EP1524313B2 - Composition pour lave-vaisselle avec des propriétés de rincage ameliorées - Google Patents

Composition pour lave-vaisselle avec des propriétés de rincage ameliorées Download PDF

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Publication number
EP1524313B2
EP1524313B2 EP04023137.5A EP04023137A EP1524313B2 EP 1524313 B2 EP1524313 B2 EP 1524313B2 EP 04023137 A EP04023137 A EP 04023137A EP 1524313 B2 EP1524313 B2 EP 1524313B2
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Prior art keywords
surfactants
acid
preferred
detergent composition
protease
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German (de)
English (en)
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EP1524313A1 (fr
EP1524313B1 (fr
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Janco Van Ommen
Robbert De Boer
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Dalli Werke GmbH and Co KG
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Dalli Werke GmbH and Co KG
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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
    • C11D3/16—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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
    • 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
    • C11D1/75—Amino oxides
    • 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
    • C11D1/88—Ampholytes; Electroneutral 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • 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
    • C11D17/0078—Multilayered 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the invention is directed to a detergent composition for dishwashers, the ingredients of which lead to an improved washing result. In particular, less “filming” is achieved while at the same time less “spotting” is achieved.
  • Machine dishwashing generally consists of a pre-wash cycle, one or more intermediate wash cycles, a final rinse cycle and a drying cycle. In principle, this applies to machine washing both in households and in the commercial sector.
  • the aim of machine washing is to achieve an optimal result without mechanical rubbing or wiping, as is the case with washing by hand.
  • the washing result should prevent the formation of a film (“filming”) or the remaining droplets ("spotting”) on the dishes.
  • a 3in1 tablet takes on the task of cleaning and rinsing and prevents the precipitation of Ca and Mg ions in the form of Salt.
  • the various functions are preferably released at different times during the flushing process.
  • the agents used for machine cleaning of dishes can be liquid, powder, paste or tablet form.
  • the use of tablets is particularly popular because of their ease of handling and dosing.
  • the object of the invention is to provide a detergent composition for use in machine dishwashers which brings about particularly good results in terms of "filming”, ie the formation of a film on the washed dishes, and at the same time the formation of droplet residues ("spotting") on the avoid washed dishes.
  • a detergent composition for machine dishwashers which (a) has at least one "carry over" surfactant, which has the general formula R 1 O (CH 2 CH 2 O) x (CH 2 CH 2 CH 2 O) y H, where R 1 is a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 30 carbon atoms, preferably 8 to 26, particularly preferably 10 to 24 carbon atoms, x is an integer between 26 and 200, y is an integer smaller is than 100 and x + y is less than 200 in amounts of 1 to 20% by weight, (b) a salt functional polymer is formed from monomers of acrylic acid and / or maleic acid in combination with at least one monomer which is selected / are from the group 2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic acid, or sulfonated styrene, it being possible for the salt functional polymer to be in acidic or neutral form.
  • R 1 is a linear or branched, saturated or unsatur
  • a “carry over” surfactant according to the present invention is to be understood as meaning a surfactant which, due to its structure and its properties, over the entire cleaning process up to the last rinse cycle in the Dishwasher "dragged". The details of this type of surfactant are discussed in greater detail below.
  • the detergent composition contains a salt function polymer that prevents the precipitation of Ca and Mg ions in the form of salts or prevents the crystal growth of precipitates that have already formed.
  • the detergent composition also includes a dispersant for non-water-soluble compounds / salts.
  • the detergent composition contains a salt function polymer that prevents the precipitation of Ca and Mg ions in the form of salts or prevents the crystal growth of precipitates that have already formed.
  • the detergent composition also includes a dispersant for non-water-soluble compounds / salts.
  • the detergent composition can be packaged in any commercially available form, e.g. liquid, paste, powder, granulate or particle form (e.g. spheres or so-called "pearls"), but is preferably used in the form of a pressed molded body.
  • the shaped body can be single-phase or multiphase.
  • a particularly preferred embodiment is a multiphase, pressed molded body, the individual phases in the washing liquor being able to be dissolved at different times.
  • Such a pressed molded body can contain a suitable disintegrant in individual (or in all) phases.
  • the mentioned ingredients carry over surfactant, salt function polymer and dispersant can be used in multiphase tablets in different phases or in different concentrations in the individual phases are present so that they are released into the washing liquor at different times (in different concentrations), but they can also be present in a uniformly distributed manner in all phases of multiphase tablets.
  • the formation of the film on the dishes is due, among other things, to the fact that the fatty acids from the triglycerides of the food residues in the dishwasher are saponified by the ingredients of the detergent composition.
  • Lime soaps as typical organic salts melt above certain temperatures. The melting temperature is determined by the chain length of the fatty acid. Below this melting temperature, however, they precipitate as insoluble soaps and settle on the dishes.
  • either the temperature profile of dishwashers can be varied in such a way that the washing water temperature does not fall below the failure limit of the lime soaps, or the calcium and magnesium ions in the washing liquor can be complexed as high as possible with the aid a salt or an agent with a salt function can be controlled.
  • Solid is understood to mean the formation of droplet residues, which can also be seen after the dishes have dried, especially on glasses. These remaining drops with dissolved salts leave stains on the dishes and glasses.
  • surfactants are used in conventional dishwashing detergents, which reduce the surface tension and thus allow the drops to run off the dishes better.
  • Suitable dispersants for the saponified fatty acids are all agents which are capable of dispersing non-water-soluble organic compounds such as lime soaps in an aqueous composition, especially at temperatures at which these compounds are present as insoluble compounds in the aqueous medium.
  • Such dispersants are known to the person skilled in the art, inter alia, from the areas of toilet cleaning articles, cutting oils, textile processing and the area of industrial cleaning. Common dispersants can easily be found on the Internet under the keyword "lime soap dispersant”. Examples of such dispersants are alkyl monopropionates, alkyl dipropionates, cocoamphocarboxyglycinates, alcohol ethoxycarboxylates, amine oxides, alkyldimethyl betaines, terephthalic acid, cocoamido propyl dimethyl betaines, alkylamino diacetates and citronella esters, as well as polymers based on acrylic acid, maleic acid and.
  • the dispersants are used in the cleaning agent compositions according to the invention in amounts from 0 to 8% by weight, preferably from 0.1 to 5% by weight, particularly preferably from 0.5 to 3% by weight and particularly preferably from 0.8 to 2% by weight.
  • Carry over surfactants are those surfactants which, due to their hydrophilic-hydrophobic balance, are “carried over” through the individual cleaning and rinsing processes in a dishwasher during the course of the cleaning and rinsing process.
  • a statement that is not binding on the Invention is to be interpreted is that these surfactants due to their hydrophilic-hydrophobic properties are not subject to the usual Nernstian distribution (i.e. are not removed with the washing liquor and the rinsing water), but also increasingly adsorb on surfaces during the cleaning and rinsing process. This means that these surfactants are not only present in the washing liquor in the first wash or rinse cycle, but also in the last rinse cycles, albeit in a lower concentration there. This has the effect that the surface tension of the water is kept reduced even in the last wash cycles, which allows the water droplets to run off the items to be washed more easily.
  • Surfactants that fulfill this task are surfactants of the general formula R1O (CH2CH2O) x (CH2CH2CH2O) yH, where R1 is a linear or branched, saturated or unsaturated hydrocarbon radical with 6 to 30 carbon atoms, preferably 8 to 26, particularly preferably 10 to 24 Represents carbon atoms, x is an integer between 26 and 200, y is an integer less than 100 and x + y is less than 200. In a preferred embodiment, in at least one of the carry over surfactants used, x is greater than 30, and particularly preferably greater than 40, but less than 200. R1 is preferably a linear, saturated hydrocarbon radical.
  • Suitable surfactants are nonionic surfactants of the formula R2O [CH2CH (CH3) O] x [CH2CH2O] y [CH2CH (OH) R3], in which R2 stands for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R3 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15, preferably of at least 25.
  • nonionic surfactants that can be used are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula R4O [CH2CH (R5) O] x [CH2] kCH (OH) [CH2] jOR6, in which R4 and R5 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R6 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R6 in the above formula can be different.
  • R4 and R5 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • R6, H, —CH3 or —CH2CH3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R6 in the above formula may be different if x is 2.
  • the value 3 for x has been chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R4, R5 and R6 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R4 and R5 have 9 to 14 carbon atoms, R6 stands for H and x assumes values of 6 to 15.
  • Particularly preferred carry over surfactants of the present invention consist of more than 45% of their molecular weight as hydrophilic groups, preferably more than 60%, particularly preferably more than 70%.
  • the melting or solidification point of preferred carry over surfactants is above 25 ° C, preferably above 30 ° C and particularly preferably above 35 ° C.
  • Preferred carry over surfactants have a cloud point in distilled water above 85.degree. C., preferably above 90.degree. C. and particularly preferably above 95.degree.
  • a carry over surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant, which results from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 25 mol, particularly preferably at least 30 mol, in particular at least 40, 50 or 80 moles of ethylene oxide per mole of alcohol or alkylphenol has emerged.
  • a preferred nonionic surfactant to be used which is solid at room temperature is made from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C16-C20 alcohol), preferably a C18 alcohol and at least 25 mol, preferably at least 30 mol and in particular at least 40, 50 or 80 mol of ethylene oxide won.
  • C16-C20 alcohol straight-chain fatty alcohol with 16 to 20 carbon atoms
  • C18 alcohol preferably a C18 alcohol and at least 25 mol, preferably at least 30 mol and in particular at least 40, 50 or 80 mol of ethylene oxide won.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • gemini surfactants are suitable as further surfactants. These are generally understood to mean those compounds which are present as dimers and have excellent adsorption behavior compared to monomeric surfactants. The gemini surfactants are discussed in more detail below.
  • All of the carry over surfactants mentioned are used in the cleaning agent compositions according to the invention in amounts of 1 to 20% by weight, preferably 1 to 10% by weight, particularly preferably 1 to 6% by weight.
  • the detergent compositions can also contain other surfactants, as explained in more detail below.
  • the cleaning composition contains at least two different carry over surfactants, for example two surfactants with the same basic formula but different contents of (EO) / (PO) units, for example two carry over surfactants can be used, both of which have the basic formula R1O (CH2CH2O) x (CH2CH2CH2O) yH, where R1 in both surfactants is a linear or branched, saturated or unsaturated hydrocarbon radical with 6 to 30 carbon atoms and x in one surfactant is an integer between 26 and 30 and in the other surfactant one is an integer between 50 and 100, y is an integer less than 100 and x + y is less than 200.
  • at least two carry over surfactants with different basic formulas described above can also be used.
  • a polymer is preferably used in the cleaning composition according to the invention.
  • Such salt function polymers are known from the prior art, in particular from the field of water treatment. Examples of such polymers are products of the Acusol 587 type (Rohm & Haas), which are advertised as calcium phosphate inhibitors, anti-filming agents and dispersants.
  • a copolymer to be used according to the invention consists of monomers of acrylic acid and / or maleic acid in combination with at least one monomer selected from 2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic acid, or sulfonated styrene, the salt functional polymer can be in acidic or neutral form.
  • the sulfonation of the individual monomers can take place before the polymerization or can only be introduced after the polymerization has taken place.
  • copolymer in this context encompasses a polymer with two or more different types of monomers, including, for example, terpolymers.
  • Such a salt function polymer has a molecular weight in the range between 3,000 and 100,000, preferably from 4,000 to 80,000.
  • the proportion of non-sulfonated monomers in the salt function polymer is preferably from 10% to 90%, preferably from 50% to 80%, the proportion of sulfonated monomers from 10 to% to 90%, preferably from 20% to 50%.
  • Such a salt function polymer is used in the composition according to the invention in amounts from 0.2 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 0.8 to 5% by weight.
  • the detergent shaped bodies can be compressed from just one detergent composition (single-phase tablets), or they can consist of several phases, layers or areas, for example two- or three-phase shaped bodies (e.g. "3 in 1"). Individual components of the cleaning agent can be separated from one another so that they are made available at different times during the cleaning process.
  • the dimensions of the three-dimensional shape of the molded bodies can be adapted to the dispenser compartment of the dishwasher, but all sensible, manageable shapes can be designed. This also includes, for example, cylindrical designs with oval or circular cross-sections and molded bodies with a plate-like or panel-like structure.
  • a preferred molded body consists of alternating thick long and thin short segments, so that individual segments of such a bolt at predetermined breaking points, which are represented by the short thin segments, can be broken off and entered into the dosing chamber or the cutlery basket of the machine. This principle of the bar-shaped molded body can also be implemented in other geometric polygonal shapes.
  • a tablet produced in this way preferably has a weight of 5 to 120 g, particularly preferably 10 to 30 g.
  • Detergent tablets for different purposes, in particular for dishwashers, are known in principle.
  • Detergent formulations of this type designed as molded bodies generally contain builders, bleaches and bleach activators, surfactants, tableting aids, disintegrants and other customary additives and auxiliaries.
  • composition of the cleaning agent can also contain the ingredients that are customary for dishwashing detergents.
  • the ingredients of the detergent composition described below are only preferred embodiments.
  • a disintegrant can be contained in all layers / phases of the cleaning tablet, but is preferred in only one or in two (at Presence of several layers / phases) contain layers / phases. This is preferred in order to dissolve a first layer / phase, which contains components which should come into effect quickly, in the rinse water in a short time and thus provide the components, while a further layer / phase, which contains components, to dissolve at a later point in time of the cleaning process should be used, dissolves more slowly because it contains no or a "slower" disintegrant.
  • All customary builders known as such can be used as builders in the detergent composition, in particular polyphosphates, pyrophosphates, metaphosphates or phosphonates, sheet silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, citrate and citric acid. Succinic acid, tartaric acid and malic acid.
  • Cobuilders and dispersants are often used as auxiliary builders. Such cobuilders or dispersants can be, inter alia, polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
  • Common bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, and peracid salts that supply H2O2, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
  • peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
  • other known bleaches or bleach systems can also be present in the composition.
  • Suitable peroxygen compounds for use in agents according to the invention are, in particular, hydrogen peroxide and, under the washing conditions, inorganic salts which release hydrogen peroxide, to which alkali metal perborates such.
  • alkali metal perborates such as sodium perborate tetrahydrate and sodium perborate monohydrate, furthermore alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate”) and persilicates and / or - Persulfate such as caroate include.
  • the bleaching system of the detergent formulation can contain inorganic or organic peracids, in particular percarboxylic acids, e.g. B.
  • C1-C12 percarboxylic acids C8-C16 dipercarboxylic acids, imidopercaproic acids or aryldipercaproic acids.
  • acids that can be used are peracetic acid, perbenzoic acid, linear or branched octanoic, nonanoic, decanoic or dodecanoic monoperic acids, decanoic and dodecanediperic acids, mono- and diperphthalic acids, monophthalic acids and terephthalic acids, phthalimidopercaproic acid, terephthalic acid peroxyl percaproic acid, terephthalic acid peroxoyl percaproic acid (PAP).
  • percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • a peracid and particularly preferably used is commercially available under the trade name Eureco ® (Ausimont, Italy) peracid.
  • Peroxygen compounds are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight and particularly preferably from 8% by weight to 25% by weight.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate can be useful.
  • the content of bleaching agents in tablets is preferably 0.5-50% by weight and in particular 1-30% by weight.
  • Quaternized imines or sulfonimines are usually used as bleach catalysts, as they are, for example, in US-A-5,360,568 , US-A-5,360,569 and EP-A-453 003 are described, as well as manganese complexes, as for example in WO-A 94/21777 are described. Further usable metal-containing bleach catalysts are in EP-A-458 397 , EP-A-458 398 and EP-A-549 272 described. Bleach catalysts are used in generally used in amounts of up to 10% by weight, in particular 0.1 to 6% by weight, based on the detergent formulation.
  • Suitable bleach activators are the N-acyl and O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used.
  • Particularly suitable bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol-mannitol- Mixtures (SORMAN).
  • compounds of the substance classes of polyacylated sugar or sugar derivatives with C1-C10 acyl residues can be used, preferably with acetyl, propionyl, octanoyl, nonanoyl or benzoyl residues, in particular acetyl residues.
  • Mono- or disaccharides and their reduced or oxidized derivatives can be used as sugars or sugar derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose.
  • bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.
  • O-acyloxime esters such as. B. O-acetylactone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate.
  • acylated oximes and oxime esters are described, for example, in US Pat EP-A-028 432 and the EP-A-267 046 .
  • N-acylcaprolactams such as, for example, N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam, N-octanoylcaprolactam or carbonylbiscaprolactam, can also be used as bleach activators.
  • bleach activators are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as they are, for example, in US Pat EP-B-332 294 and the EP-B-502 013 are described.
  • 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one can be used.
  • bleach activators from the substance classes of the N- or O-acyl compounds for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, cyanurateyl anhydrides and carboxylic anhydrides, carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives such as pentaacetyl glucose can be used.
  • acylated alkylenediamines in particular tetraacetylethylenediamine
  • acylated glycolurils in particular tetraacetylg
  • a preferred bleach activator is a quaternized glycine nitrile from the group of N-methylmorpholinium acetonitrile methyl sulfate, sulfate and hydrogen sulfate.
  • bleach system (bleach and bleach activators) all those in the DE 199 59 589 A1 mentioned bleaching agents and activators.
  • bleach systems described in the European patent application EP 02 028 958.3 are used.
  • the different constituents of the detergent composition are contained in different phases / layers / regions of the shaped bodies.
  • a component which is to be provided at an earlier point in time of the cleaning process is located in a phase / layer / area in which a disintegrant is contained.
  • the cleaning agents can also contain one or more other surfactants from the group of nonionic, anionic, cationic and / or amphoteric surfactants.
  • the detergent tablets according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms e.g. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred.
  • the preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO or 4 EO, C9-C11 alcohol with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-C18- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Cleaning agent tablets according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, they are preferred Detergent tablets, characterized in that they contain as ingredient c) nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43 , 3 ° C included.
  • Suitable nonionic surfactants which have melting points or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that these have a viscosity above 20 Pas, preferably 35 Pas and in particular above 40 Pas. Nonionic surfactants which have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the PO units preferably make up up to 25% by weight, particularly preferably 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene block polymer blend, which is 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol 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.
  • Further preferred cleaning agent tablets according to the invention contain nonionic surfactants of the formula R1O [CH2CH (CH3) O] x [CH2CH2O] y [CH2CH (OH) R2], in which R1 stands for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • R1 stands for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof
  • x stands for values between 0.5 and 1.5
  • y stands for a value of at least 15.
  • nonionic surfactants that can be used are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula R1O [CH2CH (R3) O] x [CH2] kCH (OH) [CH2] jOR2, in which R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R3 stands for H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R3 in the above formula can be different.
  • R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • R3, H, —CH3 or —CH2CH3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R3 in the above formula can be different if x 2.
  • the value 3 for x has been chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R1, R2 and R3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R1 and R2 are 9 to 14 Have carbon atoms, R3 stands for H and x assumes values from 6 to 15.
  • alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position can be used as nonionic surfactants can or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms, e.g. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred.
  • the preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO or 4 EO, C9-C11 alcohols with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-C18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, can also be used as further nonionic surfactants and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
  • 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 can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.
  • polyhydroxy fatty acid amides of the formula (I), in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II),
  • R stands for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms
  • R1 for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms
  • R2 for a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-aryl radical with 1 to 8 carbon atoms
  • C1-C4-alkyl or phenyl radicals being preferred
  • [Z] is preferably obtained by reductive amination of a reduced sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted Compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • gemini surfactants are suitable as further surfactants. These are generally understood to mean those compounds which are present as dimers and, compared to monomeric surfactants, have two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called hydrophilic "spacer". Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric, but also trimeric surfactants.
  • Suitable Gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German patent application DE-A-195 03 061 .
  • End-capped dimeric or trimeric mixed ethers according to the German patent application DE-A-195 13 391 are characterized in particular by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides are in the international patent applications WO-A-95/19953 , WO-A-95/19954 and WO-A-95/19955 to be discribed.
  • Particularly suitable enzymes in the detergent tablets according to the invention are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, glucosidases such as amylases, mannanase or cellulase, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help remove stains such as protein, fat or starchy stains. Oxidoreductases can also be used for bleaching. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and from their genetically modified variants are particularly suitable.
  • protease and amylase or protease and lipase or lipolytic enzymes for example of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, in particular, however, protease and / or lipase-containing mixtures or Mixtures with lipolytic enzymes of particular interest.
  • lipolytically acting enzymes are the known cutinases.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include, in particular, ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes can be adsorbed on carrier substances or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • As part of The detergent tablets preferred according to the present invention are characterized in that they contain protease and / or amylase.
  • detergent tablets are preferred in which the enzyme (s) is / are not contained in one phase together with the bleach-enhancing active ingredient combination.
  • Detergent tablets which are characterized in that at least one phase contains bleach, while at least one other phase contains enzymes, are likewise preferred embodiments of the present invention.
  • the cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, in particular Silver protectants are of particular importance in the field of automatic dishwashing.
  • the known substances of the prior art can be used.
  • silver protectants in particular can be selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Benzotriazole and / or alkylaminotriazole are particularly preferred.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corrosion of the silver surface.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • detergent tablets contain corrosion inhibitors, these are preferably separated from the bleaching agents. Accordingly, detergent tablets in which at least one phase contains bleach while at least one other phase contains corrosion inhibitors are preferred.
  • Preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty acids, which, viewed in isolation, represent 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. It is also possible Use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactant mixtures contain combinations of alk (en) yl sulfates, in particular mixtures of saturated and unsaturated fatty alk (en) yl sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or ⁇ -sulfo fatty acid esters.
  • mixtures are preferred which contain alk (en) yl sulfates and alkylbenzenesulfonates, alk (en) yl sulfates and ⁇ -sulfofatty acid methyl esters and / or sulfated fatty acid glycerol esters as anionic surfactants.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.1 to 5% by weight.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and especially soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable. Soap mixtures composed of 50 to 100% by weight of saturated C12-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap are particularly preferred.
  • the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of their sodium salts.
  • inorganic salts which have an alkaline reaction in water.
  • These inorganic salts with an alkaline reaction include, in particular, bicarbonates, carbonates or mixtures thereof.
  • Alkali carbonate and especially sodium carbonate are preferably used.
  • the alkali silicates are in amorphous or crystalline form with a Na 2 O to SiO 2 ratio of 1: 1 to 1: 2.8 should be mentioned.
  • the cogranulates of carbonates and silicates which are available on the market as so-called NABION (Rhodia), are also used.
  • Examples of other customary additives and auxiliaries are magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.
  • Substances which have an anti-corrosion effect on glass can also be considered as a further constituent of the cleaning agent composition.
  • All known anti-corrosion agents can be used as anti-corrosion protection for the glass. Examples of these are metal oxides, such as oxides of zinc, aluminum, tin, magnesium, calcium, strontium, silicon, titanium, zirconium, manganese and lanthanum, or insoluble inorganic zinc compounds, as they are in EP 0 383 482 are described, or zinc or magnesium salts of organic compounds, as they are in the DE 101 40 535 are described.
  • dyes and fragrances can be added to the automatic dishwashing detergents according to the invention in tablet form in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual odoriferous compounds such.
  • B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for. B.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes such.
  • the linear alkanals with 8 to 18 carbon atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal, to the ketones z.
  • the hydrocarbons mainly include the terpenes such as limonene and pinene. However, it is preferred to use mixtures of different fragrances which together produce an appealing fragrance note.
  • perfume oils can also contain natural fragrance mixtures, such as are available from vegetable sources, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the shaped bodies according to the invention, but it can also be advantageous to apply the fragrances to carriers.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with further auxiliaries. Incorporation of the fragrances as ingredient d) in the cleaning agent components according to the invention is also possible and leads to a fragrance impression when the machine is opened.
  • the agents can be colored with suitable dyes.
  • Preferred dyes the choice of which presents no difficulty to the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, as well as no pronounced substantivity to the substrates to be treated with the agents, such as glass, ceramic or plastic tableware, so as not to stain them.
  • the coloring of individual phases for optical differentiation is preferred.
  • the tablets mentioned in the examples can be used as mono-, double- and triple-phase tablets.
  • the individual components can be distributed in different areas / phases of the shaped bodies.
  • Table 1 Examples of compositions of dishwashing tablets according to the invention (all amounts in parts by weight).
  • the table shows that the addition of a carry over surfactant causes a significant reduction in the formation of stains, which is further supported by the addition of a salt-functional polymer.
  • the addition of a dispersant also improves the washing results. In particular, improved “spotting” is achieved with good “filming” compared to commercially available products.
  • the filming and spotting of the composition according to the invention is compared with the filming and spotting of compositions in which the constituents surfactant, salt function polymer or dispersant correspond to conventionally used substances.
  • the same basic formulation as in Example 3 was used as the basic composition of the cleaning composition. The results are classified as in Example 2.
  • the invention relates to a detergent composition for machine dishwashers which contains at least one carry over surfactant, as a result of which improved washing results are achieved.

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Claims (5)

  1. Composition de produit de nettoyage pour lave-vaisselle, qui comprend :
    (a) au moins un tensioactif « Carry over », qui répond à la formule générale R1O(CH2CH2 O)x(CH2CH2CH2O)yH, dans laquelle R1 représente un radical hydrocarboné linéaire ou ramifié, saturé ou insaturé, comportant 6 à 30 atomes de carbone, de préférence 8 à 26, particulièrement de préférence 10 à 24 atomes de carbone, x représente un nombre entier entre 26 et 200, y représente un nombre entier inférieur à 100 et x+y a une valeur inférieure à 200, en une quantité allant de 1 à 20 % en poids.
    (b) un polymère à fonction de sel constitué de monomères de l'acide acrylique et/ou de l'acide maléïque en combinaison avec au moins un monomère qui est (sont) choisi(s) dans le groupe : acide 2-acrylamido-2-méthylpropanesulfonique, acide méthallylsulfonique, styrène ou styrène sulfoné, le polymère à fonction de sel pouvant se présenter sous forme acide ou neutre.
  2. Composition de produit de nettoyage selon la revendication 1, caractérisée en ce qu'on utilise au moins deux tensioactifs « Carry over » différents.
  3. Composition de produit de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisée en ce qu'elle contient également un agent dispersant
  4. Composition de produit de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'elle se présente sous forme d'un corps moulé comprimé mono- ou multi-phase(s) ou d'une poudre.
  5. Utilisation d'au moins un tensioactif Carry over selon la définition de la revendication 1, en combinaison avec un polymère à fonction de sel selon la définition de la revendication 1, dans une composition de produit de nettoyage pour lave-vaisselle.
EP04023137.5A 2003-10-01 2004-09-29 Composition pour lave-vaisselle avec des propriétés de rincage ameliorées Active EP1524313B2 (fr)

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PL04023137T PL1524313T3 (pl) 2003-10-01 2004-09-29 Kompozycja do mechanicznego zmywania naczyń o ulepszonych właściwościach zmywania

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EP03022032A EP1520908A1 (fr) 2003-10-01 2003-10-01 Composition pour lave-vaisselle avec des propriétés de rinçage améliorées
EP03022032 2003-10-01
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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0514004D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
EP1897933A1 (fr) * 2006-09-05 2008-03-12 Cognis IP Management GmbH Utilisation des alcools gras alkoxylés à long chaîne comme additif au détergent pour le nettoyage de surfaces dures
DE102007019457A1 (de) 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
DE102007019458A1 (de) 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
DE102007042859A1 (de) † 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsverfahren
EP2196531B1 (fr) 2008-12-05 2014-09-03 Dalli-Werke GmbH & Co. KG Pastille de détergent revêtue d'un polymère
DE102008060471A1 (de) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
ES2648240T3 (es) 2010-06-04 2017-12-29 Dalli-Werke Gmbh & Co. Kg Composición en partículas de baja higroscopicidad que comprende uno o más compuestos quelantes de aminopolicarboxilato
ES2662525T3 (es) 2010-06-04 2018-04-06 Dalli-Werke Gmbh & Co. Kg Mezcla de un tensioactivo con un compuesto sólido para mejorar el rendimiento de enjuagado de detergentes para lavavajillas automáticos
EP2966161B1 (fr) 2014-07-08 2018-10-31 Dalli-Werke GmbH & Co. KG Cogranulé d' enzyme et catalyseur de blanchiment adapté pour des compositions détergentes
EP3053997B2 (fr) 2015-02-05 2021-01-13 Dalli-Werke GmbH & Co. KG Composition de nettoyage comprenant un catalyseur de blanchiment et de la carboxyméthylcellulose
EP3075832B1 (fr) 2015-03-30 2021-04-14 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage
US11021681B2 (en) 2015-05-07 2021-06-01 Novozymes A/S Manganese bleach catalyst granules for use in dishwash detergents
EP3190168B1 (fr) 2016-01-06 2019-04-10 Dalli-Werke GmbH & Co. KG. Catalyseur de blanchiment enrobé
EP3753856B1 (fr) * 2019-06-19 2023-10-11 Dalli-Werke GmbH & Co. KG Unité d'emballage à l'épreuve des enfants
EP3754003A1 (fr) 2019-06-21 2020-12-23 Dalli-Werke GmbH & Co. KG Emballage unitaire pour détergent dotée d'un poignée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851022A2 (fr) † 1996-12-23 1998-07-01 Unilever N.V. Compositions de rincage contenant des polymères antitartres
WO2002004583A1 (fr) † 2000-07-07 2002-01-17 Henkel Kommanditgesellschaft Auf Aktien Produit de nettoyage pour lave-vaisselle
EP1571198A1 (fr) † 2004-03-02 2005-09-07 Dalli-Werke GmbH & Co. KG. Composés au manganèse liés à des polymères dans des compositions détergentes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007985A1 (fr) * 1992-09-25 1994-04-14 The Procter & Gamble Company Composition de detergent contenant un dispersant de savon de chaux et des lipases
WO1994007974A1 (fr) * 1992-09-25 1994-04-14 The Procter & Gamble Company Composition de detergent comprenant un tensioactif dispersant le savon de chaux
GB2327948A (en) * 1997-08-02 1999-02-10 Procter & Gamble Dish-washer detergent composition containing a high cloud point surfactant
US5967157A (en) * 1996-09-11 1999-10-19 The Procter & Gamble Company Automatic dishwashing compositions containing low foaming nonionic surfactants in conjunction with enzymes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851022A2 (fr) † 1996-12-23 1998-07-01 Unilever N.V. Compositions de rincage contenant des polymères antitartres
WO2002004583A1 (fr) † 2000-07-07 2002-01-17 Henkel Kommanditgesellschaft Auf Aktien Produit de nettoyage pour lave-vaisselle
EP1571198A1 (fr) † 2004-03-02 2005-09-07 Dalli-Werke GmbH & Co. KG. Composés au manganèse liés à des polymères dans des compositions détergentes

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EP1524313A1 (fr) 2005-04-20
EP1520908A1 (fr) 2005-04-06
DK1524313T3 (da) 2007-07-23
ATE356862T1 (de) 2007-04-15
ES2283920T3 (es) 2007-11-01
DE502004003197D1 (de) 2007-04-26
EP1524313B1 (fr) 2007-03-14
PL1524313T3 (pl) 2007-08-31

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