inventive Product in which the coated second parts also have smaller particle sizes, a sieve insert is added, which replaces or covers the insert located in the machine. Another object of the present invention is therefore a kit-of-parts, which is an inventive powdered machine dishwashing detergent and a sieve insert for household dishwashers includes.

As already mentioned, the combination of center and sieve insert according to the invention allows the Formulation of agents in which also the coated second parts have smaller particle sizes exhibit. Inventive kits of parts, in which the particle sizes of the automatic dishwashing detergent (taking into account the coated second parts) in the range of 400 to 2500 microns, preferably from 500 to 1600 microns and in particular from 600 to 1200 microns are preferred.

To prevent blockages of the enclosed sieve insert by dirt residues, should Mesh size or hole size should not be too small. Here are inventive kits-of-parts 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 Screen insert.

The kit-of-parts according to the invention is not limited to the specific shape of the sieve insert, which replaces or covers the insert in the machine. It is according to the invention also possible and preferred to add to the kit-of-parts a sieve insert, the shape Having a basket, in a known manner in the dishwasher - for example to the cutlery basket - can be hung. In this way, such an enriched replaced Sieve insert the dosing chamber, i. the consumer doses the machine according to the invention Dishwashing detergent directly into this sieve insert, which in the cleaning and rinse cycle in the manner described above acts.

The high-surfactant cleaning compositions of the invention in the first part are also acceptable produce in the form of moldings. In the simplest case, this is done by tableting the above powdered detergent. In this case, the coated second part - As already described above - are later glued to the molding, or in a prepared cavity of the base molding to be glued or inserted.

However, it is preferred in the context of the present invention, not the complete preceding described powdered detergent to compress a tablet, but produce multi-phase base tablets with a surfactant-rich phase. In this way, in the at least two-phase base tablet incompatible active ingredients are separated. It is particularly preferred to use the high-surfactant-containing granules of carrier material described above, Surfactant and optionally coating material and / or Abwuderungsmittel to To press a surfactant rich molding phase.

Preferred two-phase base moldings contain, for example, a phase, which in addition to to 30, preferably up to 20 and in particular up to 15 wt .-% surfactants (based on the Phase) phosphate, sodium carbonate, silicate and bleach contain during a second phase 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 two-phase Shaped bodies can then be connected to the coated second part and result Cleaning agents according to the invention in tablet form.

The compression of such surfactant-rich powder to form bodies can cause technical difficulties because these powders tend to clump because of the high surfactant content and / or can be poor flowable. In addition, under the compressive load of the pressing operation, the Surfactant released ("squeezed"), resulting in Stempelanbackungen. To solve such Any problems that may arise 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 temples. Plastic attachments are in direct contact with the press during pressing Matrizenwandung and are usually made on polyamide. Plastic inserts are in Tabletting punches inserted with facet edge and reduce the risk of caking on the Pressing surface.

Another possibility is to use the surfactant-rich premix in the middle of a three-layer tablet to arrange. Here, 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.e. Detergents, characterized in that the first part or at least a phase of a multiphase first part contains a content of nonionic surfactants between 5 and 25 wt .-%, each based on the first part or on the phase of the first part, having.

A) Herstellung eines Körpers, der einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Acidifizierungsmittel, Chelatkomplexbildner oder der belagsinhibierenden Polymere 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) production of a body which contains one or more substances from the group of builders, acidifiers, chelating agents or scale-inhibiting polymers,

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 produced, which in step B) and in step C) with a composition ("base composition" or "base molding") is combined to form the finished detergent according to the invention.

As already mentioned, the second part can be cast, extruded, granulated, extruded, Pelletizing, sintering, foaming, etc. Particularly preferred as second parts tableted products, which, due to their compact structure, are particularly suitable for a suitable shape coat well. Processes according to the invention, in which the preparation in step A) 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), where it has proved to be advantageous if that too "second parts" or base moldings compressed premix certain physical criteria enough. Preferred methods are characterized, for example, in that to be compressed particulate premixes have a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

Also the particle size of the pre-mixture compressed to "second parts" or basic shaped bodies preferably meets certain criteria: Processes in which particulate premixes Particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, especially preferably between 400 and 1600 μm and in particular between 600 and 1400 μm, are preferred according to the invention. A further narrowed particle size in the to be pressed Premixes can be adjusted to obtain favorable molding properties. In preferred variants for the process according to the invention have to be compressed particulate Premixes have a particle size distribution at which less than 10 wt .-%, preferably less than 7.5 wt .-% and in particular less than 5 wt .-% of the particles greater than 1600 microns or less than 200 microns. Here, narrower particle size distributions are wider prefers. Particularly advantageous process variants are characterized in that the particulate premixes to be compressed have a particle size distribution more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight the particles have a particle size between 600 and 1000 microns.

When carrying out the tabletting, the process preferred according to the invention is not specified limited that only a particulate premix is pressed into a shaped body. Rather, this method step can be - especially in the production of basic moldings, see above - also extend to the effect that multilayered in a conventional manner Forming molds by preparing two or more premixes, which on each other be pressed. In this case, the first-filled premix is slightly pre-pressed to a smooth and to get parallel to the bottom of the mold body running top, and after filling the second premix to the finished molded article endverpreßt. For three- or multi-layered moldings another pre-compression takes place after each premix addition, before addition the final premix of the moldings is end-pressed. Preferably, the one described above Cavity in the base molding a trough, so that preferred embodiments of the first process according to the invention characterized in that multilayer molded bodies, having a trough, be prepared in a conventional manner by several different particulate premixes are pressed together.

The production of the moldings takes place first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent informing, in particular Compress to tablets, using conventional methods. to Preparation of the shaped bodies according to the invention is the premix in a so-called template compressed between two stamps to a fixed compressed. This process, in the following short referred to as tableting, is divided into four sections: dosage, 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 molded body by the position of the lower punch and the shape of the pressing tool can be determined. The constant dosage even at high Moldings throughputs are preferably via volumetric metering of the premix reached. As the tableting progresses, the upper punch touches the pre-mix and continues to lower in the direction of the lower punch. In this compression, the particles become of the premix is pressed closer to each other, wherein the void volume within the Filling between the punches decreases 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. ever according to the physical properties of the premix also becomes part of the premix particles crushed and it comes at even higher pressures to sinter the premix. at increasing press speed, so high throughputs, the phase of the elastic Deformation further shortened, so that the resulting moldings more or less large May have cavities. In the last step of tabletting the finished molding pushed out of the die by the lower punch and by subsequent Transpörteinrichtungen carried away. At this time, only the weight of the molded article is final determined because the compacts due to physical processes (re-stretching, crystallographic Effects, cooling etc.) can still change their shape and size.

The tableting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch to Pressure build-up used, also the lower punch moves during the pressing process on the Upper stamp too, while the upper punch presses down. For small production quantities Eccentric tablet presses are preferably used, in which the one or the stamp on an eccentric disc are fixed, which in turn on an axis with a certain rotational speed is mounted. The movement of these punches is the operation of a usual Four-stroke engine comparable. The compression can each with a top and bottom stamp take place, but it can also be attached more stamp on an eccentric disc, wherein the number of die holes is extended accordingly. The throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs you can choose rotary tablet presses, where on a so-called Matrizentisch a larger number of matrices is arranged in a circle. The number of matrices varies from 6 to 55 depending on the model, although larger dies are commercially available. Each die on the die table is assigned a top and bottom stamp, again the pressing pressure active only by the upper or lower punch, but also constructed by both stamp can be. The die table and the punches move around a common vertical standing axis, wherein the punches by means of rail-like cam tracks during the Circulated to positions for filling, compaction, plastic deformation and ejection become. At the places where a particularly serious increase or decrease in the Stamp is required (filling, compaction, ejection), these curved paths by additional Low pressure pieces, Nierderzugschienen and Aushebebahnen supported. The filling the die takes place via a rigidly arranged supply device, the so-called filling shoe, the is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, whereby the pressure build-up by passing the stamp shank heads past adjustable pressure rollers.

Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle must be run through. to Production of two-layered and multi-layered moldings, several filling shoes in a row arranged without the slightly pressed first layer ejected before further filling becomes. By suitable process control coat and point tablets can be produced in this way, which have a onion-bowl-like 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. Also 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 at the same time for pressing to be used. The throughputs of modern rotary tablet presses are 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 at. Particularly advantageous are plastic coatings, plastic inserts or plastic stamp. Rotary stamps have proved to be advantageous, wherein after Possibility of upper and lower punches should be rotatable. With rotating stamps can be dispensed with a plastic insert usually. Here should be the stamp surfaces be electropolished.

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

Tableting machines suitable for the purposes of the present invention are available, for example at the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging Systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, 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 N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). Particularly suitable is, for example, the Hydraulic double pressure press HPF 630 of the company LAEIS, D. Tabletting tools are for example by the companies 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. the Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).

The moldings can - as already mentioned above - in a predetermined spatial form and be made of a predetermined size. As a form of space virtually all useful manageable Embodiments into consideration, for example, the training as a blackboard, the bar or bar form, Cube, cuboid and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with a circular or oval cross-section. These last embodiment detects the presentation form of the tablet up to compact cylinder pieces with a height to diameter ratio above 1.

But it is also possible that the various components do not become a single tablet be pressed, but that moldings (in particular base moldings, see above) be, which have multiple layers, so at least two layers. And that's it possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. For example, if components are contained in the moldings that are mutually negative so it is possible to add the one component in the faster soluble layer too integrate and incorporate the other component in a slower soluble layer, so that the first component has already reacted when the second goes into solution. The layer structure The molding can be carried out in a batch-like manner, wherein a solution process of the inner Layer (s) already takes place at the edges of the shaped body when the outer layers not yet completely solved, but it can also be a complete enclosure of the inner Layer (s) through the respective outer layer (s) are achieved, resulting in a Prevention of premature dissolution of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a shaped body (in particular Basic shaped body, see above) from at least three layers, so two outer and at least an inner layer, wherein at least in one of the inner layers, a peroxy bleach is contained, while the stack-shaped molded body, the two outer layers and the shell-shaped Shaped body, however, the outermost layers are free from peroxy bleach. Farther it is also possible peroxy bleach and optionally present bleach activators and / or to spatially separate enzymes in a molding.

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 σ = 2 P π dt

Herein, σ is the diametrical fracture stress (DFS) in Pa, P ist the force in N, which leads to the pressure exerted on the molding, the breakage of the molding D is the shape diameter in meters and t is the height of the moldings.

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

As 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 context of the present invention, solutions or dispersions of the above Spray coating materials on the moldings, wherein the solution or Dispersant evaporates and leaves a coating on the molding. In preferred The process according to the invention is an aqueous solution of one or more of the mentioned coating materials sprayed on the molded article produced in step A), wherein the aqueous Solution, in each case based on the solution, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 10% by weight of one or more of the stated coating materials, optionally up to 20% by weight, preferably up to 10% by weight and in particular below 5% by weight one or more water-miscible solvents and the remainder water.

To shorten the drying time, the aqueous solution can be further miscible with water volatile solvents are mixed. These come in particular from the group the alcohols, with ethanol, n-propanol and iso-propanol being preferred. For cost reasons Ethanol and iso-propanol are particularly recommended.

Also, the coating of anhydrous or low-water solutions may in certain coating materials be beneficial.

As already mentioned above, for certain functional coatings a "sub-coating" can be used. be preferred to improve the adhesion of the coating. Also a protection of the functional Coating by another "topcoat" may possibly provide benefits. Out For these reasons, methods according to the invention are preferred in which the coating in Step B) the application of one or more, preferably two or three coating layers includes.

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

The composition with which the coated second part of the cleaning agent according to the invention can, as explained above in detail, any physical Taking form. In an order of increasing preference are inventive methods preferred in which the composition in step C) is a liquid, gel or pasty composition is. Particularly preferred are methods in which the composition in step C) is a particulate composition. And especially preferred Process according to the invention, characterized in that the composition in Step C) is a tablet-shaped composition, with detailed information on tableting and to preferred embodiments of the "base moldings" found above.

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

In these preferred methods, the second part may adhere to the first part solely by the shape, but it is preferred in terms of better transport and handling stability either in the first Press or glue part so that it is firmly adhered to it. Across from For mechanical fastening by pressing, gluing is preferred because of the risk of coating to destroy the second part, this is less. When gluing is bonding agent applied to one or more molding surfaces. This can be done with the above Method in which two moldings are joined together, either in the molding with cavity or in the molding that fills the cavity. In preferred methods Adhesive introduced into the cavity of the molding.

This procedure is particularly well at Muldenformkörpern realizable, since the dosage the adhesive can be realized simply by dripping liquid adhesion promoters in the trough can. Suitable dosing systems for the large-scale dosing of small quantities of liquid in Cavities are well known to those skilled in the art.

Often it is technically easier to apply adhesion promoter to the cavity filling Make moldings. In such cases, methods are particularly preferred characterized in that the adhesion promoter on one or more surfaces, preferably on a Surface, the coated second part is applied.

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, the coated second part by dipping on one side with adhesive to wet and then in the Cavity to place. This technology is technologically easy to implement, but carries the risk that adhesive contaminates the surface of the molding with cavity. The amount of glue can be controlled in this variant by varying the rheological properties of the adhesion promoter become.

Another and preferred in the context of the present invention, adhesion promoters on It is preferable to apply one surface of the coated second part to this dosing unit past adhesive dosing systems and then place 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, because the coated second part has only a small contact surface to the roller. The bonding agent can be dosed from the inside of the roller, but it is also possible to Adhesive at a location from the point of contact of the roller with the coated second Parts are removed, apply to the roller. Processes in which the application of the bonding agent (s) takes place on a surface of the coated second part, wherein preferably adhesion promoter Rollers, brushes or nonwovens are used, are therefore preferred.

The filling of the cavity (the coated second part) can completely fill the cavity but can also protrude from the cavity or fill it only partially, taking the imagination the product developers have no limits. By varying the shape of the molding with continuous hole or trough, the shape of the trough or the hole and the shape of the coated The second part makes it possible to produce a variety of shapes that are visually appealing differ greatly from each other. For example, the circular described above Ring moldings are filled with a circular hole with a form-fitting fit cylinder. But it is also possible, for example, a ball, a square adjacent to the edges, to use a three-, five- or six-sided prism or another irregular shape. ever According to the effort you want to operate, you can also octahedral, multiple capped realize prismatic or icosahedral forms for the coated second part.

Both in the case of the perforated moldings and in the hollow moldings the adhesion of the coated sinks second part in the cavity with decreasing contact area. Maximum liability between the two moldings is achieved when the ring or Muldenformkörper and the coated second part without gaps fit into one another.

Completely analogous to the above-described preparation of biphasic moldings by On or stick together of two separately pressed moldings can also be three-phase Shaped bodies are produced. Here, either the arrival or the incarnation of three offers itself However, it is also possible and preferred, a two-phase, For example, produce a two-layered tablet and another molded body or to insert into this.

The mentioned principle can be correspondingly applied to further multi-phase detergent tablets expand. Thus, for example, four-phase moldings can be produced by two biphasic Moldings are joined together. Analogous are also four-phase 3: 1 moldings produced. Of course, the two-phase moldings to be joined can also be made in other ways. So it is possible, for example, a on or produce multilayer moldings to fill the trough with an active substance (for example as a melt, powder, granules, extrudate, flakes etc.) and a further one, two- or three-phase moldings to be applied to the molding. It can be the most diverse Possibilities are varied, for example a two-layer molded body, whose trough is filled with a melt or a particulate mixture, wherein on the Shaped body side, which has the trough, another molded body is applied adherent. On In this way, the trough becomes a quasi "core" because the filling is now enclosed on all sides. Completely identical can be moved with a molded body having a through hole ("Ringformkörper") and because on both sides with another molding "closed" becomes. Is essential to the invention in all these embodiments only that at least one phase a coated second part according to the invention.

The abovementioned possibilities of joining or joining of moldings can also be used to make the entire molding or parts thereof faster soluble. For example, if two flat moldings are glued together with adhesion promoter, so under application conditions a water access to the adhesive is not yet loosened Tablet only at the edges of the molding possible. Even when using good water-soluble Primer, the compound can be practically solved only when a part of the overall shaped body is dissolved.

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

In summary: If a faster resolution of the entire shaped body or individual Parts is desired, a fast surface enlargement by separation of the adhesive bond optimal. This can be achieved by selecting a favorable form of the adhesive bond or supported. In such cases the line bonding is preferable to the surface bonding, wherein a Punktverklebung is particularly preferred.

In addition, the shape of the molded body parts to be bonded to the adhesion promoter can also be used Accelerate resolution. Here, moldings are preferred which, after dissolution of the adhesion promoter compound as free as possible against each other are movable, so no toroidal moldings, but preferably basic body having "satellite shaped bodies" on their outer surfaces. The variety There are hardly any limits to geometric design options. From procedural economic For reasons, however, moldings are preferred which are orthorhombic, tetragonal or cubic. Shaped bodies with a circular base can be made along their lateral surface gluing only by corresponding biconcave-shaped spacers, which in turn heavier are tablettable. Nevertheless, the joining together of such moldings is also according to the invention possible.

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%.

According to the invention, the packaging system of the combination detergent / cleaning product (s) and packaging system has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system 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 FDDR = 24 · 10000 A · x y [ G / m 2 / 24 H ] 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 the 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 . Thus, 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 humidity of 85% at 23 ° C can be, for example, in laboratory chambers with humidity control to +/- 2% r.L. depending on the device type. set exactly. Also over saturated Solutions of certain salts form in closed systems at a given temperature constant and well-defined relative humidities resulting in the phase equilibrium between partial pressure of water, saturated solution and soil body based.

The combinations of cleaning agent or detergent tablet (s) according to the invention and packaging system can of course in turn in secondary packaging, for example Cardboard boxes or trays are packed, with no secondary packaging further requirements 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.

The packaging system of the combination according to the invention encloses depending on the embodiment invention a certain amount of detergent or one or more detergent tablets. It is preferred according to the invention, either to a shaped body so design that it comprises an application unit of the cleaning agent, and this shaped body individually pack, or pack the number of moldings in a packaging unit, the in sum comprises an application unit. At a nominal dosage of 80 g detergent is Thus, according to the invention, it is possible to prepare a 80 g detergent tablet and to package individually, but it is also possible according to the invention, two detergent tablets each weighing 40 g Packed in a package to a combination of the invention to get. Of course, this principle can be extended so that according to the invention Combinations also three, four, five or even more detergent tablets in a packaging unit can contain. Of course, two or more moldings in one Packaging have different compositions. In this way it is possible To separate certain components spatially, for example, stability problems to avoid.

The packaging system of the combination according to the invention can be made of the most diverse Materials exist and assume any external forms. For economic reasons and however, for ease of processing, packaging systems are preferred which the packaging material has a low weight, easy to work and inexpensive is. In inventively preferred combinations, the packaging system consists of a Bag or bag of single-layer or laminated paper and / or plastic film.

The detergent tablets may be unsorted, i. as loose bulk, in a bag be filled from the materials mentioned. But it is for aesthetic reasons and for sorting the combinations in secondary packaging, the detergent tablets preferred one by one or several sorted into sacks or bags to fill. For individual application units the detergent tablets, which are located in a bag or sack, has in the Technique of the term "flow pack" naturalized. Such "flow packs" can then - again preferably sorted - optionally packed in outer packaging, what the compact supply form of the molding underscores.

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 indicated. 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 a packaging system a bag or bag of single-layer or laminated plastic film with 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, in addition to the films mentioned or papers also wax-coated papers to use in the form of cardboard as a packaging system for the detergent tablets, It is preferred in the context of the present invention, when the packaging system does not include boxes of wax-coated paper. The term "packaging system marks in the context of the present invention always the primary packaging of the detergent or shaped bodies, i. the packaging, which on its inside directly with the molding surface is in contact. At an optional secondary packaging are no requirements provided so that all the usual materials and systems can be used here.

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

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 be used, with respect to the program choice, there are no limitations. The beneficial effects are found in both low-temperature programs such as 45 ° C programs or Achieved at 50/55 ° C or 60/65 ° C programs.

Another object of the present invention is therefore a method for the purification of Dishes in a domestic dishwasher, in which a particulate according to the invention machine dishwashing detergent 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, whereby by opening the metering chamber after a possible Vorreinigungsgang the powder is released into the machine. It is alternatively possible, the powder directly into the machine and thus already in an optional Vorreinigungsgang Release active substance. Alternatively, it can be dispensed with a Vorreinigungsgang. Due to the composition according to the invention, no additional rinse aid is required in the rinse cycle to become. inventive methods in which the rinse cycle of the machine without the intentional addition of further rinse aid is therefore preferred.

The term "further rinse aid" encompasses liquid commercially available rinse aids which are from Consumers given at intervals of several rinsing cycles in a reservoir of the machine must be released and programmatically released from there. This intentional addition a rinse aid and the required for this second dosing step at intervals of some rinse cycles are not required by the use of the agents 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 and the rinse cycle are interrupted by intermediate rinses. preferred Methods are therefore characterized in that between steps a) and b) one or more intermediate rinses done.

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

The mentioned methods for cleaning dishes also make the dosage of additional Regenerating salt superfluous after several cleaning cycles. Of course they are Cleaning process is not bound to the supply form of the powdered cleaner, so that also a method for cleaning dishes in a household dishwasher, in which an inventive detergent molding in the Hauptreinigungsgang the machine is incorporated, is 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. Detergent for machine dishwashing, comprising

   a) a first part (base composition), which exerts its effect substantially in the main wash cycle of the dishwasher; and

   b) a second part, which by dint of appropriate coating develops its effect substantially in the rinse cycle of the dishwasher,

   characterized in that the second part comprises one or more substances selected from the group consisting of chelating agents, and scale inhibiting polymers, the chelating agent(s) being selected from the groups consisting of

   (i) polycarboxylic acids wherein the sum of the carboxyl and any hydroxyl groups is at least 5,

   (ii) nitrogen-containing monocarboxylic or polycarboxylic acids,

   (iii) geminal diphosphonic acids,

   (iv) aminophosphonic acids,

   (v) phosphonopolycarboxylic acids, and

   (vi) cyclodextrins

   and the scale inhibiting polymer(s) being selected from the group consisting of cationic homopolymers or copolymers, especially hydroxypropyltrimethylammonium-guar; copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers containing imino groups, polymers containing quaternized 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, especially guar derivatives, cellulose derivatives, and starch derivatives; polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides having quaternary side groups.
2. Detergent according to Claim 1, characterized in that the second part contains one or more chelating agents in amounts above 0.1% by weight, preferably above 0.5% by weight, with particular preference above 1% by weight, and in particular above 2.5% by weight, based in each case on the weight of the second part.
3. Detergent according to one of Claims 1 or 2, characterized in that the second part contains scale inhibiting polymers in amounts above 5% by weight, preferably above 10% by weight, with particular preference above 20% by weight, and in particular above 25% by weight, based in each case on the weight of the second part.
4. Detergent according to one of Claims 1 to 3, characterized in that the second part contains one or more copolymers of

   i) unsaturated carboxylic acids

   ii) monomers containing sulphonic acid groups

   iii) if desired, further ionic or nonionogenic monomers

   in amounts above 5% by weight, preferably above 10% by weight, with particular preference above 20% by weight, and in particular above 25% by weight, based in each case on the weight of the second part.
5. Detergent according to one of Claims 1 to 4, characterized in that the second part further contains from 1 to 50% by weight, preferably from 2.5 to 45% by weight, and in particular from 5 to 40% by weight of nonionic surfactant(s).
6. Detergent according to one of Claims 1 to 5, characterized in that the coating of the second part comprises an LCST (low critical solution temperature) polymer.
7. Detergent according to Claim 6, 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.
8. Detergent according to one of Claims 6 or 7, characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide, and blends of these substances.
9. Detergent according to one of Claims 6 to 8, characterized in that the lower critical separation temperature of the LCST polymer lies between 20°C and 90°C.
10. Detergent according to one of Claims 1 to 9, characterized in that the coating of the second part is composed of two or more coating layers, preferably of two or three coating layers.
11. Detergent according to one of Claims 1 to 10, characterized in that the second part has been produced by a pressing operation, especially tableting.
12. Detergent according to one of Claims 1 to 11, characterized in that the second part has a diameter of between 1 and 30 mm, preferably between 2.5 and 15 mm, and in particular between 5 and 10 mm.
13. Detergent according to one of Claims 1 to 12, characterized in that the first part contains builders in amounts of from 1 to 100% by weight, preferably from 5 to 95% by weight, with particular preference from 10 to 90% by weight, and in particular from 20 to 85% by weight, based in each case on the weight of the first part.
14. Detergent according to one of Claims 1 to 13, characterized in that the first part contains phosphate(s), preferably alkali metal phosphate(s), with particular preference pentasodium and/or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, and in particular from 30 to 70% by weight, based in each case on the weight of the first part.
15. Detergent according to one of Claims 1 to 14, characterized in that the first part contains citrate(s), preferably sodium citrate, with particular preference trisodium citrate dihydrate, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight, and in particular from 20 to 40% by weight, based in each case on the weight of the first part.
16. Detergent according to one of Claims 1 to 15, characterized in that the first part contains bleaches from the group of the oxygen or halogen bleaches, in particular the chlorine bleaches, with particular preference sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight, preferably from 5 to 20% by weight, and in particular from 10 to 15% by weight, based in each case on the weight of the first part.
17. Detergent according to one of Claims 1 to 16, characterized in that the first part contains bleach activators from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulphonates, especially n-nonanoyl- or iso-nonanoyloxybenzenesulphonate (n- or iso-NOBS), and n-methylmorpholiniumacetonitrile methyl sulphate (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% by weight, based in each case on the weight of the first part.
18. Detergent according to one of Claims 1 to 17, characterized in that the first part contains silver protectants from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and transition metal salts or transition metal complexes, with particular preference benzotriazole and/or alkylaminotriazole, in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 4% by weight, and in particular from 0.5 to 3% by weight, based in each case on the weight of the first part.
19. Detergent according to one of Claims 1 to 18, characterized in that the first part further contains one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and/or fragrances in total amounts of from 6 to 30% by weight; preferably from 7.5 to 25% by weight, and in particular from 10 to 20% by weight, based in each case on the weight of the first part.
20. Detergent according to one of Claims 1 to 19, characterized in that the first part is a liquid, gel-like or paste-like composition for machine dishwashing.
21. Detergent according to one of Claims 1 to 19, characterized in that the first part is a particulate composition for machine dishwashing.
22. Detergent according to one of Claims 1 to 19, characterized in that the first part is a tablet-form composition for machine dishwashing.
23. Detergent according to Claim 22, characterized in that the first part is a multiphase tablet, in particular a two-, three- or four-phase tablet, it being preferred for the phases to have the form of layers.
24. Detergent according to one of Claims 22 or 23, characterized in that the coated second part has the form of a further layer, of a core, or of a body bonded adhesively on or in the first part ("basic tablet").
25. Detergent according to one of Claims 22 to 24, characterized in that the first part has (a) cavity(ies) containing the second and any further parts.
26. Detergent according to Claim 25, characterized in that first part has at least two cavities one of which contains the second part while the other contains a further, functionalized part.
27. Detergent according to one of Claims 1 to 26, characterized in that the nonionic surfactant content of the first part is from 5 to 25% by weight, based in each case on the first part.
28. Detergent according to one of Claims 22 to 26, characterized in that the first part or at least one phase of a multiphase first part has a nonionic surfactant content of between 5 and 25% by weight, based in each case on the first part or on the phase of the first part.
29. Process for producing detergents for machine dishwashing, characterized by the steps of

    A) producing a body which comprises one or more substances from the group consisting of chelating agents or scale inhibiting polymers, the chelating agent(s) being selected from the groups of

    (i) polycarboxylic acids wherein the sum of the carboxyl and any hydroxyl groups is at least 5,

    (ii) nitrogen-containing monocarboxylic or polycarboxylic acids,

    (iii)geminal diphosphonic acids,

    (iv) aminophosphonic acids,

    (v) phosphonopolycarboxylic acids, and

    (vi) cyclodextrins
    and the scale inhibiting polymer(s) being selected from the group consisting of cationic homopolymers or copolymers, especially hydroxypropyltrimethylammoniumguar; copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers containing imino groups, polymers containing quaternized 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, especially guar derivatives, cellulose derivatives, and starch derivatives; polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides having quaternary side groups,

    B) coating the body produced in step A),

    C) unifying the coated body with a composition which develops its effect substantially in the main cleaning cycle of the dishwasher.
30. Process according to Claim 29, characterized in that the producing in step A) takes place by tableting.
31. Process according to one of Claims 29 or 30, characterized in that the coating in step B) comprises the application of one or more, preferably two or three, coating layers.
32. Process according to one of Claims 29 to 31, characterized in that the body produced in step A) is coated in step B) with an LCST polymer.
33. Process according to one of Claims 29 to 32, characterized in that the composition in step C) is a liquid, gel-like or paste-like composition.
34. Process according to one of Claims 29 to 32, characterized in that the composition in step C) is a particulate composition.
35. Process according to one of Claims 29 to 32, characterized in that the composition in step C) is a tablet-form composition.
36. Process according to Claim 35, characterized in that the composition in step C) is a multiphase detergent tablet which has a cavity into which the coated body from step B) is adhesively bonded or pressed.