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WO2013010701A1 - Produit de rinçage et de nettoyage - Google Patents

Produit de rinçage et de nettoyage Download PDF

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Publication number
WO2013010701A1
WO2013010701A1 PCT/EP2012/060079 EP2012060079W WO2013010701A1 WO 2013010701 A1 WO2013010701 A1 WO 2013010701A1 EP 2012060079 W EP2012060079 W EP 2012060079W WO 2013010701 A1 WO2013010701 A1 WO 2013010701A1
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Prior art keywords
weight
alkyl
monomer
water
builder
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
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PCT/EP2012/060079
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German (de)
English (en)
Inventor
Paula Barreleiro
Stefanie Juntermanns
Dorota SENDOR-MÜLLER
Thomas Eiting
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP12723717.0A priority Critical patent/EP2732017A1/fr
Publication of WO2013010701A1 publication Critical patent/WO2013010701A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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 present application relates to agents for rinsing and for cleaning dishes.
  • this application relates to liquid means for machine dishwashing and their use for rinsing and for cleaning dishes.
  • 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 a powder or as tablets.
  • one of the main objectives of the machine-washing machine manufacturers is also to improve the rinse-through performance of these products, with a recent focus on cleaning performance and rinsing performance in low-temperature cleaning cycles or in reduced-water cleaning cycles becomes.
  • new ingredients for example more active surfactants or polymers, have preferably been added to the cleaning agents.
  • new ingredients are available only to a limited extent and the amount of ingredients used for each cleaning cycle can not be increased to any extent for ecological and economic reasons, this approach has natural limits.
  • This application was therefore based on the object to provide a detergent for dishwashing, which is characterized compared to conventional Geschirtherapiesmitteln, preferably in low-temperature cleaning operations and / or cleaning operations with low water consumption, by improved rinse performance, in particular by effectively preventing staining ,
  • R- ⁇ and R 4 is hydrogen or CI_ 6 alkyl, independently from each other;
  • R 2 and R 3 are each independently CI_ 6 alkyl, hydroxy-alkyl or amino CI_ 6
  • x and y independently represent a value of 1 to 3; X "stands for a counterion;
  • a first object of the present invention is therefore the use of polymers containing
  • Ri and R 4 are independently hydrogen or C-
  • R 2 and R 3 are each independently CI_ 6 alkyl, hydroxy-alkyl or amino CI_ 6
  • x and y independently represent a value of 1 to 3; X "stands for a counterion;
  • a further subject of the present invention is therefore also a preferably automatic dishwashing process, characterized in that in at least one process step such a polymer is used as a rinse aid, in particular to avoid the formation of deposits and / or stains.
  • Another object of the present invention is therefore also a combination product comprising a packaging means and at least two, preferably exactly two, located in this packaging means, separate liquid detergent or cleaning agent A and B of the composition:
  • A - 10 to 75% by weight of builder (s);
  • liquid detergent A has a pH (20 ° C) between 6 and 9 and the liquid detergent B has a pH (20 ° C) between 9 and 14, characterized in that at least one of the washing or cleaning agents A and B contains a polymer comprising the following monomers:
  • Ri and R4 independently of one another are hydrogen or C -6 alkyl
  • R 2 and R 3 are each independently C -6 alkyl, hydroxy-C
  • x and y independently represent a value of 1 to 3;
  • the subject matter of the present invention is therefore likewise a preferably automatic dishwashing process in which a combination product according to the invention is used comes, in particular to reduce the formation of deposits and / or stains on the dishes.
  • the present application further relates to the use of a combination product according to the invention as a cleaning and rinse aid for hard surfaces, especially for reducing the formation of deposits and / or stains on dishes, in particular in automatic dishwashing.
  • the proportion of monomer (a) in the polymer is preferably 10-30%, more preferably 15-25%, based on the total number of monomers.
  • the hydrophilic monomer (b) according to the invention is preferably acrylic acid or methacrylic acid.
  • the proportion of monomer (b) in the polymer is preferably less than 15%, particularly preferably less than 10%, in particular 3-6%, based on the total number of monomers.
  • the hydrophilic non-ionic monomer (c) is according to the invention preferably is optionally monosubstituted on the nitrogen atom or disubstituted by CI_ 6 alkyl substituted acrylamide, being employed in a preferred embodiment of unsubstituted acrylamide.
  • the proportion of the monomer (c) on the polymer is preferably at least 50%, particularly preferably at least 65%, in particular 75-85%, based on the total number of monomers.
  • the liquid cleaning agents A and B present separately from one another in the combination products according to the invention contain builders in addition to other ingredients which are active in washing or cleaning.
  • the builders include, in particular, the zeolites, amorphous silicates, crystalline phyllosilicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O-10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning substances in the liquid detergents A and / or B in the context of the present application
  • preferred combination products contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.
  • alkali metal phosphate preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate)
  • pentasodium or pentapotassium triphosphate Sodium or potassium tripolyphosphate
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. 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.
  • citric acid succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • phosphate-free builders are aminocarboxylic acids and / or their salts.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the combination products according to the invention contain to increase the washing or cleaning performance enzymes.
  • enzymes include in particular proteases, amylases, lipases, cutinases, hemicellulases, which include in particular mannanases, xanthan lyases, pectin lyases, pectin esterases, pectate lyases, xyloglucanases, pullulanases and ⁇ -glucanases, cellulases 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 and cleaners, 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.
  • proteases those of the subtilisin type are preferable.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • DSM 12368 Bacillus sp. A 7-7
  • CTTase cyclodextrin glucanotransferase
  • the enzymes can be used in any form known in the art. These 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, sparing in water and / or added with stabilizers.
  • the proportion by weight of the enzymes in the total weight of the liquid cleaning agent A can be 0, 1 to 10 wt .-%. In particularly preferred combination products, the proportion by weight of the enzyme in the total weight of the cleaning agent A is from 0.2 to 9% by weight and in particular from 0.5 to 8% by weight.
  • the liquid detergent B may of course also contain enzymes, it is preferred that the enzyme content of the detergent B be less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight. and in particular less than 0.1 wt .-% is. Particularly preferred combination products are characterized in that the liquid cleaning agent B contains no enzymes.
  • one or more enzymes and / or enzyme preparations preferably solid or liquid protease preparations and / or amylase preparations are used.
  • the liquid cleaning agent A comprises a combination of protease and amylase preparations.
  • the combination products according to the invention preferably contain less than 2% by weight of bleaching agent and may also be free from bleach.
  • the adjustment of the pH values of the liquid detergents A and B is important for the cleaning performance of the resulting combination product.
  • Combination products in which the pH (20 ° C.) of the liquid cleaning agent A is between 6.5 and 8.5 and in particular between 7 and 8 are particularly preferred.
  • the pH (20 ° C.) of the liquid cleaning agent B is preferably between 9.5 and 13 and in particular between 10 and 12.
  • the liquid cleaning agents B additionally contain alkali carriers.
  • a further subject of the present application is therefore a combination product comprising a packaging means with two separate receiving chambers, as well as two separate liquid cleaning agents A and B of the composition located in these receiving chambers:
  • A - 10 to 75% by weight of builder (s);
  • liquid detergent A has a pH (20 ° C) between 6 and 9
  • liquid detergent B has a pH (20 ° C) between 9 and 14, characterized in that at least one of Washing or cleaning agent A and B comprises a polymer comprising the following monomers:
  • Ri and R4 independently represent hydrogen or CI_ 6 alkyl
  • R 2 and R 3 are each independently C -6 alkyl, hydroxy-C
  • x and y independently represent a value of 1 to 3;
  • alkali carriers are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal hydrogencarbonates or alkali metal sesquicarbonates, preference being given in this invention to the alkali metal hydroxides and alkali metal carbonates, in particular sodium hydroxide, potassium hydroxides, sodium carbonate, sodium bicarbonate or sodium sesquicarbonate be used.
  • the combination products according to the invention are distinguished not only by a very good rinse aid performance but also by improved cleaning performance on dried-on and / or burnt-on soils on hard surfaces, especially in automatic dishwashing.
  • the group of dried-on or burnt-on soils includes, for example, dried starch soils, for example oatmeal, or burnt-on residues from casseroles which, in addition to starch components such as noodles or potatoes, continue to include meat residues.
  • combination products according to the invention can be improved by the addition of organic solvents.
  • the preferred subject of the present application are therefore furthermore combination products according to the invention in which at least one of the cleaning agents A or B also contains an organic solvent.
  • organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic nischer solvents which are water-soluble, wherein "water-soluble" solvents in the sense of the present application are solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
  • Organic solvents which can be used in the compositions according to the invention are preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Di-ethylene glycol ethyl ether, propylene glycol methyl, -ethyl or -propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy t
  • the organic solvents from the group of the organic amines and / or the alkanolamines have proved to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soilings, in particular of tea stains.
  • Particularly preferred combination products contain, based on the total weight of the combination product, between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1, 5 and 6 wt.% Of an organic solvent from the Group of organic amines and alkanolamines.
  • combination products whose liquid detergent B, based on the total weight of the detergent B, a weight fraction of an organic solvent from the group of organic amines and alkanolamines between 0, 1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1, 5 and 6 wt.%, While the weight fraction of organic solvent from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferably less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt.% And most preferably less than 0.1 wt .-%, and in particular no organic solvent from the group of organic amines and alkanolamines in the cleaning agent A is included.
  • compositions according to the invention described above may contain, in addition to the ingredients described above, other substances which are active in washing and cleaning, preferably washing and cleaning substances from the group of surfactants, polymers, bleach activators, glass chlorides and the like.
  • anion inhibitors preferably anion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers, dyes and preservatives.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • alkoxylated preferably ethoxylated or ethoxylated and propoxylated alcohols or fatty alcohols as well as nonionic surfactants of the amine oxide and fatty acid alkanolamide type.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene
  • ((PO / EO / PO) surfactants Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends comprising 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 Mole of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R2 R3 preferred, in which R stands for a straight-chain or branched, saturated or mono- or polyunsaturated C6 -24 alkyl or alkenyl group; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide.
  • the radical R in the above formula may vary depending on the origin of the alcohol.
  • the group R has an even number of carbon atoms and is usually unbranched, the linear groups being selected from alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • nonionic surfactants are particularly preferred which have a C 9 .i 5 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R is -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 in which
  • R and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 -4-alkyl or alkenyl radical;
  • A, A, A "and A '" independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 - CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and
  • w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.
  • R 0 [CH 2 CH 2 O] x CH 2 CH (OH) R 2 in addition to a radical R, which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms , furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x stands for values between 1 and 90, preferably for values between 40 and 80 and in particular for values between 40 and 60.
  • 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 18 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.
  • R 0 [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH)
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is in between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R 3 in the above formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 be different.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 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.
  • 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 methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation and degrees of alkoxylation averages and resulting broken 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 ,
  • washing or cleaning agent A further contains 0.2 to 10 wt .-%, preferably 0.4 to 7 wt .-% and in particular 0.6 to 4 wt .-% nonionic surfactants, according to the invention prefers.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • amphoteric polymers also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids.
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
  • R and R 4 independently represent H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group
  • x and y independently represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof ,
  • Preferred radicals R and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • cationic or amphoteric polymers contain a monomer unit of the general formula
  • R1 HC CR2-C (0) -NH- (CH2) -N + R3R4R5
  • R, R 2 , R 3 , R 4 and R 5 independently of one another, denote a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , - CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , - CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) nl-1 and x is an integer between 1 and 6.
  • H 2 C C (CH 3 ) -C (O) -NH- (CH 2 ) X -N + (CH 3 ) 3
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacryla mid / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and also the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic mono
  • Preferred zwitterionic polymers originate from the group of acrylamidoalkyltri alkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers are selected from the group of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl ( meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / Alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • the polymers are present in prefabricated form.
  • the preparation of the polymers is suitable inter alia the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
  • the co-granulation of the polymers with inert carrier materials preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.
  • Preferred combination products contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of from 0.01 to 8% by weight, based in each case on the total weight of the combination product.
  • the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0 and 01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the combination product is.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • 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, methalyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid group-containing copolymers is preferred according to the invention.
  • 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 washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol 1 , preferably from 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol "1 .
  • Combination products characterized in that the cleaning agent A and / or the cleaning agent B further based on the total weight of the cleaning agent A or B 0.01 to 15 wt .-%, preferably 0.02 to 12 wt .-% and in particular 0, 1 to 8 wt .-% of one or more washing or cleaning active polymers, are preferred according to the invention.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • a combination product comprising a packaging means and two separate liquid washing or cleaning agents A and B of the composition in said packaging means:
  • liquid cleaning agent A has a pH (20 ° C) between 6 and 9
  • liquid cleaning agent B has a pH (20 ° C) between 9 and 14 and wherein at least one of the cleaning agent A or B, preferably the cleaning agent B, contains a polymer as described above.
  • nonionic surfactant 0.01 to 8 wt .-% cationic and / or amphoteric polymers
  • such combination products have proven advantageous in which at least one of the washing or cleaning agents A or B has a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas.
  • Combination products characterized in that the viscosity (Brookfield viscometer LVT-II at 20 U / min and 20 ° C, spindle 3) of at least one of the detergent or cleaning agent A or B between 200 and 10,000 mPas, preferably between 500 and 7000 mPas, and in particular is between 1000 and 4000 mPas, are preferred according to the invention.
  • the viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) of particularly preferred detergents or cleaners is above 500 mPas, preferably above 1000 mPas and in particular above 2000 mPas.
  • thickening agents of known type can be added to the compositions.
  • the combination products according to the invention further comprise, in addition to the two liquid detergents A and B, a packaging means.
  • a packaging means the two cleaning agents A and B are separated from each other, that is, they do not form a common phase boundary, but are rather in separate areas of the Packaging means.
  • a water-insoluble two- or multi-chamber container is suitable.
  • a two- or multi-chamber container typically has a total volume between 100 and 5000 ml, preferably between 200 and 2000 ml.
  • the volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml.
  • Preferred two- or multi-chamber containers have a bottle shape.
  • the two- or multi-chamber container preferably has at least one spout, which may be configured, for example, in the form of a common spout for all means contained in the bottle.
  • the packaging means is a water-soluble two- or multi-chamber container, for example a water-soluble bag with two or more separate receiving chambers.
  • thermoforming bodies can have two, three or more receiving chambers. These receiving chambers can be arranged in the deep-drawn part next to each other and / or one above the other and / or one inside the other.
  • Water-soluble polymers such as, for example, cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch are particularly suitable as packaging materials for the water-soluble containers.
  • the metering of the two liquid washing or cleaning agents A and B can take place, for example, in the metering chamber in the door or an additional metering container in the interior of the dishwasher or directly on the soiled dishes.
  • the two detergents or cleaning agents can also be metered onto one of the inner walls of the dishwasher, for example the inside of the door.
  • the inventive method for machine cleaning dishes in a dishwasher is characterized in that in the course of a cleaning program, which includes a prewash and a cleaning cycle, in this cleaning cycle on two consecutive times t1 and t2 two liquid cleaning agents A and B of the composition:
  • A - 10 to 75% by weight of builder (s);
  • the liquid detergent A has a pH (20 ° C) between 6 and 9 and is metered at time t1
  • the liquid detergent B a pH (20 ° C) between 9 and 14 and is metered in at time t2 and wherein at least one of the cleaning agents A or B contains a polymer comprising the following monomers:
  • Ri and R4 independently represent hydrogen or CI_ 6 alkyl
  • R 2 and R 3 are each independently CI_ 6 alkyl, hydroxy-alkyl or amino CI_ 6
  • x and y independently represent a value of 1 to 3; X "stands for a counterion;
  • the implementation of this preferred method according to the invention takes place in the interior of a commercial dishwasher.
  • the cleaning program can be selected and determined in a dishwasher usually before the dishwashing process by the consumer.
  • the dishwashing machine cleaning program used in this method according to the invention preferably comprises at least one prewash cycle and one cleaning cycle. Cleaning programs which include further cleaning or rinsing cycles, for example a rinse cycle, are preferred according to the invention.
  • the inventive method is therefore not limited to such cleaning programs that consist exclusively of a pre-rinse and a cleaning cycle.
  • the process according to the invention is particularly preferably part of a cleaning program, comprising a prewash cycle, a cleaning cycle and a rinse cycle.
  • the cleaning programs of automatic dishwashers may vary in terms of their Duration, their water consumption and the temperature of the cleaning fleet.
  • the inventive method is preferably used in conjunction with such cleaning programs in which the wash liquor is heated in the course of the cleaning cycle.
  • the cleaning cycle in the course of which the cleaning agents A and B are metered into the interior of the dishwasher, characterized in that in its course, the temperature of the cleaning liquor to values above 30 ° C, preferably above 40 ° C and especially above 50 ° C increases.
  • the temperature of the wash liquor at time t1 is in a preferred embodiment between 12 and 45 ° C, preferably between 15 and 40 ° C and in particular between 20 and 35 ° C, while the temperature of the wash liquor at time t2 preferably between 30 and 65 ° C. , preferably between 35 and 60 ° C and in particular between 40 and 55 ° C.
  • the wash liquor may have the same or different temperatures.
  • the temperature of the wash liquor at time t1 is different from the temperature of the wash liquor at time t2, wherein the temperature at time t1 may be above or below the temperature at time t2.
  • Particularly advantageous cleaning results could be achieved in methods according to the invention in which the temperature of the wash liquor was below the temperature of the wash liquor at time t 2 at time t 1. Corresponding methods are therefore preferred.
  • the temperature of the wash liquor at time t2 is preferably at least 5 ° C, preferably at least 10 ° C and especially between 10 and 40 ° C, but especially between 10 and 20 ° C above the temperature of the wash liquor at time t1.
  • the metering of the two liquid cleaning agents A and B takes place in the course of the cleaning cycle at two successive times t1 and t2, the cleaning agent A being metered in at time t1 and the cleaning agent B at time t2 and the time t1 being earlier than time t2.
  • the time t1 is preferably within the first ten minutes after the beginning of the cleaning cycle, preferably within the first eight minutes after the beginning of the cleaning cycle and in particular within the first five minutes after the beginning of the cleaning cycle.
  • the time difference between the times t1 and t2 is preferably between 2 and 30 minutes, preferably between 4 and 25 minutes and especially between 6 and 20 minutes.
  • Terpolymer A terpolymer of acrylamide, DADMAC and acrylic acid in the mixing ratio 75.6: 20: 4.4
  • Terpolymer B terpolymer of ⁇ , ⁇ -dimethylacrylamide, DADMAC and acrylic acid in a mixing ratio of 75.6: 20: 4.4
  • the rinse performance was tested on glass (Willybecher, Whiskeybecher); Porcelain (dessert dish, black, Friesland plate); Plastic (melamine plate, blue plastic plates) and stainless steel (knife, butter dish, serving tray). A total of 3 determinations were carried out and then the mean value was formed. The worst grade is 0, the best grade is 10. On the one hand the formation of fouling was determined, on the other hand staining.

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  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne des polymères contenant a) au moins un monomère représenté par la formule (I) dans laquelle R1 et R4 représentent indépendamment les uns des autres hydrogène ou C1-6-alkyle; R2 et R3 représentent indépendamment les uns des autres C1-6-alkyle, hydroxy-C1-6-alkyle ou amino-C1-6-alkyle; x et y représentent indépendamment les uns des autres une valeur de 1 à 3; X- est un contre-ion; b) au moins un monomère hydrophile portant au moins un groupe acide; c) au moins un monomère hydrophile non-ionique; les polymères selon l'invention s'étant avérés être des produits de rinçage adaptés, notamment pour réduire l'apparition de taches sur la vaisselle.
PCT/EP2012/060079 2011-07-15 2012-05-30 Produit de rinçage et de nettoyage Ceased WO2013010701A1 (fr)

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DE201110079260 DE102011079260A1 (de) 2011-07-15 2011-07-15 Klarspül- und Reinigungsmittel
DE102011079260.0 2011-07-15

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030203825A1 (en) * 1999-07-15 2003-10-30 Eric Aubay Method of reducing and preventing soil redeposition in an automatic dishwashing machine
WO2003099980A1 (fr) * 2002-05-27 2003-12-04 Rhodia Chimie Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine
WO2004056888A2 (fr) * 2002-12-23 2004-07-08 Ciba Specialty Chemicals Holding Inc. Polymeres modifies de maniere hydrophobe et utiles comme additifs pour blanchisserie
WO2007025665A2 (fr) * 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage
WO2010000629A2 (fr) 2008-06-30 2010-01-07 Basf Se Polymère amphotère pour le traitement de surfaces dures
WO2010107554A2 (fr) 2009-03-20 2010-09-23 Ciba Corporation Polymères ampholytes à séchage rapide pour compositions de nettoyage

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741767A (en) 1995-11-16 1998-04-21 Lever Brothers Company, Division Of Conopco, Inc. Peracid based dishwashing detergent composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030203825A1 (en) * 1999-07-15 2003-10-30 Eric Aubay Method of reducing and preventing soil redeposition in an automatic dishwashing machine
WO2003099980A1 (fr) * 2002-05-27 2003-12-04 Rhodia Chimie Utilisation, d'un copolymere amphotere dans une composition lavante de la vaisselle en machine
WO2004056888A2 (fr) * 2002-12-23 2004-07-08 Ciba Specialty Chemicals Holding Inc. Polymeres modifies de maniere hydrophobe et utiles comme additifs pour blanchisserie
WO2007025665A2 (fr) * 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage
WO2010000629A2 (fr) 2008-06-30 2010-01-07 Basf Se Polymère amphotère pour le traitement de surfaces dures
WO2010107554A2 (fr) 2009-03-20 2010-09-23 Ciba Corporation Polymères ampholytes à séchage rapide pour compositions de nettoyage

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DE102011079260A1 (de) 2013-01-17

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