EP1727884B1 - Produits de lavage pour lave-vaisselle - Google Patents

Produits de lavage pour lave-vaisselle Download PDF

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Publication number
EP1727884B1
EP1727884B1 EP05700894A EP05700894A EP1727884B1 EP 1727884 B1 EP1727884 B1 EP 1727884B1 EP 05700894 A EP05700894 A EP 05700894A EP 05700894 A EP05700894 A EP 05700894A EP 1727884 B1 EP1727884 B1 EP 1727884B1
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EP
European Patent Office
Prior art keywords
weight
acid
dishwasher detergent
group
branched
Prior art date
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EP05700894A
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German (de)
English (en)
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EP1727884A1 (fr
Inventor
Ulrich Pegelow
Arnd Kessler
Christian Nitsch
Maren Jekel
Pavel Gentschev
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL05700894T priority Critical patent/PL1727884T3/pl
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • This application relates to detergents or cleaners.
  • this application relates to surfactant-containing detergents or cleaners.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.
  • rinse aid In order to obtain glossy and spotless dishes, it is therefore successfully used today rinse aid.
  • the addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss.
  • the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
  • the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed.
  • the temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task is primarily to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH regulators such as citric acid or scale-inhibiting polymers.
  • Liquid rinse aid which contain as nonionic surfactants mixed ethers.
  • a variety of different materials glass, metal, silver, plastic, porcelain
  • This variety of materials must be wetted as well as possible in the rinse cycle.
  • Rinse aid formulations which contain exclusively mixed ethers as the surfactant component do not fulfill these requirements or only to a small extent, so that the rinse effect or drying effect is unsatisfactory, especially in the case of plastic surfaces.
  • the storage tank in the dishwasher must be filled with rinse aid at regular intervals, with a filling sufficient for 10 to 50 rinses, depending on the machine type. If the filling of the tank is forgotten, then glasses in particular by lime stains and coverings become unsightly. In the prior art, therefore, there are some proposed solutions to integrate a rinse aid in the automatic dishwashing detergent. These proposed solutions are tied to the offer form of the compact molded article.
  • EP-A-0 851 024 Unilever ) two-layer detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agents and a continuous medium having a melting point between 55 and 70 ° C and scale inhibitors. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) are to be released with a delay and bring about a clear rinse effect. Powdered automatic dishwashing or surfactant-containing rinse systems are not mentioned in this document.
  • Detergents and cleansing tablets which, in addition to alkoxylated alcohols, may furthermore also contain hydroxy mixed ethers, are described in US Pat German patent application DE 100 48 058 A1 (Henkel ) disclosed.
  • the European patent application EP 916 717 A1 (Henkel-Ecolab ) has hydroxy mixed ether-containing agents for cleaning hard surfaces the subject.
  • the new dishwashing agents should contain their cleaning and rinsing performance, regardless of the formulation, in particular without the addition of high-melting additives. Furthermore, the new automatic dishwashing detergents should be distinguished from conventional detergents by improved shelf life and processability.
  • automatic dishwashing detergent solid or liquid additives for machine dishwashing
  • the group of automatic dishwashing detergents therefore includes, for example, the compact automatic dishwashing detergents with combined cleaning and rinsing function ("2 in 1" products) and the compact ones automatic dishwashing detergent with combined cleaning, rinsing and desalting function ("3 in 1" products) or the simple, separately dosed rinse aid.
  • Such nonionic surfactants can be prepared, for example, by reacting an epoxide of the general formula R 1 -CH (O) CH 2 , in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24- alkyl or Alkenylrest stands with an alcohol of the general formula HO- (AO) w - (A'O) x - (A "O) y - (A ''O) z -R 2 , in which R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • A, A ', A "and A"' independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH ( CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH
  • a particularly preferred embodiment of the present application comprises automatic dishwashing detergents, characterized in that they contain, as non-ionic surfactant (s) F, a nonionic surfactant of the general 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.
  • non-ionic surfactant (s) F a nonionic surfactant of the general 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
  • the indicated C chain lengths and degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the production process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which may result in mean values for the C chain lengths as well as the degrees of alkoxylation and, consequently, fractional numbers.
  • particularly preferred nonionic surfactants present in the agents according to the invention are characterized with respect to the radicals R 1 and R 2 and the indices x and y.
  • Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these. No.
  • nonionic surfactants F of the general 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 , for is a saturated, unbranched aliphatic hydrocarbon radical having 8 to 12 carbon atoms, preferably having 8 to 10 carbon atoms, further R 2 is a saturated, linear hydrocarbon radical having 8 to 12 carbon atoms, preferably with 8 hydrocarbon radicals, and in which x is 1 or 2, while y stands for values between 18 and 24, preferably for values from 20 to 24.
  • Another particularly preferred embodiment of the present application comprises automatic dishwashing agents which contain, as nonionic surfactant (s) F, a nonionic surfactant of the general formula R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) R 2 in which R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which are preferably have from 1 to 5 hydroxyl groups and are preferably further functionalized with an ether group, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl 2-butyl radical and x stands for values between 1 and 40.
  • nonionic surfactant (s) F a nonionic surfactant of the general formula R 1 O [CH 2 CH (R
  • automatic dishwasher detergents characterized in that they contain, as nonionic surfactant (s) F, a nonionic surfactant of the general formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 containing, in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radical having 1 to 30 carbon atoms R 2 , which is a monohydroxylated intermediate group - CH 2 CH (OH) - adjacent and in which x stands for values between 1 and 90.
  • s nonionic surfactant
  • R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, further a linear or branched, saturated or unsaturated
  • the indicated C chain lengths and degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the production process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which may result in mean values for the C chain lengths as well as the degrees of alkoxylation and, consequently, fractional numbers.
  • nonionic surfactants contained in the agents according to the invention with respect to the radicals R 1 and R 2 and the index x.
  • Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these. No.
  • nonionic surfactants F of the general formula R 1 O [CH 2 H 2 O] x CH 2 CH (OH) R 2 , in which R 1 is a saturated, unbranched aliphatic hydrocarbon radical having 8 to 12 carbon atoms , preferably having 10 carbon atoms, furthermore R 2 stands for a saturated, linear hydrocarbon radical with 8 to 12 carbon atoms, preferably with 8 hydrocarbon radicals, and in which x stands for values between 14 and 26, preferably for values from 20 to 24.
  • nonionic surfactant (s) F a nonionic surfactant of the general formula embedded image in which R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , - CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably is -CH 3 , and x and y are independent CH (CH 3 ) 2 , but preferably is -CH 3 , and x and y independently of one another are values between 1 and 32, with nonionic surfactants having values of x from 15 to 32 and y of 0.5 and 1.5 completely are particularly preferred.
  • nonionic surfactant (s) F a nonionic surfactant of the general formula embedded image in which R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon
  • the surfactant systems according to the invention contain a nonionic surfactant G of the general formula R 1 -O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 , in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A ', A "and A”' independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 - , -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values
  • nonionic surfactants G have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • non-ionic surfactant (s) G is a nonionic surfactant of the general formula
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched in the 2-position or Ilneare and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • R 1 in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which have a C 9-16 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units are particularly preferred for use in the agents according to the invention.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical averages, which for a particular product may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers
  • the surfactant system according to the invention comprises two nonionic surfactants F and G.
  • the automatic dishwashing detergent according to the invention may also contain further nonionic or ionic surfactants.
  • Preferred automatic dishwashing detergents are characterized in that the surfactant system comprises the nonionic surfactants F and G in a weight ratio of F: G between 2: 9 and 90: 1, preferably between 1: 3 and 80: 1, preferably between 3: 7 and 70: 1, more preferably between 7:13 and 60: 1 and in particular between 2: 3 and 50: 1.
  • the automatic dishwashing compositions according to the invention contain from 0.01 to 10% by weight of a polymer having a molecular weight of 2000 gmol -1 or more, which has at least one positive charge.
  • automatic dishwashing detergents which, based in each case on the total weight of the automatic dishwashing detergent, are between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, more preferably between 0, 01 and 4 wt .-%, most preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent contains. a polymer having a molecular weight of 2000 gmol -1 or more, which has at least one positive charge.
  • the above positive charge polymers may in principle be cationic or amphoteric polymers.
  • Preferred machine dishwashing detergents according to the invention are characterized in that the polymer comprising cationic monomer units is a cationic polymer and / or an amphoteric polymer.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be present, for example, in the polymer chain (Alkyl) ammonium groups or other positively charged groups can be realized.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the poly-mers under the INCI names Polyquatemium 2, Polyquatemium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • particularly preferred cationic or amphoteric polymers comprise as monomer unit a compound of the general formula (I) in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group acting; x and y independently represent integers between 1 and 3.
  • R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group acting
  • x and y independently represent integers between 1 and 3.
  • X - represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula (VII) are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • polymers which have a cationic monomer unit of the general formula (I) in which R 1 and R 4 are H, R 2 and R 3 are methyl and x and y are each 1.
  • R 1 and R 4 are H
  • R 2 and R 3 are methyl
  • x and y are each 1.
  • R 1 HC R 2 -C (O) -NH- (CH 2 ) x -N + R 3 R 4 R 5 X- (II) in which R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH
  • Automated dishwashing detergents preferred according to the invention are characterized in that the polymer having a molecular weight of 2000 gmol -1 or more and having at least one positive charge contains diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.
  • amphoteric polymers have not only cationic groups but also anionic groups.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred employable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) -ammonium chloride.
  • amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl - (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth ) acrylic acid copolymers and their alkali metal and ammonium salts.
  • All of these products contain, as a first essential ingredient, one or more polymer (s) having a molecular weight of 2000 gmol -1 or above, which has at least one positive charge.
  • the compositions of the invention have a weight fraction of these polymers between 0.01 and 10 wt .-%, each based on the total weight of the automatic dishwashing detergent.
  • the weight fraction of the polymer a) is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.
  • the group of phosphonates is one of the complexing agents and includes a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriamine penta
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates. Particular preference is given to those automatic dishwashing compositions which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the weight fraction of the phosphonate (s) b) in the total weight of the automatic dishwashing agent is at least equal to the weight fraction of the polymer (s) a).
  • those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of phosphonate b) is at least 1: 1, preferably 1: 1 to 200: 1, preferably 2: 1 to 150: 1, particularly preferred 3: 1 to 120: 1, most preferably 4: 1 to 100: 1 and especially 10: 1 to 100: 1
  • the automatic dishwasher detergents according to the invention may furthermore comprise condensed phosphates.
  • the group of condensed phosphates can be divided into metaphosphates and polyphosphates.
  • the metaphosphates correspond to compounds of the general formula (MPO 3 ) x .
  • M is a cation, preferably an alkali metal
  • x is a number greater than or equal to 5.
  • the polyphosphates as well as the aforementioned phosphonates are among the complexing agents.
  • the stated degree of condensation x of the general formula (MPO 3 ) x represents a statistical average, which may be an integer or a fractional number for a specific product. Preferred degrees of condensation have a narrow homolog distribution.
  • the group of polyphosphates includes compounds of the general formula M x + 2 P x O 3x + 1 or M x H 2 P x O 3x + 1 .
  • condensed phosphates takes place, for example, by condensation of NaH 2 PO 4 or KH 2 PO 4 .
  • the resulting polyphosphates can cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium and potassium polyphosphates, can distinguish.
  • hot or cold phosphates Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • condensed phosphates are the condensed phosphates of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , in which M is a cation, preferably an alkali metal, more preferably sodium or potassium, and x is a number greater than or equal to 5, preferably greater than 5, preferably greater than 6, more preferably greater than 8, even more preferably greater than 10 and especially greater than 12.
  • M is a cation, preferably an alkali metal, more preferably sodium or potassium
  • x is a number greater than or equal to 5, preferably greater than 5, preferably greater than 6, more preferably greater than 8, even more preferably greater than 10 and especially greater than 12.
  • the particularly preferred condensed phosphates include, for example, the glassy condensed polyphosphate of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , where x is a Number between 15 and 20, the condensed polyphosphates of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , where x is a number between 40 and 50.
  • water-soluble condensed polyphosphates of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , where x is a number between 12 and 800, preferably between 12 and 600, more preferably between 12 and 400 and in particular between 12 and 100.
  • the automatic dishwashing compositions according to the invention can be two or more different condensed phosphates of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , where M for a Cation and x is a number greater than or equal to 5 included.
  • the proportion by weight of the condensed polyphosphate (s) b) is of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , where M is a cation and x is a number greater than or equal to 5, the total weight of the automatic dishwashing agent is at least equal to the weight fraction of the polymer (s) a).
  • those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of the condensed polyphosphate b) is at least 1: 1, preferably 1: 1 to 200: 1, preferably 2: 1 to 150: 1 preferably 3: 1 to 120: 1, very particularly preferably 4: 1 to 100: 1 and in particular 10: 1 to 100: 1
  • compositions of the invention have a weight fraction of one or more phosphorus-containing complexing agent from the group of phosphonates and / or the condensed phosphates of the general formula (MPO 3 ) x , M x + 2 P x O 3x + 1 and / or M x H 2 P x O 3x + 1 , in which M is a cation, preferably an alkali metal, and x is a number greater than or equal to 5 is between 1.2 and 10 wt .-%, each based on the total weight of the automatic dishwashing on , In the context of the present application, however, preference is given to those automatic dishwasher detergents in which the weight fraction of the phosphorus-containing complexing agent b) is between 1.5 and 8% by weight, preferably between 1.7 and 7% by weight and in particular between 2, 0 and 6 wt .-%, each based on the total weight of the automatic dishwashing detergent is.
  • the weight ratio of constituents i) to constituents ii) is preferably between 10: 1 and 1:10, preferably between 7: 1 and 1: 7, more preferably between 6: 1 and 1: 6, even more preferably between 5: 1 and 1: 5 and in particular between 3: 1 and 1: 3.
  • the automatic dishwashing compositions according to the invention preferably comprise further washing and cleaning-active substances, in particular washing and cleaning-active substances from the group of bleach activators, builders, surfactants, enzymes, disintegration aids, electrolytes, pH adjusters, fragrances, Perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic co-builders and-where there are no ecological prejudices against their use-also the 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 and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • 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 likewise have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • these silicates preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, be present in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.
  • these compositions preferably contain at least one crystalline layered silicate of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22 , preferably from 1.9 to 4, and y is a number from 0 to 33.
  • the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .
  • crystalline phyllosilicates of the formula (I) in which x is 2.
  • x is 2.
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 H 2 O
  • Na-SKS-10 NaHSi 2 O 5 .3H 2 O, Kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 Na-SKS-13
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • these compositions in the context of the present application contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O from 0.1 to 20% by weight, preferably from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • Such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight .-% and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt.% And in particular at least 90 wt .-% of silicate of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O is.
  • 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 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.
  • the zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix.
  • 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 are particularly preferred Pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergents and cleaning agents industry the greatest importance.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and kallum) 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.
  • Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1.91 gcm -3 , melting point 60 °) or in the form of the monohydrate (density 2.04 gcm -3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na 2 HPO 4 , soft anhydrous or 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 mol.
  • Trisatriumphosphat (tertiary sodium phosphate) Na 3 PO 4 which as Dodecahydrat, as Decahydrat (according to 19 -20% P 2 O 5 ) and in anhydrous form (corresponding to 39-40% P 2 O 5 ) can be used.
  • Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 .
  • the tetrasodium diphosphate sodium pyrophosphate
  • Na 4 P 2 O 7 which is 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)
  • potassium salt potassium diphosphate potassium 4 P 2 O 7 .
  • the technically important pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate), is an anhydrous or 6 H 2 O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n -Na with n 3.
  • the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) is marketed, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O).
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which are also useful in 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
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate). , in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, in each case based on the weight of the washing or cleaning agent.
  • potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, especially preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or Reinigugnsstoffs used.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by gel-permutron 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.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of detergents or cleaners to (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric Aminodlcarbon Acid their salts or their precursors.
  • Particularly preferred are polyaspartic acids or their salts and.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • 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
  • 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.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Machine dishwashing detergents according to the invention which contain from 10 to 80% by weight, preferably from 15 to 75% by weight, particularly preferably from 20 to 70% by weight and in particular from 25 to 65% by weight, of one or more water-soluble builders are included the present application particularly preferred.
  • the group of surfactants in addition to the nonionic surfactants described above, further includes the anionic, cationic and amphoteric surfactants.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 18 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferably also 2,3-alkyl sulfates, which are obtained as commercial products of the Shell Oil Company under the name DAN ® are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic and the monoesters and / or Diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols represent.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol radicals or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • anionic surfactants are part of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • Suldonklare phenomenon-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) COOH (VI)
  • 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 for -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H (VII)
  • H 2 C CH-X-SO 3 H (VIIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIb)
  • HO 3 SX- (R 8 ) C C (R 7 ) -X-SO 3 H (VIIc)
  • 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 polymers used in monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative.
  • acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • copolymers which are structural units of the formula X are structural units of the formula X.
  • 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.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • 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 molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred detergent or cleaning compositions are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • Bleach activators are used, for example, in detergents or cleaners to achieve improved bleaching performance when cleaned at temperatures of 60 ° C and below.
  • As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • 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 and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -
  • bleach activators it is also 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 isononyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-di-hydrofuran, n-methyl-morpholinium
  • bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as 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 preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED).
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts up to 10 Wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.
  • NOSI N-nonanoylsuccinimide
  • acelated phenolsulfonates in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS)
  • MMA n-methyl-
  • 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 (ammin) Complexes, 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 of up to 5% by weight, 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 weight of the bleach activator-containing agents used. But in special cases, more bleach activator can be used.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.
  • a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
  • zinc salts which are insoluble are zinc salts which have a solubility of not more than 10 grams of zinc salt per liter of water at 20 ° C.
  • examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ), and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
  • the zinc compounds mentioned are preferably used in amounts which have a content of the agents of zinc ions between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0% by weight. %, in each case based on the total glass corrosion inhibitor-containing agent effect.
  • the exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.
  • the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts.
  • the insoluble zinc salts have a particle size below 1.7 millimeters.
  • the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 ⁇ m. Again, this is even more true the less the zinc salt is soluble.
  • the glass corrosion inhibiting effectiveness increases with decreasing particle size.
  • the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 100 ⁇ m are preferred for the very poorly soluble zinc oxide.
  • Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. This effect that even with repeated use, the surfaces gläsemen dishes do not change corrosive, especially no turbidity, streaks or scratches but also iridescence of the glass surfaces are caused.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the spectrum of the inventively preferred zinc salts of organic acids ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to those salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular 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 the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • Examples of the 3-amino-5-alkyl-1,2,4-triazoles preferably used according to the invention may be: 5-propyl, -butyl, -pentyl, -heptyl, -octyl, -nonyl -, - decyl, -nedecyl, -dodecyl, -sononyl, -Versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - ( 4-methoxyphenyl) -, - (2-, -3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2- pyrrolidinyl) -, 3-amino-1,2,4-triazole.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • 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.
  • 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.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III , IV, V or VI.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, eg. As oxide, sulfate, nitrate, fluoride, but also organic anions such. Stearate.
  • Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the abovementioned anions.
  • the central atom is one of the above-mentioned metals in one of the abovementioned oxidation states.
  • the ligands are neutral molecules or anions that are mono- or polydentate;
  • the term "ligands" within the meaning of the invention is, for example, in " Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507 If, in a metal complex, the charge of the central atom and the charge of the ligand (s) are not zero, either one or more of the abovementioned anions or one or more, depending on whether there is a cationic or an anionic charge surplus Cations, for example sodium, potassium and ammonium ions, for charge balance Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , COSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 and mixtures thereof.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1-diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , COSO 4 , CO (NO 3 ) 2 , Ce (NO 3 ) 3 .
  • metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention.
  • the mixture of pentavalent and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from the SO 3 preparation (contact method) is suitable, as is the case by diluting a Ti (SO 4 ) 2 - Solution resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature, is applied in the molten state to the material to be coated, e.g.
  • the melting point must be chosen so that the coating material easily dissolves or melts during the silver treatment.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing agent.
  • enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis , B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
  • Development products of this ⁇ -amylase are as from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, Keistase ® available.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, also from the Company Novorymes.
  • ⁇ -amylase from Bacillus sp . A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humlcola insolens .
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • the enzymes originate, for example, either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola , or Pseudomonas , and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the purification of the relevant enzymes is preferably carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.
  • Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • calcium salts such as calcium acetate or calcium formate, and magnesium salts.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds also act as enzyme stabilizers.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabillators is enhanced by the combination with boric acid and / or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or decay accelerators are according to Römpp (9th edition, Vol. 6, p. 4440) ) and Voigt "textbook of pharmaceutical technology” (6th edition, 1987, pp. 182-184 ) Excipients, which ensure the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in resorbable form.
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents used in the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning compositions comprise such a cellulose-based disintegrating agent in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • 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.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bound by 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.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the above and described in more detail in the documents cited coarser disintegration aids are preferred in the present invention as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier.
  • microcrystalline cellulose As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline Celluloses which have primary particle sizes of about 5 microns and are compacted, for example, to granules with an average particle size of 200 microns.
  • Disintegration auxiliaries preferred in the context of the present invention preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
  • the effervescent system used in the detergent and cleaner compositions according to the invention can be selected both on the basis of economic and ecological considerations.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred within the scope of the present invention.
  • fragrance compounds e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetal-dehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methylcedryl ketone, among the alcohols anethole, citroneliol, 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 such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-Parfilm complexes can be additionally coated with other excipients.
  • Preferred dyestuffs the choice of which presents no difficulty to a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, as well as no pronounced substantivity to those with the dye-containing Agents to be treated substrates such as glass, ceramic or plastic dishes, so as not to stain them.
  • the automatic dishwashing compositions according to the invention can be made available to the consumer in different ready-made forms.
  • the automatic dishwashing agent according to the invention is preferably in the form of prefabricated dosage units.
  • Such dosing units can in principle be made up for single or multiple use, but in the context of the present application prefabricated dosing units for single use are preferred.
  • the aforementioned dosing units can be inserted, for example, in the cutlery box or the dosing compartment of the dishwasher. In the context of this application, preference is given to those metering units which can be inserted into the dispensing compartment of the dishwasher. While the metering units can in principle have any spatial shape that can be produced by a person skilled in the art, the preferred metering units provided for the metering box are characterized by certain geometries adapted to the spatial conditions of the commercially available metering units.
  • dosage units according to the invention which have a volume of between 1 and 35 ml, preferably between 2 and 30 ml, preferably between 4 and 25 ml, more preferably between 8 and 22 ml and in particular between 10 and 20 ml.
  • the weight of preferred metering units per metering unit is between 0.5 and 30 g, preferably between 1 and 25 g, preferably between 2 and 24 g, more preferably between 4 and 23 g and in particular between 8 and 22.
  • a preferred machine dishwashing detergent according to the invention characterized in that the automatic dishwashing detergent is in the form of a prefabricated dosage unit, which contains between 0.2 and 2.5 g, preferably between 0.3 and 2.2 g, more preferably between 0.4 and 1 , 9 g and especially between 0.5 and 1.5 g of nonionic surfactant (s).
  • the machine dishwashing detergents according to the invention also comprise phosphorus-containing complexing agents
  • those automatic dishwashing detergents which are in the form of a prefabricated dosage unit and between 0.2 and 4 g, preferably between 0.3 and 3 g between 0.4 and 3.0 g and especially between 0.5 and 3.0 g of the phosphorus-containing complexing agent.
  • the automatic dishwashing agents according to the invention also contain polymers having a positive charge
  • the prefabricated dosing units in particular the tablet, the extrudate, the casting, the thermoforming body or the injection-molded body or combinations of these dosing units are preferred.
  • Automatic dishwashing detergent in a prefabricated dosing unit characterized in that the prefabricated dosing unit is a tablet, an extrudate, a filled water-soluble container, preferably a filled injection-molded body, a filled casting body or a filled foil pouch, are particularly suitable within the scope of the present application prefers.
  • a first preferred prefabricated dosage unit is the tablet.
  • particulate premixes are 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, 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 by a volumetric metering of the premix.
  • the upper punch performs the premix 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 to form the shaped body comes.
  • 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 carried away by subsequent transport means. 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.
  • the lower punch is usually not moved during the pressing process. A consequence of this is that the resulting tablet has a hardness gradient, i. harder in the areas closer to the upper punch than in the areas closer to the lower punch.
  • 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 takes place via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container 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.
  • the tablets can also in the context of the present invention, multi-phase, in particular multi-layered, ausgestalten.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • 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 spatial form of another embodiment of the moldings is adapted in their dimensions of Ein Schlauerhunt of commercial household washing machines or the dosing of commercial dishwashers, so that the moldings can be metered without dosing directly into the dispenser, where they dissolve during the Ein réellevorgangs, or from where they are released during the cleaning process.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • a is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molding causing the breakage of the molding
  • D is the molding diameter in meters
  • t the height of the moldings.
  • a further preferred embodiment of the present application relates to automatic dishwashing compositions according to the invention, which are in the form of a prefabricated dosage unit, characterized in that the prefabricated dosage unit is a shaped body, preferably a multi-phase shaped body, preferably a multi-phase tablet and in particular a multi-phase Tablet with a trough, preferably with a filled trough, acts.
  • thermoforming body refers to such containers which are obtained by deep drawing of a first film-like wrapping material.
  • the deep drawing is preferably carried out by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing tray and shaping the wrapping material into this receiving trough by the action of pressure and / or vacuum.
  • the shell material may be pre-treated before or during the molding by the action of heat and / or solvent and / or conditioning by relative to ambient conditions changed relative humidity and / or temperatures.
  • the pressure action can be carried out by two parts of a tool, which behave as positive and negative to each other and deform a spent between these tools film when squeezed.
  • the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces.
  • the deep-drawn shell materials are preferably fixed after deep drawing by using a vacuum within the receiving wells and in their achieved by the deep-drawing process space shape.
  • the vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers.
  • a discontinuous vacuum for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible.
  • the continuous or discontinuous vacuum may vary in strength and, for example, at the beginning of the process (during thermoforming of the film) assume higher values than at the end (when filling or sealing or separating).
  • the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices.
  • the shell material preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.
  • the dies used and the receiving cavities located in these dies are preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C.
  • the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling fluids, preferably water, which are circulated in special cooling lines within the matrix, are particularly suitable for cooling.
  • This cooling as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, whereby not only the appearance of the process product is improved, but also at the same time the discharge of the filled into the receiving chambers means the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.
  • the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material via a continuously rotating Matrizenformwalze (optionally optionally with a counter-guided Patrizenformwalze, which lead the forming upper punch to the cavities of the Matrizenformwalze) is different.
  • the first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means.
  • the receiving troughs located in the matrices can be arranged "in series" or staggered.
  • thermoforming bodies can have one, two, three or more receiving chambers. These receiving chambers can be arranged side by side and / or one above the other in the deep-drawn part.
  • the machine dishwashing detergent according to the invention is packaged in a water-soluble or water-dispersible thermoforming body, which in addition to the solid automatic dishwasher according to the invention in a separate receiving chamber further contains a liquid or gel detergent or detergent mixture.
  • a further preferred embodiment of the present application relates to automatic dishwashing compositions according to the invention which are in the form of a prefabricated dosage unit, characterized in that the prefabricated dosage unit is a deep-drawn body, preferably a deep-drawn body with two or more receiving chambers, in particular a deep-drawn body with one above the other arranged receiving chambers acts.
  • the water-soluble or wasseridispergierbaren container can be prepared by injection molding in addition to deep drawing.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling.
  • Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify.
  • Suitable molding compositions are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • a further preferred embodiment of the present application relates to automatic dishwashing agents according to the invention, which are in the form of a prefabricated dosing unit, characterized in that the prefabricated dosing unit is an injection-molded body, preferably an injection-molded body with two or more receiving chambers.
  • the shell materials can also be cast into molds.
  • the hollow form of the resulting inventively preferred water-soluble or water-dispersible portioned agent comprises at least one solidified melt.
  • This melt can be melted Be pure substance or a mixture of several substances. It is of course possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts, which are then combined. Mixtures of mixtures of substances may be advantageous, for example, when eutectic mixtures are formed which melt significantly lower and thus lower the process costs.
  • the shell material poured into the mold comprises at least partially a washing or cleaning agent according to the invention.
  • a washing or cleaning agent according to the invention.
  • cast hollow molds which consist entirely of a washing or cleaning agent according to the invention.
  • a further preferred embodiment of the present application relates to automatic dishwashing agents according to the invention which are in the form of a prefabricated dosing unit, characterized in that the prefabricated dosing unit is a casting body, preferably a casting body having at least one depression.
  • the automatic dishwashing compositions according to the invention in particular the automatic dishwashing compositions according to the invention in the form of prefabricated metering units, preferably have a water-soluble coating.
  • a water-soluble casing is, for example, a water-soluble or water-dispersible deep-drawn or injection-molded body described above.
  • Further preferred water-soluble coatings are water-soluble coatings of tablets, castings or extrudates, in particular in the form of a spray or dip coating or in the form of a water-soluble or water-dispersible outer packaging.
  • the water-soluble coating preferably contains organic polymers or organic salts, in particular salts of carboxylic acids.
  • Another object of the present application is a method for automatic dishwashing, in which a machine dishwashing detergent according to the invention is introduced into the interior of a dishwasher before or while the dishwasher is running through a cleaning program.

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Claims (15)

  1. Produit de lavage pour lave-vaisselle comprenant
    A) 0,5 à 12% en poids d'un système tensio-actif constitué de
    a) au moins un tensio-actif non ionique F de formule générale

            R1-CH(OH)CH2O-(AO)w-(A'O)x-(A''O)y-(A'''O)z-R2,

    dans laquelle
    - R1 représente un radical alkyle ou alcényle en C6 à C24, saturé ou à une ou plusieurs insaturations, à chaîne droite ou ramifié;
    - R2 représente un radical hydrocarboné linéaire ou ramifié ayant de 2 à 26 atomes de carbone;
    - A, A', A" et A''' représentent indépendamment l'un de l'autre un radical issu du groupe formé par

            -CH2CH2, -CH2-CH2-CH2, -CH2CH(CH3),

            -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-,

            -CH2-CH(CH2-CH3),

    - w, x, y et z représentent des valeurs comprises entre 0,5 et 25, x, y et/ou z pouvant également valoir 0; et
    b) au moins un tensio-actif non ionique G de formule générale

            R1-O-(AO)w-(A'O)x-(A''O)y-(A'''O)z-R2, dans laquelle

    - R1 représente un radical alkyle ou alcényle en C6 à C24 saturé ou à une ou plusieurs insaturations, à chaîne droite ou ramifié;
    - R2 représente H ou un radical hydrocarboné linéaire ou ramifié ayant de 2 à 26 atomes de carbone;
    - A, A', A" et A''' représentent indépendamment l'un de l'autre un radical issu du groupe formé par

            -CH2CH2, -CH2-CH2-CH2, -CH2CH(CH3),

            -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-,

            -CH2-CH(CH2-CH3),

    - w, x, y et z représentent des valeurs comprises entre 0,5 et 25, x, y et/ou z pouvant également valoir 0;
    le système tensio-actif présentant les tensio-actifs non ioniques F et G dans un rapport pondéral F:G compris entre 1:4 et 100:1,
    B) 0,01 et 10% en poids d'un polymère ayant une masse molaire de 2 000 g.mol-1 ou au-delà, qui présente au moins une charge positive; et
    C) 1,2 et 10% en poids d'un ou plusieurs agents complexants phosphorés issus du groupe formé par
    i) les phosphonates et/ou
    ii) les phosphates condensés de formule générale (MPO3)x, Mx+2PxO3x+1 et/ou MxH2PxO3x+1, dans laquelle M représente un cation et x un nombre supérieur ou égal à 5.
  2. Produit de lavage pour lave-vaisselle selon la revendication 1, caractérisé en qu'il contient en tant que tensio-actif(s) non ionique(s) G, un tensio-actif non ionique de formule générale
    Figure imgb0014
     dans laquelle R1 représente un radical alkyle ou alcényle en C6 à C24, saturé ou à une ou plusieurs insaturations, à chaîne linéaire ou ramifié; chaque groupe R2 ou R3 est choisi indépendamment l'un de l'autre parmi -CH3; -CH2CH3, -CH2CH2-CH3, CH(CH3)2 et les indices w, x, y, z représentent indépendamment l'un de l'autre des nombres entiers de 1 à 6.
  3. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le système tensio-actif présente les tensio-actifs non ioniques F et G dans un rapport pondéral F:G compris entre 2:9 et 90:1, de préférence entre 1:3 et 80:1, préférentiellement entre 3:7 et 70:1, de manière particulièrement préférée entre 7:13 et 60:1, et en particulier entre 2:3 et 50:1.
  4. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le produit de lavage pour lave-vaisselle existe sous forme d'un unité de dosage préfabriquée, laquelle contient entre 0,2 et 2,5 g, de préférence entre 0,3 et 2,2 g, de manière particulièrement préférée entre 0,4 et 1,9 g, et en particulier entre 0,5 et 1,5 g de tensio-actif(s) non ionique(s).
  5. Produit de lavage pour lave-vaisselle selon la revendication 1, caractérisé en ce qu'il contient le polymère en une proportion pondérale du polymère ayant une masse molaire de 2 000 g.mol-1 ou au-delà, qui présente au moins une charge positive, dans une proportion pondérale comprise entre 0,01 et 8% en poids, de préférence entre 0,01 et 6% en poids, de manière particulièrement préférée entre 0,01 et 4% en poids, de manière tout particulièrement préférée entre 0,01 et 2% en poids, et en particulier entre 0,01 et 1% en poids, à chaque fois par rapport au poids total du produit de lavage pour lave-vaisselle.
  6. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 ou 5, caractérisé en ce que le produit de lavage pour lave-vaisselle existe sous forme d'une unité de dosage préfabriquée, laquelle contient entre 0,01 et 1 g, de préférence entre 0,01 et 0,1 g, de manière particulièrement préférée entre 0,01 et 0,07 g, et en particulier entre 0,01 et 0,05 g du polymère ayant une masse molaire de 2 000 g.mol-1 ou au-delà, qui présente au moins une charge positive.
  7. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1, 5 ou 6, caractérisé en ce que le polymère ayant une masse molaire de 2 000 g.mol-1 ou au-delà, qui présente au moins une charge positive, présente des motifs monomères de formule R1R2C=CR3R4, dans laquelle chaque radical R1, R2, R3, R4 est choisi indépendamment l'un de l'autre parmi
    i) un atome d'hydrogène;
    ii) un groupe hydroxy dérivatisé;
    iii) des groupes alkyle linéaires ou ramifiés en C1 à C30, un groupe aryle, des groupes alkyle linéaires ou ramifiés en C1 à C30, substitués par un groupe aryle;
    iv) des groupes polyalcoxylés.
  8. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 ou 5 à 7, caractérisé en ce que le polymère ayant une masse molaire de 2 000 g.mol-1 ou au-delà, qui présente au moins une charge positive, présente en tant que motifs monomères, des sels de diallyldiméthylammonium et/ou des sels de acrylamidopropyltriméthylammonium.
  9. Produit de lavage pour lave-vaisselle selon la revendication 1, caractérisé en ce que la proportion pondérale de l'agent complexant phosphoré est comprise entre 1,5 et 8% en poids, de préférence entre 1,7 et 7% en poids, et en particulier entre 2,0 et 6% en poids, à chaque fois par rapport au poids total du produit de lavage pour lave-vaisselle.
  10. Produit de lavage pour lave-vaisselle selon la revendication 9, caractérisé en ce que le produit de lavage pour lave-vaisselle existe sous forme d'une unité de dosage préfabriquée, laquelle contient entre 0,2 et 4 g, de préférence entre 0,3 et 3 g, de manière particulièrement préférée entre 0,4 et 3,0 g, et en particulier entre 0,5 et 3,0 g de l'agent complexant phosphoré.
  11. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1, 9 ou 10, caractérisé en ce qu'il comprend un ou plusieurs phosphonates issus du groupe formé par
    i) l'acide aminotriméthylènephosphonique (ATMP);
    ii) l'acide éthylène-diamine-tétra(méthylènephosphonique) (EDTMP);
    iii) l'acide diéthylène-triamine-penta(méthylènephosphonique) (DTPMP);
    iv) l'acide 1-hydroxyéthane-1,1-diphosphonique (HEDP);
    v) l'acide 2-phosphonobutane-1,2,4-tricarboxylique (PBTC);
    vi) l'acide hexaméthylène-diamine-tétra(méthylènephosphonique) (HDTMP);
    vii) l'acide nitrilotri(méthylènephosphonique) (NTMP).
  12. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1, ou 9 à 12, caractérisé en ce qu'il contient en tant qu'agent complexant phosphoré, un phosphate condensé de formule générale ((MPO3)x, Mx+2PxO3x+1 et/ou MxH2PxO3x+1, dans lequel M représente un cation, de préférence un métal alcalin, de manière particulièrement préférée du sodium ou du potassium, x représentant un nombre supérieur à 6, de manière particulièrement préférée supérieur à 8, de manière tout particulièrement préférée supérieur à 10, et en particulier supérieur à 12.
  13. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'il existe sous forme d'une unité de dosage préfabriquée ayant deux ou plusieurs phases.
  14. Produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 à 14, caractérisé en ce qu'il présente une enveloppe hydrosoluble.
  15. Procédé pour le lavage de vaisselle en machine, dans lequel on introduit un produit de lavage pour lave-vaisselle selon l'une quelconque des revendications 1 à 15 dans l'espace intérieur d'un lave-vaisselle avant ou pendant que le lave-vaisselle exécute un programme de nettoyage.
EP05700894A 2004-03-26 2005-01-12 Produits de lavage pour lave-vaisselle Not-in-force EP1727884B1 (fr)

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DE102004015392A DE102004015392A1 (de) 2004-03-26 2004-03-26 Maschinelles Geschirrspülmittel
PCT/EP2005/000285 WO2005097957A1 (fr) 2004-03-26 2005-01-12 Produits de lavage pour lave-vaisselle

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011032868A1 (fr) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Détergent pour lave-vaisselle
US8389458B2 (en) 2008-03-31 2013-03-05 The Procter & Gamble Company Automatic dishwashing composition containing a sulfonated copolymer
US8450261B2 (en) 2007-11-09 2013-05-28 The Procter & Gamble Company Cleaning compositions with monocarboxylic acid monomers dicarboxylic monomers, and monomers comprising sulfonic acid groups
EP2963100A1 (fr) 2014-07-04 2016-01-06 Kolb Distribution Ltd. Compositions aqueuses de rinçage

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DE102005034752A1 (de) * 2005-07-21 2007-01-25 Henkel Kgaa Reinigungs- und Pflegemittel mit verbesserter Emulgierfähigkeit
EP1897933A1 (fr) * 2006-09-05 2008-03-12 Cognis IP Management GmbH Utilisation des alcools gras alkoxylés à long chaîne comme additif au détergent pour le nettoyage de surfaces dures

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EP0197434B1 (fr) * 1985-04-03 1989-07-19 Henkel Kommanditgesellschaft auf Aktien Produits de rinçage pour le lavage mécanique de la vaisselle
DE3723323C2 (de) * 1987-07-15 1998-03-12 Henkel Kgaa Hydroxy-Mischether, Verfahren zu deren Herstellung sowie deren Verwendung
DE3723873A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
DE4105851A1 (de) * 1991-02-25 1992-08-27 Henkel Kgaa Verfahren zur herstellung von alkyl- und/oder alkenylsulfat-pasten mit verbesserter fliessfaehigkeit
US5576281A (en) * 1993-04-05 1996-11-19 Olin Corporation Biogradable low foaming surfactants as a rinse aid for autodish applications
TW387937B (en) * 1994-10-14 2000-04-21 Olin Corp Biodegradable surfactant and blends thereof as a rinse aid
JP2002502445A (ja) * 1996-09-11 2002-01-22 ザ、プロクター、エンド、ギャンブル、カンパニー 低発泡性自動食器洗浄組成物
US5783540A (en) * 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit
DE19738866A1 (de) * 1997-09-05 1999-03-11 Henkel Kgaa Schaumarme Tensidmischungen mit Hydroxymischethern
DE19750456A1 (de) * 1997-11-14 1999-05-27 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
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DE10048058A1 (de) * 2000-09-28 2002-04-18 Henkel Kgaa Muldentabletten und Verfahren zu ihrer Herstellung
DE10229421A1 (de) * 2002-06-29 2004-01-29 Ecolab Gmbh & Co. Ohg Bodenreinigungs- und/oder Pflegemittel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8450261B2 (en) 2007-11-09 2013-05-28 The Procter & Gamble Company Cleaning compositions with monocarboxylic acid monomers dicarboxylic monomers, and monomers comprising sulfonic acid groups
US8389458B2 (en) 2008-03-31 2013-03-05 The Procter & Gamble Company Automatic dishwashing composition containing a sulfonated copolymer
WO2011032868A1 (fr) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Détergent pour lave-vaisselle
EP2963100A1 (fr) 2014-07-04 2016-01-06 Kolb Distribution Ltd. Compositions aqueuses de rinçage

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PL1727884T3 (pl) 2009-04-30
ES2313275T3 (es) 2009-03-01
DE502005005691D1 (de) 2008-11-27

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