WO2013007410A1 - Produits de rinçage et de lavage pour vaisselle - Google Patents

Produits de rinçage et de lavage pour vaisselle Download PDF

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Publication number
WO2013007410A1
WO2013007410A1 PCT/EP2012/057877 EP2012057877W WO2013007410A1 WO 2013007410 A1 WO2013007410 A1 WO 2013007410A1 EP 2012057877 W EP2012057877 W EP 2012057877W WO 2013007410 A1 WO2013007410 A1 WO 2013007410A1
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WIPO (PCT)
Prior art keywords
carbon atoms
weight
acid
branched
nonionic
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PCT/EP2012/057877
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German (de)
English (en)
Inventor
Thomas Eiting
Nina Mussmann
Thorsten Bastigkeit
Konstantin Benda
Arnd Kessler
Inga Kerstin Vockenroth
Melanie SZEMAIT
Original Assignee
Henkel Ag & Co. Kgaa
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Publication of WO2013007410A1 publication Critical patent/WO2013007410A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • 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
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present application describes rinsing and dishwashing detergents as well as automatic dishwashing processes using these agents and the use of these detergents 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 detergents are the consumer
  • 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 object has been achieved by rinse aid compositions containing at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.
  • the object was further achieved by dishwashing agents which contain at least one anionic surfactant having at least one sulfate or sulfonate group, at least one nonionic surfactant and at least one compound selected from phosphonates, MGDA and GLDA.
  • anionic surfactants can be used in automatic dishwashing processes (for dishwashing).
  • a well-known problem with anionic surfactants is their foaming behavior.
  • Dishwasher which generally with insufficient cleaning performance connected is. For this reason, the use of anionic surfactants in automatic dishwashing is usually dispensed with.
  • 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 automatic rinse aids which contain at least one anionic surfactant having at least one sulfate or sulfonate group and at least one nonionic surfactant.
  • Another object of the present invention are machine dishwashing detergents containing at least one anionic surfactant having at least one sulfate or sulfonate group, at least one nonionic surfactant and at least one compound selected from phosphonates, MG DA and GLDA.
  • Another object of the present invention are dishwashing processes using inventive machine rinse aid or dishwashing detergent.
  • Another object of the present invention is also the use of a
  • compositions that can be used to clean soiled dishes in a machine dishwashing process differ, for example, from the automatic rinse aids which are always used in combination with automatic dishwashing detergents and do not have their own
  • compositions which contain no further potentially active cleaning substances except the said surfactants and optionally Acidovicsmitteln.
  • machine rinse aids are preferably in liquid form
  • machine dishwashing detergents in which the combination of anionic surfactants are present at least one sulfate or sulfonate group is used, in a preferred embodiment in solid form.
  • a “liquid dishwashing detergent or rinse aid” is to be understood here as meaning an agent which is in the liquid state at 25 ° C. and a pressure of 1 bar.
  • a "solid dishwashing or rinse aid” is to be understood as meaning an agent which at 25 ° C and a pressure of 1 bar in solid state.
  • Shaped body in particular a Kompaktats, especially a tablet ago.
  • the anionic surfactant having at least one sulfate or sulfonate group is preferably selected from fatty alcohol sulfates, alkanesulfonates and alkylbenzenesulfonates.
  • fatty alcohol sulfates Preference is given here Ci 2 -Ci 8 fatty alcohol sulfates (FAS), eg Sulfopon K 35 (Cognis, Germany), secondary Ci 3 -Ci7 alkanesulfonates (SAS), eg Hostapur SAS 93 (Clariant, Germany), and linear C8 C18-alkylbenzenesulfonates, in particular dodecylbenzenesulfonate (LAS).
  • FAS Ci 2 -Ci 8 fatty alcohol sulfates
  • SAS secondary Ci 3 -Ci7 alkanesulfonates
  • LAS Hostapur SAS 93
  • linear C8 C18-alkylbenzenesulfonates in particular dode
  • 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 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 and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Ci_ 4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with substituted at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar
  • N-alkoxy- or N-aryloxy-substituted compounds can be prepared by reaction with
  • Nonionic surfactants are used as preferred surfactants.
  • 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 12-14 alcohols containing 3 EO or 4 EO, C 9 n-alcohol with 7 EO, C 3 .i 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci2 -i8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci 2 -8-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 rank 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 which -2o- from C 6 monohydroxy alkanols or C 6 -2O alkylphenols or C 6 -2O fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole Alcohol was used.
  • a particularly preferred nonionic surfactant is derived from a straight chain fatty alcohol having 16 to 20 carbon atoms (C16. 2 o alcohol), preferably a C 18 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • surfactants are further used, which one or more
  • Tallow fat alcohols containing 20 to 30 EO in combination with a silicone defoamer Tallow fat alcohols containing 20 to 30 EO in combination with a silicone defoamer.
  • nonionic surfactants which have a melting point above
  • 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.
  • Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low-foaming nonionic surfactants which contain alternating ethylene oxide and ethylene oxide Have 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 preferred, in which R stands for a straight-chain or branched, saturated or mono- or polyunsaturated C6 -24 alkyl or alkenyl group; 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.
  • the group R has an even number of carbon atoms and is usually unbranched, the linear groups being selected from alcohols of native origin having 12 to 18 carbon atoms, e.g. 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.
  • 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 are particularly preferred
  • the 9 have a C .i 5 alkyl radical 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 exhibit in aqueous solution to the required low viscosity and are inventively used with particular preference.
  • those low-foaming nonionic surfactants are preferably used which have a linear or branched alkyl radical having 10 to 20, preferably 12 to 18 carbon atoms and 2 to 30, preferably 4 to 15 ethylene oxide units and optionally up to 5 propylene oxide units and up to 5 butylene oxide units.
  • 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 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 -4-alkyl or alkenyl radical;
  • A, A, A "and A '" independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 - CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 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 preferably used according to the invention, in particular in automatic dishwasher detergents.
  • 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 with 4 to 22, in particular 6 to 18,
  • R 2 is a linear or branched
  • the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula
  • 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 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) 2o-i 2o-C2-OZ, for example the C 8- i 2 fatty alcohol (EO) 22 -2 hydroxydecyl ether and the C 4 . 22 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ethers.
  • R CH (OH) CH 2 O- (CH 2 CH 2 O) 2o-i2o-R 2 is used, wherein 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 prefers.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 Cl-1 (OI-l) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 is a linear or branched one
  • 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.
  • 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 having 4 to 22 carbon atoms or mixtures thereof , R 2 is 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 Form a random statistical 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. If the value x> 2, 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 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 R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • 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 in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon 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
  • 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 are 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.
  • nonionic surfactants can not only be used as
  • 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.
  • Rinse aids according to the invention are preferably liquid and have an acidic pH, preferably a pH of from 3 to 6.
  • Rinse aids according to the invention comprise, in addition to the at least one nonionic surfactant and in addition to the at least one anionic surfactant having at least one sulfate or sulfonate group preferably at least one acidifying agent.
  • Acidakusstoff both inorganic acids and organic acids can be used.
  • Preferred organic acids are the solid mono-, oligo- and polycarboxylic acids.
  • Particularly preferred organic acids to be used are acetic acid, Citric, tartaric, succinic, malonic, adipic, maleic, fumaric, glutaric, oxalic, polyacrylic and mixtures thereof.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • the acidifying agent is preferably used in amounts of from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.4 to 8.0% by weight, in rinse aids according to the invention.
  • Dishwashing agents comprise, in addition to the at least one nonionic surfactant and in addition to the at least one anionic surfactant having at least one sulfate or sulfonate group, at least one further compound selected from phosphonates, MGDA and GLDA.
  • phosphonate compound is preferably a hydroxyalkane and / or
  • Aminoalkanephosphonat used is of particular importance.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. Phosphonates are in
  • agents according to the invention preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the dishwashing detergent.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid-N, N-diacetic acid
  • Dishwashing processes according to the invention are 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. In particular embodiments this takes
  • Dishwashing process maximum 50, 40 or 30 minutes.
  • 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.
  • 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.
  • 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 on the
  • 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.
  • metering units have a water-soluble coating.
  • 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, polyvinylpyrrolidone particles having an average particle diameter of 100 to 150 ⁇ , in particular with a middle
  • Particle diameter of 1 10 to 130 ⁇ use.
  • 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 at which 50 % By volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter
  • Particle diameters can be determined in particular by means of dynamic light scattering, which are usually carried out on dilute suspensions containing, for example, from 0.01 to 1% by weight of particles.
  • the PVP particles not only have an average particle diameter of 100 to 150 ⁇ , in particular from 1 10 to 130 ⁇ , but beyond that lies
  • Particle size of the particles used preferably completely in the specified 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 .
  • further disintegrants may also be contained in moldings according to the invention, for example
  • Effervescent systems consist of at least two components which react with one another to form gas, for example from alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • 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, in particular of the detergent tablets, preferably takes place in a manner known to the person skilled in the art by pressing more particulately
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the tabletting is preferably carried out on so-called rotary presses.
  • rotary presses it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. The minimization of
  • Weight variations can be achieved in the following ways:
  • 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% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and in particular from 4 to 14 wt .-%.
  • Machine dishwashing detergents according to the invention characterized in that the copolymeric anionic polymer is selected from the group of hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, as represented by the hydrophobic
  • Drying properties of these agents can be achieved with low deposit formation.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)
  • Monomer (s) at least one monomer from the group 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,
  • 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 partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • 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 share of Carboxylic acid-containing monomers 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 include besides
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further 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 preferably monomers of the general formula
  • R (R 2 ) C C (R 3 ) -XR 4 used, in which R to R 3 are independently -H, -CH 3 or -C 2 H 5 , X is an optional spacer group selected is from -CH 2 -, -C (0) 0- and -C (0) -NH-, and R 4 is a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • 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-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • Dishwashing agents according to the invention furthermore preferably contain further builder (s) and / or enzyme (s) to ensure their cleaning action.
  • machine dishwashing detergents according to the invention preferably comprise one or more further builders besides MGDA, GLDA and / or the phosphonates.
  • the proportion by weight of these further 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.
  • These builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.
  • phosphate Preference is also the use of phosphate.
  • the alkali metal phosphates have, with particular preference of pentasodium or.
  • Pentakaliumtriphosphat sodium or potassium tripolyphosphate
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one
  • Metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 can distinguish in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as
  • Alkaline carriers prevent limescale deposits on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance.
  • phosphates are pentasodium triphosphate, Na 5 P3O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 0 (potassium tripolyphosphate).
  • Na 5 P3O 10 sodium tripolyphosphate
  • potassium salt pentapotassium triphosphate
  • K 5 P 3 O 0 potassium tripolyphosphate
  • 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
  • Pentakaliumtriphosphat sodium or potassium tripolyphosphate
  • Pentakaliumtriphosphat in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent.
  • 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 citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • NTA nitrilotriacetic acid
  • 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 dishwasher detergents are therefore characterized by a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate (see Tables 1a and 1b 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 has proved to be advantageous for the cleaning and rinsing performance of automatic dishwasher detergents 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 n is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Inventive automatic dishwashing agents as a builder crystalline tikformige silicates of general formula NaMSi x 0 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, wherein 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.
  • 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
  • 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 in principle 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, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as those improved for use in detergents and cleaners
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • enzymes can be used which are termed hemicellulases
  • 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.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • 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 with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • 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 protein forms only a fraction of the total weight of conventional enzyme preparations.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and
  • Particularly preferred machine rinse aid according to the invention have a pH of 3 to 6 and contain
  • anionic surfactant (s) having at least one sulfate or sulfonate Group, preferably selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates;
  • nonionic (s) surfactant (s) comprising a linear or branched alkyl radical having 10 to 20, preferably 12 to 18, carbon atoms and 2 to 30, preferably 4 to 15, ethylene oxide units and optionally up to 5, in particular up to 2, propylene oxide units and up to 5, in particular up to 2, butylene oxide units;
  • Particularly preferred machine dishwasher detergents according to the invention contain
  • anionic (s) surfactant (s) selected from alkyl sulfates, alkyl sulfonates and
  • Alkylbenzenesulfonates in particular from Ci 2 -Ci 8 fatty alcohol sulfates, secondary d 3 - Ci 7 -Alkansulfonaten 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 is a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20,
  • Hydroxyalkane and / or Aminoalkanphosphonaten particularly preferably from HEDP, EDTMP and DTPMP.
  • compositions according to the invention may contain further washing or cleaning substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, Fragrances and perfume carriers included. 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.
  • oxygen bleaches being preferred.
  • the compounds which serve as bleaches and deliver in water H 2 O 2 the sodium percarbonate, the
  • 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.
  • an oxygen bleaching agent preferably sodium percarbonate, more preferably a coated sodium percarbonate.
  • the weight fraction of the bleaching agent, based on the total weight of the washing or cleaning agent, is in preferred
  • Embodiments between 2 and 30 wt .-%, preferably between 4 and 20 wt .-% and in particular between 6 and 15 wt .-%.
  • dishwasher detergents according to the invention can be used as bleach activators.
  • 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.
  • Machine dishwashing detergents preferably at least one Bleach catalyst.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligand (s) with the
  • bleach catalyst 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 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-triazacyclonon
  • Automatic dishwashing detergent characterized in that it further comprises a
  • Bleaching 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-triazacyclononane (Me 3 -TACN) or 1, 2, 4, 7 tetramethyl-1, 4, 7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, since by the aforementioned
  • Bleaching catalysts, in particular the cleaning result can be significantly improved.
  • Central atoms Mn and Co 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% by weight to 0, 30 wt .-%, each based on the total weight of
  • bleach catalyst-containing agent used. In special cases, however, more can be done
  • Bleaching catalyst can be used.
  • a further subject of the present application is therefore a method for cleaning dishes in a dishwasher using a dishwasher detergent according to the invention, wherein the dishwasher detergent preferably during the passage of a dishwashing program, before the beginning of Main wash or in the course of the main wash cycle in the interior of a
  • Dishwasher is metered.
  • the metering or the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the means by means of the metering chamber of the dishwasher in the interior of the
  • a kit for a dishwasher comprising
  • 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.
  • Dishwashing detergent tablets can be taken from the following tables:
  • Nonionic surfactant A 1 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Nonionic surfactant A la 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 J 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
  • Anionic copolymer C J 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 la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Nonionic surfactant B a 1 to 10 1 to 10 1 to 10 1 to 10 1 to 10
  • Anionic copolymer C Yes 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 LAS, SAS or FAS 0.5 to 20 2.5 to 10 0.5 to 20 2.5 to 10
  • Nonionic surfactant A la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Anionic copolymer C 03 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18
  • 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 -0 (CH 2 CH 2 0) 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
  • LAS is a linear C8-C18 alkyl benzene sulfonic acid
  • SAS is a secondary C13-C17 alkane sulfonate
  • FAS for a C 2 -C 8 fatty alcohol sulfate.
  • the dishwashing process was carried out in the dishwasher Miele G698SC Plus 3 (program: normal, 50 ° C, water hardness 21 ° dH).
  • the dishwasher tablet was added to the dosing device before the start of the cleaning program.
  • the second to fourth rinse cycles were each scored on a scale of 1 to 10, where "10” means “no drops” and "1" means “many large drops”.
  • the rinse results are shown in the following table:
  • Sulfopon 1214G is a C12-C18 fatty alcohol sulfate (FAS), while Marlon ARL is a Ci2-Ci8 fatty alcohol sulfate (FAS).
  • anionic surfactants of the sulfate and sulfonate type leads to a significant improvement in the rinse performance. Foaming of the anionic surfactant in the
  • Dishwasher is obviously so small that the cleaning performance is not adversely affected.

Abstract

L'invention concerne des produits de rinçage et de lavage pour vaisselle, contenant au moins un tensioactif anionique renfermant au moins un groupe sulfate ou sulfonate, ainsi qu'au moins un tensioactif non-ionique à faible pouvoir moussant. Ces produits se caractérisent par de très bonnes caractéristiques de rinçage lors du lavage de la vaisselle en machine.
PCT/EP2012/057877 2011-07-14 2012-04-30 Produits de rinçage et de lavage pour vaisselle WO2013007410A1 (fr)

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Citations (5)

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DE4401235A1 (de) * 1994-01-18 1995-07-20 Henkel Kgaa Klarspülmittel für die maschinelle Reinigung von Geschirr
JP2000063894A (ja) * 1998-08-21 2000-02-29 Daisan Kogyo Kk 自動食器洗浄機用洗浄剤組成物
EP1321512A2 (fr) * 2001-12-19 2003-06-25 Cognis Deutschland GmbH & Co. KG Composition de rincage et nettoyage
DE102007042907A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel

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Publication number Priority date Publication date Assignee Title
DE1628651A1 (de) * 1968-02-17 1971-10-07 Henkel & Cie Gmbh Verfahren zum maschinellen Spuelen von Geschirr
DE4401235A1 (de) * 1994-01-18 1995-07-20 Henkel Kgaa Klarspülmittel für die maschinelle Reinigung von Geschirr
JP2000063894A (ja) * 1998-08-21 2000-02-29 Daisan Kogyo Kk 自動食器洗浄機用洗浄剤組成物
EP1321512A2 (fr) * 2001-12-19 2003-06-25 Cognis Deutschland GmbH & Co. KG Composition de rincage et nettoyage
DE102007042907A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel

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