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
  • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/65—Mixtures of anionic with cationic compounds
  • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
• • 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
  • C11D1/835—Mixtures of non-ionic with cationic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

• the present invention relates to a hard surface cleaner having an improved detergency against starchy stains.
• the cleaning agent is in particular a dishwashing detergent for machine cleaning of dishes.
• Liquid cleaners for hard surface cleaning typically include different surfactant blends to remove dirt and stains.
• a detergent comprising a nonionic surfactant and C 9 to C 15 oxoalcohol EO adducts in a given weight ratio.
• WO 2011/051416 A1 discloses a machine cleaning process using a bleach-free detergent offer form. This comprises different liquid detergent preparations which can be metered in a time-shifted manner during the mechanical process.
• the said cleaning agents usually allow the removal of all types of soiling of solid surfaces, especially of crockery. Especially when cleaning dishes, machine washing with dishwashers is becoming increasingly important. Even though the cleaning performance can be increased with modern products, there is still often the problem that stubborn, dried soiling before the cleaning of the dishes are pretreated in a dishwasher. In the manual cleaning of dishes, this is rinsed not only once but several times in such cases. This leads to a higher water consumption and also to a higher concentration of required cleaning agent.
• the object of the present invention is therefore to provide a cleaning agent for hard surfaces, which stubborn, dried stains, in particular starchy stains, even at temperatures in the range of 40 ° C to 50 ° C away.
• the object is to provide a dishwashing detergent, in particular for a detergent for machine cleaning of dishes.
• a hard surface cleaner comprising one or more surfactants selected from the group of anionic, nonionic and cationic surfactants, at least one detergent-active enzyme preparation and hydroxamic acid and / or salts thereof.
• hydroxamic acid and / or hydroxamates are the salts of hydroxamic acid.
• the cleaning-active enzyme preparation which is a constituent of the cleaning agent according to the invention, is in particular a preparation of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases and mixtures thereof, preferably an amylase preparation.
• Amylases like all enzymes, work within a certain pH range of about 3.5 to 9. The optimum of the activity depends on the origin of the amylases: amylases obtained from fungal cultures have their optimum at pH 5.7, Animal and bacterial cultures derived amylases have the highest activity more in the neutral to alkaline range. The temperature optimum of the amylase activity is about 45 ° C.
• amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and improved for use in cleaning further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A7-7 (DSM 12368) and cyclodextrin glucanotransferase (CG Tase) from B. agaradherens (DSM 9948).
• Cleaning-active enzymes are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
• Prefabricated preparations include, for example, the solid preparations obtained by granulatin, extrusion or lyophilization or, especially in the case of liquid or gel agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or other auxiliaries.
• the enzymes can be encapsulated for either a solid or a liquid dosage form, for example by spray drying or extrusion of 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.
• the enzyme preparation is preferably in the detergent according to the invention in a proportion of 0.05 to 2.5 wt .-%, in particular from 0.1 to 2 wt .-%, in particular from 0.1 to 1.5 wt .-%, based contained on the total weight of the detergent.
• the total weight of the detergent corresponds to 100 wt .-%. It has been found that this proportion is sufficient to remove soils from hard surfaces, especially crockery. A higher weight fraction leads to no improvement in cleaning performance.
• the proportion of the enzyme preparation, in particular the amylase preparation, below 0.05, or below 0.1 wt .-% the cleaning effect of the surfactants otherwise contained in the detergent is not improved.
• the protein concentration, ie the enzyme concentration can be determined using known methods, for example the BCA method or the biuret method. The stated content here refers to the proportion of enzyme in the detergent.
• the cleaning agent according to the invention furthermore comprises hydroxamic acid and / or salts thereof.
• the detergent may contain exclusively hydroxamic acid or exclusively hydroxamates, ie salts of hydroxamic acid. It is also possible according to the invention that the cleaning agent comprises both hydroxamate and hydroxamate.
• the hydroxamic acid preferably corresponds to the following general formula (I)
• the radical R corresponds to a linear or branched, saturated or monosaturated or polyunsaturated hydrocarbon radical having 4 to 20 carbon atoms (C atoms).
• the cleaning agent according to the invention comprises hydroxamates, it is preferably the potassium, sodium and / or ammonium salt of the hydroxamic acid.
• the cleaning agent may contain only one salt or mixtures of different salts of the hydroxamic acid.
• the total proportion of hydroxamic acid and / or salts thereof is from 0.1 to 10% by weight, in particular from 0.2 to 8% by weight. , Particularly 0.25 to 5 wt .-%, based on the total weight of the cleaning agent.
• the cleaning agent according to the invention is preferably a dishwashing agent, in particular a dishwashing detergent for machine cleaning of dishes.
• Dishwashing detergents for machine washing of dishes are nowadays often in the form of tablets. These are pulverulent detergents which have been brought into a specific shape by means of pressure. The use of tablets allows the dosage of active substances in the detergent suitable for a cleaning cycle.
• a dishwashing detergent may be in the form of a powder or as a liquid. Together with a prescribed dosage instructions, for example in the form of a measuring spoon, information about the concentration of active substances per cleaning cycle can also be made here.
• a prescribed dosage instructions for example in the form of a measuring spoon
• a detergent according to the invention comprises hydroxamic acid and / or salts thereof in a range from 0.1 to 10% by weight, this corresponds to a proportion of 0.02 to 2 g per cleaning cycle in a dishwashing machine, starting from a customary dosage in a cleaning tablet or the recommendation to a powdered or liquid detergent, which can be dosed by the consumer himself.
• the proportion of hydroxamic acid and / or salts thereof is preferably 0.05 to 1 g per cleaning cycle in a dishwashing machine.
• a proportion of 1 g, which 5 wt .-% based on the Total weight of the cleaning agent can be very well incorporated into known formulations of cleaning agents.
• the proportion of hydroxamic acid and / or hydroxamate is more than 10% by weight, based on the total weight of the cleaning agent, corresponding to 2 g per cleaning cycle, incorporation is only possible with great difficulty. In addition, the cleaning performance can not be further increased. However, it is necessary a minimum proportion of 0.1 wt .-% and in particular of 0.25 wt .-% of hydroxamic acid and / or their salts in order to achieve an improved cleaning effect. This corresponds to an amount of hydroxamic acid and / or salts thereof of 0.02 g and 0.05 g, respectively, relative to a cleaning cycle in a dishwashing machine.
• the cleaning agent according to the invention is preferably a solid dishwashing detergent.
• a "solid dishwashing detergent” is to be understood as meaning such a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.
• the solid dishwashing detergent is present in a preferred embodiment in the form of a shaped body, in particular a Kompaktats, especially a tablet.
• An inventive cleaning agent further comprises at least one surfactant.
• This surfactant is selected from the group of anionic, nonionic and cationic surfactants.
• the cleaning agent of the invention may also contain mixtures of several surfactants selected from the same group.
• the dishwashing agent according to the invention contains at least one nonionic surfactant.
• nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
• Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.
• polyhydroxy fatty acid amides of the formula wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• the detergents according to the invention in particular detergents for machine dishwashing, contain nonionic surfactants from the group the alkoxylated alcohols.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol.
• Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
• the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
• a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
• C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
• C 18 -alcohol preferably a C 18 -alcohol
• at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
• the so-called “narrow range ethoxylates” are particularly preferred.
• Nonionic surfactants which have a melting point above room temperature.
• Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
• Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
• the nonionic surfactant solid at room temperature preferably has propylene oxide units (PO) in the molecule.
• PO propylene oxide units
• such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
• Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
• surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
• nonionic surfactants 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.
• 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 integers from 1 to 6 are available.
• 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. When native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
• Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
• nonionic surfactants in which R 1 in the above formula 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.
• nonionic surfactants having a C 9-15 alkyl group having 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.
• These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
• R 1 is -CH (OH) CH 20 - (AO) w - (A'O) x - (A "O) y - (A '" O) z -R 2 , in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical;
• 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 between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.
• nonionic surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.
• the automatic dishwashing detergent contains, based on its total weight, 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 (CH 3 ) O ] z CH 2 CH (OH) R 2 in amounts of 0.1 to 15 wt .-%, preferably from 0.2 to 10 wt .-%, particularly preferably from 0.5 to 8 wt .-% and in particular of 1.0 to 6 wt .-%.
• R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular with 6 to 16, carbon atoms or mixtures thereof
• R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular having 4 to 20, carbon atoms or mixtures thereof
• y for a value between 15 and 120 preferably 20 to 100, in particular 20 to 80 stands.
• nonionic surfactants include, for example, hydroxy mixed ethers of the general formula C 6-22 -CH (OH) CH 2 O (EO) 20-120 -C 2 -26 , for example the C 8-12 fatty alcohol (EO) 22 -2 hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
• a preferred automatic dishwashing detergent according to the invention is characterized in particular by the fact that a surfactant of the general type is used as the low-foaming nonionic surfactant Formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 20-120 - R 2 is used, wherein R 1 and R 2 independently of one another for a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms.
• R 1 is a linear or branched aliphatic hydrocarbon radical with 4 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 4, preferably 0.5 to 1.5, and y for a value of at least 15 stands.
• Also preferred according to the invention are also surfactants 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 radical Hydrocarbon radical having 4 to 22 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 is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] randomized, that is in the form of a random random distribution.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical,
• x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
• each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
• R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
• Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• each R 3 in the above formula may be different if x is 2.
• the alkylene oxide unit in the square bracket can be varied.
• the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
• R 1, R 2 and R 3 are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
• particularly preferred surfactants are in which the radicals R 1 and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
• Nonionic surfactants of the general formula are preferred here R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2) y -CH 2 CH (OH) -R 2, wherein R, R 1 and R 2 independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40
• R 1 is -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 , in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
• Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.
• the nonionic surfactant is selected from nonionic surfactants of the general formula R 1 is -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which R 1 and R 2 are independently an alkyl group or alkenyl group having 4 to 22 carbon atoms; R 3 and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and x and y independently represent values between 1 and 40.
• R 1 is -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which R 3 and R 4 are H and the indices x and y independently of one another assume values of from 1 to 40, preferably from 1 to 15.
• R 1 is -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which the radicals R 1 and R 2 independently of one another represent saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.
• R 1 is -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which one of the radicals R 1 and R 2 is branched.
• R 1 is -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which the indices x and y independently of one another assume values of 8 to 12.
• the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the production process commercial products of the formulas mentioned are usually not from an individual representative, but from mixtures, which can result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.
• nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
• Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
• the proportion by weight of the nonionic surfactant in the total weight of the cleaning agent according to the invention in a preferred embodiment is from 0.1 to 20 wt .-%, particularly preferably from 0.5 to 15 wt .-%, in particular from 2.5 to 10 wt .-% ,
• Preferred cleaning agents are further characterized in that they contain less than 1.0 wt .-% and in particular no anionic surfactant, since the addition of anionic surfactants with respect to the tablet (phase) properties, in particular their hardness, friability and Nachhärte disadvantageous has proved.
• builder substances such as silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builder substances, may be advantageous.
• Organic builder substances which may be present in the cleaning agent according to the invention 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.
• citric acid adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof.
• 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.
• Particularly preferred cleaning agents according to the invention in particular automatic dishwasher detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders.
• Citrates are preferably used in combination with carbonates and / or hydroxycarbonates. Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-%, each based on the weight of the automatic dishwashing detergent.
• Preferred automatic dishwashing detergents are therefore characterized by a builder combination of citrate and carbonate and / or bicarbonate.
• the dishwashing detergent contains, in addition to citrate and (hydrogen) carbonate, at least one further phosphorus-free builder, wherein the further phosphorus-free builder is preferably is selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), more preferably from MGDA and GLDA, wherein the weight fraction of the builders, based on the total weight of the cleaning agent, preferably 5 to 80 wt .-%, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is.
• MGDA methylglycinediacetic acid
• GLDA glutamic acid diacetate
• ASDA aspartic acid diacetate
• HEIDA hydroxyethyliminodiacetate
• IDS iminod
• the wt .-% - proportion of (hydrogen) carbonate and citrate is preferably as stated above.
• the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably from 2 to 40% by weight, in particular from 5 to 30% by weight, especially from 7 to 20% by weight.
• the combination of at least three builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular automatic dishwashing detergents.
• polymeric polycarboxylates are furthermore suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 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.
• the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
• soluble builders such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in liquid cleaning agents.
• the content of (homo) polymeric polycarboxylates is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.
• Detergents according to the invention can furthermore comprise, as builder, crystalline layered silicates of the general formula NaMSixO 2 + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
• the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
• Particularly preferred machine dishwasher detergents according to the invention are free of silicates.
• the agents according to the invention may contain alkali metal hydroxides.
• These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
• Alternative cleaners are free of alkali metal hydroxides.
• compositions according to the invention can furthermore contain phosphonate (e) as builder.
• Phosphonates which can be used according to the invention are preferably selected from aminotrimethylenephosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylene triamine penta (methylenephosphonic acid) (DTPMP); 1-hydroxyethane-1,1-diphosphonic acid (HEDP); 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); Hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and nitrilotri (methylenephosphonic acid) (NTMP), with particular preference to use 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriamine penta (methylenephosphonic acid) (DTPMP).
• Phosphonate (s) are preferably used in inventive compositions in amounts of 0.5 to 20 wt .-%, in particular from 0.5 to
• compositions according to the invention may contain further ingredients.
• these include, for example, other surfactants, additives for improving the flow and drying behavior, for adjusting the viscosity, for stabilization and other customary in manual dishwashing detergents and additives, such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors, preservatives, organic salts, Disinfectants, enzymes, pH adjusters and skin feel-improving or nourishing additives.
• Polymers suitable as additives maleic acid-acrylic acid copolymer Na salt are, in particular (for example, Sokalan CP 5 ® BASF, Ludwigshafen (Germany)), modified Polyacrylic acid Na-salt (for example Sokalan ® CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate-Na-salt (for example Sokalan ® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (for example, Silwet ® L-77 from BASF, Ludwigshafen company (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (such as Silwet ® L-7608 from BASF, Ludwigshafen (Germany)), and polyether (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether)), preferably water-soluble linear polyether having terminal polyether as Tegopren ® 5
• suitable builders are especially polyaspartic acid sodium salt, Ethylendiamintriacetatkokosalkylacetamid (eg Rewopol® ® CHT 12 from Evonik, Essen (Germany)), methylglycine-trisodium salt and acetophosphonic.
• Blends with surfactant or polymeric additives exhibit synergism 5863 in the case of Tegopren 5843 and Tegopren ® ®.
• the use of Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass.
• the additives mentioned are dispensed with.
• a preferred cleaning agent, in particular dishwashing agent, further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst.
• Preferred cleaning agents according to the invention include an oxygen bleaching agent from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
• Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
• bleaching agents from the group of organic bleaching agents can also be used.
• Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
• Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred.
• a particularly preferred oxygen bleach is sodium percarbonate.
• 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.
• the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt 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.
• complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
• ligands are used which have nitrogen donor functions.
• bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
• Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
• TACN 1,4,7-triazacyclononane
• TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
• 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane Me TACN
• Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (with OAc
• auxiliaries and additives in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, or mixtures comprising, for example, the Euperlane ® from..
• UV stabilizers for example glycol distearate, for example Cutina ® AGS from Cognis, or mixtures comprising, for example, the Euperlane ® from.
• bronopol 2-bromo-2-nitropropane-1,3-diol for example, the technical referred to as bronopol 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), for example as Myacide ® BT or Boots Bronopol BT of the company Boots is commercially available
• disinfectants for example, dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial Hydrolysate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, and vegetable animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes) in amounts of usually not more than 5% by weight.
• dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C
• Dishwashing agents according to the invention contain in a preferred embodiment as further constituent at least one zinc salt.
• the zinc salt may be an inorganic or organic zinc salt.
• the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
• the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
• the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
• zinc acetate is used as the zinc salt.
• the zinc salt is preferably present in dishwashing detergents according to the invention in an amount of from 0.01 to 3% by weight, more preferably in an amount of from 0.05 to 2% by weight, in particular in an amount of from 0.1 to 1% by weight. %, contain.
• the present application relates to automatic dishwashing detergents in a preferred embodiment.
• Automatic dishwashing detergents are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process.
• the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
• the cleaning agents according to the invention are preferably in the form of a shaped body, in particular a compactate, in particular a tablet. However, they may also be present in combination with other forms of supply, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.
• the shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.
• Inventive agents can be formulated as single-phase or multi-phase products.
• Machine dishwashing detergents with one, two, three or four phases are particularly preferred.
• Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
• Particularly preferred are in particular two- or multi-phase tablets, for example Two-layer tablets, in particular two-layer tablets with a trough and a molded body located in the trough.
• Detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
• the cleaning agents according to the invention in particular the prefabricated metering units, in a preferred embodiment have a water-soluble sheath.
• the object underlying the present invention is achieved by a method for cleaning hard surfaces, in particular dishes, in which the surface is processed in a manner known per se using a previously described cleaning agent.
• the cleaning is done with a cleaning machine, especially with a dishwasher.
• the purification is carried out at a temperature in the range of 30 ° C to 70 ° C, in particular from 35 ° C to 60 ° C, especially from 40 ° C to 50 ° C.
• the enzymes contained in the enzyme preparation in particular the amylase, are very active and can thus enable good cleaning of hard surfaces, in particular dishes.
• the present invention relates to the use of a cleaning agent according to the invention for cleaning hard surfaces, in particular for removing starch-containing stains.
• the hard surfaces are preferably dishes.
• the present invention relates to the use of a previously described cleaning agent for cleaning dishes in a dishwasher.
• the present invention relates to the use of hydroxamic acid and / or salts thereof for improving the cleaning performance of hard surface cleaners, in particular for removing starchy stains.
• a solid detergent having the following composition was prepared: phosphate 18 to 45% by weight Sodium citrate / citric acid 0 to 10% by weight phosphonate 0 to 2% by weight silicate 0 to 6% by weight soda 12 to 20% by weight Sodium percarbonate Ecox C ® 0.7 10 to 16% by weight bleach catalyst 0.01 to 0.10% by weight TAED 1 to 2.7% by weight Nonionic surfactants (20 to 40 EO) 2 to 8% by weight polyacrylate 0 to 5% by weight Copolymer acrylate and AMPS 5 to 10% by weight Copolymer acrylate and DADMAC 0 to 5% by weight PEG 4000 (powder) 0 to 2% by weight Sokalan ® HP 11 0 to 1.3% by weight protease 0.5 to 7% by weight amylase 0.1 to 2.5% by weight benzotriazole 0.2 to 0.5% by weight Perfume 0.05 to 0.2% by weight dye 0.5 to 2% by weight Zinc acetate (anhydrous) 0.15 to
• the cleaning performance was determined in a Miele ® GSL in the 50 ° program according to the IKW method.
• aqueous solutions of corn starch, potato starch, wheat starch and rice starch (total starch concentration: 0.65% by weight) were prepared.
• total starch concentration: 0.65% by weight were prepared.
• 1.625 g of each starch were dissolved in a total of 993.5 g of water. 26.5 g of this solution were placed on plates and spread on the surface. The plates were weighed before use. After drying the starch solution (at room temperature, overnight), the plates were at 80 ° C in a Drying oven dried for a period of 4 hours. The plates then cooled to room temperature and were weighed.
• the plates thus prepared were then cleaned in a Miele® GSL dishwasher in the 50 ° program. After cleaning, the plates were again dried at 80 ° C in a drying oven for one hour. After the plates had cooled to room temperature, they were weighed again. The cleaning performance results from the ratio of weighed strength (determined by the weighing after drying) and the starch residues after cleaning.
• spaghetti and creme brulee were added as stubborn soiling. These were also spread on plates and dried at 80 ° C for 4 hours in a drying oven before the plates were cleaned in a dishwasher. The procedure corresponded to that of the IKW method.
• the detergent 1 corresponded to the above-mentioned composition. It contained an enzyme preparation as an active substance for removing starch. Experiment V1 thus represents the comparative example.
• hydroxamates leads to an improvement in persistent starch soiling, which can not be better removed by enzyme preparation contained in the commercially available detergent alone.
• the Improved cleaning performance of the longer chain hydraxamate AM2A may be due to the longer hydrophobic residue R than AM28A, which allows the hydroxamate to interact better with and thus remove hydrophobic starch stain.

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