WO2012123452A1 - Détergents pour vaisselle - Google Patents

Détergents pour vaisselle Download PDF

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Publication number
WO2012123452A1
WO2012123452A1 PCT/EP2012/054380 EP2012054380W WO2012123452A1 WO 2012123452 A1 WO2012123452 A1 WO 2012123452A1 EP 2012054380 W EP2012054380 W EP 2012054380W WO 2012123452 A1 WO2012123452 A1 WO 2012123452A1
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WIPO (PCT)
Prior art keywords
carbon atoms
dishwashing
acid
weight
branched
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.)
Ceased
Application number
PCT/EP2012/054380
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German (de)
English (en)
Inventor
Thomas Eiting
Dorota SENDOR-MÜLLER
Thorsten Bastigkeit
Konstantin Benda
Arnd Kessler
Inga Kerstin Vockenroth
Melanie SZEMAIT
Dominique SCHUL
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO2012123452A1 publication Critical patent/WO2012123452A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present application describes dishwashing detergents as well as automatic dishwashing processes using these dishwashing detergents as well as the use of these dishwashing detergents for removing stains in automatic dishwashing.
  • Dishwashing detergents are available to the consumer in a variety of forms.
  • the automatic dishwashing detergents have gained great importance with the spread of household dishwashers.
  • These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.
  • One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.
  • the object to provide a machine dishwashing detergent with improved cleaning properties against bleachable stains include, in particular stains by tea or vegetable dyes, such as vegetables or fruits.
  • These improved cleaning properties should especially in low-temperature cleaning operations, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below, and / or should be achieved in short-term cleaning procedures.
  • anionic surfactants can be used for dishwashing.
  • a well-known problem with anionic surfactants is their foaming behavior. Foaming on use results in a pressure drop in the dishwasher, which is generally associated with inadequate cleaning performance. For this reason is usually on dispensed with the use of anionic surfactants in automatic dishwashing.
  • a first subject of the present invention is therefore a dishwashing detergent which comprises the following components:
  • the anionic surfactant having at least one sulfate or sulfonate group is preferably selected from fatty alcohol sulfates, alkanesulfonates and alkylbenzenesulfonates.
  • Preferred here are C 2 -C 8 fatty alcohol sulfates (FAS), eg Sulfopon K 35 (Cognis, Germany), secondary C 13 -C 17 alkanesulfonates (SAS), eg Hostapur SAS 93 (Clariant, Germany), and linear C 8 -C 18 -alkylbenzenesulfonates, in particular dodecylbenzenesulfonate (LAS).
  • FAS C 2 -C 8 fatty alcohol sulfates
  • SAS secondary C 13 -C 17 alkanesulfonates
  • LAS Hostapur SAS 93
  • linear C 8 -C 18 -alkylbenzenesulfonates in particular dodecylbenzenes
  • the terms “sulfate” and “sulfonate” in addition to the relevant anionic compounds which are present in the form of salts also include the free acids, ie the corresponding alkyl sulfuric acids or alkylsulfonic acids.
  • the anionic surfactant having at least one sulfate or sulfonate group in dishwashing compositions according to the invention in an amount of 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 2.5 to 10 wt. -%, contain.
  • Dishwashing agents according to the invention preferably contain oxygen bleaching agents as bleaching agents.
  • oxygen bleaching agents as bleaching agents.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate.
  • the proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • the bleach catalysts which can be used according to the invention are preferably bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in oxidation state II, III, IV or V which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN)
  • Suitable manganese complexes are, for example, [M ⁇ - ⁇ O ⁇ -OAc CTACN ⁇ KClO ⁇ , [ ⁇ ' " ⁇ ⁇ ( ⁇ -0) 2 ( ⁇ - OAc) 1 (TACN) 2] (BPh 4) 2,
  • Machine dishwashing detergent characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me 3 -TACN ) or 1, 2, 4, 7-tetramethyl-1, 4,7-triazacyclononan (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me 3 -TACN ) or 1, 2, 4, 7-tetramethyl-1, 4,7-triazacyclononan (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • the abovementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.
  • Bleach activators which can be used according to the invention give, under perhydrolysis conditions, aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups.
  • Preference is given to polyacylated alkylene-diamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • Automatic dishwashing detergents characterized in that they contain as bleach activator a bleach activator from the group of the acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • TAED tetraacetylenediamine
  • the dishwashing agent according to the invention is preferably a solid dishwashing detergent.
  • a "solid dishwashing detergent” is to be understood as meaning a dishwashing detergent which is in a solid state of aggregation at 25 ° C. and a pressure of 1 bar.
  • a further subject of the present invention is also a machine dishwashing process using the abovementioned solid dishwashing agents, in particular in the form of a previously mentioned shaped body, in particular for removing, above all improved removal, of bleachable stains, in particular stains selected from stains caused by tea or vegetable dyes , especially tea.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C, preferably below 50 ° C.
  • the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, more preferably a maximum of 60 minutes.
  • the dishwashing process lasts for a maximum of 50, 40, or 30 minutes.
  • the present application relates to automatic dishwashing detergents.
  • Automatic dishwashing detergents are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process.
  • the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
  • the automatic dishwashing compositions according to the invention are preferably in the form of a shaped body, in particular a compactate, in particular a tablet. However, they may also be present in combination with other forms of supply, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.
  • the shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • Machine dishwashing detergents with one, two, three or four phases are particularly preferred.
  • Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • Two-phase or multi-phase tablets for example two-layer tablets, in particular two-layer tablets with a trough and a shaped body located in the trough, are particularly preferred.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwashing compositions according to the invention in particular the prefabricated dosage units, in a preferred embodiment have a water-soluble coating.
  • dishwashing agents according to the invention also contain at least one nonionic surfactant.
  • R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2 , in which R is a linear or branched aliphatic Hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.
  • the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z is CH 2 CH (OH) R 2 in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1.0 to 6% by weight.
  • R 0 [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and y is a value between 15 and 120, preferably 20 to 100, in particular 20 to 80.
  • the group of these nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula C 6 .
  • R is CH (OH) CH 2 O- (CH 2 CH 2 O) 20 .
  • 20 - R 2 is used, wherein R and R 2 independently of one another are a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms, are particularly preferred.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 Carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 4, preferably 0.5 to 1.5, and y for a value of at least 15 stands.
  • Also preferred according to the invention are also surfactants of the general formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH 2 CH (CH 3 ) 0] and [CH 2 CH 2 0] randomized, ie in the form of a random random distribution.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is in between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each 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 range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R, R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants used are nonionic surfactants of the general formula R 0 (AlkO) x M (OAlk) y OR 2 , where
  • R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms
  • x and y independently represent values between 1 and 70;
  • M is an alkyl radical selected from the group consisting of CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.
  • Nonionic surfactants of the general formula are preferred here.
  • R is -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2
  • R, R and R 2 independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms
  • R -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.
  • nonionic surfactant is selected from nonionic surfactants of the general formula
  • R and R 2 independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms
  • R 3 and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
  • - x and y independently represent values between 1 and 40.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the Herste II method exist commercial products of the formulas usually not from an individual representative, but from 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, consequently, fractional numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • the proportion by weight of the nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. %.
  • the weight% ratio of anionic surfactant having at least one sulfate or sulfonate group to nonionic surfactant is from 3: 1 to 1: 3, especially from 2: 1 to 1: 2, more preferably from 1 , 5: 1 to 1: 1, 5.
  • Inventive moldings contain polyvinylpyrrolidone particles in a further preferred embodiment. These particles facilitate, inter alia, the disintegration of the moldings and serve insofar as disintegration aids or tablet disintegrating agents. It has been found to be particularly advantageous according to the invention, Polyvinylpyrrolidon particles having an average particle diameter of 100 to 150 ⁇ , in particular with a mean particle diameter of 1 10 to 130 ⁇ to use.
  • average particle diameter or “average diameter” is meant 50 particle diameter in the present invention, the volume mean D, which can be determined by conventional methods.
  • the volume average D 50 particle diameter is that point in the particle size distribution in which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter
  • Particle diameters can be determined in particular by means of dynamic light scattering, which are usually carried out on dilute suspensions containing, for example, from 0.01 to 1% by weight of particles.
  • the PVP particles not only have an average particle diameter of 100 to 150 ⁇ m, in particular from 110 to 130 ⁇ m, but moreover, the particle size of the particles used is preferably completely within the stated intervals. This is ensured by using grain size fractions with the indicated particle sizes obtained by a sieving process.
  • the PVP particles are preferably present in compositions according to the invention in an amount of from 0.1 to 5% by weight, in particular in an amount of from 0.2 to 3% by weight, in particular in an amount of from 0.3 to 1, 8 wt .-%, contained.
  • disintegrants usually that they increase their volume upon ingress of water, whereby on the one hand increases the intrinsic volume (swelling), but on the other hand by the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles .
  • other disintegrants may also be present in moldings according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their derivatives and Alginates or casein derivatives.
  • gas-evolving effervescent systems can also be used as further disintegrants.
  • Preferred effervescent systems consist of at least two constituents which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifier which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the further disintegration aids are, if used, preferably in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular 0.5 to 2 wt .-%, each based on the total weight of desintegrationsakusstoffumblen agent used.
  • the shaped body according to the invention contains no further disintegration auxiliaries apart from the PVP particles.
  • the production of the shaped bodies according to the invention, in particular of the detergent tablets, preferably takes place in a manner known to the person skilled in the art by compression of particulate starting substances.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process hereinafter referred to as tableting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the tabletting is preferably carried out on so-called rotary presses.
  • the ingredients provided for tabletting can be added in the form of a common particulate premix at the same time or in the form of individual, separate powders or granules offset in time or at the same time in the mold, wherein the dosage of a prefabricated particulate premix is preferred.
  • compacts having a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N, which in addition is a particularly good one can preferably be obtained by using a pressing force of 40 to 65 kN, more preferably 48 to 60 kN Have trickle behavior.
  • the granules can thus preferably be pressed with relatively low pressing force into compact materials having a relatively high hardness, which moreover preferably have a very good trickling behavior. Accordingly, it is conversely advantageous for the production of compact materials of lower hardness preferably a lower pressing force must be used, as for the production of conventional compactates.
  • Automatic dishwashing detergents according to the invention contain as further constituent in a preferred embodiment at least one anionic polymer.
  • Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates.
  • the proportion by weight of the anionic polymer in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and in particular from 4 to 14 wt .-%.
  • Automatic dishwashing detergents characterized in that the copolymeric anionic polymer is selected from the group of hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, since the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents with simultaneously low deposit formation can be achieved.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids. Copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used according to the invention as copolymeric polycarboxylates.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - propyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwasher detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol 1 , preferably from 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Automatic dishwashing detergent characterized in that the automatic dishwashing detergent comprises as anionic copolymer a copolymer comprising
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • Dishwashing agents according to the invention furthermore preferably contain builder (s) and enzyme (s) to ensure their cleaning action.
  • automatic dishwashing agents according to the invention preferably contain one or more builders.
  • the proportion by weight of the builders in the total weight of automatic dishwashing detergents according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • the builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.
  • phosphate Preference is also the use of phosphate.
  • the alkali metal phosphates have, with particular preference of pentasodium or.
  • Pentakaliumtriphosphat sodium or potassium tripolyphosphate
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HP0 3 ) n and orthophosphoric H 3 P0 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na 5 P 3 O 0 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 0 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning substances in automatic dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 5 to 60% by weight, preferably from 15 to 45% by weight, in particular from 20 to 40% by weight, in each case based on the weight of the automatic dishwashing detergent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • machine dishwasher detergents contain citrate as one of their essential builders.
  • Machine dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.
  • the citrates are preferably used in combination with carbonates and / or bicarbonate.
  • Preferred automatic dishwasher detergents are therefore characterized by a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate (see Table 1 a and 1 b below).
  • builder combinations of phosphate, citrate and carbonate / bicarbonate can be realized.
  • the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably from 5 to 80% by weight, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • the content of the automatic dishwashing agents on (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Inventive automatic dishwashing agents crystalline builder layered silicates of general formula NaMSi x C> 2x + i ⁇ y H 2 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
  • the agents according to the invention may contain alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • Alternative automatic dishwashing detergents are free of alkali metal hydroxides.
  • Dishwashing agents preferably comprise enzyme (s) as a further constituent.
  • enzyme include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners.
  • a- Amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • Particularly preferred automatic dishwasher detergents according to the invention contain
  • anionic surfactant (s) having at least one sulfate or sulfonate group, preferably selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates;
  • d) optionally 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 2.5 to 10 wt .-% of nonionic (s) surfactant (s), preferably of the general formula
  • e) optionally 1 to 15 wt .-% of a copolymeric anionic polymer comprising carboxylic acid group-containing monomer (s) and sulfonic acid group-containing monomer (s).
  • Such automatic dishwashing agents comprise a) from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight, of anionic surfactant (s) selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates, in particular from C 2 -C 8 -fatty alcohol sulfates, secondary C 13 -C 7 -alkanesulfonates and linear C 8 -C 8 -alkylbenzenesulfonic acids;
  • anionic surfactant selected from alkyl sulfates, alkyl sulfonates and alkylbenzenesulfonates, in particular from C 2 -C 8 -fatty alcohol sulfates, secondary C 13 -C 7 -alkanesulfonates and linear C 8 -C 8 -alkylbenzenesulfonic acids
  • R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z is from 0 to 40 and y is from 15 to 120, especially from 20 to 80;
  • e) optionally 1 to 15 wt .-% of a copolymeric anionic polymer comprising carboxylic acid group-containing monomer (s) and sulfonic acid group-containing monomer (s).
  • compositions according to the invention may contain further washing- or cleaning-active substances, preferably from the group of glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers.
  • Another object of the present application is therefore a method for cleaning dishes in a dishwasher using a dishwashing detergent according to the invention, wherein the dishwashing agent preferably during the passage of a dishwasher, before the main wash cycle or in the course of the main wash cycle in the interior of a Dishwasher is metered.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered into the interior of the dishwasher by means of the metering chamber of the dishwasher.
  • no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
  • a kit for a dishwasher comprising
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning properties, in particular also in low-temperature cleaning processes and in short-lasting purification processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C., and / or a time of less than 90 minutes, preferably less than 60 minutes, in particular less than 45 Minutes.
  • Nonionic surfactant A 1 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Bleaching catalyst 0.001 to 2 0.0025 to 1 0.001 to 2 0.0025 to 1
  • Nonionic surfactant A 1 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Bleaching catalyst 0.001 to 2 0.0025 to 1 0.001 to 2 0.0025 to 1
  • Bleaching catalyst 0.001 to 2 0.0025 to 1 0.001 to 2 0.0025 to 1
  • Nonionic surfactant A la 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • Nonionic surfactant B ° 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10
  • R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x and z represent values between 0 and 40 and y represents a value of at least 15 stands;
  • R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms
  • M is an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms
  • a nonionic surfactant B of the general formula R -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 is used, in of the
  • R, R and R 2 independently represent an alkyl or alkenyl radical having 6 to 22 carbon atoms
  • a nonionic surfactant B of the general formula R-O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O-R 2 is used in the
  • R and R 2 independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms
  • R 3 and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
  • an anionic polymer C from the group of copolymeric polycarboxylates and copolymeric polysulfonates an anionic polymer C comprising
  • LAS stands for a linear C8-C18-alkylbenzenesulfonic acid
  • SAS stands for a secondary C 13 -C 17 -alkanesulfonate
  • FAS for a C 2 -C 8 -fatty alcohol sulfate.
  • the dishwashing process was carried out in the dishwasher Bosch SMS86M12 DE / 01 (program: 40 ° C, water hardness 21 ° dH).
  • the dishwasher tablet was added to the dosing device before the start of the cleaning program.
  • Mn-TACN contains 5
  • Sulfopon K 35 is a C12-C18 fatty alcohol sulfate (FAS), while Hostapur SAS 93 is a C13-C17 secondary alkanesulfonate (SAS).
  • anionic surfactants of the sulfate and sulfonate type leads to an improvement in the cleaning performance of tea.
  • the foaming of the anionic surfactant in the dishwasher is obviously so low that the cleaning performance is not adversely affected thereby.

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Abstract

Détergents pour vaisselle qui contiennent au moins un tensio-actif anionique renfermant au moins un groupe sulfate ou un groupe sulfonate, des agents de blanchiment ainsi qu'un activateur de blanchiment et/ou catalyseur de blanchiment. Lesdits détergents se caractérisent par un très bon pouvoir nettoyant lors du lavage de vaisselle à la machine, en particulier pour ce qui concerne des salissures à blanchir, spécifiquement des salissures provoquées par le thé.
PCT/EP2012/054380 2011-03-17 2012-03-13 Détergents pour vaisselle Ceased WO2012123452A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0554943A2 (fr) * 1992-02-03 1993-08-11 Unilever N.V. Composition détergente
GB2283494A (en) * 1993-11-03 1995-05-10 Procter & Gamble Machine dishwashing
EP0677576A2 (fr) * 1994-04-13 1995-10-18 The Procter & Gamble Company Compositions détergente pour le lavage automatique de la vaisselle contenant des activateurs de blanchiment
US5747438A (en) * 1993-11-03 1998-05-05 The Procter & Gamble Company Machine dishwashing detergent containing coated percarbonate and an acidification agent to provide delayed lowered pH
WO2000050551A1 (fr) * 1999-02-22 2000-08-31 The Procter & Gamble Company Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes
DE69429930T2 (de) * 1993-12-21 2002-11-07 The Procter & Gamble Company, Cincinnati Percarbonat und amylase enthaltende waschmittelzusammensetzungen
JP2003213295A (ja) * 2002-01-24 2003-07-30 Lion Corp 自動食器洗浄機用洗剤組成物
JP2005239809A (ja) * 2004-02-25 2005-09-08 Kao Corp 自動食器洗浄機用洗剤組成物
JP2006206893A (ja) * 2004-12-27 2006-08-10 Lion Corp 食器洗い機用洗浄剤組成物およびその製造方法、ならびに該食器洗い機用洗浄剤製品

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0554943A2 (fr) * 1992-02-03 1993-08-11 Unilever N.V. Composition détergente
GB2283494A (en) * 1993-11-03 1995-05-10 Procter & Gamble Machine dishwashing
US5747438A (en) * 1993-11-03 1998-05-05 The Procter & Gamble Company Machine dishwashing detergent containing coated percarbonate and an acidification agent to provide delayed lowered pH
DE69429930T2 (de) * 1993-12-21 2002-11-07 The Procter & Gamble Company, Cincinnati Percarbonat und amylase enthaltende waschmittelzusammensetzungen
EP0677576A2 (fr) * 1994-04-13 1995-10-18 The Procter & Gamble Company Compositions détergente pour le lavage automatique de la vaisselle contenant des activateurs de blanchiment
WO2000050551A1 (fr) * 1999-02-22 2000-08-31 The Procter & Gamble Company Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes
JP2003213295A (ja) * 2002-01-24 2003-07-30 Lion Corp 自動食器洗浄機用洗剤組成物
JP2005239809A (ja) * 2004-02-25 2005-09-08 Kao Corp 自動食器洗浄機用洗剤組成物
JP2006206893A (ja) * 2004-12-27 2006-08-10 Lion Corp 食器洗い機用洗浄剤組成物およびその製造方法、ならびに該食器洗い機用洗浄剤製品

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