EP1409623B1 - Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux - Google Patents

Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux Download PDF

Info

Publication number
EP1409623B1
EP1409623B1 EP02764687A EP02764687A EP1409623B1 EP 1409623 B1 EP1409623 B1 EP 1409623B1 EP 02764687 A EP02764687 A EP 02764687A EP 02764687 A EP02764687 A EP 02764687A EP 1409623 B1 EP1409623 B1 EP 1409623B1
Authority
EP
European Patent Office
Prior art keywords
acid
mpas
preferred
surfactants
agents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02764687A
Other languages
German (de)
English (en)
Other versions
EP1409623A1 (fr
Inventor
Arnd Kessler
Christian Nitsch
Rolf Bayersdörfer
Wolfgang Wick
Sven Müller
Peter Schmiedel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1409623A1 publication Critical patent/EP1409623A1/fr
Application granted granted Critical
Publication of EP1409623B1 publication Critical patent/EP1409623B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 of using these agents.
  • the invention relates to automatic dishwashing detergents which contain nonionic surfactants which have particularly low viscosities in aqueous solution.
  • Machine dishwashing in home dishwashers is a process that is radically different from washing clothes in home washing machines. While in a washing machine the material to be cleaned is permanently moved in the liquor and in this way the cleaning is mechanically assisted, in a dishwasher the Spolflotte is applied by a spray system to the surfaces to be cleaned. There, the cleaning liquor must automatically counteract even stubborn dirt, without any support by mechanical influences occurs. The level of performance of automatic dishwashing detergents must therefore be incomparably higher than that of conventional laundry detergents.
  • German Offenlegungsschrift discloses 2 059 403 (Economics Laboratories) Tallow fatty alcohol-ethylene oxide condensates as surface-active ingredients of automatic dishwashing detergents.
  • nonionic surfactants from the group of the alcohol alkoxylates, which further comprise randomly distributed ethylene oxide and propylene oxide units in addition to a linear alkyl radical.
  • the agents to be provided should be superior to conventional agents, even in comparison with lower dosages, especially in greasy soils.
  • the compositions should be able to be provided both as conventional machine dishwashing detergents ("cleaners") in powder or granular form or as a tablet or pourable offer form, as well as a combination product (“2in1” products combining cleaners and clear wipers and "3in1 Products that combine cleaners, rinse aids and salt substitutes).
  • machine dishwashing detergents which meet the abovementioned profile of requirements can be prepared if they contain builders and certain nonionic surfactants and optionally further ingredients of cleaning agents.
  • the present invention relates to automatic dishwashing compositions containing builder (s), surfactant (s) and optionally further ingredients, characterized in that they contain 0.1 to 50 wt .-% of one or more nonionic surfactants, which in 80 wt. % solution in distilled water has a viscosity (Brookfield, spindle 31, 30 rpm 20 ° C) of less than 450 mPas.
  • the lower viscosity of the surfactant at high concentrations causes a significantly improved solubility of the overall formulation.
  • the dissolution of a granule or tablet or liquid formulation drop, each containing high levels of surfactant will be faster if the surfactant does not pass through gel phases or if it is highly concentrated Surfactant solutions (which are formed at 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 power and granulation with the surfactant solution lower mixing power of the mixing tools are required to achieve an equally good distribution of the surfactants.
  • Another advantage of the agents according to the invention is their better storage stability compared to compositions with conventional surfactants. Despite the low viscosity of the surfactants, the formulation does not tend to bleed or agglomerate even when stored under high humidity and / or temperature.
  • the surfactant has an even lower viscosity in a highly concentrated aqueous solution.
  • preferred means are those in which the nonionic surfactant (s) in 80% by weight solution in distilled water has a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C) of less as 400 mPas, preferably less than 300 mPas, more 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) having a viscosity in 80% strength by weight solution in distilled water (Brookfield, spindle 31, 30 rpm, 20 ° C.). of less than 150 mPas.
  • s nonionic surfactant
  • values of 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 above-mentioned conditions 80% by weight solution in distilled water, Brookfield viscometer, spindle 31, 30 revolutions per minute, 20 ° C.).
  • nonionic surfactant (s) in a 90% strength 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.
  • the surfactants may be advantageous for certain formulations if the surfactants are liquid at room temperature. This has, in addition to the easier processability with powdered or granular agents, the additional advantage that the surfactants do not have to be melted during processing, whereby the manufacturing costs can be further reduced.
  • Nonionic surfactants which have a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of less than 450 mPas in 80% strength by weight solution in distilled water can have a molecular structure of different composition. Depending on the type and length of the hydrophobic and the hydrophilic radical in the molecule, the properties of the surfactants can be controlled so that desired properties are present.
  • nonionic surfactants having the properties described above are used in the middle according to the invention in amounts of from 0.1 to 50% by weight, in each case based on the total agent.
  • Preferred automatic dishwasher detergents according to the invention comprise the nonionic surfactant (s) in amounts of from 0.5 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight. and in particular from 5 to 20 wt .-%, each based on the total agent.
  • Automatic dishwashing detergents according to the invention contain nonionic surfactant (s) containing surfactants of the general formula I.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 -CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • the nonionic surfactants of formula 1 can be prepared by known methods from the corresponding alcohols R 1 -OH and Ethlyne- or alkylene oxide.
  • the radical R 1 in the above formula 1 may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
  • R 1 in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 1 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which have a C 9-15 -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 have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants contained in the agents according to the invention with respect to the radical R. 1 , the rests R 2 and R 3 and the indices w, x, y and z characterized.
  • Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these.
  • the agents according to the invention may comprise further surfactants from the groups of nonionic, anionic, cationic or amphoteric surfactants.
  • additional nonionic surfactants it is preferred to use alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) per Mcl of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, 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 from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl 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) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [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 dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
  • preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.
  • Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, so 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.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the 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.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt.%, Particularly 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 rinse aids 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% by weight of the total molecular weight of the nonionic surfactant.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants 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 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (C) H) R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x 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 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • rinse aids are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.
  • R 1 and R 2 are linear or branched, saturated or uns
  • anionic, cationic and / or amphoteric surfactants in conjunction with the surfactants mentioned, these having only secondary importance owing to their foaming behavior in automatic dishwashing detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight. %, for example from 0.01 to 2.5% by weight, in each case based on the agent.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Suitable alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 - Oxoalkohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the agents according to the invention contain one or more builders.
  • Builders are used in the compositions of the invention especially for binding calcium and magnesium.
  • Typical 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 silicatic 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 because they often have a higher water solubility.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Particularly preferred automatic dishwasher detergents contain as builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentacatium triphosphate (sodium or potassium tripolyphosphate).
  • phosphates preferably alkali metal phosphates with particular preference of pentasodium or pentacatium triphosphate (sodium or potassium tripolyphosphate).
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which metaphosphoric (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight Can distinguish representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ).
  • Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 reacts acidic, it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH 2 PO 4 , is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate Despite the higher price in the detergent industry, the more soluble, therefore highly effective, potassium phosphate are often preferred over corresponding sodium compounds. -
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of 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 agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakalium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is marketed, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the washing and cleaning industry.
  • alkali carriers may be present.
  • Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, wherein for the purposes of this invention, the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate are preferably used.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • compositions according to the invention may contain the builder (s), depending on the intended use, in different amounts.
  • automatic dishwasher detergents according to the invention are preferred which contain the barley (s) in amounts of from 5 to 90% by weight, preferably from 7.5 to 85% by weight and in particular from 10 to 80% by weight, in each case based on the total Means, included.
  • automatic dishwashing detergents In addition to builders, bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances, etc., are preferred ingredients of automatic dishwashing detergents. In addition, further ingredients may be present, automatic dishwashing agents according to the invention being preferred which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • solid mono-, oligo-and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid.
  • the anhydrides of these acids can be used as Acidisersstoff, in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, ie at least "bidentate". In this case, so usually stretched connections through Complex formation via an ion closed to rings. The number of bound ligands depends on the coordination number of the central ion.
  • Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complex-forming polymers ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of 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 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 conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and 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.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • organic cobuilders in the automatic dishwashing compositions according to the invention it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of detergents or cleaners.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here ,
  • Polymeric polycarboxylates are also suitable as builder or beta inhibitor; these are, 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.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 1000 to 4000 g / mol, may again be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid group-containing copolymers 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives .
  • Further preferred copolymers are those which preferably contain acrolein and acrylic acid / acrylate salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • they are hydrolysis products average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • 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 to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.
  • the agents according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances being of importance. These substances will be 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 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • 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, ⁇ -phthalimidoperoxycaproic acid [Phthatoiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium hydantoin compounds, such as 1 3-dichloro-5,5-dimethylhydantoin are also suitable.
  • DICA dichloroisocyanuric acid
  • Preferred automatic dishwashing agents according to the invention additionally contain bleaching agents in amounts of from 1 to 40% by weight, preferably from 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.
  • bleach activators which aid in the action of the bleaches 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 the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylosuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholin
  • 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 saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred methyl-morpholinium acetonitrile methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total agent, used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • acylated phenolsulfonates in particular n-nonano
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous,
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic. acting enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in Holl substances to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.
  • liquid enzyme formulations Particularly preferred in the context of the present invention is the use of liquid enzyme formulations.
  • automatic dishwashing detergents according to the invention are preferred which additionally enzyme (s) in amounts of 0.01 to 15 wt .-%. preferably from 0.1 to 10 wt .-% and in particular from 0.5 to 6 wt .-%, each based on the total agent.
  • Dyes and fragrances can be added to the machine dishwashing detergents according to the invention in order to improve the esthetic impression of the resulting products and to provide the consumer with not only the performance of a visually and sensorially "typical and unmistakable. Product.
  • perfume oils or fragrances include individual perfume compounds
  • synthetic ester-type esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons are used, such as benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydro xycitronellal, lilial and bourgeonal, to the ketones eg the Jonone, ⁇ -isomethylionone and Methylce
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • compositions made according to the invention may (or parts thereof) be colored with suitable dyes.
  • suitable dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • the detergents according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. In order to obtain crystal-clear and spotless dishes, one uses therefore successfully today rinse aid.
  • the addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss.
  • the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
  • the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed.
  • the temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are broad in the art described. Your task is primarily to prevent limescale and deposits on the dishes.
  • compositions according to the invention can be formulated as "normal" cleaners, which are used together with commercially available supplements (rinse aid, regenerating salt).
  • rinse aid regenerating salt
  • inventive products can be dispensed with the inventive products on the additional dosage of rinse agents, as the present invention contained in the detergents low viscosity surfactants cause excellent flow properties of the wash liquor and significantly reduce deposits on the dishes compared to conventional surfactants.
  • the invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.
  • Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.
  • R 1 (R 2 ) C C (R 3 ) COOH (VII)
  • 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 is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H (VIII)
  • H 2 C CH-X-SO 3 H (VIIIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIIb)
  • HO 3 SX- (R 6 ) C C (R 7 ) -X-SO 3 H (VIIIc)
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the polymers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • copolymers according to the invention in the compositions may 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.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the compositions according to the invention is also preferred and characterized in that the agents contain one or more copolymers containing the structural units of the formula X.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • machine dishwashing detergents which comprise one or more copolymers as ingredient b), the structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (IX), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (X), - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y -SO 3 H] p - (XI), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XI), - [CH 2
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.
  • the monomer distribution of the copolymers used in the agents according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % 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 particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight 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 use.
  • Preferred automatic dishwashing agents 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 content of one or more copolymers in the compositions according to the invention can vary depending on the intended use and the desired product performance, preferred automatic dishwashing compositions according to the invention being characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. %, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.
  • polyacrylates and the above-described copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally further ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the polyacrylates have been described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons.
  • Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).
  • a mixture of surfactants 575 and 673 from the table in the specification text was prepared by ethoxylating an unbranched and saturated C 11 alcohol in the presence of KOH as a catalyst in an autoclave at 150 ° C with ethylene oxide. After the ethylene oxide had reacted, propylene oxide was fed to the autoclave and, after the reaction, the procedure was repeated with ethylene oxide followed by propylene oxide.
  • the resulting surfactant mixture can be defined by the formula CH 3 (CH 2 ) 10 -O- (CH 2 -CH 2 -O) 3 - (CH 2 -CH (CH 3 ) -O) 3 - (CH 2 -CH 2 -O) 2 - (CH 2 - CH (CH3) -O) 1.5 -H describe.
  • the surfactant mixture has a viscosity (Brookfield, spindle 31, 30 rpm, 20 ° C.) of 100 mPas in 80% strength by weight solution in distilled water.
  • a plaque test is carried out in a 65 ° C. universal cleaning program in a Miele dishwasher which has been converted to continuous operation.
  • the program was carried out without commercially available rinse aid (storage tank of the dishwasher emptied) and with up to 21 ° d hardened water (bypassing the ion exchanger).
  • test conditions Dishwasher: Miele Konti Detergent: 45g dosed in the main rinse cycle Water hardness: 21 ° dH Program: Universal 65 ° C Cycles: 30 Dirt load: 50g liquid dirt dosed in the main rinse cycle Composition: 30% protein / protein 30% strength 30% fat 10% water / emulsifier
  • the evaluation of the covering test is made by visual inspection of the objects in a box whose walls are lined with black velvet, giving the marks 0-6. Higher values indicate less porous surfaces.
  • compositions E2 and V2 were used in a universal cleaning program.
  • the program was carried out without commercially available rinse aid (storage tank of the dishwasher) and with hardened water to 21 ° d (bypassing the ion exchanger).
  • formulation E2 is in part significantly superior to formulation V2 in filming and is at least equivalent to spotting.

Landscapes

  • 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)

Claims (10)

  1. Agents pour le lavage mécanique de la vaisselle, contenant une ou plusieurs substances de support, un ou plusieurs agents tensioactifs ainsi que, de manière facultative, d'autres constituants, caractérisés en ce qu'ils contiennent, à concurrence de 0,1 à 50 % en poids, un ou plusieurs agents tensioactifs non ioniques répondant à la formule générale I
    Figure imgb0010
     dans laquelle R1 représente un radical alcényle ou alkyle en C6-C24 saturé ou bien mono respectivement polyinsaturé, à chaîne droite ou ramifiée ; chaque groupe R2, respectivement R3 est choisi, de manière respectivement indépendante, parmi un groupe -CH3, un groupe -CH2CH3, un groupe -CH2CH2CH3, un groupe -CH(CH3)2, et les indices w, x, y, z représentent, indépendamment l'un de l'autre, des nombres entiers de 1 à 6, qui présentent, dans une solution à 80 % en poids dans de l'eau distillée, une viscosité (Brookfield, broche 31, 30 tours/minute, 20 °C) inférieure à 450 mPa.s.
  2. Agents pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisés en ce que le/les agents tensioactifs non ioniques présentent, dans une solution à 80 % en poids dans de l'eau distillée, une viscosité (Brookfield, broche 31, 30 tours/minute, 20 °C) inférieure à 400 mPa.s, de préférence inférieure à 300 mPa.s, de manière particulièrement préférée inférieure à 250 mPa.s et en particulier inférieure à 200 mPa.s.
  3. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 ou 2, caractérisés en ce que le/les agents tensioactifs non ioniques présentent, dans une solution à 90 % en poids dans de l'eau distillée, une viscosité (Brookfield, broche 31, 30 tours/minute, 20 °C) inférieure à 250 mPa.s, de préférence inférieure à 200 mPa.s, de manière particulièrement préférée inférieure à 150 mPa.s et en particulier inférieure à 100 mPa.s.
  4. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 3, caractérisés en ce qu'ils contiennent le/les agents tensioactifs non ioniques dans des quantités de 0,5 à 40 % en poids, de préférence de 1 à 30 % en poids, de manière particulièrement préférée de 2,5 à 25 % en poids, et en particulier de 5 à 20 % en poids, chaque fois rapportés à l'agent dans sa totalité.
  5. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 4, caractérisés en ce que R1 représente un radical alkyle contenant de 6 à 24, de préférence de 8 à 20, de manière particulièrement préférée de 9 à 15 et en particulier de 9 à 11 atomes de carbone.
  6. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 5, caractérisés en ce que R2 respectivement R3 représentent un radical -CH3, w et x représentant, indépendamment l'un de l'autre, des valeurs de 3 ou 4 et y et z représentant, indépendamment l'un de l'autre, des valeurs de 1 ou 2.
  7. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 6, caractérisés en ce qu'ils contiennent le/les substances de support dans des quantités de 5 à 90 % en poids, de préférence de 7,5 à 85 % en poids, et en particulier de 10 à 80 % en poids, chaque fois rapportés à l'agent dans sa totalité.
  8. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 7, caractérisés en ce qu'ils contiennent en outre une ou plusieurs enzymes dans des quantités de 0,01 à 15 % en poids, de préférence de 0,1 à 10 % en poids, et en particulier de 0,5 à 6 % en poids, chaque fois rapportés à l'agent dans sa totalité.
  9. Agents pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 8, caractérisés en ce qu'ils contiennent en outre des agents de blanchiment dans des quantités de 1 à 40 % en poids, de préférence de 2,5 à 30 % en poids, et en particulier de 5 à 20 % en poids, chaque fois rapportés à l'agent dans sa totalité.
  10. Procédé pour le lavage de la vaisselle dans un lave-vaisselle en mettant en oeuvre un agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 9.
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)

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

Family

ID=7692895

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02764687A Expired - Lifetime EP1409623B1 (fr) 2001-07-24 2002-07-13 Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux

Country Status (8)

Country Link
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)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3504041A (en) * 1966-02-14 1970-03-31 Wyandotte Chemicals Corp Nonionic condensation products having enhanced activity
US3625901A (en) * 1969-12-02 1971-12-07 Economics Lab Surface active dishwashing rinse aids
JPS5925838B2 (ja) * 1977-12-19 1984-06-21 ライオン株式会社 自動食器洗い機用洗浄剤組成物
US4836951A (en) * 1986-02-19 1989-06-06 Union Carbide Corporation Random polyether foam control agents
US5110503A (en) 1990-05-15 1992-05-05 Elliot Cohen Demulsifying
EP0724013A1 (fr) * 1995-01-30 1996-07-31 Colgate-Palmolive Company Concentrés de détergents versables qui maintiennent ou augmentent leur viscosité après dilution dans l'eau
US5698507A (en) * 1996-09-10 1997-12-16 Colgate-Palmolive Co. Nonaqueous gelled automatic dishwashing composition
US6013613A (en) * 1996-09-11 2000-01-11 The Procter & Gamble Company Low foaming automatic dishwashing compositions
ES2183152T3 (es) * 1996-12-02 2003-03-16 Kao Corp Compuesto tensoactivo.
CA2363097C (fr) * 1999-02-22 2004-04-06 The Procter & Gamble Company Procede d'elimination de taches sur une surface
IT1312557B1 (it) * 1999-05-04 2002-04-22 Condea Augusta Spa Tensioattivo nonionico a basso potere schiumogeno
US6680286B1 (en) * 2000-11-14 2004-01-20 Sanyo Chemical Industries, Ltd. Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer
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

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
HUP0401493A2 (hu) 2004-12-28
US20040167051A1 (en) 2004-08-26
PL198825B1 (pl) 2008-07-31
PL368060A1 (en) 2005-03-21
EP1409623A1 (fr) 2004-04-21
WO2003010262A1 (fr) 2003-02-06

Similar Documents

Publication Publication Date Title
EP1299513B1 (fr) Produit de nettoyage pour lave-vaisselle
EP1409623B1 (fr) Detergents pour lave-vaisselle comportant des tensioactifs faiblement visqueux
EP1417291B1 (fr) Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre
EP2487232B1 (fr) Produit de nettoyage
EP2115112B1 (fr) Détergents
EP2118255B1 (fr) Composition detergente
WO2005108537A1 (fr) DETERGENT CONTENANT UN TENSIO-ACTIF DE RINÇAGE ET UNE α-AMYLASE SPECIALE
EP1409625B1 (fr) Detergents pour lave-vaisselle comportant des tensioactifs a coefficients de diffusion determines
WO2002070640A1 (fr) Produits vaisselle '3 en 1' et procede de fabrication de ces produits
EP1409624B1 (fr) Detergents pour lave-vaisselle comportant des tensioactifs a tension superficielle dynamique basse
EP1664257B1 (fr) Detergents pour lave-vaisselle contenant un melange polymere special
EP1103599B1 (fr) Agent de rinçage particulaire et composition pour lavage de la vaiselle en machine
DE10140535B4 (de) Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz
EP1664256B1 (fr) Compostions detergentes pour lave-vaisselle conprenant des polym res speciaux
DE10133136B4 (de) Nichtwäßrige"3in1"-Geschirrspülmittel
EP2963102A2 (fr) Produit de nettoyage comprenant de l'acide hydroxamique et/ou ses sels
DE10133137A1 (de) Wäßrige"3in1"-Geschirrspülmittel
WO2025131947A1 (fr) Détergent pour lave-vaisselle automatique doté d'un nouveau système de blanchiment
WO2001023507A1 (fr) Produits pour le nettoyage d'articles en argent en lave-vaisselle
DE10311886A1 (de) Nichtwäßrige flüssige Geschirreinigungsmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20031209

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: RO SI

17Q First examination report despatched

Effective date: 20050331

17Q First examination report despatched

Effective date: 20050331

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: RO SI

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50212732

Country of ref document: DE

Date of ref document: 20081016

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2312618

Country of ref document: ES

Kind code of ref document: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090203

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

26N No opposition filed

Effective date: 20090604

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081203

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080903

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20160726

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20160721

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 407191

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170713

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20180829

Year of fee payment: 17

Ref country code: IT

Payment date: 20180724

Year of fee payment: 17

Ref country code: FR

Payment date: 20180725

Year of fee payment: 17

Ref country code: DE

Payment date: 20180723

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20190703

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50212732

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200201

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190713

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20201130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190714

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200713