DE20022229U1 - Dishwasher detergent with additional benefits - Google Patents

Description

Henkel KGaA
VTP

Semrau / BL
15.02.2001

Utility model branching

H 4753 DE:U
"Machine dishwashing detergent with added benefits"

The present utility model version is a branch of the patent application DE 100 32 611.0 dated July 7, 2000. The present invention relates to cleaning agents, in particular machine dishwashing agents with controlled release of active ingredients. In particular, the present invention relates to machine dishwashing agents that have a system that allows a controlled release of at least one active ingredient in the cleaning process and at least one active ingredient in the post-treatment process.

For a long time, it was common practice to provide cleaning agents to consumers in the form of bulk-packaged goods and to leave it up to the consumer to dose the cleaning agent according to the application requirements, which depended on the water hardness, the type, quantity and/or degree of soiling of the items to be cleaned, the amount of cleaning solution and other parameters.

In response to the consumer's desire for easier and more convenient cleaning agents, these were increasingly made available in a form that made individual dosing unnecessary: cleaning agents were formulated in measured portions containing all the components required for a cleaning cycle. In the case of solid products, such portions were often formed into shaped bodies (sometimes containing several phases) such as granules, beads, tablets ("tabs"), blocks, briquettes, etc., which were dosed into the liquor as a whole. Liquid products were introduced into water-soluble coatings that dissolved on contact with the aqueous liquor and released the contents into the liquor.

The disadvantage of these solutions is that all components required during a cleaning cycle are added to the aqueous solution at the same time. This not only leads to problems of incompatibility between certain components of a cleaning agent and other components, but also makes it impossible to dose specific components into the solution at a specific time.

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The state of the art has now described ways in which individual cleaning agent components can be dosed in a targeted manner and at a defined point in time during use. For example, the temperature-controlled release of active ingredients is described, which makes it possible to release active ingredients such as surfactants, bleaches, soil-release polymers and the like either in the rinsing or cleaning cycle or even in the post-treatment cycle, for example in the rinse cycle in automatic dishwashing. Corresponding products with integrated rinse aid are now available on the market.

These so-called "2 in 1" products simplify handling and relieve the consumer of the additional burden of dosing two different products (detergent and rinse aid). However, two dosing processes are required at intervals to operate a household dishwasher, as the regeneration salt in the machine's water softening system must be refilled after a certain number of wash cycles. These water softening systems consist of ion exchange polymers which soften the hard water flowing into the machine and are regenerated by rinsing with salt water after the wash program.

The aim of the present invention was to provide a product that only needs to be dosed once per application, without the need to dose another product after a higher number of wash cycles and thus a double dosing process. A product should be provided that, in addition to the "built-in rinse aid", makes it unnecessary to refill the regeneration salt container and thus further simplifies handling. The performance of the product should reach or exceed the performance level of conventional three-product dosing systems (salt-detergent-rinse aid) or new two-product dosing systems (..2inr-detergent-rinse aid).

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

The present invention relates to cleaning agents for machine dishwashing, comprising

a) a first part (base composition) which exerts its effect essentially in the main cleaning cycle of the dishwasher; and

b) a second part which, by means of a suitable coating, develops its effect essentially in the rinse cycle of the dishwasher,

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in which the second part contains one or more substances from the group of builders, acidifying agents, chelating agents or scale-inhibiting polymers.

These substances, the use of which in the final rinse cycle has not yet been described in the prior art, mean that final rinse cycles can be carried out with normal hard tap water instead of softened water without any loss of performance. The groups mentioned include substances, some of which are particularly suitable in the context of the present invention. These are described below.

The most important ingredients of automatic dishwashing detergents are builders. The second part of the cleaning agents for automatic dishwashing according to the invention can contain all builders usually used in cleaning agents, in particular zeolites, silicates, carbonates, organic cobuilders and phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _2x+ IH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x takes on the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ ' yH ₂ O are preferred.

Amorphous sodium silicates with a Na ₂ O : SiO ₂ modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and in particular 1:2 to 1:2.6, which are delayed in dissolution, can also be used. The delayed dissolution compared to conventional amorphous sodium silicates can be 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 in X-ray diffraction experiments the silicates do not produce sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This can be interpreted as meaning that the products have microcrystalline areas of size 10 to several hundred nm, with values up to max. 50 nm and especially up to max. 20 nm being preferred. Such so-called X-ray amorphous silicates also have a delayed dissolution compared to conventional water glasses. Particularly preferred are compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The fine-crystalline, synthetic zeolite containing bound water used is preferably zeolite A and/or P. Zeolite P is zeolite MAP® (commercial product of Cros-

ti *i· ·· *

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field) are particularly preferred. However, zeolite X and mixtures of A, X and/or P are also suitable. Commercially available and preferably used in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta S.p.A. under the brand name VEGOBOND AX* and is represented by the formula

nNa ₂ O · (1-n)K ₂ 0 ' AI ₂ O ₃ ' (2 - 2.5)SiO ₂ · (3.5 - 5.5) H ₂ O

Suitable zeolites have an average particle size of less than 10 μηη (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, the use of the well-known phosphates as builder substances is also possible, provided that such use should not be avoided for ecological reasons. Of the many commercially available phosphates, the alkali metal phosphates are the most important in the detergent and cleaning agent industry, with particular preference given to pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, among which metaphosphoric acids (HPO ₃ J _n and orthophosphoric acid H ₃ PO ₄ can be distinguished alongside higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or limescale incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 g/cm ³ , melting point 60°) and as a monohydrate (density 2.04 g/cm ³ ). Both salts are white powders that are very easily soluble in water. When heated, they lose their water of crystallization and turn into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ^° C, and into sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below) at higher temperatures. NaH ₂ PO ₄ reacts acidically; it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 g/ ^cm3 , has a melting point of 253° [decomposition to form potassium polyphosphate (KPO ₃ )] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (density 2.066 g/ ^cm3 , water loss at 95°), 7 mol. (density 1.68 g/ ^cm3 , melting point 48° with loss of 5 H ₂ O) and

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12 mol. water (density 1.52 g ^/l , melting point 35° with loss of 5 H ₂ O), becomes anhydrous at 100° and changes into the diphosphate Na ₄ P ₂ O ₇ on higher heating. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 g/ ^cm3 and a melting point of 73-76°C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 1OO ^e C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 g/ ^cm3 . Trisodium phosphate is easily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 g/ ^cm3 , has a melting point of 1340° and is easily soluble in water with an alkaline reaction. It is produced, for example, by heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, and therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 g/cm ³ , melting point 988°, also given as 880°) and as decahydrate (density 1.815-1.836 g/cm ³ , melting point 94° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to >200° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness-forming 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 mg/ ^l , which is soluble in water, the pH of the 1% solution at 25° being 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ produces higher molecular weight sodium and potassium phosphates, which can be divided into cyclic types, sodium or potassium metaphosphates, and chain-like types, sodium or potassium polyphosphates. A variety of names are used, particularly for the latter: fused or calcined phosphates, Graham's salt, Kurrol's salt 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 a non-hygroscopic, white, water-soluble salt of the general formula NaO-[P(O)(ONa)-O] _n -Na with n=3, which crystallizes in water or with 6 H ₂ O. In 10Og water, the following dissolve at room temperature:

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temperature about 17 g, at 60° about 20 g, at 100° about 32 g of the salt free of water of crystallization; after heating the solution at 100° for two hours, about 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the production of pentasodium triphosphate, phosphoric acid is reacted with soda solution or caustic soda in a stoichiometric ratio and the solution is dehydrated by spraying. Like Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, is sold in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). Potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

(NaPO ₃ J ₃ + 2 KOH -> Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These can be used according to the invention in the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

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

Acidifying agents are also suitable as ingredients for the second part within the scope of the present invention. Substances from this group are, for example, boric acid as well as alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, with citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used. From this group, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are also preferred. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight), is commercially available and can also be used preferably as an acidifying agent within the scope of the present invention.

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The preferred cleaning agents according to the invention are characterized in that the second part contains one or more acidifying agents from the group citric acid, adipic acid, malic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, in each case based on the weight of the second part.

Another possible group of ingredients for the second part are the chelating agents. Chelating agents are substances that form cyclic compounds with metal ions, where a single ligand occupies more than one coordination site on a central atom, i.e. is "bidentate". In this case, normally stretched compounds are closed to form rings by complex formation via an ion. The number of bound ligands depends on the coordination number of the central ion.

Common chelate complexing agents that are preferred within the scope of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, i.e. polymers that carry functional groups either in the main chain itself or laterally to it, which can act as ligands and usually react with suitable metal atoms to form chelate complexes, can also be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from just one macromolecule or belong to different polymer chains. The latter leads to cross-linking of the material, provided that the complex-forming polymers were not already cross-linked via covalent bonds.

Complexing groups (ligands) of common complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and crown ether residues, some of which have very specific activities towards ions of different metals. The base polymers of many complex-forming polymers, including those of commercial importance, are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities through polymer-analogous conversions.

Particularly preferred within the scope of the present invention are cleaning agents in which the second part contains one or more chelating 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,

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(iii) geminal diphosphonic acids,

(iv) Aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) Cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, each based on the weight of the second part.

All complexing agents of the prior art can be used within the scope of the present invention. These can belong to different chemical groups. Preferably used individually or in a mixture with one another:

(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-(ß-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) _1, its higher homologues with up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid, its higher homologues with up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof,

d) Aminophosphonic acids such as ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) or nitrilotri(methylenephosphonic acid),

e) Phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and

f) Cyclodextrins.

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

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With regard to the scale-inhibiting polymers as an ingredient of the second part, cleaning agents are particularly preferred which are characterized in that the second part contains one or more scale-inhibiting polymers from the group of cationic homo- or copolymers, in particular hydroxypropyltrimethylammonium guar; copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, polymers which have 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, in particular guar, cellulose and starch derivatives; polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, in each case based on the weight of the second part.

Another preferred ingredient for the second part are certain copolymers containing sulfonic acid groups. Cleaning agents whose second part contains one or more copolymers of

i) unsaturated carboxylic acids

ii) Monomers containing sulfonic acid groups

(iii) optionally other ionic or non-ionic monomers

in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, each based on the weight of the second part, preferred embodiments of the present invention.

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

R ¹ (R ² )C=C(R ³ )COOH (I),

in which R' to R ³ independently of one another represent -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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or represent -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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Among the unsaturated carboxylic acids which can be described by the formula I, 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) are particularly preferred.

Among the monomers containing sulfonic acid groups, those of the formula II are preferred,

R ⁵ (R ⁶ )C=C(R ⁷ )-X-SO3H (II),

in which R ⁵ to R ⁷ independently of one another represent -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, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or COOH as defined above or represent -COOH or COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group which is selected from -(CH ₂ J _n - with η = O to 4, -COO-(CH ₂ ) _k - with k = 1 to 6, C(O)-NH-C(CH ₃ J ₂ - and -C(O)-NH-CH(CH _{2CH3 )} -.

Preferred among these monomers are those of the formulas Iia, lib and/or lic,

H ₂ C=CH-X-SO ₃ H (Ha),

H ₂ C=C(CHa)-X-SO ₃ H (Hb),

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

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 J ₂ and X represents an optionally present spacer group selected from -(CH ₂ ) _n - with η = O to 4, -COO-(CH ₂ ) _k - with k = 1 to 6, -C(OJ-NH-C(CH ₃ ) ₂ - and -C(O)-NH-CH(CH ₂ CH ₃ )-.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-ipropanesulfonic acid (X = -C(O)NH-CH(CH ₂ CH ₃ ) in formula Ha), 2-acrylamido-2-propanesulfonic acid (X = -C(O)NH-C(CH ₃ J ₂ in formula Ha), 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 Hb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C(O)NH-CH ₂ CH(OH)CH ₂ -in formula Hb), allylsulfonic acid (X = CH ₂ in formula Ha), methallylsulfonic acid (X = CH ₂ in formula Hb). Allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula Ha), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula lib), 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula lib), styrenesulfonic acid (X = C ₆ H ₄ in formula Ha), vinylsulfonic acid (X not present in formula Ha), 3-sulfopropyl acrylate (X = -C(O)NH-CH ₂ CH ₂ CH ₂ -in formula Ha), 3-sulfopropyl methacrylate (X = -C(O)NH-CH ₂ CH ₂ CH ₂ - in formula lib),

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Sulfomethacrylamide (X = -C(O)NH- in formula Mb), sulfomethylmethacrylamide (X = -C(O)NH-CH ₂ - in formula Hb) and water-soluble salts of the acids mentioned.

Other ionic or non-ionic monomers that can be used are, in particular, ethylenically unsaturated compounds. The content of monomers from group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers contained in the second part particularly preferably consist only of monomers from groups i) and ii).

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

i) one or more unsaturated carboxylic acids selected from the group consisting of acrylic acid, methacrylic acid and/or maleic acid

ii) one or more sulfonic acid group-containing monomers of the formulas Ha, Hb and/or lic:

H ₂ C=CH-X-SO ₃ H (Ha),

H ₂ C=C(CHa)-X-SO ₃ H (lib),

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

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 J ₂ and X represents an optionally present spacer group selected from -(CH ₂ J _n with η = O 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 other ionic or non-ionic monomers.

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

For example, a RM according to the invention is preferred which is characterized in that the second part contains one or more copolymers which contain structural units of the formula III

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

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in which m and ρ each represent a whole natural number between 1 and 2000 and Y represents a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y represents -O-(CH ₂ ) _n - with η = 0 to 4, -O-(CeH ₄ )-, -NH-C(CH ₃ ) ₂ - or NH-CH(CH ₂ CH ₃ )- being preferred.

These polymers are produced by copolymerizing acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the second part of the cleaning agents according to the invention is also preferred and is characterized in that one or more copolymers are used which contain structural units of the formula IV

-[CH ₂ -C(CH ₃ )COOH] _m -[CH ₂ -CHC(O)-Y-SO3H]p- (IV),

in which m and ρ each represent a whole natural number between 1 and 2000 and Y represents a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y represents -O-(CH ₂ ) _n - with η = 0 to 4, -O-(C ₆ H ₄ )-, -NH-C(CH ₃ J ₂ - or NH-CH(CH ₂ CH ₃ )- being preferred.

In a completely analogous manner, acrylic acid and/or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, whereby the structural units in the molecule are changed. Thus, cleaning agents according to the invention are preferred whose second part contains one or more copolymers containing structural units of the formula V

-[CH ₂ -CHCOOH] _m -[CH ₂ -C(CH ₃ )C(O)-Y-SO ₃ HJp- (V),

in which m and ρ each represent a whole natural number between 1 and 2000 and Y represents a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y represents -O-(CH ₂ ) _n - with η = O to 4, -O-(C ₆ H ₄ )-, -NH-C(CH ₃ ) ₂ - or NH-CH(CH ₂ CH ₃ )- being preferred, is 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 which comprise structural units of the formula VI

-[CH ₂ -C(CH ₃ )COOH] _1n -[CH ₂ -C(CH ₃ )C(O)-Y-SO ₃ H]P- (Vl) ₁

H4753DE:U13

in which m and ρ each represent a whole natural number between 1 and 2000 and Y represents a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y represents -O-(CH ₂ ) _n - with η = 0 to 4, -O-(C ₆ H ₄ )-, -NH-C(CH ₃ J ₂ - or NH-CH(CH ₂ CH ₃ )- being 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). In this way, preferred cleaning agents according to the invention are obtained, which are characterized in that one or more copolymers are contained in the second part, the structural units of the formula VII

-[HOOCCH-CHCOOH] _n I-[CH ₂ -CHC(O)-Y-SO ₃ H]P- (VII),

in which m and ρ each represent a whole natural number between 1 and 2000 and Y represents a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y represents -O-(CH ₂ ) _n - with η = 0 to 4, -O-(C ₆ H ₄ )-, -NH-C(CH ₃ ) ₂ - or NH-CH(CH ₂ CH ₃ )- being preferred, and to cleaning agents which are characterized in that the second part contains one or more copolymers which comprise structural units of the formula VIII

-[HOOCCH-CHCOOH] _m -[CH ₂ -C(CH3)C(O)OY-SO3H] _p - (VIII),

in which m and ρ each represent a whole natural number between 1 and 2000 and Y represents a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, with spacer groups in which Y represents -O-(CH ₂ J _n - with η = 0 to 4, -O-(C ₆ H ₄ )-, -NH-C(CH ₃ J ₂ - or NH-CH(CH ₂ CH ₃ )- being preferred.

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

The monomer distribution in the copolymers contained in the second part according to the invention is preferably, for copolymers which contain only monomers from groups i) and ii),

H4753DE:U14

because 5 to 95 wt.% i) or ii), particularly preferably 50 to 90 wt.% monomer from group i) and 10 to 50 wt.% monomer from group ii), each based on the polymer.

Among terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred.

The molecular weight of the polymers contained in the second part according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agents are characterized in that the copolymers have molecular weights of from 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 additional benefit of being able to dispense with the dosing of regeneration salt, the products according to the invention also make the additional dosing of a rinse aid superfluous. The rinse effect can be significantly improved if the cleaning agents according to the invention contain surfactants, in particular non-ionic surfactants. The surfactants can be contained in the first part (the "base composition") and enter the rinse cycle via lye carryover or other phenomena, or they can be part of the second part, which, due to the coating, essentially only develops its effect in the rinse cycle of the dishwasher.

In the context of the present invention, cleaning agents are preferred in which the second part additionally contains 1 to 50% by weight, preferably 2.5 to 45% by weight and in particular 5 to 40% by weight of non-ionic surfactant(s), the weight data referring to the second part including the coating.

Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol are preferably used as nonionic surfactants, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 C atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 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 .,,-alcohol with 7 EO, C ₁₃ . _{C 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 averages which may be a whole or a fractional number for a specific product.

* &iacgr;&idigr; . &iacgr; I ·

H4753DE:U15

Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO(G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

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

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

^R1

R-CO-N-[Z] (IX)

in which RCO stands for an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ stands for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] stands for a linear or branched polyhydroxyalkyl radical 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.

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

H4753DE:U 16 " '"' ' "

^R1-0 - ^R2

R-CO-N-[Z] (X)

in which 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^-alkyl or phenyl radicals being preferred and [Z] is a linear polytihydroxalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

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

Low-foaming nonionic surfactants are used as preferred surfactants. The cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of alkoxylated alcohols. In particular, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 C atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -U-alcohols with 3 EO or 4 EO, C ₁₁ -alcohols with 7 EO, C ₁₃ . _{C 15} -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -ie-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 -i8-alcohol with 5 EO. The degrees of ethoxylation stated represent statistical averages which can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particularly preferred are cleaning agents according to the invention which contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred cleaning agents are characterized in that they contain nonionic surfactant(s) in the second part with a melting point above 20 ^° C, preferably above 25°C, particularly preferably between 25 and 60 ^° C and in particular between 26.6 and 43.3 ^° C.

H4753DE:U17

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

Nonionic surfactants that are preferably used as solids at room temperature come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant which has been obtained from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.

A particularly preferred nonionic surfactant which is solid at room temperature and is used is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C ₁₆ -20 alcohol), preferably a C 16 -alcohol, and at least 12 moles, preferably at least 15 moles and in particular 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) obtained from C ₆ -2o-monohydroxyalkanols or C 6 -2o-alkylphenols or C ₁₆ -2o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol.

The nonionic surfactant which is solid at room temperature preferably also has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred rinse aids are therefore

H4753DE:U18

characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.

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

Non-ionic surfactants that can be used with particular advantage 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 OJy[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 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and &khgr; is between 0.5 and 1.5 and y is at least 15.

Other preferred nonionic surfactants are the end-capped poly(oxyalkylated) 4fe nonionic surfactants of the formula

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, isopropyl, η-butyl, 2-butyl or 2-methyl-2-butyl radical, &khgr; are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value &khgr; is > 2, each R ³ in the above formula can 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 C atoms being particularly preferred. For the radical R ^{3 ,} H, -CH ₃ or -CH ₂ CH ₃ are particularly preferred. Particularly preferred values for &khgr; are in the range from 1 to 20, in particular from 6 to 15.

H4753DE:U19

As described above, each R ³ in the above formula can be different if &khgr; 2 is 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if &khgr; 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 can be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for &khgr; has been chosen here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (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 can be

R ¹ O[CH ₂ CH(R ³ JO] _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 &khgr; stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred surfactants are those in which the radicals R ¹ and R ² have 9 to 14 C atoms, R ³ stands for H and &khgr; assumes values from 6 to 15.

Summarising the last-mentioned statements, cleaning agents according to the invention are preferred which contain end-capped poly(oxyalkylated) nonionic surfactants of the formula

R ¹ O[CH ₂ CH(R ³ P] _x [CH ₂ ]KCH(OH)[CH ₂ ]JOR ²

in which R' and R ² represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ³ represents H or a methyl, ethyl, n-propyl, isopropyl, η-butyl, 2-butyl or 2-methyl-2-butyl radical, &khgr; represents values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5, wherein surfactants of the type

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

in which &khgr; stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Of course, the surfactants mentioned above can also be contained in the first part of the cleaning agents according to the invention. It is also possible that the

H 4753 DE:U 20

the second part is formulated surfactant-free and the surfactants mentioned above are all present in the first part (see below).

In addition to one or more substances from the groups of builders, acidifiers, chelating agents or deposit-inhibiting polymers and the optionally contained surfactants, the second part can contain other common ingredients of cleaning agents. In particular, a content of bleaching agents and/or bleach activators and/or bleach catalysts and/or enzymes and/or corrosion inhibitors (silver protection agents) and/or dyes and/or fragrances in the second part can bring further application-related advantages.

According to the invention, the second part has a suitable coating which causes the ingredients of the second part to be released and to develop their effect essentially only in the final rinse cycle of the dishwasher. Such a coating, often referred to in modern German as "coating", usually has thicknesses of 10 to 1000 μm, depending on the material selected, with layer thicknesses between 20 and 800 μm, in particular between 50 and 400 μm, being preferred within the scope of the present invention.

The coating can be of uniform composition, e.g. consist of a single material, but it is also possible for multi-layer coatings to be used, with two-, three- or four-layer coatings being preferred within the scope of the present invention.

The coating protects the second part from premature dissolution in the main cleaning cycle and any intermediate rinse cycles. In the final rinse cycle, the coating must be quickly dissolved or otherwise destroyed in order to release the ingredients of the second part. Several release mechanisms can be considered here, which use the changed properties of the coating materials depending on varying external conditions. In this way, the conditions prevailing in the dishwasher, which are different in the main cleaning and final rinse cycles, are used to transfer the second part to the final rinse cycle. By changing the external conditions, the coating "switches" and releases the second part. Temperature-controlled and/or enzyme-controlled and/or redox-controlled and/or electrolyte-controlled and/or pH-controlled systems are suitable as "switch ^1" .

Temperature-controlled systems can, for example, consist of coating the second part with a substance that only melts above a certain temperature and is then washed away, or only becomes soluble in the application medium above a certain temperature. Such coating substances, which are described in detail below, are, for example, paraffins.

H 4753 DE:U 21

Another mechanism for temperature control can be implemented using substances that dissolve better at low temperatures than at high temperatures. Such substances with a so-called "low critical solution temperature" are referred to as LCST substances or substances with a lower critical separation temperature. In order to prevent these substances from dissolving when water first enters the machine (before the main cleaning cycle), they must be provided with an additional coating that dissolves or is otherwise destroyed during the main cleaning cycle. At the hot temperatures of the cleaning cycle, the LCST substance protects the second part, while at the low temperatures of the rinse cycle it dissolves and releases the ingredients.

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

The cleaning agent can be used particularly advantageously in mechanical processes where the active ingredient is to be released in a rinse cycle after the cleaning step. Examples include the mechanical cleaning of dishes in both the home and the commercial sector. Due to the packaging according to the invention, the active ingredients remain at least partially unchanged after heat treatment in a liquid medium, e.g. after the main rinse cycle, and the active ingredient is only released after cooling following the heat treatment, i.e. in the rinse cycle.

According to the preferred embodiment of the present invention, the second part is coated with an LCST substance. These substances are usually polymers. Depending on the application conditions, 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. Cleaning agents in which the lower critical demixing temperature of the LCST polymer is between 20 ^° C and 90 ^° C are preferred.

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 cleaning agents which are characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances are preferred according to the invention.

H4753DE.U 22

Examples of alkylated and/or hydroxyalkylated polysaccharides are methylhydroxypropylmethylcellulose (MHPC), ethyl(hydroxyethyl)cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydroxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose (PC) and mixtures thereof, with carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxypropylcellulose as well as the alkali salts of CMC and the slightly ethoxylated MC or mixtures of the foregoing being preferred.

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethyl cellulose (CMC). Other polymers that show a lower critical demixing temperature in water and that 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-mentioned (co)polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide/propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly(VATGW), 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 substances. By such additives or by the degree of cross-linking of the polymers, the LCST (lower critical separation temperature) can be modified accordingly.

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

H 4753 DE.U 23

The further substance preferably has a melting range which lies between about 35 ^° C and about 75°C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.

The above-mentioned properties are usually fulfilled by so-called waxes. "Waxes" refers to a range of natural or artificially obtained substances that generally melt above 35°C without decomposing and are relatively low-viscosity and non-stringy even just above the melting point. Their consistency and solubility are highly temperature-dependent. Waxes are divided into three groups according to their origin: natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or rump fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

Chemically modified waxes include, for example, hard waxes such as montan ester waxes, sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of substances that meet the above-mentioned requirements with regard to the softening point can also be used as coating materials. Higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), have proven to be suitable synthetic compounds. Synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea), are also suitable. Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerine monostearate palmitate. Shellac, for example Schellack-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as another substance.

Waxes within the scope of the present invention also include, for example, so-called wax alcohols. Wax alcohols are high molecular weight, water-insoluble fatty alcohols with generally about 22 to 40 carbon atoms. Wax alcohols occur, for example, in the form of wax esters of high molecular weight fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are ügnoceryl alcohol (1-

H 4753 DE.U 24

Tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating can optionally also contain wool wax alcohols, which are triterpenoid and steroid alcohols, for example lanolin, which is available for example under the trade name Argowax® (Pamentier & Co). Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds, can also be used at least partially as a component of the coating within the scope of the present invention.

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

All water-soluble, water-dispersible and water-insoluble polymers which have a melting point above the lower critical demixing temperature of the LCST polymer used according to the invention or which are soluble above this temperature are also suitable as coating materials. Suitable polymers are polyethylene glycols, polyvinyl alcohols, polyacrylic acid and their derivatives which are solid at room temperature. Gelatin has also proven to be suitable.

Sometimes it can be sufficient to protect the LCST polymer layer if it is initially shielded from cold water by a water-soluble coating. This water-soluble coating only needs to have a sufficiently delayed solubility so that the layer is stable for a sufficiently long time. For example, polyalkylene glycols with a preferably higher molecular weight can be used for this.

The second part can be coated with the LCST substance and/or the other material in a manner known per se. The substances can be sprayed on, for example, as a melt or in the form of a solution or dispersion, or the mixture can be immersed in the melt, solution or dispersion or mixed with it in a suitable mixer. Coating in a fluidized bed apparatus is also possible. All processes established in pharmacy and food technology for the production of coated tablets, capsules and particles are suitable for the spraying process. The polymer suspension or solution is either sprayed on discontinuously in small portions, with the particles being transported on a conveyor belt through a liquid curtain and then dried in an air stream, for example, or sprayed continuously with simultaneous drying by the blown-in air stream in fluidized bed, fluidized bed or airborne layer coating devices. The coating process is also conceivable if LCST polymers are added to the coating syrups in sufficiently high concentrations. The second layer is applied in the same way.

In a further preferred embodiment of the invention, the ingredients of the second part are released by an enzyme-controlled coating. In this case, enzymatically degradable

H 4753 DEW 25

re (enzyme-sensitive) materials are used as coating material. The enzymes usually contained in cleaning agents cause a breakdown of the enzyme-sensitive coating material after a certain exposure time and thus a release of the active ingredient(s) contained in the second part of the cleaning agent,

Cellulose derivatives, starch or starch derivatives, partially oxidized starch derivatives, glycerides, certain proteins and mixtures of these are preferred enzymes in cleaning agents. Proteases, amylases and/or lipases are preferred enzymes.

Agents according to the invention can be produced in such a way that conventional solid cleaning agents or components thereof, which are present as granules and/or agglomerates, as pellets, extrudates, tablets or in capsule form, are coated with the enzyme-sensitive material. If such enzyme-containing agents or components for cleaning agents are introduced into cleaning liquors together with conventional cleaning agents, the release of the enclosed active ingredients only occurs after the enzyme-sensitive coating materials have been at least partially degraded.

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

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

Solid agents according to the invention can be produced in such a way that conventional solid cleaning agents or components thereof, which are present as granules and/or agglomerates, as pellets, extrudates, tablets or in capsule form, are coated with the redox-sensitive material.

·

·

H4753DE:U26

If agents containing redox-sensitive materials or components for cleaning agents containing redox-sensitive materials are introduced into cleaning liquors together with conventional cleaning agents, the release of the enclosed active substances only occurs after at least partial oxidative degradation of the redox-sensitive coating materials.

Within the scope of the present invention, a (physico-)chemical switch can also be used which causes an electrolyte-controlled release of active ingredients. The difference in the electrolyte content between the cleaning cycle and the rinsing cycle in automatic dishwashing machines can be exploited here. A further preferred embodiment of the invention therefore relates to a cleaning agent in which the second part is coated with an electrolyte-sensitive substance, the active ingredient(s) of the second part being released as a result of a change in the electrolyte concentration.

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 during application. The following classes of materials can be considered as electrolyte-sensitive materials :

a) Cellulose derivatives, e.g. methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, carboxymethylcellulose with various degrees of substitution

b) Polyvinyl alcohols with different degrees of saponification and molecular weights

c) Polyelectrolytes e.g. polyacrylates and particularly preferably polystyrene sulfonate

These materials have good solubility in pure water or with low ionic load, but become difficult or insoluble in the presence of higher salt concentrations. The salt concentration required to make the substances insoluble varies. With these "switches" too , it may be necessary to apply a second coating that prevents the first coating layer from dissolving with pure water at the start of the cleaning program .

If we look at the process of machine dishwashing, the pH value of the washing solution is around 10 during cleaning . Accordingly, the main products for machine dishwashing available on the market contain alkali. In particular, in the vast majority of machine dishwashers and their various cleaning programs, the washing solution is pumped out after the cleaning cycle and replaced with fresh water. This leads to a drop in the pH value of around 1 to 2 pH units, regardless of the temperature of the water . The exact value of the pH drop depends on the amount of residual lye remaining in the machine, which is around 2%.

H4753DE:U27

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

In this embodiment of the invention, (physico-)chemical switches are used as coating material for the second part which experience a change in the physico-chemical properties when the pH of the application liquor changes. In particular, it is preferred that substances are used as (physico-)chemical switches which have an increased solubility in water as a result of a change in the pH occurring in the application liquor. Alternatively or additionally, switch substances are preferred which show a change, in particular a decrease, in the diffusion density when the pH of the application liquor changes accordingly. Advantageous agents are those, in particular automatic dishwashing detergents, which contain a substance as a (physico-)chemical switch which undergoes a change in its physico-chemical properties when the pH value in the application liquor changes in the range from 11 to 6, preferably from 10 to 7, and which preferably has an increased solubility in water and/or a decrease in diffusion density when the pH value decreases in the range from 10 to 7, in particular from 10 to 8.

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

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

Polymers with pH-dependent solubility are particularly well-known in the pharmaceutical industry. Here, for example, acid-insoluble polymers are used to give tablets a coating that is resistant to gastric juice but soluble in intestinal juice. Such acid-insoluble polymers are usually based on derivatives of polyacrylic acid, which is present in an undissociated and thus insoluble form in the acidic range, but is neutralized in the alkaline range, typically at pH 8, and dissolves as a polyanion.

Examples of the reverse case - soluble in the acidic range, insoluble in the alkaline range - are also known in the state of the art. These substances, in which the polymer molecules usually carry amino-substituted side chains, are used, for example, to produce gastric juice-soluble tablets.

H4753DE:U28

Coatings are used. They usually dissolve at pH values below 5. Polymers in which the solubility change from soluble to insoluble occurs at higher pH values are not known from the pharmaceutical industry, since these pH values have no physiological significance.

Particularly preferred suitable substances are basic (co)polymers which have amino groups or aminoalkyl groups. 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®).

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

In a further embodiment of the present invention, polymers are therefore used whose water solubility changes between pH 6 and 7 and which are less soluble at higher pH values than at lower ones. 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 pH values, which makes the polymer soluble. At higher pH values, the molecule changes to the uncharged state and becomes insoluble. As a rule, the transition - hereinafter referred to as the "switching point", depending on the pK _B value of the basic groups and their density along the polymer chain, takes place in the range of acidic pH values. The present invention therefore also relates to a polymer in which the switching point is in a range between pH 6 and 7.

This shift of the switching point is achieved 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 occurs in the range of higher pH values. It must therefore be possible to influence the solubility decisively through this small change in the charge state. The polymer must therefore have exactly such hydrophilicity that it is insoluble in a completely uncharged state, but soluble with even a small charge.

The following methods can be used to adjust the hydrophilicity:
• Copolymerization of a monomer with a basic function with a more hydrophilic monomer. The switching point is influenced by the incorporation ratio of the respective comonomers.

H4753DE:U29 * **"

• Hydrophilization of the polymer carrying basic groups 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 with different pKg values. The switching point can be influenced by the ratio of both groups and the resulting hydrophilicity of the molecule.

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

It is not necessary for the polymer of the coating of the second part to dissolve completely under the appropriate pH conditions to release the active ingredient. Rather, it is sufficient if, for example, the permeability of a polymer film changes and, for example, the penetration of water into the active ingredient formulation is made possible. This means that a secondary effect, e.g. the activation of an effervescent system or the swelling of a water-swellable disintegrant, which are particularly well known from the pharmaceutical industry, can ensure the complete release of the active ingredient.

In a further preferred embodiment of the invention, so-called pH shift boosters are used in addition to the switches mentioned above. This can at least largely prevent residues, which consist in particular of the pH-dependent soluble substance itself, from being found after the final rinse cycle. Suitable pH shift boosters in the sense of this invention are all substances and formulations that are able to increase the extent of the pH shift either locally, i.e. in the direct vicinity of the pH shift-sensitive substance used, or also generally, i.e. in the entire rinsing liquor. 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, alkylsulfuric 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 of the invention, it is also possible to add the pH shift booster to the machine externally either after the end of the cleaning cycle or at the beginning of the rinsing cycle or to release it through a special delivery system (by coating with a slowly dissolving coating agent) or through diffusion from a matrix material.

As already mentioned, the coating of the second part of the cleaning agents according to the invention can also consist of several layers. In some cases, this is necessary in order to protect certain coating layers during the main cleaning process with a second layer (see above), but in some cases an undercoating may also be necessary in order to create a well-adhering and uniform substrate for the functional coating. Of course, the

H4753DE:U30"

A combination of an undercoating with a functional coating and a further protective layer is conceivable. In this embodiment, the second part has a three-layer coating. Cleaning agents in which the coating of the second part consists of several coating layers, preferably 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 that may protect the "functional coating".

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

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

Carrageenan is an extract from North Atlantic red algae, which belongs to the Floridea family and is named after the Irish coastal town of Carragheen. It is formed and structured similarly to agar. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with a molecular weight of 100,000-800,000 and a sulfate content of around 25%, which is very easily soluble in warm water. Carrageenan is made up of three main components: the yellow-forming /-fraction consists of D-galactose-4-sulfate and 3,6-anhydro-aD-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (in contrast, agar contains 3,6-anhydro-ot-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 easily soluble in cold water. The i-carrageenan, which is made up 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 carrageenan types are also designated with Greek letters, α, β, γ, μ, ν, σ , ω. The type of cations present (K, NH ₄ , Na, Mg, Ca) also influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as coating materials within the scope of the present invention are also called carrageenans.

The guar, also called guar flour, which can be used as a coating material in the context of the present invention, is a grey-white powder which is obtained by grinding the endosperm of the

H4753DE.U 31

It is obtained from the guar bean (Cyamopsis tetragonobolus), which is endemic to India and Pakistan and is now also cultivated in other countries, e.g. in the south of the USA, and belongs to the legume family. The main component of guar is guaran (guar gum, Cyamopsis gum), which makes up up to 85% by weight of the dry substance; minor components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, ie a polysaccharide whose linear chain is made up of unsubstituted (see formula XI) and mannose units substituted in the C6 position with a galactose residue (see formula (XII)) in a ß-D-(1-»4) linkage.

_? ^HCH2OH

Galactose ► \~^~~^°\

&EEgr;&thetas;&Lgr;-^"*^&Lgr;

HOI
CH ₂ OH O-CH ₂

-* Mannose ► &EEgr;&Ogr;~\--^ ^-- '^^&Lgr;

3 ²

Xl XII

The ratio of XI:XII is approximately 2:1; contrary to original assumptions, the Xll units are not arranged strictly alternating, but in pairs or triplets in the polygalactomannan molecule. Information on the molar mass of guaran varies significantly, with values of approximately 2.2-10 ⁵ -2.2 10 ⁵ g/mol depending on the degree of purity of the polysaccharide - the high value was determined using a highly purified product - and corresponds to approximately 1350-13500 sugar units per macromolecule. Guaran is insoluble in most organic solvents.

Pectins, which can also be used as coating materials, are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. Pectins essentially consist of chains of 1,4-a-glycoside-linked galacturonic acid units, whose acid groups are 20-80% esterified with methanol, whereby a distinction is made between high-esterification (>50%) and low-esterification pectins (<50%). Pectins have a pleated sheet structure and are thus in the middle of starch and cellulose molecules. Their macromolecules also contain some glucose, galactose, xylose and arabinose and have slightly acidic properties.

H 4753 DE.-U

OH

OH

Fruit pectin contains 95% galacturonic acid, beet pectin up to 85%. The molecular weights of the various pectins vary between 10,000 and 500,000. The structural properties also depend heavily on the degree of polymerization; for example, fruit pectins form asbestos-like fibers when dried, whereas flax pectins form fine, granular powders.

The pectins are produced by extraction with diluted acids mainly from the inner parts of citrus fruit peels, fruit residues or sugar beet pulp.

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

H 4753 DE.-U

H ₃ CCO-CH ₂

M ⁺ COO"

Y 0 0

= Na,K,1/2 Ca

Basic unit of xanthan

Celluloses and their derivatives are also suitable as coating materials. Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose derivatives that can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based coating materials within the scope of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But celluloses in which the hydroxy groups have been replaced by functional groups that are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali cellulose, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses.

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

Suitable non-ionic organic coating materials are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by conventional methods, for example acid- or enzyme-catalyzed methods. Preferably, the hydrolysis products are those with average molar masses of 1 to 2000 mol.

H4753DE:U34 "" "

masses in the range from 400 to 500,000 g/mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, where DE is a common measure of the reducing effect of a polysaccharide in comparison to dextrose, which has a DE of 100. Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g/mol are suitable.

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

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

Among proteins and modified proteins, gelatine is of outstanding importance as a coating material. Gelatine is a polypeptide (molar mass: approx. 15,000->250,000 g/mol) that is primarily obtained by hydrolyzing the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatine largely corresponds to that of the collagen from which it was obtained and varies depending on its origin. The use of gelatine as a water-soluble coating material is extremely widespread, particularly in the pharmaceutical industry in the form of hard or soft gelatine capsules.

H 4753 DE:U 35

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

a) water-soluble non-ionic polymers from the group of

al) 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/alkylaminoalkylmethacrylic acid copolymers b5) Alkylacrylamide/methacrylic acid/alkylaminoalkymethacrylic acid copolymers b6) Alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid

Copolymers
b7) Alkylacrylamide/alkymethacrylate/alkylaminoethyl methacrylate/alkyl methacrylate-

Copolymers
b8) Copolymers of

b8i) unsaturated carboxylic acids

b8ii) cationically derivatized unsaturated carboxylic acids

b8iii) optionally further ionic or non-ionic monomers

c) water-soluble zwitterionic polymers from the group of

el) Acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali

and ammonium salts
c2) Acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their

Alkali and ammonium salts
c3) Methacroylethyl betaine/methacrylate copolymers

d) water-soluble anionic polymers from the group of

H 4753 DE.Ü 36

d1) Vinyl acetate/crotonic acid copolymers

d2) Vinylpyrrolidone/vinylacrylate copolymers

d3) Acrylic acid/ethyl acrylate/N-tert.butylacrylamide-teφolymers

d4) Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in mixtures, copolymerised 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 monomer of the non-ionic type,

d5ii) at least one monomer of the ionic type,

d5iii) of polyethylene glycol and
d5iv) a networked

d6) copolymers obtained by copolymerisation 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 .ie-alcohols

d7) Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
d8) Tetra- and pentapolymers of

d8i) Crotonic acid or allyloxyacetic acid

d8ii) vinyl acetate or vinyl propionate

d8iii) branched AIIyI 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

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 monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of

el) quaternized cellulose derivatives
e2) Polysiloxanes with quaternary groups
e3) cationic guar derivatives

e4) polymeric dimethyldialiylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid

H4753DE:U37

e5) Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate

e6) Vinylpyrrolidone-methoimidazolinium chloride copolymers
e7) quaternized polyvinyl alcohol
e8) Polymers listed under the INCI names Polyquatemium 2, Polyquatemium 17, Polyquatemium 18 and Polyquatemium 27.

Water-soluble polymers within the meaning of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.

The outer coatings of the second part of the cleaning agents according to the invention can be made from individual polymers mentioned above, but mixtures or multi-layer structures made from the polymers can also be used. The polymers are described in more detail below.

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

Polyvinylpyrrolidones, such as those sold under the name Luviskol® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers within the scope of the invention.

Polyvinylpyrrolidones [PoIy(I-vinyl-2-pyrrolidinone)], abbreviated PVP, are polymers of the general formula (XIII)

' (XIII),

which are produced by radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization processes using radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only produces products with low molecular weights. Commercially available polyvinylpyrrolidones have molecular weights in the range of approx. 2500-750000 g/mol, which are characterized by the K values and - depending on the K value - have glass transition temperatures of 130-175°. They are offered as white, hygroscopic powders or as aqueous solutions. Polyvinylpyrrolidones are readily soluble in water.

H 4753 DE:U

water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone/vinyl ester copolymers, such as those sold under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone/vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (XIV)

-CH ₂ -CH-

(XIV)

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

The polymerization of vinyl esters is carried out 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

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold, for example, under the trademarks Culminal® and Benecel® (AQUALON).

Cellulose ethers can be described by the general formula (XV),

ROCK

OR ROCH ₂

in R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (Xl) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. CeIIuIo-

&bull;&diams; · t

H4753DE:U39

Cellulose ethers are manufactured industrially by etherifying alkali cellulose (e.g. 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 hydroxy groups of an anhydroglucose unit of the cellulose have reacted with the etherification reagent or how many moles of the etherification reagent have been added to an anhydroglucose unit on average. Hydroxyethyl celluloses are water-soluble from a DS of approx. 0.6 or an MS of approx. 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) or 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in very different degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or the addition of electrolytes.

Polyvinyl alcohols, abbreviated to PVAL, are polymers with the general structure

[-CH ₂ -CH(OH)-J _n
which in small proportions also contain structural units of the type

[-Ch ₂ -CH(OH)-CH(OH)-CH ₂ ]

Since the corresponding monomer, vinyl alcohol, is not stable in free form, polyvinyl alcohols are produced via polymer-analogous reactions by hydrolysis, but in technical terms in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. These technical processes also make it possible to obtain PVALs that contain a predeterminable residual proportion of acetate groups.

Commercially available PVAL (e.g. Mowiol® types from Hoechst) are available as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molecular weights of approx. 20,000-100,000 g/mol) and have different degrees of hydrolysis of 98-99 or 87-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual content of acetyl groups of approx. 1-2 or 11-13 mol%.

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

H4753DE:U40

Other polymers suitable according to the invention are water-soluble amphopolymers. The general term ampho-polymers includes amphoteric polymers, i.e. 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, zwitterionic polymers which contain quaternary ammonium groups and -COO" or -SO ₃ * groups in the molecule, and polymers which contain -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 available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N-(1,1,3,3-tetramethylbutyl)acrylamide and two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically dehydrated unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or non-ionic monomers. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphoteric polymers according to the invention. Other suitable amphoteric polymers are, for example, the octylacrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate^-hydroxypropyl methacrylate copolymers available under the names Amphomer ⁸ and Amphomer® LV-71 (DELFT NATIONAL).

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

Anionic polymers suitable according to the invention include:

Vinyl acetate/crotonic acid copolymers, such as those sold under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).

In addition to monomer units of the above-mentioned formula (X), these polymers also contain monomer units of the general formula (XVI):

[-CH(CH ₃ )-CH(COOH)-] _n (XVI)

Vinylpyrrolidone/vinyl acrylate copolymers, available for example under the trademark Luviflex® (BASF). A preferred polymer is the vinylpyrrolidone/acrylate terpolymer available under the name Luviflex® VBM-35 (BASF).

· · ■

· · i

H4753DE:U41

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 mixtures, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and/or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by polymerization under heat in a homogeneous phase by stirring the polyalkylene glycols into the monomers of vinyl esters, esters of acrylic acid or methacrylic acid in the presence of radical formers.

Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and as esters of acrylic acid or methacrylic acid, those which are obtainable with aliphatic alcohols with a low molecular weight, 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.

Polyethylene glycols and polypropylene glycols are particularly suitable as polyalkylene glycols. Polymers of ethylene glycol corresponding to the general formula XVII

H-(O-CH ₂ -CH ₂ ) _n -OH (XVII)

suffice, where &eegr; can take on values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols, which can lead to confusion. In technical terms, it is common to state the average relative molecular weight after the term "PEG", so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approx. 190 to approx. 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is given a hyphen and the hyphen is followed directly by a number that corresponds to the number &eegr; in the above-mentioned formula V. According to this nomenclature (so-called INC! nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Polyethylene glycols are commercially available under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.

> ·■·■ t » <

H 4753 DE:U 42

Polypropylene glycols (abbreviation PPG) are polymers of propylene glycol, which correspond to the general formula XVIII

H-(O-CH-CH ₂ ) _n -OH (XVIII)

I
_CH3

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

In particular, vinyl acetate copolymers grafted onto polyethylene glycols and 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 monomer of the non-ionic type,
(ii) at least one monomer of the ionic type,
iii) polyethylene glycol and
(iv) a networked

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

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

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucroses with 2 to 5 allyl groups per saccharin molecule.

The grafted and crosslinked copolymers described above are preferably formed from:
i) 5 to 85 wt.% of at least one monomer of the non-ionic type,

H4753DE:U43

ii) 3 to 80 wt.% of at least one ionic type monomer,

iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and

iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of crosslinking agent being determined by the

ratio of the total weights of i), ii) and iii).

by copolymerization of at least one monomer of each of the following three groups
Copolymers obtained:
(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 .i ₈ alcohols

Short-chain carboxylic acids or alcohols are understood to mean those with 1 to 8 carbon atoms, whereby the carbon chains of these compounds can optionally be interrupted by divalent hetero groups such as -O-, -NH-, -S_.

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

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) as well as monomer units of one or more allyl or methallyl esters of the formula XIX:

^{R1 R3}

I I

R^CC(O)-O-CH ₂ -C=CH ₂ (XIX)

_CH3

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-chain or branched C^-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.

The above-mentioned 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 of allyl or methallyl ethers of formula XIV.

Tetra- and pentapolymers from
i) Crotonic acid or allyloxyacetic acid

H4753DE:U44

ii) Vinyl acetate or vinyl propionate

iii) branched allyl or methallyl esters

iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group ethylene,
Vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic
in α-position branched monocarboxylic acid.

Suitable anionic polymers as external coating materials for the second part are particularly polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

Useful organic coating materials include polycarboxylic acids, which can be used in the form of their sodium salts or in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol.

For the purposes of this document, the molar masses given for polymeric polycarboxylates are weight-average molar masses M _w of the respective acid form, which were generally determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molar weight values due to its structural similarity to the polymers examined. These figures differ significantly from the molar weight figures for which polystyrene sulfonic acids are used as a standard. The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular masses of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their relative molecular mass, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.

H 4753 DE:U 45

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

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

Other preferred coating materials are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable coating materials are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and/or glucoheptonic acid.

Other polymers that can preferably be used as coating materials are cationic polymers. Among the cationic polymers, permanently cationic polymers are preferred. According to the invention, "permanently cationic" refers to polymers that have a cationic group regardless of the pH value of the agent (i.e. both the coating layer and the rest of the cleaning agent molded body). These are generally polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example,

quaternized cellulose derivatives, such as those commercially available under the names Celquat® and Polymer JR ^S. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 Emulsion (containing a hydroxyl-amino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quatemium-80),

· · * II

H4753DE:U46

Cationic guar derivatives, such as the products sold under the trade names Cosmedia®Guar and Jaguar®,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat®100 (polydimethyldiallylammonium chloride) and Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755.
Vinylpyrrolidone-methoimidazolinium chloride copolymers, such as those sold 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, with detailed information being found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here.

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

Also preferably used as coating materials are carboxylic or dicarboxylic acids, or those with an even number of carbon atoms. Particularly preferred carboxylic or dicarboxylic acids are those with at least 4, preferably with at least 6, particularly preferably with at least 8 and in particular those with 8 to 13 carbon atoms. Particularly preferred dicarboxylic acids are, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and mixtures thereof. But also tetrade-

H4753DE.U 47 "*

canic acid, pentadecanoic acid and thapsic acid are suitable coating materials. Particularly preferred carboxylic acids are those with 12 to 22 carbon atoms, with those with 18 to 22 carbon atoms being particularly preferred. The use of the disintegration aids described above is particularly recommended for acid coating layers, with usual use concentrations for the disintegration aids in the coating layers being 0.1 to 5% by weight, based on the coating layer.

The second part of the cleaning agents according to the invention can be in the form of granules and/or agglomerates, pellets, extrudates, tablets or capsules, with preferred embodiments of the second part being those which have a specific size. Preferred cleaning agents according to the invention are those in which 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. Strictly speaking, the term "diameter" only applies to spherical second parts, since only these have a single diameter. If the second part has a different shape - for example cylindrical, ellipsoidal, cuboid or cube-shaped, etc. - the above information applies to the large (surface) diameter.

As already mentioned, the second part can be produced by all common methods. In the case of bodies preferred within the scope of the present invention, which have 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 , production by casting processes, by sintering, by extrusion, by calendering or by tabletting is preferred. With regard to the ingredients of the second part, cleaning agents in which the second part was produced by a pressing process, in particular tabletting, are particularly preferred.

Regardless of how the second coated part is made up, it can be combined with a first part of any design. The first part can, for example, be a cleaning agent powder or be in the form of a compact molded body. Liquid or gel-like first parts can also be realized with the appropriate design, but are less preferred due to the sedimentation and stability problems of the second parts in such a matrix.

Before describing the options for designing the first part and the finished cleaning agent from the two parts, there follows a description of the ingredients that can be contained in the first part. All of the substances listed below can also be part of the second part in whole or in part.

Builders have already been described above as a possible component of the second part. In preferred embodiments of the present invention, these are also contained in the first part, with cleaning agents being preferred in which the first part contains builders in amounts

·· ·· · ·· &bull; &bull; &bull; · I · *·· &bull; · · ·
» · · &bull;
····

H4753DE:U48

from 1 to 100% by weight, preferably from 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 to 85% by weight, each based on the weight of the first part.

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

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

Non-ionic 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 being in the range of 0.5 to 5% by weight, preferably between 1 and 2% by weight. If formulations are to be provided in which the first part provides the "built-in rinse aid", higher surfactant contents are possible; see below for more information.

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

In addition to the builders, substances from the groups of surfactants (see above), bleaching agents, bleach activators, enzymes, polymers, dyes and fragrances are particularly important ingredients in cleaning agents. Important representatives from the above-mentioned substance classes are described below.

Among the compounds used as bleaching agents that provide H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical

H4753DE:U49

Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with alkyl peroxyacids and aryl peroxyacids being particularly examples. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-Decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(6-aminopercaproic acid) can be used.

Substances which release chlorine or bromine can also be used as bleaching agents in the cleaning agents according to the invention for machine dishwashing. Suitable chlorine 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 their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Preferred cleaning agents according to the invention are those in which the first part contains bleach activators from the groups of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methylmorpholinium acetonitrile methylsulfate (MMA), in amounts of from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5% by weight, in each case based on the weight of the first part.

The bleaching agents mentioned can also be introduced into the machine dishwashing detergents according to the invention, in whole or in part, via the second part, in order to achieve a "post-bleaching" effect in the final rinse cycle.

Bleach activators, which support the effect of the bleaching agents, can be part of both the first and the second part. Known bleach activators are compounds that contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, i.ö-diacetyl^-dioxo-hexahydro-I^.S-triazine DADHT and isatoic anhydride ISA.

H4753DE:U50 **

Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators. Substances which carry O- and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Preference is given to multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, 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 as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be incorporated into the cleaning agents. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methylmorpholinium acetonitrile methylsulfate (MMA), are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the entire agent.

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, particularly preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalUCarbonyO complexes, chlorides of cobalt or manganese, manganese sulfate are used in usual amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the entire agent. However, in special cases more bleach activator can also be used.

H4753DE:U

Other ingredients can also be part of the first or second part. Cleaning agents are preferred in which the first part also contains one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, colorants and/or fragrances in total amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight and in particular 10 to 20% by weight, in each case based on the weight of the first part.

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

The corrosion inhibitors mentioned can be contained in the first or second part to protect the items being washed or the machine, whereby silver protection agents are particularly important in the field of machine dishwashing. The known substances of the state of the art can be used. In general, silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and/or alkylaminotriazole are particularly preferred. In addition, active chlorine-containing agents are often found in cleaning formulations, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaning agents, organic redox-active compounds containing oxygen and nitrogen are particularly used, such as divalent and trivalent phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preference is given to transition metal salts selected from the group of manganese and/or cobalt salts and/or complexes, particularly preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the items being washed.

Enzymes that can be used in the cleaning agents according to the invention are particularly those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly suitable are those derived from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified

H4753DE:U 52 · ² - *""'"'''"'''""

Enzymatic active substances obtained from variants. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or of protease, amylase and üpase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and/or lipase-containing mixtures or mixtures with lipolytic enzymes are of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

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

Dyes and fragrances can be added to the machine dishwashing detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to the performance. Individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are e.g. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate. Ethers include benzyl ethyl ether, aldehydes include linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, ketones include ionones, a-isomethylionone and methylcedryl ketone, alcohols include anethole, citroneliol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, and hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferred, which together produce an appealing scent. Such perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
The fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers that increase the adhesion of the perfume to the laundry and ensure long-lasting fragrance through a slower fragrance release.

·
■ ·

H4753DE:U53

The textiles are scented. Cyclodextrins, for example, have proven to be effective carrier materials, whereby the cyclodextrin perfume complexes can also be coated with other auxiliary substances. It is also possible to incorporate the fragrances into the second part and this leads to a scent impression when the machine is opened, as the fragrances are only released in the rinse cycle.

It is preferable to separate corrosion inhibitors from bleaching agents, for example by containing substances from one group in the first part and those from the other group in the second part. It is of course also possible to design the first part in multiple phases and to separate the substances from one another within the first part.

Separating the bleaching agents from other ingredients can also be advantageous. Cleaning agents according to the invention in which one part contains bleaching agents while another contains enzymes are also preferred. Cleaning agents in which one part contains bleaching agents while another contains bleach activators are also preferred. Here too, it is of course possible to design the first part in several phases and to separate the substances from one another within the first part.

As already mentioned, the first part can be provided in liquid, gel or pasty form as well as in solid form and in particular in powder form or in the form of a compact shaped body. In an order of increasing preference, cleaning agents according to the invention are preferred in which the first part is a liquid, gel or pasty composition for machine dishwashing. Cleaning agents in which the first part is a particulate composition for machine dishwashing are particularly preferred.

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

This tablet-shaped composition of the first part of the cleaning agents according to the invention is described with the term "base molded body" and, in the context of the present invention, characterizes the molded body produced by tableting processes known per se. In preferred embodiments of the present invention, the base molded body is produced first and the coated second part is applied to or introduced into this base molded body in a further work step. The resulting product is referred to below with the generic term "molded body or "tablet".

The basic molded body can take on any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical,

H4753DE.U 54

Cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and eight-sided prismatic and rhombohedral shapes are preferred. Completely irregular bases such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the basic shaped body has corners and edges, these are preferably rounded. As an additional optical differentiation, a design with rounded corners and beveled ("chamfered") edges is preferred.

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

Such tablets can be made into the finished cleaning agent according to the invention by containing the second coated part in the form of a further layer. Of course, the second part can also have a different shape, for example that of a hemisphere, which is glued to a surface of the base molded body. Since spherical bodies or bodies that are as similar as possible to the shape of a sphere can be coated best, it is preferable to adapt the shape of the first part to the preferred shape of the second part and to provide the first part with a cavity into which the second part is inserted and optionally fixed. Those cleaning agents in which the coated second part has the shape of a further layer, a core or a body glued onto or into the first part ("base tablet") are preferred according to the invention, with cleaning agents in which the first part has (a) cavity(ies) in which the second and optionally further parts are contained being particularly preferred.

The shape of the cavity(ies) can also be freely selected within wide limits. For reasons of process economy, through holes, the openings of which are located on opposite surfaces of the molded bodies, and depressions with an opening on one side of the molded body have proven to be useful. In preferred basic molded bodies, the cavity has the shape of a through hole, the openings of which are located on two opposite molded body surfaces. The shape of such a through hole can be freely selected, with molded bodies being preferred in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections. Completely irregular hole shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the molded bodies, in the case of square holes, those with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The geometrical forms mentioned above can be combined with each other as desired. For example, shaped bodies with rectangular or square bases and circular

·

·

H4753DE.U 55

Round holes can be produced just as well as round molded bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. For reasons of process economy and aesthetic consumer perception, molded bodies with holes are particularly preferred in which the molded body base and the hole cross-section have the same geometric shape, for example molded bodies with a square base and a centrally machined square hole. Ring molded bodies, i.e. circular molded bodies with a circular hole, are particularly preferred.

If the above-mentioned principle of the hole open on two opposite sides of the molded body is reduced to one opening, the result is trough-shaped molded bodies. Cleaning agents according to the invention in which the cavity in the basic molded body has the shape of a trough are also preferred. As with the "hole-shaped bodies", the shaped bodies in this embodiment can also take on any geometric shape, with concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and eight-sided-prismatic and rhombohedral shapes being particularly preferred. Completely irregular bases such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped body has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled ("chamfered") edges is preferred.

The shape of the trough can also be freely selected, with molded bodies being preferred in which at least one trough can take on a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and eight-sided prismatic as well as rhombohedral shape. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the molded bodies, troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The size of the depression or the through hole in comparison to the entire molded body depends on the intended use of the molded body and on the size of the second part that is to be inserted into the cavity. The size of the cavity can vary depending on whether a smaller or larger amount of active substance is to be contained. Regardless of the intended use, cleaning agents are preferred in which the volume ratio of base molded body to cavity is 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.

Similar statements can be made about the surface area of the molded body with the cavity ("base molded body") or the opening area of the cavity on the total surface of the

H4753DE:U56

Molded bodies are preferred in which the area of the opening(s) of the cavity(s) makes up 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 molded body.

Of course, the present invention is not limited to combining a first part with just a second part. In particular in the embodiment of the molded body with a cavity, it is possible and preferred to provide a basic molded body that has several cavities that contain inserted additional parts. These inserted additional parts (hereinafter referred to as "cores") can all be "second parts" in the sense of the present invention, i.e. have a suitable coating and contain the ingredients mentioned. However, it is also possible to produce a molded body with, for example, two cavities ("base molded body" = first part), one cavity of which is filled with a "second part" in the sense of the present invention, while the second cavity contains another core, for example an additional "rinse core" made of surfactant formulated with delayed dissolution or a rapidly dissolving pre-rinse phase made of enzyme and/or bleach formulated with accelerated dissolution. Corresponding cleaning agents in which the first part has at least two cavities, one of which contains the second part, while the other contains a further, functionalized part, are preferred according to the invention.

As already mentioned, according to the invention, molded bodies can also be provided which additionally contain a pre-wash phase. In addition to the example of the three-part tablet with different solubilities mentioned, this embodiment can also be implemented through the form of application: a base tablet which comprises a "second part" in the sense of the present invention can be provided with a notch. The consumer can then break off part of the tablet along the notch and place it in the cutlery basket, while the rest of the tablet is placed in the dosing box. The broken off part, the composition of which can be the same as or different from that of the base tablet, develops its effect in the pre-wash cycle, while the rest is only used in the main wash cycle via the dosing chamber. By choosing an external coating over the functional coating, the "second part" in the sense of the present invention can be part of both the broken off part and the other part of such a tablet.

Of course, the first and second parts (and any other parts) of the cleaning agents according to the invention do not necessarily have to be packaged as a compact molded body, even if this is preferred by the consumer for handling reasons. It is also possible, for example, to produce a first and a second part (and any other parts) separately and to package them together in a bag made of water-soluble film, which is placed in the machine by the consumer. Regardless of the type of packaging,

H4753DE:U57 "" "

tion, the second part unfolds its effect through the coating mainly in the rinse cycle of the dishwasher.

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

Thus, cleaning agents according to the invention are preferred which are characterized in that the content of non-ionic surfactants in the first part is 5 to 25% by weight, based in each case on the first part. In the case of agents according to the invention of this embodiment, the amounts of surfactants remaining in the machine after the main wash cycle and the intermediate wash cycles ensure adequate drainage behavior in the final rinse cycle, so that the water running off the items to be washed does not leave any stains when drying. When using these agents according to the invention, the final rinse cycle does not need to be filled with additional, intentionally added rinse aids.

Powders or granules containing higher surfactants can be produced using conventional granulation processes, for example. For this purpose, carrier materials are placed in a mixer and mixed/granulated with the surfactant(s). If several surfactants are used, these can be added either together or one after the other. If finely divided material is then added ("powdered"), the powder properties of the granules can be significantly improved. The known substances of the prior art can be used as powdering agents; disilicates in particular have proven to be particularly advantageous in the context of the present invention.

However, other finely divided substances such as soda or phosphate, or overdried water glasses, ground ingredients from cleaning agents, etc. are also suitable.

It is particularly preferred within the scope of the present invention to granulate carrier materials such as zeolites, sodium carbonate, sodium tripolyphosphate, maltodextrins, polyvinyl alcohols, starch and/or their derivatives as well as cellulose and/or their derivatives with the addition of the nonionic surfactants identified above as preferred and then to spray them with a sodium silicate solution in a manner known per se in order to achieve at least partial coating of the granulate particles. Instead of the silicate solution, a solution of polyvinyl alcohol can also advantageously be used. After production, the granules can be dried in a manner known per se (advantageously by fluidized bed drying) and optionally additionally "powdered" with finely divided substances such as zeolite and/or silica. The granules with a high surfactant content can then be processed into cleaning agents in a manner known per se with other components (bleaching agents, enzymes, etc.).

H4753DE:U58

The coated second parts can be added directly to these powdered cleaning agents, resulting in a particulate cleaning agent according to the invention. The coated second parts in such machine dishwashing agents according to the invention are formulated by their coating in such a way that they do not dissolve in the main wash cycle (and also in optional pre-wash cycles) or only dissolve to a minor extent. This ensures that the active substances are only released in the final rinse cycle and develop their effect there. In addition to this chemical formulation, depending on the type of dishwasher, physical formulation is required so that the coated second parts are not pumped out when the water in the machine is changed and are therefore no longer available for the final rinse cycle. Common household dishwashers contain a sieve insert in front of the drain pump, which pumps the water or cleaning solution out of the machine after the individual cleaning cycles, which is intended to prevent the pump from becoming clogged with dirt residues. If heavily soiled dishes are washed by the consumer, this sieve insert must be cleaned regularly, which is no problem due to the easy accessibility and removal. The coated second parts in the cleaning agents according to the invention are now preferably designed in terms of their size and shape so that they do not pass through the sieve insert of the dishwasher even after the cleaning cycle, i.e. after exposure to movement in the machine and the cleaning solution. In this way, it is ensured that coated second parts are in the dishwasher in the final rinse cycle, which release the active substance(s) under the influence of the water flowing into the final rinse cycle and bring about the desired final rinse effect. Machine dishwashing agents preferred within the scope of the present invention are characterized in that the coated second parts have particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm.

In the dishwashing agents according to the invention, the coated second parts with the above-mentioned sizes can protrude from the matrix of the other particulate ingredients, but the other particles can also have sizes that are in the above-mentioned range, so that overall a cleaning agent is formulated that consists of large cleaning agent particles and coated second parts. In particular, if the coated second parts are colored, for example have a red, blue, green or yellow color, it is advantageous for the appearance of the product, i.e. the entire cleaning agent, if the coated second parts are visibly larger than the matrix of the particles of the other ingredients of the cleaning agent. Here, machine dishwashing agents according to the invention are preferred which (without taking into account the coated second parts) have particle sizes between 200 and 3000 pm, preferably between 300 and 2500 pm and in particular between 400 and 2000 pm.

H 4753 DE:U 59

The visual appeal of such compositions can be increased not only by coloring the coated second parts but also by contrasting coloring of the powder matrix or by the shape of the coated second parts. Since technically uncomplicated processes can be used to manufacture the coated second parts, it is easy to offer them in a wide variety of shapes. In addition to the particle shape, which is almost spherical, cylindrical or cube-shaped particles can be produced and used. Other geometric shapes can also be realized. Special product designs can contain star-shaped rinse aid particles, for example. Discs or shapes that show plants and animal bodies as a base, for example a tree, flower, blossom, sheep, fish, etc., can also be produced without any problems. Interesting visual stimuli can also be created in this way by producing the coated second parts in the shape of a stylized glass in order to visually emphasize the rinse aid effect in the product. There are no limits to the imagination here.

If the cleaning agents according to the invention are formulated as a powder mixture, then on the one hand partial demixing can occur when the package is subjected to vibration - particularly when the sizes of the coated second parts and the cleaning agent matrix differ greatly - and on the other hand the dosage can be different in two consecutive cleaning cycles, since the consumer does not always necessarily dose the same amount of cleaning agent and coated second parts. If it is desired to always use the same amount per cleaning cycle, this can be achieved by packaging the agents according to the invention in bags made of water-soluble film, as is familiar to those skilled in the art. Particulate automatic dishwashing agents in which a dosage unit is welded into a bag made of water-soluble film are also the subject of the present invention.

As a result, the consumer only has to place one bag, which contains, for example, a cleaning agent powder and several optically prominent coated second parts, into the dosing compartment of his dishwasher. This embodiment of the present invention is therefore a visually attractive alternative to conventional cleaning agent tablets.

The above-described desired retention of the coated second parts in the machine even when changing the water can be achieved not only by increasing the size of the rinse aid particles mentioned above but also by reducing the size of the holes in the sieve insert. In this way, machine dishwashing detergents can be formulated that have a uniform average particle size that is smaller than, for example, 4 to 12 mm. For this purpose, a sieve insert is added to the product according to the invention, in which the coated second parts also have smaller particle sizes, which replaces or covers the insert in the machine. A further subject of the present invention is therefore a kit of parts that contains an inventive

&iacgr;_# ·* *■

H4753DE:U60

powdered automatic dishwashing detergent according to the invention and a sieve insert for household dishwashers.

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

To prevent the enclosed sieve insert from becoming clogged with dirt residue, the mesh width or hole size should not be too small. In this case, kits of parts according to the invention are preferred, in which the mesh width or hole size of the sieve insert is 1 to 4 mm and the coated second parts are larger than this mesh width or hole size of the sieve insert.

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

The cleaning agents according to the invention with a high surfactant content in the first part can also be produced in the form of molded bodies. In the simplest case, this is done by tabletting the above-mentioned powdered cleaning agents. The coated second part can then be glued onto the molded body later, as already described above, or glued or inserted into a prepared cavity of the base molded body.

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

H4753DE:U61

Preferred two-phase base molded bodies contain, for example, a phase which, in addition to up to 30, preferably up to 20 and in particular up to 15% by weight of surfactants (based on the phase), contains phosphate, sodium carbonate, silicate and bleach, while a second phase contains enzymes, bleach activators, silver protective agents and dyes as well as up to 20, preferably up to 10 and in particular up to 5% by weight (based on the phase) of surfactant. Such two-phase molded bodies can then be combined with the coated second part and produce cleaning agents according to the invention in tablet form.

Pressing such surfactant-rich powders into molded bodies can lead to technical difficulties, as these powders tend to clump due to the high surfactant content and/or can be difficult to pour. In addition, the surfactant can be released ("squeezed out") under the pressure of the pressing process, which leads to caking of the stamp. To solve such problems that may arise, common solutions from the state of the art are available, with the use of rotating stamps being particularly important.

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

Another possibility is to arrange the surfactant-rich premix in the middle of a three-layer tablet. The upper and lower layers can be formulated in such a way that caking problems do not occur.

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

Another object of the present invention is a process for producing cleaning agents for machine dishwashing, which comprises the steps

A) Manufacture of a body containing one or more substances from the group of builders, acidifiers, chelating agents or scale-inhibiting polymers,

B) coating the body produced in step A),

H 4753 DE:U 62

C) Association of the coated body with a composition which exerts its effect in the

essentially unfolds in the main cleaning cycle of the dishwasher includes.

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

As already mentioned, the second part can be produced by casting, extrusion, granulation, extrusion, pelletization, sintering, foaming, etc. Particularly preferred as second parts are tableted products, which can be coated particularly well due to their compact structure when in a suitable shape. Processes according to the invention in which production in step A) takes place by tabletting are therefore particularly preferred.

The tabletting of the "second part" in step A) proceeds analogously to the tabletting of a base molding as an option for step C), whereby it has proven advantageous if the premix pressed into " second parts" or base moldings satisfies certain physical criteria . Preferred processes are characterized, for example, in that particulate premixes to be pressed have a bulk density of at least 500 g/l, preferably at least 600 g/l and in particular at least 700 g/l .

The particle size of the premixture pressed into "second parts" or basic moldings preferably also satisfies certain criteria: Processes in which particulate premixtures have particle sizes between 100 and 2000 pm, preferably between 200 and 1800 pm, particularly preferably between 400 and 1600 pm and in particular between 600 and 1400 pm, are preferred according to the invention. A further narrowed particle size in the premixtures to be pressed can be set to achieve advantageous molding properties. In preferred variants of the process according to the invention, particulate premixtures to be pressed have a particle size distribution in which less than 10% by weight, preferably less than 7.5 % by weight and in particular less than 5% by weight of the particles are larger than 1600 pm or smaller than 200 pm. Narrower particle size distributions are further preferred. Particularly advantageous process variants are characterized in that the particulate premixtures to be pressed have a Particle size distribution in which more than 30 wt.%, preferably more than 40 wt.% and in particular more than 50 wt. % of the particles have a particle size between 600 and 1000 pm.

When carrying out tableting , the preferred method according to the invention is not limited to merely pressing a particulate premix into a shaped body. Rather , this process step can be carried out - particularly in the production of basic shaped bodies.

H4753DE:U63

pern, see above - can also be expanded to include producing multi-layered moldings in a manner known per se by preparing two or more premixes which are pressed together. The premix added first is lightly pre-pressed to obtain a smooth upper side running parallel to the bottom of the molding, and after the second premix has been added, it is finally pressed to form the finished molding. In the case of three- or multi-layered moldings, a further pre-pressing takes place after each premix addition, before the molding is finally pressed after the last premix is added. Preferably, the cavity in the base molding described above is a depression, so that preferred embodiments of the first method according to the invention are characterized in that multi-layered moldings which have a depression are produced in a manner known per se by pressing several different particulate premixes together.

The molded bodies are first produced by dry mixing the components, which can be fully or partially pre-granulated, and then shaping them, in particular pressing them into tablets, using conventional methods. To produce the molded bodies according to the invention, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, which is referred to below as tableting, is divided into four stages: dosing, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, whereby the filling quantity and thus the weight and shape of the resulting molded body are determined by the position of the lower punch and the shape of the pressing tool. Consistent dosing even with high molded body throughputs is preferably achieved by volumetric dosing of the premix. As the tabletting process continues, the upper punch touches the premix and continues to descend towards the lower punch. During this compaction, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches continuously decreases. From a certain position of the upper punch (and thus from a certain pressure on the premix), plastic deformation begins, during which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and at even higher pressures the premix sinters. As the pressing speed increases, i.e. as the throughput increases, the phase of elastic deformation is shortened more and more, so that the resulting molded bodies can have more or less large cavities. In the last step of tabletting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point, only the weight of the molded body is finally determined, since the pressed bodies can still change their shape and size due to physical processes (re-stretching, crystallographic effects, cooling, etc.).

'V

H4753DE:U64

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only the upper punch is used to build up pressure, but the lower punch also moves towards the upper punch during the pressing process, while the upper punch presses downwards. For small production quantities, eccentric tablet presses are preferably used, in which the punch(s) are attached to an eccentric disk, which in turn is mounted on an axis with a certain rotational speed. The movement of these press punches is comparable to the operation of a conventional four-stroke engine. Compression can be carried out with an upper and lower punch, but several punches can also be attached to an eccentric disk, with the number of die holes increased accordingly. The throughput of eccentric presses varies depending on the type, from a few hundred to a maximum of 3000 tablets per hour.

For higher throughputs, rotary tablet presses are chosen in which a large number of dies are arranged in a circle on a so-called die table. The number of dies varies between 6 and 55 depending on the model, although larger dies are also available commercially. Each die on the die table is assigned an upper and lower punch, whereby the pressing pressure can be actively built up by just the upper or lower punch, but also by both punches. The die table and the punches move around a common vertical axis, with the punches being brought into the positions for filling, compacting, plastic deformation and ejection with the help of rail-like curved tracks during rotation. At points where a particularly significant raising or lowering of the punches is required (filling, compacting, ejecting), these curved tracks are supported by additional low-pressure pieces, low-pull rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, with the pressure being built up by the punch shaft heads rolling past adjustable pressure rollers.

To increase throughput, rotary presses can also be fitted with two filling shoes, whereby only a semicircle has to be passed through to produce a tablet. To produce two- and multi-layered tablets, several filling shoes are arranged one behind the other without the lightly pressed first layer being ejected before further filling. By using suitable process control, it is also possible to produce shell and dot tablets which have an onion-skin-like structure, whereby in the case of dot tablets the top of the core or core layers is not covered and thus remains visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughput of modern rotary tablet presses is over a million tablets per hour.

H 4753 DE:U 65

When tabletting with rotary presses, it has proven to be advantageous to carry out the tabletting with as little variation in the weight of the tablet as possible. This also reduces the variation in the hardness of the tablet. Small variations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low rotor speed

- Large filling shoes

- Adjustment of the filling shoe blade speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

All non-stick coatings known from technology can be used to reduce stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating stamps have also proven to be advantageous, although the upper and lower stamps should be designed to rotate if possible. With rotating stamps, a plastic insert is generally not necessary. In this case, the stamp surfaces should be electropolished.

It was also shown that long pressing times are advantageous. These can be set using pressure rails, several pressure rollers or low rotor speeds. Since the hardness fluctuations of the tablet are caused by the fluctuations in the pressing forces, systems should be used that limit the pressing force. Elastic punches, pneumatic compensators or spring elements in the force path can be used here. The pressure roller can also be designed to be spring-loaded.

Tableting machines suitable for the purposes of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other suppliers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE/LU) and Mediopharm Kamnik (SI). The hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable. Tableting tools are available from companies such as Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber % Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notier Werkzeugbau, Tamm. Other suppliers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

H 4753 DE:U 66

As mentioned above, the molded bodies can be manufactured in a predetermined spatial shape and a predetermined size. Virtually all sensibly manageable designs can be considered as spatial shapes, for example the design as a panel, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces and, in particular, cylindrical designs with a circular or oval cross-section. This last design covers the presentation form from the tablet to compact cylinder pieces with a height to diameter ratio of more than 1.

It is also possible, however, that the various components are not pressed into a single tablet, but that molded bodies (in particular basic molded bodies, see above) are obtained which have several layers, i.e. at least two layers. It is also possible that these different layers have different dissolving rates. This can result in advantageous application properties of the molded bodies. If, for example, the molded bodies contain components which have a negative mutual influence, it is possible to integrate one component into the more rapidly dissolving layer and incorporate the other component into a more slowly dissolving layer, so that the first component has already reacted when the second goes into solution. The layer structure of the molded bodies can be stacked, whereby a dissolution process of the inner layer(s) at the edges of the molded body already occurs when the outer layers are not yet completely dissolved, but it is also possible to achieve a complete enveloping of the inner layer(s) by the layer(s) further out, which leads to a prevention of the premature dissolution of components of the inner layer(s).

In a further preferred embodiment of the invention, a molded body (in particular a base molded body, see above) consists of at least three layers, i.e. two outer layers and at least one inner layer, with a peroxy bleaching agent being contained in at least one of the inner layers, while in the stack-shaped molded body the two cover layers and in the shell-shaped molded body the outermost layers are free of peroxy bleaching agent. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and/or enzymes present from one another in a molded body.

After pressing, the detergent molded bodies are highly stable. The breaking strength of cylindrical molded bodies can be determined using the diametrical breaking stress. This can be determined according to

2P

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■nDt

H4753DE:U67 '*" "

Here, σ is the diametral fracture stress (DFS) in Pa, P is the force in N ₁ that results in the pressure exerted on the molded body that causes the fracture of the molded body, D is the molded body diameter in meters and t is the height of the molded bodies.

The second step of the method according to the invention comprises applying the coating. For this purpose, common methods of coating bodies can be used, in particular dipping the body in or spraying the body with a melt, solution or dispersion of the coating materials mentioned.

Since immersing detergent tablets in melts or solutions or dispersions only leads to the desired thin coatings with great technical effort, it is preferred in the context of the present invention to spray solutions or dispersions of the coating materials mentioned onto the tablets, the solvent or dispersant evaporating and leaving a coating on the tablet. In preferred processes according to the invention, an aqueous solution of one or more of the coating materials mentioned is sprayed onto the tablets produced in step A), the aqueous solution containing, in each case based on the solution, 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight of one or more of the coating materials mentioned, optionally up to 20% by weight, preferably up to 10% by weight and in particular less than 5% by weight of one or more water-miscible solvents, and the remainder water.

To shorten the drying time, other water-miscible, volatile solvents can be added to the aqueous solution. These come primarily from the alcohol group, with ethanol, n-propanol and iso-propanol being preferred. Ethanol and iso-propanol are particularly recommended for cost reasons.

Coating with water-free or low-water solutions can also be advantageous for certain coating materials.

As already mentioned above, an "undercoating" may be preferred for certain functional coatings in order to improve the adhesion of the coating. Protection of the functional coating by a further "topcoating" may also have advantages. For these reasons, processes according to the invention are preferred in which the coating in step B) comprises the application of one or more, preferably two or three, coating layers.

As already mentioned, coatings with temperature-inverse solution characteristics are particularly preferred from a functional point of view (see above). Thus, processes in which the body produced in step A) is coated with an LCST polymer in step B) are also preferred.

H 4753 DE:U 68

The composition with which the coated second part is made into the cleaning agent according to the invention can - as explained in detail above - take on any physical form. In an order of increasing preference, preferred are processes according to the invention in which the composition in step C) is a liquid, gel-like or pasty composition. Particularly preferred are processes in which the composition in step C) is a particulate composition. And particularly preferred are processes according to the invention which are characterized in that the composition in step C) is a tablet-like composition, with detailed information on tableting and preferred embodiments of the "base tablets" being given above.

It has already been pointed out that an embodiment in which the base molded body has one or more cavities, at least one of which contains the coated second part, is particularly preferred. This also means that processes are preferred in which the composition in step C) is a multiphase cleaning agent tablet which has a cavity into which the coated body from step B) is glued or pressed.

In these preferred methods, the second part can adhere to the first part by the mold alone, but it is preferred to either press it into the first part or to glue it in so that it is firmly bonded to it for better transport and handling stability. Gluing is preferred over mechanical fastening by pressing because the risk of destroying the coating of the second part is lower. During gluing, adhesion promoter is applied to one or more molded body surfaces. In the above-mentioned methods in which two molded bodies are bonded together, this can be done either on the molded body with a cavity or on the molded body that fills the cavity. In preferred methods, adhesion promoters are introduced into the cavity of the molded body.

This procedure is particularly easy to implement with trough-shaped bodies, since the adhesive can be dosed simply by dripping liquid adhesion promoters into the trough. Suitable dosing systems for the large-scale dosing of small amounts of liquid into cavities are well known to those skilled in the art.

It is often technically easier to apply the adhesion promoter to the molded body filling the cavity. In such cases, methods are particularly preferred which are characterized in that the adhesion promoter is applied to one or more surfaces, preferably to one surface, of the coated second part.

This application of adhesion promoter to preferably one surface of the coated second part can be done in different ways. For example, it is possible to

H 4753 DE:U 69

The second part is then dipped into a coating of adhesive on one side and then placed in the cavity. This technique is technologically simple to implement, but carries the risk that the adhesive will contaminate the surface of the molded body with the cavity. The amount of adhesive can be controlled in this variant by varying the rheological properties of the adhesion promoters.

Another possibility, which is preferred within the scope of the present invention, for applying adhesion promoter to preferably a surface of the coated second part is to guide this dosing unit past adhesive dosing systems and then place it in the cavity. This is achieved by means of adhesion promoter-dosing nozzles, brushes or fleeces soaked in adhesion promoters, or by means of rollers. The latter process design is particularly easy to implement, since the coated second part has only a small contact area with the roller. The adhesion promoter can be dosed from inside the roller, but it is also possible to apply the adhesion promoter to the roller at a point that is away from the point of contact between the roller and the coated second parts. Processes in which the adhesion promoter(s)^) is applied to a surface of the coated second part, preferably using adhesion promoter-transferring rollers, brushes or fleeces, are therefore preferred.

The filling of the cavity (the coated second part) can fill the cavity completely, but it can also protrude from the cavity or only partially fill it, whereby there are no limits to the imagination of the product developers. By varying the shape of the molded body with a through hole or depression, the shape of the depression or hole and the shape of the coated second part, a wide variety of molded body variations can be produced that differ greatly from one another visually. For example, the circular ring molded body with a circular hole described above can be filled with a form-fitting cylinder. However, it is also possible to use a sphere, a cuboid that only touches the edges, a three-, five- or six-sided prism or another irregular shape. Depending on the effort you want to put in, octahedral, multi-capped prismatic or icosahedral shapes can also be realized for the coated second part.

In both hole-forming and trough-forming, the adhesion of the coated second part in the cavity decreases as the contact area decreases. Maximum adhesion between the two moldings is achieved when the ring or trough-forming and the coated second part fit together in a form-fitting manner without gaps.

Completely analogous to the above-described production of two-phase moldings by bonding two separately pressed moldings together or into one another, three-phase moldings can also be produced. In this case, either bonding three separately produced moldings together or into one another is recommended, but it is also possible and preferred to use a two-phase,

· ■

H4753DE:U70

For example, to produce a two-layer tablet and to insert another shaped body onto or into it.

The principle mentioned can be extended accordingly to other multi-phase detergent moldings. For example, four-phase moldings can be produced by joining two two-phase moldings together. Four-phase 3:1 moldings can also be produced in a similar way. Of course, the two-phase moldings to be joined can also be produced in other ways. For example, it is possible to produce a single- or multi-layer trough molding, fill the trough with an active substance (for example as a melt, powder, granulate, extrudate, flakes, etc.) and apply another single-, two- or three-phase molding to the molding. A wide variety of options can be varied, for example a two-layer trough molding, the trough of which is filled with a melt or a particulate mixture, with another molding being firmly applied to the side of the molding that has the trough. In this way, the cavity becomes a "core" as it were, since the filling is now enclosed on all sides. A completely identical procedure can be used with a molded body that has a hole through it ("ring molded body") and is then "closed" on both sides with another molded body. The only essential feature of the invention in all of these embodiments is that at least one phase is a coated second part in the sense of the invention.

The above-mentioned possibilities for joining or interlocking molded bodies can also be used to make the entire molded body or parts of it dissolve more quickly. For example, if two flat molded bodies are glued together with an adhesion promoter, under application conditions water can only get into the adhesive at the edges of the molded body if the tablet has not yet dissolved. Even when using adhesion promoters that are easily soluble in water, the connection can practically only be dissolved when part of the entire molded body has dissolved.

The disadvantages mentioned can be overcome by applying the bonding agent in a targeted manner. For example, when joining two molded bodies with their flat surfaces, it is possible and preferred not to apply the bonding agent to the connecting surface, but only to apply "bonding agent points" to the contact edge or corners. These are immediately exposed to water when applied, so that the two molded bodies separate from each other more quickly. If two cube-shaped molded bodies are joined together in this way, the bonding agent does not have to be applied to all four edges. In fact, applying bonding agent points to only the four corners can help to separate the connection even more quickly. For even faster separation, individual bonding agent points can be omitted, so that, for example, only two diagonally opposite contact corners are provided with bonding agent.

H4753DE:U71

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

In addition, the shape of the molded body parts to be connected with the bonding agent can also accelerate the dissolution. Molded bodies are preferred here which can move as freely as possible against each other after the bonding agent connection has been dissolved, i.e. not toroidal molded bodies, but preferably base bodies which have "satellite molded bodies" on their outer surfaces. There are hardly any limits to the variety of geometric design options. For process-economic reasons, however, molded bodies which are orthorhombic, tetragonal or cubic are preferred. Molded bodies with a circular base area can only be bonded along their outer surface using appropriately biconcave shaped intermediate pieces, which in turn are more difficult to tablet. Nevertheless, joining such molded bodies together is also possible according to the invention.

The cleaning agents according to the invention, in particular cleaning agent tablets, can be packaged after production, whereby the use of certain packaging systems has proven particularly useful, since these packaging systems on the one hand increase the storage stability of the ingredients, but in the case of tablets with cavities and an inserted second part on the other hand surprisingly also significantly improve the long-term adhesion of the cavity filling. A further subject of the present invention is therefore a combination of (a) cleaning agent according to the invention, in particular cleaning agent tablets, and a packaging system containing the cleaning agent(s) or cleaning agent tablets, whereby the packaging system has a moisture vapor permeability rate of 0.1 g/m ² /day to less than 20 g/m ² /day when the packaging system is stored at 23°C and a relative equilibrium humidity of 85%.

According to the invention, the packaging system of the combination of cleaning agent or cleaning agent molded body(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 is stored at 23°C and a relative equilibrium humidity of 85%. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, whereby minimal deviations are permissible according to DIN 53122 (23 ± 1°C, 85 ± 2% rel. humidity). The moisture vapor transmission rate of a given packaging system or material can be determined using other standard methods and is also specified, for example, in ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet

H4753DE:U72

form") and in the TAPPI Standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and 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, with the container closed at the top with the material to be tested. From the surface of the container that is closed with the material to be tested (permeation area), the weight increase of the calcium chloride and the exposure time, the moisture vapor permeability rate can be determined according to

FDDR ₌ ^24100QO -*[ _g /^ /24*]

A y

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

The relative equilibrium humidity, often referred to as "relative air humidity", is 85% at 23°C when measuring the moisture vapor permeability rate in the context of the present invention. The capacity of air to absorb water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g/m ^3. For example, 1 m ³ of air at 17° is saturated with 14.4 g of water vapor, at a temperature of 11° saturation is already present with 10 g of water vapor. The relative air humidity is the ratio, expressed in percent, of the actual 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 air humidity = (12/14.4)100 = 83%. If this air is cooled, then the saturation (100% r. L.) is at the so-called Dew point (in the example: 14°) is reached, i.e. if it cools further, precipitation forms in the form of mist (dew). Hygrometers and psychrometers are used to quantitatively determine humidity.

The relative equilibrium humidity of 85% at 23°C can, for example, be set to +/- 2% RH in laboratory chambers with humidity control, depending on the type of device. Even over saturated solutions of certain salts, constant and well-defined relative humidities are formed in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the solid.

The combinations according to the invention of cleaning agent or cleaning agent shaped body(s) and packaging system can of course be packaged in secondary packaging, for example cardboard boxes or trays, whereby no further requirements need to be placed on the secondary packaging. Secondary packaging is therefore possible, but not necessary.

H 4753 DE:U 73

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

The packaging system of the combination according to the invention encloses a certain amount of cleaning agent or one or more cleaning agent tablets, depending on the embodiment of the invention. According to the invention, it is preferred either to design a tablet in such a way that it comprises an application unit of the cleaning agent and to package this tablet individually, or to pack the number of tablets in a packaging unit that in total comprises one application unit. With a target dosage of 80 g of cleaning agent, it is therefore possible according to the invention to produce a cleaning agent tablet weighing 80 g and to package it individually, but it is also possible according to the invention to pack two cleaning agent tablets weighing 40 g each in one package in order to achieve a combination according to the invention. This principle can of course be expanded so that combinations according to the invention can also contain three, four, five or even more cleaning agent tablets in one packaging unit. Of course, two or more tablets in one package can have different compositions. In this way, it is possible to spatially separate certain components from one another in order to avoid stability problems, for example.

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

The detergent tablets can be filled unsorted, i.e. as a loose bulk, into a bag made of the materials mentioned. However, for aesthetic reasons and to sort the combinations in secondary packaging, it is preferable to fill the detergent tablets individually or in groups into sacks or bags. The term "flow pack" has become common in technology for individual application units of the detergent tablets that are in a sack or bag. Such "flow packs" can then - again preferably sorted - optionally be packed in secondary packaging, which underlines the compact presentation of the tablet.

The bags or pouches made of single-layer or laminated paper or plastic film that are preferred as a packaging system can be designed in a variety of ways, for example as inflated bags without a center seam or as bags with a center seam that are sealed using heat (hot fusion), adhesives or adhesive tapes.

H 4753 DE:U 74

Layered bag or sack materials are the well-known papers, which can optionally be impregnated, and plastic films, which can optionally be coextruded. Plastic films which can be used as a packaging system within the scope of the present invention are given, for example, in Hans Domininghaus "Die Kunststoffe und ihre Eigenschaften", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.

Particularly preferred combinations within the scope of the present invention contain, as a packaging system, a sack or bag made of single-layer or laminated plastic film with a thickness of 10 to 200 pm, preferably 20 to 100 pm and in particular 25 to 50 pm.

Although it is possible to use wax-coated paper in the form of cardboard boxes as a packaging system for the cleaning agent tablets in addition to the films or papers mentioned, it is preferred within the scope of the present invention if the packaging system does not include boxes made of wax-coated paper. The term "packaging system" within the scope of the present invention always refers to the primary packaging of the cleaning agent or tablets, i.e. the packaging which is in direct contact with the surface of the tablet on its inside. There are no requirements for optional secondary packaging, so that all conventional materials and systems can be used here.

As already mentioned above, the cleaning agents or cleaning agent tablets of the combination according to the invention contain other cleaning agent ingredients in varying amounts depending on their intended use. Regardless of the intended use of the tablets, it is preferred according to the invention that the cleaning agent or the cleaning agent tablet(s) has/have a relative equilibrium humidity of less than 30% at 35°C.

The relative equilibrium humidity of the cleaning agents or cleaning agent moldings can be determined using common methods, whereby the following procedure was chosen for the present investigations: A waterproof 1-liter container with a lid, which has a closable opening for the introduction of samples, was filled with a total of 300 g of cleaning agent or cleaning agent moldings and kept at a constant 23°C for 24 hours in order to ensure a uniform temperature of the container and substance. The water vapor pressure in the space above the moldings can then be determined using 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.

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H4753DE:U75

Also preferred are embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations in which the packaging system has a microperforation can also be implemented with preference according to the invention.

The compositions according to the invention can be used in all standard household dishwashers, with no restrictions on the choice of program. The advantageous effects are achieved both in low-temperature programs such as 45°C programs or glass programs and in 50/ ⁵⁵ °C or 60/65°C programs.

Claims (30)

1. Detergent for machine dishwashing, comprising a) a first part (base composition) which exerts its effect essentially in the main cleaning cycle of the dishwasher; and b) a second part which, by means of a suitable coating, exerts its effect essentially in the final rinse cycle of the dishwasher, characterized in that the second part contains one or more substances from the group of builders, acidifying agents, chelating agents or scale-inhibiting polymers. 2. Cleaning agent according to claim 1, characterized in that the second part contains one or more builders from the group sodium carbonate, sodium hydrogen carbonate and trisodium citrate in amounts above 10% by weight, preferably above 15% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, in each case based on the weight of the second part. 3. Cleaning agent according to one of claims 1 or 2, characterized in that the second part contains one or more acidifying agents from the group citric acid, adipic acid, malic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, in each case based on the weight of the second part. 4. Cleaning agent according to one of claims 1 to 3, characterized in that the second part contains one or more chelating agents from the groups of (a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, b) nitrogen-containing mono- or polycarboxylic acids, c) geminal diphosphonic acids, d) Aminophosphonic acids, e) phosphonopolycarboxylic acids, f) Cyclodextrins in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, each based on the weight of the second part. 5. Cleaning agent according to one of claims 1 to 4, characterized in that the second part contains one or more deposit-inhibiting polymers from the group of cationic homo- or copolymers, in particular hydroxypropyltrimethylammonium guar; copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, polymers which have 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, in particular guar, cellulose and starch derivatives; polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, in each case based on the weight of the second part. 6. Cleaning agent according to one of claims 1 to 5, characterized in that the second part comprises one or more copolymers of a) unsaturated carboxylic acids b) Monomers containing sulfonic acid groups c) optionally further ionic or non-ionic monomers in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, each based on the weight of the second part. 7. Cleaning agent according to one of claims 1 to 6, characterized in that the second part additionally contains 1 to 50 wt.%, preferably 2.5 to 45 wt.% and in particular 5 to 40 wt.% of nonionic surfactant(s). 8. Cleaning agent according to one of claims 1 to 7, characterized in that the coating of the second part comprises an LCST polymer. 9. Cleaning agent according to claim 8, 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. 10. Cleaning agent according to one of claims 8 or 9, characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances. 11. Cleaning agent according to one of claims 8 to 10, characterized in that the lower critical demixing temperature of the LCST polymer is between 20°C and 90°C. 12. Cleaning agent according to one of claims 1 to 11, characterized in that the coating of the second part consists of several coating layers, preferably two or three coating layers. 13. Cleaning agent according to one of claims 1 to 12, characterized in that the second part was produced by a pressing process, in particular tabletting. 14. Cleaning agent according to one of claims 1 to 13, characterized in that 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. 15. Cleaning agent according to one of claims 1 to 14, characterized in that the first part contains builders in amounts of 1 to 100% by weight, preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight and in particular 20 to 85% by weight, in each case based on the weight of the first part. 16. Cleaning agent according to one of claims 1 to 15, characterized in that the first part contains phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably 25 to 75% by weight and in particular 30 to 70% by weight, in each case based on the weight of the first part. 17. Cleaning agent according to one of claims 1 to 16, characterized in that the first part contains citrate(s), preferably sodium citrate, particularly preferably trisodium citrate dihydrate, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight and in particular 20 to 40% by weight, in each case based on the weight of the first part. 18. Cleaning agent according to one of claims 1 to 17, characterized in that the first part contains bleaching agents from the group of oxygen or halogen bleaching agents, in particular chemical bleaching agents, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably 5 to 20% by weight and in particular 10 to 15% by weight, in each case based on the weight of the first part. 19. Cleaning agent according to one of claims 1 to 18, characterized in that the first part contains bleach activators from the groups of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methylmorpholinium acetonitrile methylsulfate (MMA), in amounts of 0.25 to 15% by weight, preferably 0.5 to 10% by weight and in particular 1 to 5% by weight, each based on the weight of the first part. 20. Cleaning agent according to one of claims 1 to 19, characterized in that the first part contains silver protective agents from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, particularly preferably benzotriazole and/or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular 0.5 to 3% by weight, in each case based on the weight of the first part. 21. Cleaning agent according to one of claims 1 to 20, characterized in that the first part further contains one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, colorants and/or fragrances in total amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight and in particular 10 to 20% by weight, in each case based on the weight of the first part. 22. Cleaning agent according to one of claims 1 to 21, characterized in that the first part is a liquid, gel-like or pasty composition for machine dishwashing. 23. A cleaning agent according to any one of claims 1 to 21, characterized in that the first part is a particulate composition for machine dishwashing. 24. Cleaning agent according to one of claims 1 to 21, characterized in that the first part is a tablet-shaped composition for machine dishwashing. 25. Cleaning agent according to claim 24, characterized in that the first part is a multiphase tablet, in particular a two-, three- or four-phase tablet, it being preferred that the phases have the form of layers. 26. Cleaning agent according to one of claims 24 or 25, characterized in that the coated second part has the form of a further layer, a core or a body glued onto or into the first part ("base tablet"). 27. Cleaning agent according to one of claims 24 to 26, characterized in that the first part has (a) cavity(ies) in which the second and optionally further parts are contained. 28. Cleaning agent according to claim 27, characterized in that the first part has at least two cavities, one of which contains the second part, while the other contains a further, functionalized part. 29. Cleaning agent according to one of claims 1 to 28, characterized in that the content of nonionic surfactants in the first part is 5 to 25% by weight, in each case based on the first part. 30. Cleaning agent according to one of claims 24 to 28, characterized in that the first part or at least one phase of a multiphase first part has a content of nonionic surfactants between 5 and 25 wt. %, in each case based on the first part or on the phase of the first part.