EP1299517B2 - Produits de lavage pour lave-vaisselle a utilite supplementaire - Google Patents

Produits de lavage pour lave-vaisselle a utilite supplementaire Download PDF

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Publication number
EP1299517B2
EP1299517B2 EP01962788A EP01962788A EP1299517B2 EP 1299517 B2 EP1299517 B2 EP 1299517B2 EP 01962788 A EP01962788 A EP 01962788A EP 01962788 A EP01962788 A EP 01962788A EP 1299517 B2 EP1299517 B2 EP 1299517B2
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European Patent Office
Prior art keywords
cleaning agents
agents according
polymers
acid
preferred
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EP01962788A
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German (de)
English (en)
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EP1299517A1 (fr
EP1299517B1 (fr
Inventor
Arnd Kessler
Rolf Bayersdörfer
Christian Nitsch
Bernd Richter
Matthias Sunder
Thomas Holderbaum
Peter Schmiedel
Rainer Sorg
Maren Jekel
Ulrich Pegelow
Harald Volk
Manfred Greger
Markus Schlienz
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KESSLER, ARND
Henkel AG and Co KGaA
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Kessler Arnd
Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the present invention relates to detergents, in particular controlled-release machine dishwashing detergents.
  • the present invention relates to machine dishwashing detergents which have a system which allows a controlled release of at least one active ingredient in the cleaning process and at least one active ingredient in the post-treatment process.
  • the invention also relates to a method for producing such machine dishwashing detergents.
  • the invention also relates to cleaning methods using said machine dishwashing detergents.
  • detergents were formulated in metered portions containing all the components required for a cleaning cycle.
  • portions In the case of solid products, such portions have often been shaped into moldings (sometimes containing several phases) such as granules, beads, tablets ("tabs"), ashlars, briquettes, etc., which are dosed as a whole into the liquor.
  • Liquid products were incorporated into water-soluble coatings which dissolve on contact with the aqueous liquor and release the contents into the liquor.
  • a disadvantage of these solutions is that all components that are needed in the course of a cleaning cycle, reach the same time in the aqueous liquor. Not only do problems of incompatibility of certain components of a cleaning agent with other components occur, but it also becomes impossible to meter targeted components into the fleet at a defined time.
  • the present invention was based on the object to provide a product that must be dosed only once per application, without even after a higher number of rinsing cycles, the dosage of another product and thus a double dosing would be necessary.
  • a product should be provided which, in addition to the "built-in rinse aid", eliminates the need to refill the regeneration brine tank, further simplifying handling. In doing so, the performance of the product should reach or exceed the performance level of conventional three-product dosing (salt-detergent rinse aid) or novel two-product dosing ("2in1" rinse-aid).
  • the most important ingredients of automatic dishwashing detergents are builders.
  • all builders customarily used in detergents it is possible for all builders customarily used in detergents to be present, in particular zeolites, silicates, carbonates, organic cobuilders and phosphates.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -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 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed are.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying: In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses.
  • compacted / compacted amorphous silicates particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white readily water-soluble powders which lose the water of crystallization on heating at 200 ° C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7), (at higher temperature in sodium trimetaphosphate Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH 2 PO 4 , is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° C and goes on stronger heating in the diphosphate Na 4 P 2 O 7 above.
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • Suitable builders are carbonates, bicarbonates and the salts of oligocarboxylic acids, for example gluconates, succinates and in particular citrates.
  • Acidifying agents are also suitable as an ingredient for the second part in the context of the present invention.
  • Substances from this group can be used, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • Sokalan® DCS commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).
  • Particularly preferred cleaning agents according to the invention are characterized in that the second part comprises one or more acidifying agents from the group of citric acid, adipic acid, malic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid in amounts above 5% by weight, preferably above 10 Wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part.
  • the second part comprises one or more acidifying agents from the group of citric acid, adipic acid, malic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid in amounts above 5% by weight, preferably above 10 Wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part.
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, usually stretched verb are closed by complex formation over an ion to rings. The number of bound ligands depends on the coordination number of the central ion.
  • Typical and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complexing polymers ie polymers that carry either in the main chain itself or side by side to this functional groups that can act as ligands and react with suitable metal atoms usually to form chelate complexes. are used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • the second part comprises one or more scale-inhibiting polymers from the group of cationic homopolymers or copolymers, in particular hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallyl ammonium chloride and acrylamide, polymers having imino groups, polymers having quaternized ammonium alkyl methacrylate groups as monomer units, cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate and acrylamide, respectively; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium
  • R 1 (R 2 ) C C (R 3 ) COOH (I)
  • R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above, or -COOH or -COOR 4 wherein R 4 is a saturated or unsaturated, straight or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H (II)
  • H 2 C CH-X-SO 3 H (IIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (IIb)
  • HO 3 SX- (R 6 ) C C (R 7 ) -X-SO 3 H (IIc)
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers contained in the second part consist only of monomers of groups i) and ii).
  • the copolymers contained in the second part may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • Corresponding cleaning agents which are characterized in that the sulfonic acid groups are present in the copolymer partially or fully neutralized, are preferred according to the invention.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight of the polymers according to the invention contained in the second part can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the products of the invention also make the additional dosage of a rinse aid superfluous.
  • the clear rinse effect can be significantly improved if the detergents according to the invention contain surfactants, in particular nonionic surfactants.
  • the surfactants may be present in the first part (of the "base composition") and be sent to the rinse cycle via caustic carryover or other phenomena, as well as being part of the second part which, due to the coating, essentially only unfolds its effect in the final rinse cycle of the dishwashing machine.
  • cleaning agents are preferred in which the second part additionally contains 1 to 50% by weight, preferably 2.5 to 45% by weight and in particular 5 to 40% by weight of nonionic surfactant (s ), wherein the weights are based on the second part including coating.
  • nonionic surfactant s
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of this nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (IX) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (X) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • 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
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants from the group of the alkoxylated alcohols.
  • alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • detergents according to the invention which contain a nonionic surfactant which has a melting point above room temperature.
  • preferred detergents are characterized by having in the second part nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43.3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that these have a Viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred cleaning agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred cleaning agent according to the invention contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each of R 3 in the above formula may be different if x ⁇ 2 is.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • the surfactants mentioned above may additionally be present in the first part of the cleaning agents according to the invention.
  • the second part is formulated surfactant-free and the aforementioned surfactants are all present in the first part (see below).
  • the second part may contain other conventional ingredients of cleaning agents.
  • a content of bleaching agents and / or bleach activators and / or bleach catalysts and / or enzymes and / or corrosion inhibitors (silver protectants) and / or dyes and / or fragrances in the second part can bring further performance advantages.
  • the second part has a suitable coating which causes the contents of the second part to be released substantially only in the final rinse cycle of the dishwasher and to exert their effect.
  • a coating which is often referred to as "coating” in German, usually has thicknesses of 10 to 1000 .mu.m, with layer thicknesses between 20 and 800 .mu.m, in particular between 50 and 400 .mu.m, being preferred within the scope of the present invention.
  • the coating can be uniformly composed, e.g. consist of a single substance, but it is also possible that multi-layer coatings are used, in the context of the present invention, two, three or four-layer coatings are preferred.
  • the coating protects the second part from premature dissolution in the main cleaning cycle and any intermediate rinsing.
  • the coating In the rinse cycle, the coating must be rapidly dissolved or otherwise destroyed to release the ingredients of the second part.
  • several release mechanisms come into consideration that use altered properties of the coating materials as a function of varying external conditions. In this way prevailing conditions in the dishwasher, which are different in the main cleaning and rinse cycle, used to convert the second part in the rinse cycle.
  • the coating By changing the outer condition, the coating "switches” and releases the second part.
  • a "switch” offer temperature-controlled and / or enzyme-controlled and / or redox-controlled and / or electrolyte-controlled and / or pH-controlled systems.
  • Temperature-controlled systems may be, for example, to coat the second part with a substance that only above melts at a certain temperature and then washed away or becomes soluble above a certain temperature in the application medium.
  • encapsulating substances which will be described in detail below, are, for example, paraffins.
  • Another mechanism of temperature control can be realized with substances that dissolve better at low temperatures than at high.
  • Such substances with a so-called "low critical solution temperature” are referred to as LCST substances or as substances with lower critical demixing temperature.
  • LCST substances In order to prevent these substances from dissolving when they first enter the machine (before the main cleaning cycle), they must be provided with a further coating which dissolves during the main cleaning cycle or is otherwise destroyed.
  • the LCST substance protects the second part while it dissolves at the low temperatures of the rinse cycle and releases the ingredients.
  • Cleaning agents preferred in the context of the present invention are therefore characterized in that the coating of the second part comprises an LCST polymer.
  • the cleaning agent can be used particularly advantageously in mechanical processes where the active ingredient is to be released in a rinse after the cleaning step. Examples are the mechanical cleaning of dishes both in the household and in the commercial sector.
  • the packaging according to the invention the active ingredients remain after a heat treatment in a liquid medium, eg. B. after the main rinse, at least partially unchanged and the active ingredient is released after cooling after the heat treatment, ie in the rinse cycle.
  • the second part is coated with an LCST substance.
  • these substances are usually polymers.
  • 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.
  • An LCST polymer suitable in the context of the present invention is, for example, polyvinylcaprolactam (PVCap).
  • LCST polymer is selected from cellulose derivatives, mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylamides and / or acrylates or acrylic acids.
  • the LCST substances are particularly preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
  • Corresponding detergents which are characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, copolymers of the polyisopropylacrylamide and blends of these substances are preferred according to the invention.
  • alkylated and / or hydroxyalkylated polysaccharides are methylhydroxypropylmethylcellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose ( HBC), hydroxybutyl methylcellulose (HBMC), hydroxyethyl carboxymethyl cellulose (HEC), hydroxyethyl carboxymethyl cellulose (HEECMC), hydroxyethyl ethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), hydroxyethyl methyl cellulose (HEMC), methyl hydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose (MHEPC), methyl cellulose (MC) and propylcellulose (PC) and mixture
  • LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of interconnected networks of the above (co) polymers.
  • polyethylene oxide or copolymers thereof such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin, and certain alginates.
  • LCST low critical demixing temperature
  • the second part is coated with a further material which is soluble at a temperature above the lower separation temperature of the LCST substance or has a melting point above this temperature or a retarded solubility, ie above the lower separation temperature of LCST layer can be released.
  • This layer serves to separate the mixture of active ingredient and LCST substance from water or other media that dissolve them before the heat treatment can protect.
  • This additional layer should not be liquid at room temperature and preferably has a melting point or softening point at a temperature equal to or above the lower critical demixing temperature of the LCST polymer.
  • the melting point of this layer is particularly preferably between the lower critical demixing temperature and the temperature of the heat treatment.
  • the LCST polymers and the further substance are mixed together and applied to the material to be encapsulated.
  • the further substance preferably has a melting range of between about 35 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.
  • waxes are understood to mean a number of natural or artificially produced substances which generally melt above 35 ° C. without decomposition and are already relatively low viscous and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
  • the natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
  • vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe
  • the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes.
  • suitable as coating materials are compounds from other classes of substances which fulfill the stated requirements with regard to the softening point.
  • Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved.
  • synthetically produced waxes from lower carboxylic acids and fatty alcohols for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea)
  • synthetic or partially synthetic esters of lower alcohols with fatty acids from natural sources can be used.
  • This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate.
  • Shellac for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used as further substance.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms.
  • the wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating may optionally also contain wool wax alcohols, which are understood to mean triterpenoid and steroid alcohols, for example lanolin, which is obtainable, for example, under the trade name Argowax® (Pamentier & Co).
  • wool wax alcohols which are understood to mean triterpenoid and steroid alcohols, for example lanolin, which is obtainable, for example, under the trade name Argowax® (Pamentier & Co).
  • fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the coating in the context of the present invention.
  • Suitable materials having a melting point above the LCST of the underlying coating material are saturated aliphatic hydrocarbons (paraffins).
  • Suitable as coating materials are all water-soluble, water-dispersible and water-insoluble polymers which have a melting point which is above the lower critical demixing temperature of the LCST polymer used according to the invention or is soluble above this temperature.
  • Suitable polymers are solid polyethyleneglycols, polyvinyl alcohols, polyacrylic acid and their derivatives at room temperature.
  • gelatin has also proved to be suitable. Particular preference is given to using polyvinyl acetate (PVAc) as the material for protecting the LCST layer (topcoating).
  • LCST polymer layer Sometimes it may already be sufficient to protect the LCST polymer layer if it is shielded by a water-soluble coating of initially cold water.
  • This water-soluble coating need only have a sufficiently delayed solubility, so that the layer is sufficiently stable for a long time.
  • Polyalkylenglycole be used with preferably higher molecular weight.
  • the second part can be coated in a manner known per se with the LCST substance and / or the further material.
  • the substances can be sprayed, for example, as a melt or in the form of a solution or dispersion, or the mixture can be immersed in the melt, solution or dispersion or mixed with it in a suitable mixer. Coating in a fluidized bed apparatus is also possible.
  • the spraying process is suitable for all production processes established in pharmacy and food technology of coated tablets, capsules and particles.
  • the polymer suspension or solution is sprayed either batchwise in small portions, the particles are transported on a conveyor belt through a liquid curtain and then dried in air flow or sprayed continuously with simultaneous drying by the injected air flow in fluidized bed, fluidized bed or Flug harshumhüllungs confusen ,
  • the coating method is also conceivable if LCST polymers are added to the coating syrups in a sufficiently high concentration.
  • the application of the second layer is analogous.
  • the ingredients of the second part are released by an enzyme-controlled coating.
  • enzymatically degradable (enzyme-sensitive) materials are used as coating material.
  • the enzymes usually contained in cleaning agents cause, after a certain exposure time, a degradation of the enzyme-sensitive coating material and, consequently, a release of the active substance or detergents enclosed in the second part.
  • Suitable enzyme-sensitive materials are preferably cellulose derivatives, starch or starch derivatives, partially oxidized starch derivatives, glycerides, certain proteins and mixtures of these. Enzymes used in detergents are preferably proteases, amylases and / or lipases.
  • Agents according to the invention can be prepared in such a way that conventional solid detergents or components therefor, which are present as granules and / or agglomerates, as pellets, extrudates, tablets or in capsule form, are coated with the enzyme-sensitive material. If such enzyme-containing agents or components for cleaning agents are introduced into cleaning liquors together with conventional cleaning agents, the release of the enclosed active substances takes place only after the at least partial degradation of the enzyme-sensitive coating materials.
  • a further preferred embodiment of the invention is that a (redox system is used as the (physico -) - chemical switch, which causes a controlled drug release.
  • the redox materials can also be used as coating material, in particular of shaped articles, for example tablets, or capsules of active ingredients of cleaning agents, in the redox-controlled release of active substance. After a certain exposure time of redox-active components usually contained in cleaning agents, there is a chemical change of the redox-sensitive coating material and, consequently, a release of the active ingredient or detergents enclosed in the coated moldings, granules or capsules.
  • redox-sensitive materials are oxidation-sensitive organic and inorganic substances, including polymers. Particularly preferred is the use of polyvinylpyridine as a redox-sensitive material.
  • redox-active ingredients of cleaning agents are in particular oxidizing agents such as percarbonate and the like, especially in combination with bleach activators, especially tetraacetylethylenediamine (TAED) and other common bleach activators to call.
  • TAED tetraacetylethylenediamine
  • Solid compositions according to the invention can be prepared by coating conventional solid detergents or components therefor, which are present as granules and / or agglomerates, as pellets, extrudates, tablets or in capsule form, with the redox-sensitive material. If redox-sensitive materials containing agents or redox-sensitive materials containing components for cleaning agents are introduced together with conventional cleaning agents in cleaning liquors, the release of the entrapped active ingredients takes place only after the at least partial oxidative degradation of the redox-sensitive coating materials.
  • a (physico-) chemical switch can be used, which causes an electrolyte-controlled drug release.
  • the difference in the electrolyte content between the cleaning cycle and the rinse cycle in automatic dishwashing can be exploited.
  • a further preferred embodiment of the invention therefore relates to a cleaning agent in which the second part is coated with an electrolyte-sensitive substance, wherein the active substance (s) of the second part is released as a result of an occurring change in the electrolyte concentration.
  • the rinse liquor pH is about 10. Accordingly, the main commercially available dishwashing products on the market are alkaline. In particular, in the vast majority of machine dishwashers and their different cleaning programs, the rinsing liquor is pumped off after the cleaning cycle and replaced by fresh water. It comes, regardless of the temperature of the water, to a drop in the pH by about 1 to 2 pH units. The exact value of the pH drop depends on the amount of residual liquor left in the machine, which is around 2%.
  • such (physico-) chemical switches are used as coating material for the second part, which undergo a change in the physicochemical properties when the pH of the application liquor changes.
  • such substances be used as (physico) chemical switch, which have an increased solubility in water as a result of a change in the pH occurring in the application liquor.
  • those switch substances are preferred which have a change, in particular a decrease in the diffusion density, with the corresponding change in the pH of the application liquor.
  • means, in particular automatic dishwasher detergents, which contain a substance as a (physico-) chemical switch are advantageous, which, in the case of a change in pH occurring in the application liquor in the range from 11 to 6, preferably from 10 to 7, a change in their physical properties. experiences chemical properties and thereby preferably at a decreasing pH in the range of 10 to 7, in particular from 10 to 8, an increased solubility in water and / or a decrease in the diffusion density.
  • Suitable substances that can be used as such (physico) chemical switch are basic in nature and especially basic polymers and / or copolymers.
  • the principle of pH-dependent water solubility is generally based on protonation or deprotonation of functional side groups of the polymer molecules, as a result of which their charge state changes accordingly.
  • the polymer must now be such that it dissolves in the stable charged state at a certain pH in water, in the uncharged state at another pH, however, precipitates.
  • it is preferred that the polymers used according to the invention have a lower water solubility at a higher pH than at lower pH values or even become insoluble in water at relatively high pH values.
  • Acid-insoluble polymers are used to give tablets an enteric-coated, but colonic-soluble, coating.
  • acid-insoluble polymers are usually based on derivatives of polyacrylic acid, which is present in the acidic region in undissoziierter and thus insoluble form, in the alkaline range, but typically neutralized at pH 8 and goes as a polyanion in solution.
  • insoluble in the alkaline range - examples are known in the art. These substances, in which the polymer molecules mostly carry amino-substituted side chains, are e.g. used for the preparation of gastric juice-soluble tablet coatings. They usually dissolve at pH values below 5. Polymers in which the solubility change from soluble to insoluble at higher pHs are not known in the pharmaceutical arts because these pHs are physiologically meaningless.
  • Particularly preferred suitable substances are basic (co) polymers which have amino groups or aminoalkyl groups.
  • Comonomers may be, for example, conventional acrylates, methacrylates, maleinates or derivatives of these compounds.
  • a particularly suitable aminoalkyl-methacrylate copolymer is sold by the company Röhm (Eudragit®).
  • the dissolution kinetics of a filmed substance or the decrease in its mechanical stability may be important for the application.
  • the solution kinetics of the switch substances used according to the invention is pH-dependent at room temperature down to the alkaline range, ie the films are significantly longer stable at pH 10 than at a pH of 8.5, although they are thermodynamically soluble at both pH values are.
  • polymers are used whose water solubility varies between pH 6 to 7 and which are less soluble at higher pH than at lower pH.
  • Suitable polymers contain, as already described above, basic groups, for example primary, secondary or tertiary amino groups, imino groups, amido groups or pyridine groups, generally those which have a quaternizable nitrogen atom. These are protonated at lower pHs, whereby the polymer is soluble. At higher pH, the molecule becomes uncharged and becomes insoluble. As a rule, the transition takes place - referred to below as the "switching point", depending on the pK B value of the basic groups and their density along the polymer chain, in the range of acidic pH values.
  • Subject of the present invention is therefore also a polymer in which the switching point is in a range between pH 6 and 7.
  • a particularly preferred polymer of this class of substances is an N-oxidized polyvinylpyridine.
  • the polymer of the coating of the second part completely dissolves at the appropriate pH conditions to release the drug. Rather, it suffices if, for example, the permeability of a polymer film changes, e.g. the penetration of water into the drug formulation is made possible. Thereby, a secondary effect, e.g. the activation of an effervescent system or the swelling of a water-swellable disintegrant, which are known in particular from the pharmaceutical industry, ensure the complete release of the active ingredient.
  • pH-shift boosters are used in addition to the above-mentioned switches.
  • suitable pH-shift boosters are all substances and formulations which are capable of controlling the extent of the pH shift either locally, i. in the immediate vicinity of the particular pH-shift-sensitive substance used, or also generalized, i. in the entire rinsing, to enlarge.
  • organic and / or inorganic water-soluble acids or acid-reacting salts include all organic and / or inorganic water-soluble acids or acid-reacting salts, in particular at least one substance from the group of alkylbenzenesulfonic acids, alkylsulfuric acids, citric acid, oxalic acid and / or alkali metal hydrogensulfates.
  • the pH-shift booster can be incorporated into the cleaning agent. In a further embodiment of the invention, however, it is also possible to supply the pH-shift booster externally to the machine either after the end of the cleaning cycle or at the beginning of the rinse cycle or by a special delivery system (by coating with a slowly dissolving coating agent). or by diffusion from a matrix material.
  • the coating of the second part of the cleaning agent according to the invention can also consist of several layers. In part, this is necessary to protect certain coating layers by a second layer during the main cleaning cycle (see above), but in some cases a sub-coating may be required to create a well-adhering and uniform surface for the functional coating. Of course, the combination of a Untercoatings with a functional coating and another protective layer is conceivable.
  • the second part has a three-layer coating. Detergents in which the coating of the second part consists of several coating layers, preferably of two or three coating layers, are preferred according to the invention.
  • Preferred coating materials for an optional inner or outer coating layer are the polymers known from the prior art.
  • cleaning agents are preferred in which the coating layer on the second part consists of a polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons.
  • the media into which cleaning agents are usually introduced preference is given in particular to cleaning agents in which the outer coating layer on the second part consists of a water-soluble polymer.
  • Such preferred polymers may be of synthetic or natural origin. If polymers are used on a native or a fractional basis as a coating material, then the coating material is preferably selected from one or more substances from the group of carrageenan, guar, pectin, xanthan, cellulose and its derivatives, starch and its derivatives, and gelatin.
  • Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar built extract of North Atlantic, belonging to the Floridean red algae.
  • the carrageenan precipitated from the algae's hot water extract is a colorless to sand-colored powder with molecular weights of 100,000-800,000 and a sulphate content of about 25%, which is very slightly soluble in warm water.
  • Carrageenan has three main components:
  • the yellow-forming f- fraction consists of D-galactose-4-sulfate and 3,6-anhydro- ⁇ -D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (Agar, in contrast, contains 3,6-anhydro- ⁇ -L-galactose).
  • the non-gelling I fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water.
  • the i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming.
  • Other types of carrageenan are also denoted by Greek letters: ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ .
  • the type of cations present K, NH 4, Na, Mg, Ca
  • Semisynthetic products which contain only one type of ion and can also be used as coating materials in the context of the present invention are also called Carrag (h) eenates.
  • Guar also known as guar flour
  • guar flour can be used as a coating material in the context of the present invention. It is an off-white powder that has been cultivated by milling the endosperm of the endemic species originally native to India and Pakistan, now also cultivated in other countries, for example in the southern United States the legume belonging to Guar bean (Cyamopsis tetragonobolus) is obtained.
  • the main constituent of the guar is with up to about 85% by weight of the dry substance guar gum (guar gum, Cyamopsis gum); Secondary components are proteins, lipids and cellulose.
  • Guaran itself is a polygalactomannan, ie a polysaccharide, the linear chain of which is unsubstituted (see formula XI) and substituted in the C6 position with a galactose residue (see formula (XII)) mannose units in ⁇ -D- (1 ⁇ 4 ) Link is established.
  • the ratio of XI: XII is about 2: 1; the XII units are not strictly alternating, contrary to initial assumptions, but are arranged in pairs or triplets in the polygalactomannan molecule.
  • Data on the molecular weight of the guaran vary with values of about 2.2 ⁇ 10 5 -2.2 ⁇ 10 6 g / mol, depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to about 1350 -13,500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.
  • the pectins which can also be used as coating material, are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves.
  • the pectins consist essentially of chains of 1,4- ⁇ -glycoside. connected galacturonic acid units whose acid groups are esterified to 20-80% with methanol, with a distinction between highly esterified (> 50%) and low-esterified pectins ( ⁇ 50%).
  • the pectins have a leaflet structure and are thus in the middle of starch and cellulose molecules. Their macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.
  • Fruit pectin contains 95%, beet pectin to 85% galacturonic acid.
  • the molecular weights of the various pectins vary between 10,000 and 500,000.
  • the structural properties are also highly dependent on the degree of polymerization; thus, e.g. dried pectins are asbestos-like fibers, whereas flax pectins are fine, granular powders.
  • the pectins are prepared by extraction with dilute acids mainly from the inner parts of citrus fruit peel, Obstresten or sugar beet pulp.
  • Xanthan gum can also be used according to the invention as an outer coating material for the second part.
  • Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular mass of 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
  • Xanthan can be described by the following formula:
  • the celluloses and their derivatives are also suitable as coating materials.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • As a coating material it is also possible to use cellulose derivatives which are obtainable by cellulose-based polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • starch and starch derivatives can also be used as coating materials.
  • Suitable nonionic organic coating materials are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 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, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: about 20-30% straight-chain amylose (MW 50,000-150,000) and 70-80% branched-chain amylopectin (MW 300,000-2,000,000); Amounts of lipids, phosphoric acid and cations.
  • starch derivatives which are obtainable from starch by polymer-analogous reactions.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • gelatin as a coating material is of outstanding importance.
  • Gelatin is a polypeptide (molecular weight: about 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules.
  • Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.
  • the outer coatings of the second part of the cleaning agents according to the invention may be made of any of the above-mentioned polymers, but it is also possible to use mixtures or multilayered layer structures of the polymers.
  • the polymers are described in more detail below.
  • the vinyl ester polymers are vinyl ester-accessible polymers having the moiety of formula (XIV) as a characteristic building block of the macromolecules.
  • the vinyl acetate polymers (R CH 3 ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.
  • Cellulose ethers can be described by the general formula (XV) R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (XI) is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide).
  • Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit.
  • Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1.
  • Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively.
  • Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n in small proportions also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but in particular technically by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.
  • PVAL eg Mowiol® grades from Hoechst
  • PVAL eg Mowiol® grades from Hoechst
  • they come on the market as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (corresponding to molar masses of about 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.
  • the water-solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • polymers which are suitable according to the invention are water-soluble amphopolymers.
  • Amphoteric polymers ie polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO - - or -SO 3 - groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters.
  • preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers.
  • Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoniumchlorid, as they are commercially available under the name Merquat®2001 N, according to the invention are particularly preferred amphopolymers.
  • Further suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).
  • Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers.
  • Further suitable zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL).
  • Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by subjecting the polyalkylene glycols to the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.
  • Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.
  • Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols.
  • Polymers of ethylene glycol corresponding to general formula XVII H- (O-CH 2 -CH 2 ) n -OH (XVII) satisfy, where n can assume values between 1 (ethylene glycol) and several thousand.
  • n can assume values between 1 (ethylene glycol) and several thousand.
  • Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
  • polyethylene glycols for example, among the Trade names include Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trading name with higher numbers.
  • the polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
  • the nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  • the non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.
  • crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.
  • terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and Monomer units of one or more allyl or methallyl esters of the formula XIX: wherein R 3 is -H or -CH 3 , R 2 is -CH 3 or -CH (CH 3 ) 2 and R 1 is -CH 3 or a saturated straight or branched C 1-6 alkyl radical and the sum of the carbon atoms in the radicals R 1 and R 2 is preferably 7, 6, 5, 4, 3 or 2.
  • the anionic polymers are especially suitable for polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.
  • Useful organic coating materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form.
  • Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or containing as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymeric coating materials are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred coating materials.
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • polymers are cationic polymers.
  • the cationic polymers the permanent cationic polymers are preferred.
  • "permanently cationic” refers to polymers which have a cationic group, irrespective of the pH of the composition (that is to say both the coating layer and the other detergent formulation). These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.
  • Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.
  • Also preferably used as coating materials are carbonic or dicarboxylic acids, or those having an even number of C atoms.
  • Particularly preferred carboxylic or dicarboxylic acids are those having at least 4, preferably at least 6, more preferably at least 8 and especially those having 8 to 13 carbon atoms.
  • Particularly preferred dicarboxylic acids are, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and mixtures thereof. But also tetradecanoic acid, Pentadecanoic acid and thapsic acid are suitable coating materials.
  • carboxylic acids are those having 12 to 22 carbon atoms, with those having 18 to 22 carbon atoms being particularly preferred.
  • the use of the above-described disintegration aids is recommended especially in the case of acid coating layers, with typical use concentrations for the disintegration aids in the coating layers being 0.1 to 5% by weight, based on the coating layer.
  • the second part of the cleaning agents according to the invention may be present as granules and / or agglomerate, as pellets, extrudates, tablets or in capsule form, preference being given to embodiments which have a certain size as the second part.
  • Cleaning agents according to the invention are preferred in which the second part has a diameter between 1 and 30 mm, preferably between 2.5 and 15 mm and in particular between 5 and 10 mm.
  • the term "diameter” applies only to spherical second parts, since only these have a single diameter. If the second part is shaped differently - for example, cylindrical, ellipsoidal, cuboid or cube-shaped, etc., the above statement applies to the size (area) diameter.
  • the second part can be produced by all current methods.
  • preferred bodies having volumes between 0.1 and 10 cm 3 , preferably between 0.25 and 7.5 cm 3 and in particular between 0.5 and 5 cm 3 , the production by casting, by Sintering, by extrusion, by calendering or by tabletting preferred.
  • ingredients of the second part particular preference is given to detergents in which the second part has been produced by a pressing process, in particular tableting.
  • the second coated part can be combined with a first part of any design.
  • the first part may be, for example, a detergent powder or present as a compact molding. Even liquid or gel-like first parts can be realized with an appropriate design, but because of the sedimentation and stability problem of the second parts in such a matrix but less preferred.
  • Builders have already been described above as a possible component of the second part. These are also contained in preferred embodiments of the present invention in the first part, wherein cleaning agents are preferred in which the first part builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95 wt .-%, particularly preferably from 10 to 90 wt .-% and in particular from 20 to 85 wt .-%, each based on the weight of the first part.
  • the first part comprises phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, in particular from 30 to 70% by weight, based in each case on the weight of the first part.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • cleaning agents according to the invention in which the first part citrate (s), preferably sodium citrate, particularly preferably trisodium citrate dihydrate, in amounts of 10 to 60 wt .-%, preferably from 15 to 50 wt .-% and in particular from 20 to 40 Wt .-%, each based on the weight of the first part, also contains preferred embodiments of the present invention.
  • Nonionic surfactants have also been described in detail above. These may also be part of the first part, their amount in the first part usually in the range of 0.5 to 5 wt .-%, preferably between 1 and 2 wt .-%, is located. If formulations are to be provided where the first part provides for the "built-in rinse aid", higher surfactant contents are possible, see below for more information.
  • Cleaning agent according to one of Claims 1 to 17, characterized in that the first part comprises bleaching agents selected from the group consisting of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight. , preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the first part contains.
  • bleaching agents selected from the group consisting of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight. , preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the first part contains.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as (B) the aliphatic or substituted aliphatic peroxy acids such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-de
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the first part comprises bleach activators from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate ( n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), in amounts of from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5 wt .-%, each based on the weight of the first part contains.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonanoylsuccinimide
  • the said bleaching agents can also be introduced wholly or partly via the second part into the automatic dishwashing detergent according to the invention in order to achieve a "subsequent bleaching" in the rinse cycle.
  • Bleach activators which aid in the action of the bleaches can be both part of the first and second part.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • bleach catalysts can also be incorporated into the detergents.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • ingredients may also be part of the first or second part.
  • cleaning products preferably, in which the first part further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt. -% and in particular from 10 to 20 wt .-%, each based on the weight of the first part contains.
  • Further preferred cleaning agents are characterized in that the first part silver protectants from the group of the triazoles, the benzotriazoles, the Bisbenzotriazole, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the first part.
  • the corrosion inhibitors mentioned may be contained in the first or second part for the protection of the items to be washed or the machine, with silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy entanglements.
  • hydrolases include the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy entanglements.
  • bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.
  • Dyes and fragrances can be added to the machine dishwasher detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • the separation of the bleach from other ingredients may be advantageous.
  • Detergents according to the invention in which one part contains bleach while another contains enzymes are also preferred. Also preferred are detergents wherein one part contains bleach while another contains bleach activators. Again, it is of course possible to design the first part of multiphase and to separate the substances within the first part of each other.
  • the first part can be provided both liquid, gelatinous or pasty as well as solid and, in particular, in powder form or in the form of a compact molding.
  • detergents according to the invention are preferred in which the first part is a liquid, gelatinous or pasty machine dishwashing composition.
  • Particularly preferred cleaning agents according to the invention are those in which the first part is a tablet-shaped machine dishwashing composition.
  • This tablet-like composition of the first part of the cleaning agent according to the invention is described by the term "base molding” and characterized in the context of the present invention, the moldings produced by known tabletting operations.
  • the base molding is first prepared and the coated second part in a further step on or in this base molding introduced or introduced.
  • the resulting product is hereinafter referred to by the generic term "shaped article" or "tablet".
  • the basic shaped body may take any geometric shape, in particular, concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five, seven and octagonal prismatic and rhombohedral shapes are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the base molding has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.
  • Preferred basic shaped bodies have a plurality of phases which enable a separation of incompatible ingredients.
  • cleaning agents according to the invention are preferred, which are characterized in that the first part is a multiphase tablet, in particular a two-, three- or four-phase tablet, wherein it is preferred that the phases have the form of layers.
  • Such tablets can thereby be formulated into the finished cleaning agent according to the invention by containing the second coated part in the form of a further layer.
  • the second part may also have a different shape, for example that of a hemisphere, which is glued to a surface of the base molding. Since it is best to coat spherical or ball-shaped bodies as closely as possible, it is preferable to adapt the shape of the first part to the preferred shape of the second part and to provide the first part with a cavity into which the second part is inserted and optionally fixed becomes.
  • cleaning agents in which the coated second part has the form of a further layer, a core or a glued on or in the first part ("base tablet”) body are preferred according to the invention, wherein cleaning agents are particularly preferred, in which the first part having a cavity (s) in which the second and optionally further parts are contained.
  • the shape of the cavity (s) can be freely selected within wide limits. For reasons of process economy, through holes whose openings are located on opposite surfaces of the moldings, and wells with an opening on a molded body side have proven.
  • the cavity has the shape of a through hole whose openings are located on two opposite mold body surfaces.
  • the shape of such a through hole can be chosen freely, wherein moldings are preferred in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections. Even completely irregular hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized.
  • those with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • moldings with a rectangular or square base and circular holes can be made as well as round moldings with octagonal holes, the variety of possible combinations are no limits.
  • moldings with a hole are particularly preferred in which the mold body base area and the hole cross section have the same geometric shape, for example shaped bodies with a square base area and a centrally machined square hole.
  • Particularly preferred are ring shaped bodies, i. circular shaped bodies with a circular hole.
  • the shaped bodies can also assume any geometric shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic and rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped body has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.
  • the shape of the trough can be chosen freely, with moldings are preferred in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedrale, octahedral, conical, pyramidal, ellipsoidal , five-, seven- and octagonal-prismatic as well as rhombohedral form.
  • Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized.
  • wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • the size of the trough or the through hole compared to the entire shaped body depends on the desired use of the shaped body and the size of the second part to be inserted into the cavity. Depending on whether a smaller or larger amount of active substance should be included, the size of the cavity may vary. Regardless of the intended use, cleaning agents are preferred in which the volume ratio of base molding to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, more preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1 , is.
  • Shaped bodies are preferred in which the area of the opening (s) of the cavity (s) constitutes 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the shaped body.
  • the present invention is not limited to combining a first part with only a second part.
  • a base molding having a plurality of cavities containing inserted further parts.
  • These inserted further parts may all be “second parts” within the meaning of the present invention, i. have a suitable coating and contain the ingredients mentioned.
  • an additional "rinse aid core” of gluverzögert ready-made surfactant or a fast-dissolving pre-rinse phase from dissolution accelerated ready-made enzyme and / or bleach for example, an additional “rinse aid core” of losenverzögert ready-made surfactant or a fast-dissolving pre-rinse phase from dissolution accelerated ready-made enzyme and / or bleach.
  • Corresponding cleaning agents in which the first part has at least two cavities, one of which contains the second part, while the other includes a further, functionalized part, are preferred according to the invention.
  • a base tablet comprising a "second part" according to the present invention can be provided with a notch. The consumer may then break off part of the tablet along the notch and place it in the cutlery basket while the remainder of the tablet is placed in the dosage box.
  • the broken part the composition of which may be the same as or different from the base tablet, unfolds its effect in the pre-rinse cycle, while the remainder via the metering chamber is only used in the main wash cycle.
  • the "second part" for the purposes of the present invention may be both part of the broken part and of the other part of such a tablet.
  • first and second parts (and optionally other parts) of the cleaning agent according to the invention need not necessarily be made up as a compact molding, even if this is preferred for handling reasons for the consumer. It is also possible, for example, a first and a second (and optionally other parts) separately prepared and packaged together in a bag of water-soluble film, which is placed by the consumer in the machine. Regardless of the type of packaging, the second part unfolds its effect essentially in the rinse cycle of the dishwasher by the coating.
  • agents that not only save the consumer the dosage of regenerating salt, but also already contain the rinse aid.
  • This can be realized by incorporation of surfactant (s) in the second part (see above).
  • Another way is to incorporate the surfactants into the first part, which advantageously is in solid form, i. is present as a powder or tablet.
  • cleaning agents according to the invention are preferred, which are characterized in that the content of the first part of nonionic surfactants from 5 to 25 wt .-%, each based on the first part.
  • the amounts of surfactants remaining in the machine after the main rinse and the intermediate rinses cause an adequate run-off behavior in the rinse cycle, so that the water running off the items does not stain during drying.
  • the rinse cycle does not need to be charged with additional intentionally added rinse aid when using these agents according to the invention.
  • formerly surfactant-containing powder or granules can be done for example by conventional granulation.
  • carrier materials are placed in a mixer and mixed with the / the surfactant (s) / granulated, which in the case of several surfactants used, these can be added either together or in succession.
  • subsequently finely divided material is added (“powdered"), the powder properties of the granules can be significantly improved again.
  • the known substances of the prior art can be used, in the context of the present invention, in particular disilicates have proven to be particularly advantageous.
  • other finely divided substances such as soda or phosphate, or overdried water glasses, ground ingredients of cleaning agents, etc ..
  • granulate carrier materials such as zeolites, sodium carbonate, sodium tripolyphosphate, maltodextrins, polyvinyl alcohols, starch and / or their derivatives, and also cellulose and / or their derivatives with the addition of the nonionic surfactants identified above as preferred and then in themselves known manner with a sodium silicate solution to spray in order to achieve at least partial coating of the granules.
  • silicate solution it is also possible with advantage to use a solution of polyvinyl alcohol.
  • the granules can be dried after production in a conventional manner (advantageously by fluidized bed drying) and optionally additionally "powdered” with finely divided substances such as zeolite and / or silicic acids.
  • the high-surfactant-containing granules can then be prepared in a conventional manner with other components (bleach, enzymes, etc.) to detergents.
  • the coated second parts can be added directly, so that a particulate inventive detergent results.
  • the coated second parts in such machine dishwashing detergents according to the invention are prepared by their coating so that they do not dissolve or only to a minor extent in the main wash cycle (and also in optional pre-wash cycles). This ensures that the active substances are released only in the rinse cycle and unfold their effect here.
  • physical packing is required in addition to this chemical preparation, so that the coated second parts are not pumped out when changing the water in the machine and are thus no longer available to the rinse cycle.
  • Domestic dishwashers contain before the drain pump, which pumps the water or the cleaning solution after each cleaning cycles out of the machine, a strainer, which is to prevent clogging of the pump by dirt residues.
  • coated second parts in the cleaning agents according to the invention are now in terms of their size and shape preferably designed so that they the sieve insert of the dishwasher, even after the cleaning cycle, i. after exposure to movement in the machine and the cleaning solution, do not happen. In this way, it is ensured that coated in the final rinse cycle second parts are in the dishwasher, which release the active substance (s) under the action of the water flowing to the rinse cycle and bring the desired Klarillon soap.
  • preferred automatic dishwashing detergents are characterized in that the coated second parts have particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm.
  • the coated second parts having the above-mentioned sizes may protrude from the matrix of the other particulate ingredients, but the other particles may likewise have sizes which are in the stated range, so that overall a detergent is formulated which consists of large detergent particles and coated second parts.
  • the coated second parts are colored, ie, for example, have a red, blue, green or yellow color, it is advantageous for the appearance of the product, ie the entire cleaning agent, if the coated second parts are visibly larger than the matrix of the particles of the remaining ingredients of the cleaning agent.
  • automatic dishwashing agents according to the invention are preferred which (without consideration of the coated second parts) have particle sizes between 200 and 3000 ⁇ m, preferably between 300 and 2500 ⁇ m and in particular between 400 and 2000 ⁇ m.
  • optical appeal of such compositions can be increased not only by the coloration of the coated second parts, but also by contrasting coloring of the powder matrix or by the shape of the coated second parts. Since technically uncomplicated methods can be used in the production of the coated second parts, it is easily possible to offer these in a wide variety of forms.
  • particle shape which has approximately spherical shape, for example, cylindrical or cube-shaped particles can be produced and used. Other geometric shapes can be realized.
  • Specific product embodiments may include, for example, star shaped rinse aid particles. Slices or forms that show as a base plant and animal body, such as tree, flower, flower, sheep, fish, etc., are easy to produce. Interesting optical incentives can be created in this way also by making the coated second parts in the form of a stylized glass to underline the Klar Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff Kunststoff
  • the cleaning agents according to the invention are formulated as a powder mixture, partial segregation may occur, in particular in the case of greatly varying sizes of coated second parts and detergent matrix, on the one hand when the package is shaken.
  • the dosage may be different in two successive cleaning cycles, since the consumer is not always necessarily the same amount of detergent and coated second parts dosed. If it would be desirable to use a technically the same amount per cleaning cycle, this can be achieved by means of the packaging of the agents according to the invention in bags made of water-soluble film familiar to the person skilled in the art. Particulate machine dishwashing detergents in which a dosing unit is shrink-wrapped in a bag made of water-soluble film are also the subject of the present invention.
  • the consumer has only one bag containing, for example, a detergent powder and a plurality of visually protruding coated second parts to insert in the dispenser of his dishwasher.
  • This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.
  • the above-described desired restraint of the coated second parts in the machine even with water changes can be realized in addition to the above-mentioned increase in the rinse aid particles by reducing the size of the holes in the sieve.
  • automatic dishwashing detergents which have a uniform average particle size which is smaller than, for example, 4 to 12 mm.
  • the product according to the invention, in which also the coated second parts have smaller particle sizes is added to a sieve insert which replaces or covers the insert located in the machine.
  • Another object of the present invention is therefore a kit-of-parts comprising a powdered machine dishwashing detergent according to the invention and a sieve insert for household dishwashers.
  • kits-of-parts according to the invention in which the particle sizes of the automatic dishwashing detergent (taking into account the coated second parts) are in the range from 400 to 2500 .mu.m, preferably from 500 to 1600 .mu.m and in particular from 600 to 1200 .mu.m, are preferred.
  • kits-of-parts according to the invention are preferred in which the mesh size or hole size of the sieve insert is 1 to 4 mm and the coated second parts are larger than this mesh size or hole size of the sieve insert.
  • the kit-of-parts according to the invention is not limited to the particular shape of the sieve insert, in which this substitutes or covers the insert located in the machine. It is also possible and preferred according to the invention to add a sieve insert to the kit-of-parts which has the shape of a basket which can be hung in the dishwasher in a known manner, for example on the cutlery basket. In this way, a sieve insert thus configured replaces the dosing chamber, i. The consumer doses the machine dishwashing detergent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.
  • the detergents according to the invention with a high surfactant content in the first part can also be prepared in the form of shaped bodies. In the simplest case, this is done by tableting the above-mentioned powdered detergent.
  • the coated second part - as already described above - later be glued to the molding, or glued or inserted into a prepared cavity of the base molding.
  • Preferred biphasic base tablets contain, for example, a phase containing up to 30, preferably up to 20 and especially up to 15% by weight of surfactants (based on phase) of phosphate, sodium carbonate, silicate and bleach, while a second phase contains enzymes, bleach activators , Silver protectants and dyes and up to 20, preferably up to 10 and in particular up to 5 wt .-% (based on the phase) of surfactant.
  • Such biphasic moldings can then be joined to the coated second part and give inventive cleaning agents in tablet form.
  • Plastic inserts or attachments are in direct contact with the die wall during compression and are usually manufactured on polyamide. Plastic inserts are inserted into tabletting punches with faceted edges and reduce the risk of caking on the pressing surface.
  • Another possibility is to arrange the surfactant-rich premix in the middle of a three-layer tablet.
  • the upper and lower layers can be formulated so that caking problems do not occur.
  • multiphase embodiments are preferred for a surfactant-rich base tablet, i.
  • Cleaning agents which are characterized in that the first part or at least one phase of a multiphase first part has a content of nonionic surfactants between 5 and 25 wt .-%, each based on the first part or on the phase of the first part ,
  • step A the body referred to above as “second part” is prepared, which is coated in step B) and combined in step C) with a composition ("base composition” or “base molding”) to form the finished cleaning agent according to the invention.
  • base composition or “base molding”
  • the second part can be produced by casting, extruding, granulating, extruding, pelleting, sintering, foaming, etc.
  • Particularly preferred as second parts are tabletted products which, because of their compact structure, can be coated particularly well with a suitable mold. Processes according to the invention in which the preparation in step A) is carried out by tableting are therefore particularly preferred.
  • step A) The tableting of the "second part" in step A) is analogous to a tabletting of a base molding as an option for step C), wherein it has proven to be advantageous if the pre-mixture compressed into "second parts" or basic molded articles meets certain physical criteria.
  • Preferred processes are characterized, for example, by the fact that particulate premixes to be compressed have a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
  • the particle size of the pre-mixture pressed into "second parts" or base moldings preferably also satisfies certain criteria: Processes in which particle-shaped premixes have particle sizes between 100 and 2000 .mu.m, preferably between 200 and 1800 .mu.m, more preferably between 400 and 1600 .mu.m and in particular between 600 and 1400 ⁇ m, are preferred according to the invention. A further narrowed particle size in the premixes to be compressed can be adjusted to obtain advantageous molded body properties.
  • particulate premixes to be compressed have a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles is greater than 1600 ⁇ m or smaller than 200 ⁇ m.
  • Particularly advantageous process variants are characterized in that the particulate premixes to be compressed have a particle size distribution in which more than 30 wt .-%, preferably more than 40 wt .-% and in particular more than 50 wt .-% of the particles have a particle size between 600 and 1000 microns have.
  • the preferred process according to the invention is not restricted to the fact that only a particulate premix is pressed into a shaped body. Rather, this process step - in particular in the production of base moldings, see above - can also be extended to the effect that one prepares in a conventional manner multilayer moldings by preparing two or more premixes which are pressed together.
  • the first-filled premix is slightly pre-pressed to get a smooth and parallel to the mold bottom extending top, and end-pressed after filling the second premix to the finished shaped body.
  • a further pre-compression takes place after each premix addition, before the shaped article is end-pressed after the last premix has been added.
  • the cavity described above in the base molding is a trough, so that preferred embodiments of the first method according to the invention are characterized in that multi-layered moldings having a trough, are prepared in a conventional manner by several different particulate premixes are pressed together.
  • the production of the moldings is carried out first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent InformML, in particular compression to tablets, wherein conventional methods can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and transported away by subsequent transfer devices. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drik to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Tableting machines suitable for the purposes of the present invention are obtainable, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the moldings can - as already mentioned above - be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the various components are not pressed into a unitary tablet, but that moldings (in particular base moldings, see above) are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution.
  • moldings in particular base moldings, see above
  • the layer structure of the moldings can be carried out both in a batch-like manner, whereby a dissolution process of the inner layer (s) takes place at the edges of the molded article already then, however, if the outer layers are not yet fully dissolved, complete envelopment of the inner layer (s) by the further outer layer (s) may be achieved, preventing the premature dissolution of internal components Layer (s) leads.
  • a shaped body in particular basic shaped body, see above
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the stacked shaped body the Both outer layers and the shell-shaped body, the outermost layers, however, are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the second step of the process of the invention comprises applying the coating.
  • conventional methods of coating bodies can be used, in particular the immersion of the body in or the spraying of the body with a melt, solution or dispersion of said coating materials.
  • an aqueous solution of one or more of the stated coating materials is sprayed onto the shaped bodies produced in step A), the aqueous solution, based in each case on the solution, being from 1 to 20% by weight, preferably from 2 to 15% by weight.
  • % and in particular 4 to 10 wt .-% of one or more of said coating materials optionally up to 20 wt .-%, preferably up to 10 wt .-% and in particular below 5 wt .-% of one or more water-miscible solvent and as the rest water, contains.
  • water-miscible volatile solvents can be added to the aqueous solution.
  • these are in particular from the group of alcohols, with ethanol, n-propanol and iso-propanol being preferred.
  • ethanol and isopropanol are particularly recommended.
  • the coating of anhydrous or low-water solutions may be advantageous for certain coating materials.
  • step B) comprises the application of one or more, preferably two or three coating layers.
  • step A) is coated in step B) with an LCST polymer.
  • composition with which the coated second part is made up for the cleaning agent according to the invention can take on any physical form, as described in detail above.
  • the base molding has one or more cavities, of which at least one contains the coated second part, are preferred.
  • the composition in step C) is a multi-phase detergent tablet having a cavity into which the coated body from step B) is glued or is pressed.
  • the second part may adhere to the first part only by the mold, but it is preferable to either press or glue into the first part for better transportation and handling stability, so that it is adhesively bonded thereto.
  • Gluing is preferred over mechanical fastening by pressing, since the risk of destroying the coating of the second part is less.
  • adhesion promoter is applied to one or more molding surfaces. This can be done in the above-mentioned method in which two moldings are joined together, either in the molded body with cavity or in the molding that fills the cavity. In preferred methods, adhesion promoters are introduced into the cavity of the molding.
  • adhesion promoter is applied to one or more surfaces, preferably to one surface, of the coated second part.
  • adhesion promoter to preferably one surface of the coated second part can be done in different ways. It is possible, for example, to wet the coated second part in the dipping process on one side with adhesive and then to place it in the cavity. This technique is technologically easy to implement, but involves the risk that adhesive contaminates the surface of the molding with cavity. The amount of adhesive can be controlled in this variant by varying the rheological properties of the adhesion promoter.
  • a further possibility, which is preferred in the context of the present invention, of applying adhesion promoters to preferably one surface of the coated second part consists of passing this dosing unit past adhesive dosing systems and subsequently placing it in the cavity. This is achieved by adhesion promoter dosing nozzles, impregnated with adhesion promoters brushes or nonwovens or by rolling.
  • the latter method design is particularly easy to implement, since the coated second part has only a small contact surface to the roller.
  • the bonding agent can be metered from the interior of the roll, but it is also possible to apply the bonding agent at a position which is remote from the point of contact of the roller with the coated second parts, on the roller. Methods in which the application of the adhesion promoter (s) takes place on a surface of the coated second part, preferably using adhesion promoter-transferring rolls, brushes or nonwovens, are therefore preferred.
  • the filling of the cavity can fill the cavity completely, but it can also protrude from the cavity or fill it only partially, the imagination of the product developers are no limits.
  • the shape of the molded body with a continuous hole or trough, the shape of the trough or the hole and the shape of the coated second part, it is possible to produce a variety of shape body variations that differ visually from one another.
  • the circular ring shaped body described above can be filled with a circular hole with a form-fit cylinder.
  • a ball, a square adjacent to the edges, a three-, five- or six-sided prism or another irregular shape it is also possible to realize octahedral, multi-capped prismatic or icosahedral forms for the coated second part.
  • the adhesion of the coated second part in the cavity decreases with decreasing contact area. Maximum adhesion between the two moldings is achieved when the ring or mold body and the coated second part without gaps fit together form-fitting.
  • the said principle can be extended accordingly to further multi-phase detergent tablets.
  • four-phase moldings can be produced by connecting two biphasic moldings to one another.
  • four-phase 3: 1 moldings can be produced.
  • the two-phase molded bodies to be joined can also be produced in other ways.
  • an active substance for example, as a melt, powder, granules, extrudate, flakes, etc.
  • a wide variety of options can be varied, for example, a two-layer molded body, the trough is filled with a melt or a particulate mixture, wherein on the molded body side, which has the trough, another molded body is applied adherent.
  • the trough is virtually the "core", since the filling is now enclosed on all sides.
  • Completely identical can be moved with a molding which has a through hole ("ring molding") and because on both sides with a further molding "closed” is. Is essential to the invention in all these embodiments only that at least one phase is a coated second part in the context of the invention.
  • the primer can overcome the disadvantages mentioned.
  • the adhesion promoter need not be applied on all four edges. It can rather contribute to even faster separation of the compound, apply only at the four corners adhesion promoter points. For even faster separation can be dispensed with individual adhesion promoter points, so that, for example, only two diagonally opposite contact corners are provided with adhesion promoter.
  • the shape of the molded body parts to be joined with the adhesion promoter can also accelerate the dissolution.
  • moldings are preferred which are as free as possible against each other after dissolution of the bonding agent compound, so no toroidal moldings, but preferably basic body having "satellite shaped bodies" on their outer surfaces.
  • moldings which are orthorhombic, tetragonal or cubic are preferred.
  • Shaped bodies with a circular base surface can only be glued along their lateral surface by means of correspondingly biconcave-shaped intermediate pieces, which in turn are more difficult to be tabletted. Nevertheless, the joining together of such moldings is possible according to the invention.
  • a further subject of the present invention is therefore a combination of (a) cleaning agent according to the invention, in particular cleaning agent shaped body (s) and a packaging system containing the cleaning agent (s), the packaging system having a moisture vapor transmission rate of 0.1 g / m 2 / Day to less than 20 g / m 2 / day, when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85%.
  • the packaging system of the combination of detergent and cleaning composition shaped bodies (s) and packaging system has according to the invention has a moisture vapor permeability rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system at 23 ° C and a relative Equilibrium moisture content of 85% is stored.
  • the temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
  • the moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity").
  • the measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested.
  • A is the area of the material to be tested in cm 2
  • x is the weight gain of calcium chloride in g
  • y is the exposure time in h.
  • the relative equilibrium moisture in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C.
  • the absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is expressed in g / m 3 .
  • saturation content For example, 1 m 3 of air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor.
  • the relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature.
  • inventive combinations of detergent or detergent tablet (s) and packaging system can of course be in turn in secondary packaging, such as cardboard or trays, packed, with no secondary requirements on the secondary packaging must be made.
  • secondary packaging such as cardboard or trays, packed, with no secondary requirements on the secondary packaging must be made.
  • the secondary packaging is therefore possible, but not necessary.
  • Packaging systems preferred in the present invention have a moisture vapor transmission rate of from 0.5 g / m 2 / day to less than 15 g / m 2 / day.
  • the packaging system of the combination according to the invention encloses a certain amount of cleaning agent or one or more detergent tablets. It is inventively preferred either to make a shaped body such that it comprises an application unit of the cleaning agent, and to pack this shaped body individually, or to pack the number of moldings in a packaging unit, which in sum comprises an application unit.
  • a desired dosage of 80 g of detergent it is thus possible according to the invention to produce a 80 g detergent detergent body and pack individually, but it is also possible according to the invention to pack two 40 g detergent tablets in a package in order to arrive at a combination according to the invention.
  • combinations according to the invention can also contain three, four, five or even more detergent tablets in one packaging unit.
  • two or more moldings in a package may have different compositions. In this way, it is possible to spatially separate certain components, for example to avoid stability problems.
  • the packaging system of the combination according to the invention may consist of a wide variety of materials and take on any external forms. For economic reasons and for reasons of easier processability, however, packaging systems are preferred in which the packaging material has a low weight, is easy to process and inexpensive.
  • the packaging system consists of a bag or sack of single-layer or laminated paper and / or plastic film.
  • the detergent tablets may be unsorted, i. as a loose filling, be filled in a bag of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent tablets individually or in a plurality of different sizes into sacks or bags. For individual application units of the detergent tablets, which are located in a bag or bag, the term "flow pack" has become common in the art. Such "flow packs” can then - again preferably sorted - optionally be packaged in outer packaging, which emphasizes the compact form of the molded article.
  • the preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become.
  • Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded.
  • Plastic films which can be used in the context of the present invention as a packaging system, for example, in Hans Domining House "The plastics and their properties", 3rd edition, VDI Verlag, Dusseldorf, 1988, page 193 .
  • the figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.
  • particularly preferred combinations contain as packaging system a bag or bag of single-layer or laminated plastic film having a thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.
  • the packaging system does not comprise cardboard boxes of wax-coated paper.
  • the detergents or detergent tablets of the combination according to the invention contain, depending on their intended use, further ingredients of detergents in varying amounts. Regardless of the intended use of the moldings, it is preferred according to the invention that the cleaning agent or the detergent moldings have / have a relative equilibrium moisture content of less than 30% at 35.degree.
  • the relative equilibrium moisture content of the cleaning agents or detergent tablets can be determined by conventional methods, the following procedure being selected in the context of the present investigations: A water-impermeable 1-liter vessel with a lid which has a closable opening for the introduction of samples filled with a total of 300 g detergent or detergent tablets and held for 24 h at a constant 23 ° C to ensure a uniform temperature of the vessel and substance.
  • the water vapor pressure in the space above the moldings can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England).
  • the water vapor pressure is now measured every 10 minutes until two consecutive values show no deviation (equilibrium humidity).
  • the above-mentioned hygrometer allows a direct display of the recorded values in% relative humidity.
  • the packaging system is reclosable. Combinations in which the packaging system has a microperforation can also be realized according to the invention with preference.
  • compositions according to the invention can be used in all household dishwashing machines, with no limitations as regards the choice of program.
  • the beneficial effects are achieved both in low temperature programs such as 45 ° C programs or glasses programs as well as in 50/55 ° C or 60/65 ° C programs.
  • a further subject of the present invention is therefore a method for cleaning dishes in a domestic dishwasher, in which a particulate automatic dishwashing agent according to the invention is introduced into the main cleaning cycle of the machine.
  • the introduction into the main cleaning gear can be done by filling the dosing with the powder, which is released by opening the dosing after a possible Vorthesesgang the powder in the machine.
  • it can be dispensed with a Vorthesesgang. Due to the composition according to the invention, no additional rinse aid needs to be metered in the rinse cycle. inventive methods in which the rinse cycle of the machine is carried out without the deliberate addition of further rinse aid, are therefore preferred.
  • cleaner includes liquid commercial rinse aid, which must be given by the consumer at intervals of several rinsing cycles in a reservoir of the machine and programmatically released from there. This deliberate addition of a rinse aid and the required for this second dosing at a distance of some rinsing cycles are not required by the use of the means according to the invention.
  • step b) the additional intentional dosage of commercially available rinse aid is not required, so that methods are preferred in which in step b) no further rinse aid is intentionally added.
  • the mentioned methods for cleaning dishes also make the dosage of additional regenerating salt after several cleaning cycles superfluous.
  • the cleaning methods are not tied to the offer form of the powdered cleaner, so that a method for cleaning dishes in a domestic dishwasher, in which a detergent tablet according to the invention is introduced into the main cleaning cycle of the machine, an embodiment of the present invention.

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Claims (36)

  1. Agent de nettoyage pour le lavage de vaisselle en machine, comprenant
    a) une première partie (composition de base) qui déploie son activité essentiellement dans le processus de nettoyage principal du lave-vaisselle et
    b) une deuxième partie, qui, grâce à un revêtement approprié, déploie son activité essentiellement dans le processus de rinçage du lave-vaisselle,
    caractérisé en ce que la deuxième partie contient une ou plusieurs substances du groupe constitué par les polymères inhibant les dépôts, où le ou les polymères inhibant les dépôts sont choisis dans le groupe constitué par les homopolymères ou copolymères cationiques, en particulier la gomme guar d'hydroxypropyltriméthylammonium, les copolymères de méthacrylate d'aminoéthyle et d'acrylamide, les copolymères de chlorure de diméthyldiallylammonium et d'acrylamide, les polymères avec des groupes imino, les polymères qui présentent comme unités monomères des groupes alkylméthacrylate d'ammonium quaternisés, les polymères cationiques de monomères tels que l'alkyl(méth)acrylate ou l'alkyl(méth)acrylamide de trialkylammonium ; les sels de dialkyldiallyldiammonium ; les produits de transformation, analogues à des polymères, d'éthers ou d'esters de polysaccharides avec des groupes ammonium latéraux, en particulier les dérivés de la gomme guar, de la cellulose et de l'amidon ; les produits de polyaddition d'oxyde d'éthylène avec des groupes ammonium ; les polymères d'éthylèneimine quaternaires et les polyesters et les polyamides avec des groupes latéraux quaternaires.
  2. Agent de nettoyage selon la revendication 1, caractérisé en ce que la deuxième partie contient un ou plusieurs complexants chélateurs en des quantités supérieures à 0,1% en poids, de préférence supérieures à 0,5% en poids, de manière particulièrement préférée supérieures à 1% en poids et en particulier supérieures à 2,5% en poids, à chaque fois par rapport au poids de la deuxième partie.
  3. Agent de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que la deuxième partie contient le ou les polymères inhibant les dépôts en des quantités supérieures à 5% en poids, de préférence supérieures à 10% en poids, de manière particulièrement préférée supérieures à 20% en poids et en particulier supérieures à 25% en poids, à chaque fois par rapport au poids de la deuxième partie.
  4. Agent de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la deuxième partie contient un ou plusieurs copolymères i) d'acides carboxyliques insaturés, ii) de monomères contenant des groupes acide sulfonique iii) le cas échéant d'autres monomères ioniques ou non ionogènes en des quantités supérieures à 5% en poids, de préférence supérieures à 10% en poids, de manière particulièrement préférée supérieures à 20% en poids et en particulier supérieures à 25% en poids, à chaque fois par rapport au poids de la deuxième partie.
  5. Agent de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la deuxième partie contient en outre 1 à 50% en poids, de préférence 2,5 à 45% en poids et en particulier 5 à 40% en poids d'agent(s) tensioactif(s) non ionique(s).
  6. Agent de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le revêtement de la deuxième partie comprend un polymère LCST (low critical solution temperature, température de solution critique basse).
  7. Agent de nettoyage selon la revendication 6, caractérisé en ce que le polymère LCST est choisi parmi les dérivés de cellulose, les acrylamides mono-N-alkylés ou di-N-alkylés, les copolymères d'acrylamides mono-N-substitués ou di-N-substitués avec des acrylamides et/ou des acrylates resp. des acides acryliques.
  8. Agent de nettoyage selon l'une quelconque des revendications 6 ou 7, caractérisé en ce que le polymère LCST est choisi parmi les éthers de cellulose, le polyisopropylacrylamide, les copolymères du polyisopropylacrylamide ainsi que les mélanges de ces substances.
  9. Agent de nettoyage selon l'une quelconque des revendications 6 à 8, caractérisé en ce que la température inférieure critique de séparation du mélange du polymère LCST est comprise entre 20°C et 90°C.
  10. Agent de nettoyage selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le revêtement de la deuxième partie est constitué par plusieurs couches de revêtement, de préférence de deux ou trois couches de revêtement.
  11. Agent de nettoyage selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la deuxième partie a été réalisée par un processus de compression, en particulier avec formation de comprimés.
  12. Agent de nettoyage selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la deuxième partie présente un diamètre entre 1 et 30 mm, de préférence entre 2,5 et 15 mm et en particulier entre 5 et 10 mm.
  13. Agent de nettoyage selon l'une quelconque des revendications 1 à 12, caractérisé en ce que la première partie contient des builders en des quantités de 1 à 100% en poids, de préférence de 5 à 95% en poids, de manière particulièrement préférée de 10 à 90% en poids et en particulier de 20 à 85% en poids, à chaque fois par rapport au poids de la première partie.
  14. Agent de nettoyage selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la première partie contient un ou des phosphates, de préférence un ou des phosphates de métal alcalin, de manière particulièrement préférée le triphosphate pentasodique ou pentapotassique (tripolyphosphate de sodium resp. de potassium) en des quantités de 20 à 80% en poids, de préférence de 25 à 75% en poids et en particulier de 30 à 70% en poids, à chaque fois par rapport au poids de la première partie.
  15. Agent de nettoyage selon l'une quelconque des revendications 1 à 14, caractérisé en ce que la première partie contient un ou des citrates, de préférence le citrate de sodium, de manière particulièrement préférée le citrate trisodique dihydraté, en des quantités de 10 à 60% en poids, de préférence de 15 à 50% en poids et en particulier de 20 à 40% en poids, à chaque fois par rapport au poids de la première partie.
  16. Agent de nettoyage selon l'une quelconque des revendications 1 à 15, caractérisé en ce que la première partie contient des agents de blanchiment du groupe des agents de blanchiment à base d'oxygène ou d'halogène, en particulier les agents de blanchiment à base de chlore, en préférant en particulier le perborate de sodium et le percarbonate de sodium, en des quantités de 2 à 25% en poids, de préférence de 5 à 20% en poids et en particulier de 10 à 15% en poids, à chaque fois par rapport au poids de la première partie.
  17. Agent de nettoyage selon l'une quelconque des revendications 1 à 16, caractérisé en ce que la première partie contient des activateurs de blanchiment du groupe des alkylènediamines polyacylées, en particulier la tétraacétyléthylènediamine (TAED), des N-acylimides, en particulier le N-nonanoylsuccinimide (NOSI), des phénolsulfonates acylés, en particulier le n-nonanoyloxybenzènesulfonate ou l'isononanoyloxybenzènesulfonate (n-NOBS resp. iso-NOBS) et le n-méthyl-morpholinium-acétonitrile-méthylsulfate (MMA), en des quantités de 0,25 à 15% en poids, de préférence de 0,5 à 10% en poids et en particulier de 1 à 5% en poids, à chaque fois par rapport au poids de la première partie.
  18. Agent de nettoyage selon l'une quelconque des revendications 1 à 17, caractérisé en ce que la première partie contient des agents de protection de l'argent du groupe des triazoles, des benzotriazoles, des bisbenzotriazoles, des aminotriazoles, des alkylaminotriazoles et des sels ou des complexes des métaux de transition, de manière particulièrement préférée le benzotriazole et/ou l'alkylaminotriazole, en des quantités de 0,01 à 5% en poids, de préférence de 0,05 à 4% en poids et en particulier de 0,5 à 3% en poids, à chaque fois par rapport au poids de la première partie.
  19. Agent de nettoyage selon l'une quelconque des revendications 1 à 18, caractérisé en ce que la première partie contient en outre une ou plusieurs substances des groupes des enzymes, des inhibiteurs de corrosion, des inhibiteurs de dépôts, des co-builders, des colorants et/ou des parfums, en des quantités totales de 6 à 30% en poids, de préférence de 7,5 à 25% en poids et en particulier de 10 à 20% en poids, à chaque fois par rapport au poids de la première partie.
  20. Agent de nettoyage selon l'une quelconque des revendications 1 à 19, caractérisé en ce que la première partie est une composition liquide, sous forme de gel ou pâteuse pour le lavage de vaisselle en machine.
  21. Agent de nettoyage selon l'une quelconque des revendications 1 à 19, caractérisé en ce que la première partie est une composition sous forme de particules pour le lavage de vaisselle en machine.
  22. Agent de nettoyage selon l'une quelconque des revendications 1 à 19, caractérisé en ce que la première partie est une composition sous forme de comprimé pour le lavage de vaisselle en machine.
  23. Agent de nettoyage selon la revendication 22, caractérisé en ce que la première partie est un comprimé à plusieurs phases, en particulier un comprimé à deux, trois ou quatre phases, en préférant que les phases présentent la forme de couches.
  24. Agent de nettoyage selon l'une quelconque des revendications 22 ou 23, caractérisé en ce que la deuxième partie revêtue présente la forme d'une autre couche, d'un noyau ou d'un corps, collé sur resp. dans la première partie ("comprimé de base").
  25. Agent de nettoyage selon l'une quelconque des revendications 22 à 24, caractérisé en ce que la première partie présente une ou plusieurs cavités dans lesquelles sont contenues la deuxième partie et le cas échéant d'autres parties.
  26. Agent de nettoyage selon la revendication 25, caractérisé en ce que la première partie présente au moins deux cavités, dont l'une contient la deuxième partie alors que l'autre contient une autre partie fonctionnalisée.
  27. Agent de nettoyage selon l'une quelconque des revendications 1 à 26, caractérisé en ce que la teneur de la première partie en agents tensioactifs non ioniques est de 5 à 25% en poids, à chaque fois par rapport à la première partie.
  28. Agent de nettoyage selon l'une quelconque des revendications 22 à 26, caractérisé en ce que la première partie ou resp. au moins une phase d'une première partie à plusieurs phases présente une teneur en agents tensioactifs non ioniques entre 5 et 25% en poids, à chaque fois par rapport à la première partie ou à la phase de la première partie.
  29. Procédé pour la préparation d'agents de nettoyage pour le lavage de vaisselle en machine, caractérisé par les étapes
    A) préparation d'un corps qui contient une ou plusieurs substances du groupe des polymères inhibant les dépôts, où le ou les polymères inhibant les dépôts sont choisis dans le groupe constitué par les homopolymères ou copolymères cationiques, en particulier la gomme guar d'hydroxypropyltriméthylammonium ; les copolymères de méthacrylate d'aminoéthyle et d'acrylamide, les copolymères de chlorure de diméthyldiallylammonium et d'acrylamide, les polymères avec des groupes imino, les polymères qui présentent comme unités monomères des groupes alkylméthacrylate d'ammonium quaternisés, les polymères cationiques de monomères tels que l'alkyl(méth)acrylate ou l'alkyl(méth)acrylamide de trialkylammonium ; les sels de dialkyldiallyldiammonium ; les produits de transformation, analogues à des polymères, d'éthers ou d'esters de polysaccharides avec des groupes ammonium latéraux, en particulier les dérivés de la gomme guar, de la cellulose et de l'amidon ; les produits de polyaddition d'oxyde d'éthylène avec des groupes ammonium ; les polymères d'éthylèneimine quaternaires et les polyesters et les polyamides avec des groupes latéraux quaternaires
    B) revêtement du corps préparé dans l'étape A)
    C) réunion du corps revêtu avec une composition qui déploie son activité essentiellement dans le processus de nettoyage principal du lave-vaisselle.
  30. Procédé selon la revendication 29, caractérisé en ce que la préparation dans l'étape A) est réalisée par compression en comprimés.
  31. Procédé selon l'une quelconque des revendications 29 ou 30, caractérisé en ce que le revêtement dans l'étape B) comprend l'application d'une ou de plusieurs, de préférence de deux ou de trois, couches de revêtement.
  32. Procédé selon l'une quelconque des revendications 29 à 31, caractérisé en ce que le corps préparé dans l'étape A) est revêtu dans l'étape B) par un polymère LCST.
  33. Procédé selon l'une quelconque des revendications 29 à 32, caractérisé en ce que la composition dans l'étape C) est une composition liquide, sous forme de gel ou pâteuse.
  34. Procédé selon l'une quelconque des revendications 29 à 32, caractérisé en ce que la composition dans l'étape C) est une composition sous forme de particules.
  35. Procédé selon l'une quelconque des revendications 29 à 32, caractérisé en ce que la composition dans l'étape C) est une composition sous forme de comprimés.
  36. Procédé selon la revendication 35, caractérisé en ce que la composition dans l'étape C) est un comprimé d'agent de nettoyage à plusieurs phases, qui présente une cavité dans laquelle le corps revêtu de l'étape B) est collé ou inséré par compression.
EP01962788A 2000-07-07 2001-06-27 Produits de lavage pour lave-vaisselle a utilite supplementaire Expired - Lifetime EP1299517B2 (fr)

Applications Claiming Priority (3)

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DE10032611A DE10032611A1 (de) 2000-07-07 2000-07-07 Maschinengeschirrspülmittel mit Zusatznutzen
DE10032611 2000-07-07
PCT/EP2001/007334 WO2002004588A1 (fr) 2000-07-07 2001-06-27 Produits de lavage pour lave-vaisselle a utilite supplementaire

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EP1299517A1 EP1299517A1 (fr) 2003-04-09
EP1299517B1 EP1299517B1 (fr) 2005-08-31
EP1299517B2 true EP1299517B2 (fr) 2010-05-19

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US (1) US20040106534A1 (fr)
EP (1) EP1299517B2 (fr)
AT (1) ATE303432T1 (fr)
AU (1) AU2001283894A1 (fr)
DE (2) DE10032611A1 (fr)
ES (1) ES2248383T5 (fr)
WO (1) WO2002004588A1 (fr)

Cited By (1)

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ATE303432T1 (de) 2005-09-15
DE10032611A1 (de) 2002-01-24
DE50107299D1 (de) 2005-10-06
WO2002004588A1 (fr) 2002-01-17
AU2001283894A1 (en) 2002-01-21
EP1299517A1 (fr) 2003-04-09
EP1299517B1 (fr) 2005-08-31
ES2248383T5 (es) 2010-10-25
US20040106534A1 (en) 2004-06-03

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