EP1409623A1 - Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux - Google Patents

Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux

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Publication number
EP1409623A1
EP1409623A1 EP02764687A EP02764687A EP1409623A1 EP 1409623 A1 EP1409623 A1 EP 1409623A1 EP 02764687 A EP02764687 A EP 02764687A EP 02764687 A EP02764687 A EP 02764687A EP 1409623 A1 EP1409623 A1 EP 1409623A1
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EP
European Patent Office
Prior art keywords
weight
acid
mpas
automatic dishwashing
surfactants
Prior art date
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Application number
EP02764687A
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German (de)
English (en)
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EP1409623B1 (fr
Inventor
Arnd Kessler
Christian Nitsch
Rolf Bayersdörfer
Wolfgang Wick
Sven Müller
Peter Schmiedel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1409623A1 publication Critical patent/EP1409623A1/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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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

Definitions

  • the present invention relates to automatic dishwashing detergents and methods for using these detergents.
  • the invention relates to machine dishwashing detergents which contain nonionic surfactants which have particularly low viscosities in aqueous solution.
  • Automatic dishwashing in household dishwashers is a process that is fundamentally different from washing clothes in household washing machines. While in a washing machine the goods to be cleaned are permanently moved in the liquor and the cleaning is mechanically supported in this way, the washing liquor is applied to the surfaces to be cleaned in a dishwasher by a spray system. There, the cleaning liquor must automatically counteract stubborn dirt without being supported by mechanical influences. The performance level of machine dishwashing detergents must therefore be much higher than that of conventional textile detergents.
  • the object of the present invention was to provide automatic dishwasher detergents which meet the increased performance requirements.
  • the agents to be made available should be superior to conventional agents, particularly in the case of greasy soiling, even when the dosage is lower.
  • the detergents should be able to be provided both as conventional machine dishwashing detergents (“cleaners”) in powder or granule form or as tablets or pourable supply form, and also as a combination product (“2-in-1” products that combine detergents and rinse aids, and “ 3in1 "products that combine detergent, rinse aid and salt substitute). It has now been found that automatic dishwashing detergents which meet the above-mentioned requirement profile can be provided if they contain builders and certain nonionic surfactants and optionally further ingredients of detergents.
  • the present invention relates to machine dishwashing detergents containing builder (s), surfactant (s) and optionally further ingredients and also 0.1 to 50% by weight of one or more nonionic surfactants which are in 80% by weight solution in distilled water have a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C) of less than 450 mPas.
  • the lower viscosity of the surfactant at high concentrations results in a significantly improved solubility of the overall formulation.
  • the dissolution of a granule or a tablet or a drop of a liquid formulation, which each contain high amounts of surfactant is faster if the surfactant does not pass through gel phases or if it is highly concentrated Surfactant solutions (which are formed in the first moment when water enters) are so low-viscosity that further dilution is quick and easy.
  • the low viscosity of the surfactants used according to the invention in highly concentrated solutions further improves the energy efficiency during production.
  • lower pumping capacities are required for moving the surfactant solutions and lower stirring capacities of the mixing tools for granulation with the surfactant solution in order to achieve an equally good distribution of the surfactants.
  • agents according to the invention are their better storage stability compared to agents with conventional surfactants. Despite the low viscosity of the surfactants, the formulation does not tend to bleed or clump, even when stored under high humidity and / or temperature.
  • the surfactant has an even lower viscosity in a highly concentrated aqueous solution.
  • Agents according to the invention are preferred here, in which the nonionic surfactant (s) in 80% by weight solution in distilled water have a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of less than 400 mPas, preferably less than 300 mPas, particularly preferably less than 250 mPas and in particular less than 200 mPas.
  • Particularly preferred automatic dishwashing agents according to the invention contain one or more nonionic surfactant (s) which have a viscosity in 80% strength by weight solution in distilled water (Brookfield, spindle 31, 30 rpm, 20 ° C.) less than 150 mPas / exhibit.
  • s nonionic surfactant
  • values below 145 mPas, below 140 mPas, below 135 mPas, below 130 mPas, below 125 mPas, below 120 mPas, below 115 mPas, below 110 mPas, below 105 mPas or even below 100 mPas under the mentioned conditions 80% by weight solution in distilled water, Brookfield viscometer, spindle 31, 30 revolutions per minute, 20 ° C).
  • automatic dishwashing agents according to the invention are particularly preferred, which are characterized in that the nonionic surfactant (s) in 90% by weight solution in distilled water have a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C) of less than 250 mPas, preferably less than 200 mPas, particularly preferably less than 150 mPas and in particular less than 100 mPas.
  • a viscosity Brookfield, spindle 31, 30 rpm, 20 ° C
  • the surfactants are liquid at room temperature. In addition to being easier to process in powder or granular form, this has the additional advantage that the surfactants do not have to be melted during processing, as a result of which the production costs can be reduced further.
  • Nonionic surfactants which in 80% by weight solution in distilled water have a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of less than 450 mPas, can have different molecular structures. Depending on the type and length of the hydrophobic and the hydrophilic residue in the molecule, the properties of the surfactants can be controlled in such a way that desired properties are present.
  • nonionic surfactants with the properties described above are used in the agents according to the invention in amounts of 0.1 to 50% by weight, in each case based on the total agent.
  • Preferred automatic dishwashing agents according to the invention contain the nonionic surfactant (s) in amounts of 0.5 to 40% by weight, preferably 1 to 30% by weight, particularly preferably 2.5 to 25% by weight. % and in particular from 5 to 20 wt .-%, each based on the total agent.
  • Nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants within the scope of the present invention.
  • surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • Dishwashing detergents are preferred which contain surfactants of the general formula I as nonionic surfactant (s)
  • R 1 represents 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 , -CH2CH 2 -CH3, CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred nonionic surfactants of the formula I can be prepared by known methods from the corresponding alcohols R 1 -OH and ethyl or alkylene oxide.
  • the radical R 1 in formula I above can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is generally not shown, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • preferred dishwasher detergents according to the invention are those in which R 1 in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from - CH 2 CH 2 -CH 3 or CH (CH 3 ) are also suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 and R 3 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • nonionic surfactants which have a C 1 -C 4 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred for use in the agents according to the invention.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • the specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the form mentioned mostly do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for the degrees of ethoxylation or alkoxylation.
  • the table below particularly preferably contains nonionic surfactants present in the agents according to the invention with respect to the radical R 1 , the radicals R 2 and R 3 and the indices w, x, y and z. Preferred agents according to the invention contain one or more surfactants from the table below or mixtures thereof.
  • the agents according to the invention can contain further surfactants from the groups of nonionic, anionic, cationic or amphoteric surfactants.
  • the additional 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 mol ethylene oxide (EO) per Mcl alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12- i 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci 2 - ⁇ alcohol with 3 EO and C ⁇ 2- i ⁇ alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • surfactants are polyhydroxy fatty acid amides of the formula (II),
  • R- ' for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • C 1-4 -alkyl or phenyl radicals being preferred
  • [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 rest.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the automatic dishwashing agents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.
  • Suitable non-ionic surfactants which have melting or softening points in the temperature range mentioned, in addition to the niite surfactants contained in the compositions according to the invention, are, for example, low-foaming non-ionic surfactants, which can be solid or highly viscous at room temperature. If highly viscous non-ionic surfactants are used at room temperature, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-2 alcohol), preferably a C ⁇ 8 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • C 16-2 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
  • C ⁇ 8 alcohol preferably a C ⁇ 8 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • particularly preferred agents include ethoxylated (s) nonionic surfactant (s), which / from C 6 - 2 o-monohydroxy alkanols or C 6 - 2 o-alkyl phenols or C 16-2 o-Fettalkohoien and more than 12 mol, more preferably than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
  • s ethoxylated
  • nonionic surfactant s
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and make up in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred rinse aid according to the invention contains nonionic surfactants of the formula
  • R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or - CH 2 CH 3 are particularly preferred for the radical R 3 .
  • 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 can be different if x ⁇ 2. This allows the alkylene oxide unit in the square brackets to be varied.
  • the value 3 for x has been chosen here by way of example and may well be larger, 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 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
  • rinse aids according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30
  • k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
  • x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • anionic, cationic and / or amphoteric surfactants can also be used, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants are sulfonate-type fonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 2- i 8 - onoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci ⁇ - cis fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 6 alkyl sulfates and C12-C 1 5 alkyl sulfates and C 14 -C 5 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 , 21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -i 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, Paimkern- or Taig fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the agents according to the invention can contain, for example, cationic compounds of the formulas IV, V or VI as cationic active substances:
  • the agents according to the invention contain one or more builders as a further ingredient.
  • Builders are mainly used in the compositions according to the invention for binding calcium and magnesium.
  • Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • Trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention.
  • the potassium salts are preferable to the sodium salts, since they often have a higher solubility in water.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Particularly preferred automatic dishwashing detergents contain phosphates, preferably alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • phosphates preferably alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the general term for the alkali metal (in particular
  • Metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H3PO 4 in addition to higher molecular weight Can distinguish representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 4 exists as a dihydrate (density 1, 91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 ⁇ 7 ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na 3 P 3 ⁇ 9 ) and Maddrell's salt (see below).
  • NaH 2 P0 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1.68 gladly “ 3 , melting point 48 ° with loss of 5 H 2 0) and 12 mol. Water ( Density 1.52 "3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 7 when heated.
  • Disodium hydrogenphosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K HP0 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 0 5 ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P 2 O ⁇ ), a density of 2.536 ′′ 3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or three-base potassium phosphate), K 3 P0 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the cleaning agent industry over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na P 2 0 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° under water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P 2 0 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 0 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 0 5 , 25% K 2 0). The potassium poly phosphates are widely used in the detergent and cleaning agent industry.
  • Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.
  • Alkali carriers can be present as further constituents.
  • Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances are considered to be alkali carriers.
  • the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate are preferably used.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • the agents according to the invention can contain the builders in different amounts, depending on the application.
  • automatic dishwashing agents according to the invention are preferred, each of which contains the builder (s) in amounts of 5 to 90% by weight, preferably 7.5 to 85% by weight and in particular 10 to 80% by weight on the entire average.
  • bleaches In addition to the builders, bleaches, bleach activators, enzymes, silver preservatives, colorants and fragrances, etc. are preferred ingredients of automatic dishwashing detergents. In addition, other ingredients may be present, machine dishwashing detergents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.
  • Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • the anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
  • Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being at least “bidentate”. In this case, stretching is normally carried out Connections through Complex formation closed by an ion to form rings. The number of ligands bound depends on the coordination number of the central ion.
  • Common chelate complexing agents which are preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of customary complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals.
  • the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
  • machine dishwashing detergents which contain one or more chelating complexing agents from the groups of
  • Hydroxyl groups is at least 5,
  • Dishwashing detergent included.
  • All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:
  • polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
  • Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
  • Deposit-inhibiting polymers can also have cobuilder properties.
  • Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates can be used. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders or scale inhibitors, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group. Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as giuconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500000 g / mol.
  • DE dextrose equivalent
  • Both maitodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it may be preferred To use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention can contain further customary ingredients of cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidanoic acid paprooxyaprooxyacroperaproic acid , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1,9-diperoxyazeiaic acid, diperocysebacic acid,
  • Diperoxybrassylic acid the diperoxyphthalic acids, 2-decyidiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the cleaning agents according to the invention for machine dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Preferred automatic dishwashing agents according to the invention additionally contain bleaching agents in amounts of 1 to 40% by weight, preferably of " 2.5 to 30% by weight and in particular of 5 to 20% by weight, in each case based on the total agent.
  • Bleach activators that support the effect of the bleaching agents have already been mentioned above as a possible ingredient of the rinse aid particles.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1, 3,5-triazine DADHT and isatoic anhydride ISA.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • bleach catalysts can also be incorporated into the rinse aid particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Bleach activators from the group of multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-
  • Isononanoyloxybenzenesulfonate n- or iso-NOBS
  • n-methyl-morpholinium-acetonitrile- Methyl sulfate MMA
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Suitable enzymes in the cleaning agents according to the invention are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch
  • protease and amylase or protease and lipase or lipolytic enzymes for example of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • liquid enzyme formulations are particularly preferred.
  • automatic dishwasher detergents according to the invention which additionally contain enzyme (s) in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and in particular from 0.5 to 6% by weight, in each case based on the total composition ,
  • Dyes and fragrances can be added to the automatic dishwashing agents according to the invention in order to improve the aesthetic impression of the resulting products and, in addition to the performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, ⁇ -Isomethylionon and Methylcedrylketon, to the alcohols Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol and Terpineol, to the hydrocarbons belong mainly the terpenes like Limonen and Pinen. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oiibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents produced according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.
  • the cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being of particular importance in the field of automatic dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g.
  • salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • the automatic cleaning of dishes in domestic dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles.
  • the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out.
  • the temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are broad in the prior art described. Your main task is to prevent limescale and deposits on the dishes.
  • the agents according to the invention can be formulated as "normal" cleaners, which are used together with commercially available supplements (rinse aid, regeneration salt).
  • rinse aid e aid, regeneration salt
  • the additional dosage of rinse aid can be dispensed with, since the agents according to the invention contain them
  • Low-viscosity surfactants cause the rinse liquor to have excellent drainage properties and significantly reduce deposits on the dishes compared to conventional surfactants.
  • These so-called "2-in-1" products simplify handling and take away the burden of the additional dosage of two different products (detergent and Rinse aid).
  • automatic dishwashing detergents according to the invention which additionally contain 0.1 to 70% by weight of copolymers from i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic
  • copolymers have the effect that the items of crockery treated with such agents become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents.
  • the invention is characterized by an improved “cleanability” of the treated substrates in later cleaning processes and by a considerable reduction in the drying time compared to comparable agents without the use of polymers containing sulfonic acid groups.
  • drying time is generally understood to mean the meaning, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface.
  • unsaturated carboxylic acids of the formula VII are preferred as the monomer
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • H 2 C C (CH 3 ) -X-S0 3 H (VIIIb),
  • ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds.
  • the amount of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer.
  • Polymers to be used particularly preferably consist only of monomers of groups i) and ii).
  • copolymers are made of
  • R (R 2 ) C C (R 3 ) COOH (VII), in which R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
  • Particularly preferred copolymers consist of
  • H 2 C C (CH 3 ) -X-S0 3 H (VIIIb),
  • copolymers which are contained in the agents according to the invention can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii ) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula IX
  • These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula X.
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • Agents according to the invention which contain one or more copolymers are structural units of the formula XI
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XIII
  • automatic dishwashing agents which contain, as ingredient b), one or more copolymers which have structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV
  • the sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
  • the monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,
  • the molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses 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 content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.
  • polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
  • the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
  • Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or Sokalan ® PA25 (BASF).
  • a mixture of the surfactants 575 and 673 from the table in the description text was prepared by ethoxylating an unbranched and saturated Cn alcohol in the presence of KOH as catalyst in an autoclave at 150 ° C. with ethylene oxide. After the ethylene oxide had reacted, propylene oxide was fed into the autoclave and after its reaction the procedure was repeated with ethylene oxide and then with propylene oxide.
  • the resulting surfactant mixture can be represented by the formula
  • the surfactant mixture has a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of 100 mPas.
  • Granular machine dishwashing detergents of the composition given in Table 1 were produced by granulation in a 30 liter ploughshare mixer from Lödige.
  • Table 1 Granular automatic dishwashing detergents [% by weight]
  • Example E1 the nonionic surfactant described above was used; in comparative example V1, Poly Tergent® SLF 18 B-45 from Olin was used, which in 80% by weight solution in distilled water had a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of 494 mPas having. Performance evaluation:
  • the evaluation of the covering test is carried out by visual inspection of the objects in a box, the walls of which are lined with black velvet, with grades 0-6 being assigned. Higher values indicate surfaces free of deposits.
  • Two-layer detergent tablets for automatic dishwashing of the composition given in Table 2 were produced by producing two particulate premixes and then compressing them.
  • Table 2 two-phase detergent tablets for automatic dishwashing [% by weight]
  • Example E2 the nonionic surfactant described above was used; in comparative example V2, Poly Tergent® SLF 18 B-45 from Olin was used, which in 80% by weight solution in distilled water had a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of 494 mPas having.
  • compositions E2 and V2 were used in a universal cleaning program. The program was carried out without a commercial rinse aid (the dishwasher's storage tank was emptied) and with water that had been hardened to 21 ° d (bypassing the ion exchanger).
  • the rinse aid effect is assessed by visual inspection in a box, the walls of which are lined with black velvet, with grades 0-4 being assigned separately for the formation of drops and deposits (spotting / filming).
  • the evaluation follows the following scheme:
  • recipe E2 is in some cases clearly superior to recipe V2 in filming and is at least equivalent in spotting.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne des détergents pour lave-vaisselle, à rendement renforcé, qui atteignent des niveaux de nettoyage élevés, à doses réduites, même à de basses températures et avec des temps de lavage courts et qui peuvent être produits aussi bien comme des détergents pour lave-vaisselle traditionnels (« nettoyants »), sous forme de poudre ou de granulés, que sous forme de comprimés ou sous forme déversable, que sous forme de produit combiné (produits « 2 en 1 », qui regroupent détergents et liquides de rinçage ; ainsi que des produits « 3 en 1 » qui regroupent détergents, liquides de rinçage et sels régénérants). Lesdits détergents pour lave-vaisselle contiennent entre 0,1 et 50 % en poids d'un ou de plusieurs tensioactifs non ioniques, qui présentent une viscosité (Brookfield, Spindle 31, 30 U/mn, 20°C) inférieure à 450 mPas, dans une solution à 80 % en poids dans de l'eau distillée.
EP02764687A 2001-07-24 2002-07-13 Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux Expired - Lifetime EP1409623B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10136001 2001-07-24
DE10136001A DE10136001A1 (de) 2001-07-24 2001-07-24 Maschinelle Geschirrspülmittel mit niederviskosen Tensiden
PCT/EP2002/007822 WO2003010262A1 (fr) 2001-07-24 2002-07-13 Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux

Publications (2)

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EP1409623A1 true EP1409623A1 (fr) 2004-04-21
EP1409623B1 EP1409623B1 (fr) 2008-09-03

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US (1) US7094739B2 (fr)
EP (1) EP1409623B1 (fr)
AT (1) ATE407191T1 (fr)
DE (2) DE10136001A1 (fr)
ES (1) ES2312618T3 (fr)
HU (1) HUP0401493A3 (fr)
PL (1) PL198825B1 (fr)
WO (1) WO2003010262A1 (fr)

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DE10136001A1 (de) * 2001-07-24 2003-02-13 Henkel Kgaa Maschinelle Geschirrspülmittel mit niederviskosen Tensiden
DE10136000A1 (de) * 2001-07-24 2003-02-13 Henkel Kgaa Maschinelles Geschirrspülmittel mit Tensiden niederer dynamischer Oberflächenspannung
DE10136002A1 (de) * 2001-07-24 2003-02-13 Henkel Kgaa Maschinelle Geschirrspülmittel mit Tensiden bestimmten Diffusionskoeffizientens
DE102004048591A1 (de) * 2004-04-27 2005-11-24 Henkel Kgaa Reinigungsmittel mit Klarspültensid und einer speziellen α-Amylase
DE102007019457A1 (de) 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
GB0917740D0 (en) * 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
WO2016172482A1 (fr) 2015-04-23 2016-10-27 The Procter & Gamble Company Compositions concentrées de nettoyage personnel et procédés correspondants
MX369415B (es) 2015-04-23 2019-11-07 Procter & Gamble Composiciones de limpieza personal concentradas.
MX371306B (es) 2015-04-23 2020-01-24 Procter & Gamble Composiciones concentradas para la limpieza personal y usos.
CN107530249B (zh) 2015-04-23 2021-09-07 宝洁公司 浓缩型个人清洁组合物及方法
EP3181676B1 (fr) 2015-12-17 2019-03-13 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181671B1 (fr) 2015-12-17 2024-07-10 The Procter & Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181675B2 (fr) * 2015-12-17 2022-12-07 The Procter & Gamble Company Composition de détergent de lave-vaisselle automatique
US11179301B2 (en) 2016-10-21 2021-11-23 The Procter And Gamble Company Skin cleansing compositions and methods
US11185486B2 (en) 2016-10-21 2021-11-30 The Procter And Gamble Company Personal cleansing compositions and methods
US10806686B2 (en) 2017-02-17 2020-10-20 The Procter And Gamble Company Packaged personal cleansing product
US10675231B2 (en) 2017-02-17 2020-06-09 The Procter & Gamble Company Packaged personal cleansing product
EP3969555A1 (fr) 2019-06-21 2022-03-23 Ecolab USA, Inc. Compositions tensio-actives non ioniques solides

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Also Published As

Publication number Publication date
US7094739B2 (en) 2006-08-22
ES2312618T3 (es) 2009-03-01
HUP0401493A3 (en) 2012-10-29
ATE407191T1 (de) 2008-09-15
DE50212732D1 (de) 2008-10-16
DE10136001A1 (de) 2003-02-13
EP1409623B1 (fr) 2008-09-03
HUP0401493A2 (hu) 2004-12-28
US20040167051A1 (en) 2004-08-26
PL198825B1 (pl) 2008-07-31
PL368060A1 (en) 2005-03-21
WO2003010262A1 (fr) 2003-02-06

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