WO2012123451A1 - Détergents pour vaisselle - Google Patents

Détergents pour vaisselle Download PDF

Info

Publication number
WO2012123451A1
WO2012123451A1 PCT/EP2012/054379 EP2012054379W WO2012123451A1 WO 2012123451 A1 WO2012123451 A1 WO 2012123451A1 EP 2012054379 W EP2012054379 W EP 2012054379W WO 2012123451 A1 WO2012123451 A1 WO 2012123451A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
weight
dishwashing detergent
acid
branched
Prior art date
Application number
PCT/EP2012/054379
Other languages
German (de)
English (en)
Inventor
Thomas Eiting
Dorota SENDOR-MÜLLER
Thorsten Bastigkeit
Konstantin Benda
Arnd Kessler
Inga Kerstin Vockenroth
Melanie SZEMAIT
Dominique SCHUL
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2012123451A1 publication Critical patent/WO2012123451A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols

Definitions

  • dishwashing detergents which are preferably in the form of tablets, as well as automatic dishwashing processes using these dishwashing detergents and the use of these dishwashing detergents for removing stains in automatic dishwashing.
  • Dishwashing detergents are available to the consumer in a variety of forms.
  • the automatic dishwashing detergents have gained great importance with the spread of household dishwashers.
  • These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.
  • One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.
  • This application was based on the object to provide a machine dishwashing detergent with improved cleaning properties, in particular against greasy stains, these improved cleaning properties especially in low-temperature cleaning operations, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below, and / or in short-term cleaning process, especially in cleaning processes lasting less than 60 minutes.
  • solid dishwashing agents which contain at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.
  • anionic surfactants can be used for dishwashing.
  • a well-known problem with anionic surfactants is their foaming behavior. Foaming on use results in a pressure drop in the dishwasher, which is generally associated with inadequate cleaning performance. For this reason, the use of anionic surfactants in automatic dishwashing is usually dispensed with.
  • the cleaning performance of dishwashing detergents containing nonionic surfactants can be increased by the addition of surfactants with sulfate and / or sulfonate groups.
  • a first subject of the present invention are therefore solid dishwashing detergents, especially solid automatic dishwashing detergents containing at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.
  • a “solid dishwashing detergent” is to be understood as meaning 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 in the form of a shaped body, in particular a compactate, above all a tablet.
  • the anionic surfactant having at least one sulfate or sulfonate group is preferably selected from fatty alcohol sulfates, alkanesulfonates and alkylbenzenesulfonates.
  • Preferred here are C 2 -C 8 fatty alcohol sulfates (FAS), eg Sulfopon K 35 (Cognis, Germany), secondary C 13 -C 17 alkanesulfonates (SAS), eg Hostapur SAS 93 (Clariant, Germany), and linear C 8 -C 18 -alkylbenzenesulfonates, in particular dodecylbenzenesulfonate (LAS).
  • FAS C 2 -C 8 fatty alcohol sulfates
  • SAS secondary C 13 -C 17 alkanesulfonates
  • LAS Hostapur SAS 93
  • linear C 8 -C 18 -alkylbenzenesulfonates in particular dodecylbenzenes
  • the terms “sulfate” and “sulfonate” in addition to the relevant anionic compounds which are present in the form of salts also include the free acids, ie the corresponding alkyl sulfuric acids or alkylsulfonic acids.
  • the anionic surfactant having at least one sulfate or sulfonate group in dishwashing compositions according to the invention in an amount of 0.1 to 20 wt .-%, more preferably, 0.5 to 15 wt .-%, in particular 2.5 to 10 Wt .-%, contained.
  • 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 is 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 an arbitrary 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, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula
  • 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-CO-N- [Z] in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear , branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -alkyl or phenyl radicals
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • 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.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 2 _ 4 - alcohols with 3 EO or 4 EO, Cg alcohol with 7 EO, C.
  • ethoxylated nonionic surfactants which are from C 6 . 20 - monohydroxyalkanols or C 6 . 20- alkylphenols or C 6 . 20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 6, 20 -alcohol), preferably a C 8 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • surfactants are further used which contain one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer.
  • 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 Pas, preferably above 35 Pas and in particular above 40 Pas. 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 in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred 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.
  • 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.
  • 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.
  • R2 R3 is preferred in which R 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 stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide.
  • the radical R in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural 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 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.
  • R 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.
  • R 2 or R 3 is a radical -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.
  • nonionic surfactants which have a C 9 . 5 alkyl 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 is -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 in which
  • R and R 2 are each independently a straight-chain or branched, saturated or mono- or polyunsaturated C 2-4 o alkyl or alkenyl radical;
  • 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 0 [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 is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 denotes 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 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z is CH 2 CH (OH) R 2 in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1.0 to 6% by weight.
  • R 0 [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and y is a value between 15 and 120, preferably 20 to 100, in particular 20 to 80.
  • non-ionic surfactants include, for example, hydroxy mixed ethers of the general formula C 6 _ 22 -CH (OH) CH 2 O- (EO) 20-i20-C 2 -26, for example, the C 8-12 fatty alcohol (EO) 22 - 2-hydroxydecyl ether and the C 4 . 22 fatty alcohol (EO) 40 - 8 O-2-hydroxyalkyl ether.
  • R is CH (OH) CH 2 O- (CH 2 CH 2 O) 20-i20-R 2 , where R and R 2 independently of one another are a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms are particularly preferred.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 Cl-1 (OH) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 4, preferably 0.5 to 1.5, and y is a value of at least 15 stands.
  • Also preferred according to the invention are also surfactants of the general formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical 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 ) 0] and [CH 2 CH 2 0] randomized, ie in the form of a random random distribution.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals 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 is in 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 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each of R 3 in the above formula may be different if x> 2.
  • 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, the range of variation 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 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R, R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20, and more preferably from 6 to 18 surfactants are preferred in which the radicals R and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants used are nonionic surfactants of the general formula R 0 (AlkO) x M (OAlk) y OR 2 , where
  • R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms
  • x and y independently represent values between 1 and 70;
  • M is an alkyl radical selected from the group consisting of CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.
  • Nonionic surfactants of the general formula are preferred here.
  • R 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
  • R, R and R 2 independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms
  • 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.
  • nonionic surfactant is selected from nonionic surfactants of the general formula
  • R and R 2 independently represent an alkyl or alkenyl radical 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. Preference is given here in particular to compounds of the general formula R - 0 (CH 2 CH 2 0) x CR 3 R 4 (OCH 2 CH 2) y OR 2, in which R 3 and R 4 are H, and the subscripts x and y are independently from each other assume values from 1 to 40, preferably from 1 to 15.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation and 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 ,
  • Nonionic surfactant which have a melting point above room temperature.
  • the proportion by weight of the nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. %.
  • the weight% ratio of anionic surfactant having at least one sulfate or sulfonate group to nonionic surfactant is from 3: 1 to 1: 3, especially from 2: 1 to 1: 2, more preferably from 1 , 5: 1 to 1: 1, 5.
  • Another object of the present invention is also a machine dishwashing process using the aforementioned solid dishwashing detergent, in particular in the form of a previously mentioned shaped body, in particular for the removal, especially improved removal, of greasy soilings, especially for the removal of stains by egg yolk.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C, preferably below 50 ° C.
  • the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, more preferably a maximum of 60 minutes.
  • the dishwashing process lasts for a maximum of 50, 40, or 30 minutes.
  • the present application relates to automatic dishwashing detergents.
  • 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 automatic dishwashing compositions 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.
  • Automatic dishwashing detergent characterized in that it is in the form of a prefabricated Dosing unit with two or more phases are present, are particularly preferred.
  • Two-phase or multi-phase tablets for example two-layer tablets, in particular two-layer tablets with a trough and a shaped body located in the trough, are particularly preferred.
  • Automatic dishwasher 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 automatic dishwashing compositions according to the invention in particular the prefabricated dosage units, in a preferred embodiment have a water-soluble coating.
  • Inventive moldings contain in a preferred embodiment polyvinylpyrrolidone particles. These particles facilitate, inter alia, the disintegration of the moldings and serve insofar as disintegration aids or tablet disintegrating agents. It has been found to be particularly advantageous according to the invention, Polyvinylpyrrolidon particles having an average particle diameter of 100 to 150 ⁇ , in particular with a mean particle diameter of 1 10 to 130 ⁇ to use.
  • the term "average particle diameter” or “average diameter” is meant 50 particle diameter in the present invention, the volume mean D, which can be determined by conventional methods.
  • the volume average D 50 particle diameter is that point in the particle size distribution in which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter
  • the mean particle diameters can be determined in particular by means of dynamic light scattering, which is usually carried out on dilute suspensions containing, for example, 0.01 to 1% by weight.
  • % Particles are included.
  • the PVP particles not only have an average particle diameter of 100 to 150 ⁇ m, in particular from 110 to 130 ⁇ m, but moreover, the particle size of the particles used is preferably completely within the stated intervals. This is ensured by using grain size fractions with the indicated particle sizes obtained by a sieving process.
  • the PVP particles are preferably present in compositions according to the invention in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1, 8 wt .-%, contained.
  • disintegrants usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), but on the other hand by the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles .
  • other disintegrants may also be present in moldings according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives and Alginates or casein derivatives.
  • gas-evolving effervescent systems can also be used as further disintegrants.
  • Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifier which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the further disintegration aids are, if used, preferably in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular 0.5 to 2 wt .-%, each based on the total weight of desintegrationsakusstoffumblen agent used.
  • the shaped body according to the invention contains no further disintegration auxiliaries apart from the PVP particles.
  • the production of the shaped bodies according to the invention preferably takes place in a manner known to the person skilled in the art by compression of particulate starting substances.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process in the Hereafter referred to as tabletting, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and expulsion.
  • the tabletting is preferably carried out on so-called rotary presses.
  • the ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the mold, wherein the dosage of a prefabricated particulate premix is preferred.
  • compacts having a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which in addition is a particularly good one can preferably be obtained by using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN Have trickle behavior.
  • the granules can thus preferably be pressed with relatively low pressing force into compact materials having a relatively high hardness, which moreover preferably have a very good trickling behavior. Accordingly, it is conversely advantageous for the production of compact materials of lower hardness preferably a lower pressing force must be used, as for the production of conventional compactates.
  • Automatic dishwashing detergents according to the invention contain as further constituent in a preferred embodiment at least one anionic polymer.
  • Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.
  • the proportion by weight of the anionic polymer in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20 Wt .-%, preferably from 0.5 to 18 wt .-%, particularly preferably from 1, 0 to 15 wt .-% and in particular from 4 to 14 wt .-%.
  • Automatic dishwashing detergents characterized in that the copolymeric anionic polymer is selected from the group of hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, since the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents with simultaneously low deposit formation can be achieved.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used according to the invention as copolymeric polycarboxylates.
  • 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.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the use of 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 containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • 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 automatic dishwasher detergents are characterized in that the copolymers have molar masses 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 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Automatic dishwashing detergent characterized in that the automatic dishwashing detergent comprises as anionic copolymer a copolymer comprising
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4- Trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1, 3,5-dimethylhexene-1, 4,4-dimehtylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms, such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene
  • Dishwashing agents according to the invention furthermore preferably contain builder (s) and enzyme (s) to ensure their cleaning action.
  • automatic dishwashing agents according to the invention preferably contain one or more builders.
  • the proportion by weight of the builders in the total weight of automatic dishwashing detergents according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • the builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.
  • phosphate Preference is also the use of phosphate.
  • alkali metal phosphates have, with particular preference of pentasodium or.
  • Pentakaliumtriphosphat sodium or potassium tripolyphosphate
  • the detergents and cleaning agents industry the greatest importance.
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HP0 3 ) n and orthophosphoric H 3 P0 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.
  • Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na 5 P 3 O 0 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 0 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning substances in automatic dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 5 to 60% by weight, preferably from 15 to 45% by weight, in particular from 20 to 40% by weight, in each case based on the weight of the automatic dishwashing detergent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or 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.
  • the free acids also typically 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.
  • Machine dishwasher detergents contain citrate as one of their essential builders.
  • Machine dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.
  • the citrates are preferably used in combination with carbonates and / or bicarbonate.
  • Preferred automatic dishwashing agents are therefore by a builder combination of phosphate and carbonate / bicarbonate or from citrate and Carbonate / bicarbonate labeled (see Tables 1 a and 1 b below).
  • builder combinations of phosphate, citrate and carbonate / bicarbonate can be realized.
  • the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably from 5 to 80% by weight, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • 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.
  • the content of the automatic dishwashing agents on (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Inventive automatic dishwashing agents crystalline builder layered silicates of general formula NaMSi x C> 2x + i ⁇ y H 2 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • 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 automatic dishwasher detergents according to the invention are silicate-free.
  • the agents according to the invention may contain alkali metal hydroxides.
  • 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 automatic dishwashing detergents are free of alkali metal hydroxides.
  • Dishwashing agents preferably comprise enzyme (s) as a further constituent.
  • enzyme include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases 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 or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% 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.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, the a-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.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • enzymes can be used, which are summarized by the term hemicellulases.
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • 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.
  • 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.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations 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, low in water and / or added with stabilizers or further auxiliaries.
  • 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.
  • additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are prepared by methods known per se, For example, by shaking or rolling granulation or applied 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 protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • Particularly preferred automatic dishwasher detergents according to the invention contain
  • anionic surfactant (s) having at least one sulfate or sulfonate Group, preferably selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates;
  • R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof
  • x and z is from 0 to 40 and y is from 15 to 120, especially from 20 to 80.
  • Such automatic dishwashing agents comprise a) from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight, of anionic surfactant (s) selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates, in particular from C 2 -C 8 -fatty alcohol sulfates, secondary C 13 -C 7 -alkanesulfonates and linear C 8 -C 8 -alkylbenzenesulfonic acids;
  • anionic surfactant selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates, in particular from C 2 -C 8 -fatty alcohol sulfates, secondary C 13 -C 7 -alkanesulfonates and linear C 8 -C 8 -alkylbenzenesulfonic acids
  • R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z is from 0 to 40 and y is from 15 to 120, especially from 20 to 80;
  • compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate.
  • the proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • the automatic dishwasher detergents according to the invention may contain bleach activators.
  • bleach activators These compounds give under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • Automatic dishwashing detergent characterized in that it is a bleach activator bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and more preferably 1, 0 to 6 Wt .-%, used.
  • the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst.
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • 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-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • Suitable manganese complexes are, for example [ ⁇ ' " ⁇ ⁇ ( ⁇ -0) 2 ( ⁇ - OAc) 1 (TACN) 2] (BPh 4) 2,
  • Machine dishwashing detergent characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me 3 -TACN ) or 1, 2, 4, 7-tetramethyl-1, 4,7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me 3 -TACN ) or 1, 2, 4, 7-tetramethyl-1, 4,7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalyst
  • the abovementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.
  • the active substance combinations described above are particularly suitable for cleaning dishes in automatic dishwashing processes.
  • Another object of the present application is therefore a method for cleaning dishes in a dishwasher using a dishwashing detergent according to the invention, wherein the dishwashing detergent is preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
  • no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
  • a kit for a dishwasher comprising
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning properties, in particular also in low-temperature cleaning processes and in short-lasting purification processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C., and / or a time of less than 90 minutes, preferably less than 60 minutes, in particular less than 45 Minutes.
  • Nonionic surfactant A la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Nonionic surfactant B ⁇ 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Nonionic surfactant A '0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Anionic copolymer C 6 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18
  • Nonionic surfactant A 1 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Nonionic surfactant B ⁇ 1 to 10 1 to 10 1 to 10 1 to 10
  • Anionic copolymer C 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18
  • Bleaching catalyst 0 to 2 0.0025 to 1 0 to 2 0.0025 to 1
  • nonionic surfactant A of the general formula R 0 [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 is a linear or branched aliphatic 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 and z represent values between 0 and 40 and y represents a value of at least 15 stands;
  • R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms
  • M is an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms
  • a nonionic surfactant B of the general formula R -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 is used, in of the
  • R, R and R 2 independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms
  • a nonionic surfactant B of the general formula R-O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O-R 2 is used in the
  • R and R 2 independently represent an alkyl or alkenyl radical 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
  • an anionic polymer C from the group of copolymeric polycarboxylates and copolymeric polysulfonates
  • an anionic polymer C comprising
  • LAS stands for a linear C8-C18-alkylbenzenesulfonic acid
  • SAS stands for a secondary C 3 -C 7 -alkanesulfonate
  • FAS for a C 2 -C 8 -fatty alcohol sulfate.
  • Embodiment Example 1 Cleaning Performance
  • the dishwashing process was carried out in the dishwasher Bosch SMS86M12 DE / 01 (program: 40 ° C, water hardness 21 ° dH).
  • the dishwasher tablet was added to the dosing device before the start of the cleaning program.
  • Sulfopon K35 is a C12-C18 fatty alcohol sulfate (FAS), while Hostapur SAS 93 is a C13-C17 secondary alkanesulfonate (SAS).
  • anionic surfactants of sulfate and sulfonate type leads to an improvement in the cleaning performance of egg yolk (32% fat).
  • the foaming of the anionic surfactant in the dishwasher is obviously so low that the cleaning performance is not adversely affected.

Abstract

Détergents solides pour vaisselle qui contiennent au moins un tensio-actif anionique renfermant au moins un groupe sulfate ou un groupe sulfonate, ainsi qu'au moins un tensio-actif non ionique à faible pouvoir moussant. Lesdits détergents se caractérisent par un très bon pouvoir nettoyant lors du lavage de vaisselle à la machine, en particulier en cas de salissures grasses.
PCT/EP2012/054379 2011-03-17 2012-03-13 Détergents pour vaisselle WO2012123451A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110005696 DE102011005696A1 (de) 2011-03-17 2011-03-17 Geschirrspülmittel
DE102011005696.3 2011-03-17

Publications (1)

Publication Number Publication Date
WO2012123451A1 true WO2012123451A1 (fr) 2012-09-20

Family

ID=45878920

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/054379 WO2012123451A1 (fr) 2011-03-17 2012-03-13 Détergents pour vaisselle

Country Status (2)

Country Link
DE (1) DE102011005696A1 (fr)
WO (1) WO2012123451A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012209507A1 (de) * 2012-06-06 2013-12-12 Henkel Ag & Co. Kgaa Geschirrspülmittel
DE102014009835B4 (de) 2014-07-03 2020-12-24 Weylchem Wiesbaden Gmbh Verfahren zur Herstellung sekundärer Natrium-Alkansulfonate
DE102014009836B4 (de) 2014-07-03 2017-04-06 Weylchem Wiesbaden Gmbh Natriumsalze sekundärer Alkansulfonate enthaltende Compounds, ihre Herstellung und Verwendung sowie Wasch-, Desinfektion- und Reinigungsmittel enthaltend diese

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880778A (en) * 1973-05-25 1975-04-29 Chevron Res Automatic dishwashing compositions
DE4401235A1 (de) * 1994-01-18 1995-07-20 Henkel Kgaa Klarspülmittel für die maschinelle Reinigung von Geschirr
WO1997013833A1 (fr) * 1995-10-06 1997-04-17 Unilever N.V. Systeme anti-mousse destine a des compositions de lavage automatique de la vaisselle
WO2000002980A2 (fr) * 1998-07-10 2000-01-20 Gerald Thomas Hinton Detergent
US6083893A (en) * 1994-05-16 2000-07-04 The Proctor And Gamble Co. Shaped semi-solid or solid dishwashing detergent
DE19903289A1 (de) * 1999-01-28 2000-08-03 Henkel Kgaa Abriebstabile Wasch- und Reinigungsmittelformkörper mit hohem Niotensidanteil
US6162777A (en) * 1999-03-25 2000-12-19 Colgate-Palmolive Company Automatic dishwashing tablets
DE10048058A1 (de) * 2000-09-28 2002-04-18 Henkel Kgaa Muldentabletten und Verfahren zu ihrer Herstellung
DE10062007A1 (de) * 2000-12-13 2002-07-04 Henkel Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
EP1229103A2 (fr) * 2001-02-01 2002-08-07 Cognis Deutschland GmbH & Co. KG Hydroxyéthers mixtes à haut degré d'éthoxylation
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
US20070000067A1 (en) * 2005-06-29 2007-01-04 Jichun Shi Use of an effervescent product to clean soiled dishes by hand washing
DE102007042860A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880778A (en) * 1973-05-25 1975-04-29 Chevron Res Automatic dishwashing compositions
DE4401235A1 (de) * 1994-01-18 1995-07-20 Henkel Kgaa Klarspülmittel für die maschinelle Reinigung von Geschirr
US6083893A (en) * 1994-05-16 2000-07-04 The Proctor And Gamble Co. Shaped semi-solid or solid dishwashing detergent
WO1997013833A1 (fr) * 1995-10-06 1997-04-17 Unilever N.V. Systeme anti-mousse destine a des compositions de lavage automatique de la vaisselle
WO2000002980A2 (fr) * 1998-07-10 2000-01-20 Gerald Thomas Hinton Detergent
DE19903289A1 (de) * 1999-01-28 2000-08-03 Henkel Kgaa Abriebstabile Wasch- und Reinigungsmittelformkörper mit hohem Niotensidanteil
US6162777A (en) * 1999-03-25 2000-12-19 Colgate-Palmolive Company Automatic dishwashing tablets
DE10048058A1 (de) * 2000-09-28 2002-04-18 Henkel Kgaa Muldentabletten und Verfahren zu ihrer Herstellung
DE10062007A1 (de) * 2000-12-13 2002-07-04 Henkel Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
EP1229103A2 (fr) * 2001-02-01 2002-08-07 Cognis Deutschland GmbH & Co. KG Hydroxyéthers mixtes à haut degré d'éthoxylation
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
US20070000067A1 (en) * 2005-06-29 2007-01-04 Jichun Shi Use of an effervescent product to clean soiled dishes by hand washing
DE102007042860A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel

Also Published As

Publication number Publication date
DE102011005696A1 (de) 2012-09-20

Similar Documents

Publication Publication Date Title
EP2235153B1 (fr) Détergents
EP2115112B1 (fr) Détergents
EP2358853B1 (fr) Détergents pour lave-vaisselle
DE102011084934A1 (de) Klarspül- und Geschirrspülmittel
DE102007006628A1 (de) Reinigungsmittel
EP2859078B1 (fr) Détergents pour vaisselle
WO2012123451A1 (fr) Détergents pour vaisselle
EP2718414A1 (fr) Détergent vaisselle protégeant l'argenterie
DE102010063625A1 (de) Geschirrspülmittelkompaktate
DE102013226430A1 (de) Geschirrspülmittelkompaktate
EP2576746B1 (fr) Détergents pour lave-vaisselle en poudre comprimée
EP2576749B1 (fr) Produits à vaisselle compactés
EP2576750A1 (fr) Produits à vaisselle compactés
WO2013007410A1 (fr) Produits de rinçage et de lavage pour vaisselle
WO2011151190A1 (fr) Produits à vaisselle compactés
WO2012123452A1 (fr) Détergents pour vaisselle
DE102010063626A1 (de) Geschirrspülmittelkompaktate
WO2013182509A1 (fr) Détergents pour vaisselle
EP2723844B1 (fr) Détergents pour vaisselle avec protection de décor améliorée
EP2890771A1 (fr) Produit pour laver la vaisselle contenant un alkyléthersulfate
WO2012143315A1 (fr) Détergent sans phosphates pour lave-vaisselle
WO2011151192A1 (fr) Produits à vaisselle compactés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12710469

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12710469

Country of ref document: EP

Kind code of ref document: A1