COPOLYMERS AND THEIR USE IN CLEANING COMPOSITIONS

Description

[0001] The present invention relates to copolymers obtainable from the radical copolymerization of at least the following components: cationic monomers selected from the group consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, polyethylene glycol macromonomers and neutral acrylamide monomers, cleaning compositions containing such copolymers, and the use of the copolymers or the cleaning compositions, in particular for producing gloss on hard surfaces, for hydrophilizing hard surfaces and for achieving a repair effect on hard surfaces.

[0002] Commercial cleaning formulations enable the efficient cleaning of hard surfaces in industrial, household, or public areas. They generally consist of an aqueous solution of surfactants, particularly non-ionic and anionic surfactants, alcohol(s) to facilitate drying, bases to adjust the pH, and, optionally, quaternary amines as disinfectants.

[0003] WO 2013 / 170001 and WO 2013 / 170002 describe cleaning formulations containing alkoxylated polyethyleneimine polymers which improve the gloss on hard surfaces.

[0004] WO 2009 / 156067 describes cleaning formulations containing graft copolymers of saccharides which can be used to improve the gloss retention of hard surfaces and / or have hydrophilizing properties.

[0005] WO 2003 / 031546 describes aqueous antimicrobial cleaning compositions for the treatment of hard surfaces, with the result of maintaining or improving the gloss of the hard surfaces.

[0006] WO 98 / 49263 describes aqueous, acidic surface cleaners containing a polymer additive that achieve improved surface gloss.

[0007] US 2014 / 0005095 describes cleaning compositions for hard surfaces that achieve a shiny, streak-free surface.

[0008] EP 1196523 B1 describes cleaning compositions intended for the treatment of hard surfaces in industry, the home or the general public and which are particularly intended to impart hydrophilic and protective properties to these surfaces.

[0009] Although existing systems already achieve good results, there remains considerable room for improvement. A significant shortcoming of these cleaning formulations is that residues of the cleaning formulation often remain on the hard surface after drying in the form of streaks, smears, or spots, thereby minimizing the surface's shine.

[0010] The object of the present invention was to develop polymer additives which are water-soluble or water-dispersible and can be added to cleaning compositions, in particular with the result that advantageous gloss effects can be observed on the hard surfaces after their application.

[0011] Surprisingly, it has been found that this object can be achieved by copolymers obtainable from the radical copolymerization of at least components a), b) and c) a) 25.0 to 80.0 mol% of one or more cationic monomers selected from the group consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, and b) 1.0 to 50.0 mol% and preferably 1.0 to 10.0 mol% of one or more polyethylene glycol macromonomers selected from monomers of formula (IV) as defined in the claims, and c) 15.0 to 74.0 mol% of one or more neutral acrylamide monomers.

[0012] The present invention therefore relates to copolymers obtainable from the radical copolymerization of at least components a), b) and c) a) 25.0 to 80.0 mol% of one or more cationic monomers selected from the group consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, and b) 1.0 to 50.0 mol% and preferably 1.0 to 10.0 mol% of one or more polyethylene glycol macromonomers selected from monomers of formula (IV) as defined in the claims, and c) 15.0 to 74.0 mol% of one or more neutral acrylamide monomers.

[0013] In the context of the present invention, the term "(meth)acrylic" encompasses both the corresponding acrylic compound and the corresponding methacrylic compound.

[0014] The term "hard surface" in the context of the invention means a surface made of dimensionally stable materials, e.g., plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum, and metal such as stainless steel, typically surfaces in kitchen and sanitary areas, for example, in kitchens, bathrooms, and toilets, in the home, but also in the industrial sector, for example, in butcher shops, slaughterhouses, dairies, storage tanks for food or industrial products, as well as in public areas, such as building facades, in swimming pools, or in train stations.

[0015] WO 2012 / 076365 A1 discloses cationic copolymers containing cationic structural units and macromonomeric structural units and their use as additives for building material systems, in particular based on calcium sulfate.

[0016] WO 2008 / 049549 A2 describes hydrophobically modified cationic copolymers comprising at least three different structural units, one of which contains a terminal phenyl group or a specifically substituted phenyl group. These copolymers, particularly in combination with anionic surfactants, can significantly improve water retention in aqueous construction material systems based on hydraulic binders, such as cement, even in the presence of high salt loads.

[0017] WO 2008 / 141844 A1 describes dispersions comprising inorganic particles, water, and at least one water-soluble polymer. The at least one water-soluble polymer has repeating units derived from monomers with at least one quaternary ammonium group, repeating units derived from monomers with at least one carboxyl group, and repeating units derived from ester monomers containing polyalkoxyalkylene groups and having a number-average molecular weight in the range of 3000 g / mol to 10,000 g / mol. The dispersions can be used in particular for the production of concrete and can be processed over a very long period of time.

[0018] WO 2008 / 046652 A1 describes graft polymers obtainable by copolymerization of at least one specific macromonomer and at least one further monomer which has a polymerizable ethylenically unsaturated double bond and their use as dispersants, for example in pigment concentrates.

[0019] US 2011 / 0144264 A1 describes the use of substances such as polyethylene glycol or poly(ethylene-co-propylene) glycol (meth)acrylic acid esters, which can contribute to stabilization during the process of latex production by emulsion polymerization of at least one polymerizable monomer.

[0020] JP 2008-056711 A discloses copolymers with a number-average molecular weight of 5,000 to 1,000,000, which contain structural units formed by polymerizing certain cationic monomers, polyoxyalkylene-modified monomers, and crosslinkable monomers, and which may additionally contain further structural units formed by polymerizing other monomers copolymerizable with the aforementioned monomers. The copolymers can be used, for example, as antistatic agents for thermoplastic polymers. US 2014 / 213748 describes further cationic polymers that can be used in cleaning agents.

[0021] An advantage of the invention is that the copolymers according to the invention can be added to cleaning compositions and can provide a beneficial cleaning effect when applied to a hard surface.

[0022] A further advantage of the invention is that the copolymers according to the invention can be added to cleaning compositions, thereby producing a shine effect on the hard surface to which they have been applied.

[0023] A further advantage of the invention is that the copolymers according to the invention can be added to cleaning compositions and impart hydrophilic properties to the hard surface to which they have been applied. The contact angle between the treated surface and a drop of water or a drop of an aqueous cleaning composition can be reduced. The presence of traces or stains left on hard surfaces by water or aqueous cleaning compositions that have come into contact with them is related to the phenomenon of contraction of the water droplets or drops of aqueous cleaning compositions upon contact with the hard surface, leaving traces on the surface upon subsequent drying.In addition, by reducing the contact angle between the treated surface and a water droplet, the drying speed of a surface can be improved.

[0024] Furthermore, repair effects can be advantageously achieved on the hard surface to which the copolymers according to the invention or the cleaning compositions containing them have been applied.

[0025] The copolymers according to the invention or the cleaning compositions containing them can be applied in such a way that they remain on the hard surface after application ("leave-on" application) or are removed from it and preferably rinsed off with water ("rinse-off" application).

[0026] The copolymers according to the invention or the cleaning compositions containing them can be used advantageously, for example, on hard surfaces in bathrooms or kitchens, on floors or on toilets.

[0027] Preferably, the one or more cationic (meth)acrylamide monomers of component a) are selected from monomers of the formula (I) wherein R1 stands for hydrogen or methyl.

[0028] Particularly preferably, the one or more cationic monomers of component a) are selected from the group consisting of diallyldimethylammonium chloride and (3-methacrylamidopropyl)trimethylammonium chloride.

[0029] The one or more polyethylene glycol macromonomers of component b) are selected from monomers of formula (IV): H 2 C=CR x< -ZO-(C 3 H 6 O) l -(CH 2 CH 2 O) p -H (IV) wherein R x< H or methyl, ZO(CH 2 ) 4 , l is, on a molar average, a number from 0 to 7 and preferably from 0 to 6, and p is, on a molar average, a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150.

[0030] Preferably, in formula (IV), R x< H, l = 0 and p, on a molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150.

[0031] Particularly preferably, the one or more polyethylene glycol macromonomers of component b) are selected from the group consisting of monomers of the formula (IV-A) wherein pAim molar average, a number from 1 to 150, preferably from 1 to 120, particularly preferably from 11 to 120 and especially preferably from 22 to 120.

[0032] Preferably, the one or more neutral acrylamide monomers of component c) are selected from the monomers of the formula (III) wherein R2 and R3 may each be the same or different and independently of one another each represent hydrogen and / or an aliphatic hydrocarbon radical having 1 to 20 and preferably 1 to 4 C atoms.

[0033] Particularly preferably, the one or more neutral acrylamide monomers of component c) are selected from the group consisting of acrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide and N-isopropylacrylamide and especially preferably, the one or more neutral acrylamide monomers of component c) are selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide.

[0034] The copolymers according to the invention are preferably obtainable from the radical copolymerization of at least components a), b) and c), wherein in the copolymerization

[0035] Component a) is used in an amount of 25.0 to 80.0 mol%, component b) is used in an amount of 1.0 to 4.4 mol%, and

[0036] Component c) is used in an amount of 15.6 to 74.0 mol%.

[0037] In a preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of only components a), b) and c), ie in this preferred embodiment of the invention no further monomer which is different from the monomers of components a), b) and c) is used to prepare the copolymers according to the invention.

[0038] In a further preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c).

[0039] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), in a particularly preferred embodiment of the invention at least one of the monomers of component d) is selected from the group consisting of N-vinyl-substituted lactams having 5 to 7 ring atoms and the monomers of the following general formula (V): wherein R 11< is the same or different and is represented by H and / or methyl; X is the same or different and is represented by NH-(C n H 2n ) with n = 1, 2, 3 or 4; and R 13< is the same or different and is represented by OH, SO 3 H, PO 3 H 2 , O-PO 3 H 2 and / or para-substituted C 6 H 4 -SO 3 H-

[0040] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), the monomers of component d) in a particularly preferred embodiment of the invention are selected from the group consisting of N-vinyl-substituted lactams having 5 to 7 ring atoms and the monomers of the general formula (V).

[0041] Among the N-vinyl-substituted lactams with 5 to 7 ring atoms, N-vinylpyrrolidone is preferred.

[0042] The groups SO 3 H, PO 3 H 2 , O-PO 3 H 2 and para-substituted C 6 H 4 -SO 3 H in the monomers of formula (V) can also be present in salt form, preferably as NH 4 +< -, alkali or alkaline earth salt and particularly preferably as NH 4 +< - or as Na +< -salt.

[0043] Among the monomers of formula (V) in which R 13< N(CH 3 ) 2, those monomers are preferred which are selected from the group consisting of [3-(methacryloylamino)-propyl]-dimethylamine (R 11< = methyl; X = NH-(C n H 2n ) with n = 3 and R 13< = N(CH 3 ) 2 ) and [3-(acryloylamino)-propyl]-dimethylamine (R 11< = H; X = NH-(C n H 2n ) with n = 3 and R 13< = N(CH 3 ) 2 ).

[0044] Among the monomers of formula (V), preferred are those selected from the group consisting of [3-(acryloylamino)propyl]dimethylamine, [3-(methacryloylamino)propyl]dimethylamine, 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid, and particularly preferred are those selected from the group consisting of 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid.

[0045] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), in a further particularly preferred embodiment of the invention at least one of the monomers of component d) is selected from the group consisting of the monomers of the following general formula (VIII): wherein W is the same or different and is represented by -CO-O-(CH 2 ) x, x is an integer from 1 to 6, preferably 2 or 3, R 1< is the same or different and is hydrogen and / or methyl, and R 3< and R 4< are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4, C atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8, C atoms, an aryl radical having 6 to 14 C atoms and / or polyethylene glycol (PEG).

[0046] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), the monomers of component d) are, in a further particularly preferred embodiment of the invention, selected from the monomers of the formula (VIII).

[0047] Among the monomers of formula (VIII), those selected from the group consisting of [2-(methacryloyloxy)ethyl]dimethylamine, [2-(acryloyloxy)ethyl]dimethylamine, [2-(methacryloyloxy)ethyl]diethylamine and [2-(acryloyloxy)ethyl]diethylamine are preferred.

[0048] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), in a further particularly preferred embodiment of the invention at least one of the monomers of component d) is selected from the group consisting of the monomers of the following general formulas (IX) and / or (X): wherein R 11< is the same or different and is represented by H and / or methyl; Z is the same or different and is represented by O and / or NH; wherein R 11< is the same or different and is represented by H and / or methyl; Q is the same or different and is represented by O and / or NH; and R 15< is the same or different and is represented by H, (C n H 2n )-SO 3 H with n = 0, 1, 2, 3 or 4; (C n H 2n )-OH with n = 0, 1, 2, 3 or 4; (C n H 2n )-PO 3 H 2 with n = 0, 1, 2, 3 or 4; (C n H 2n )-OPO 3 H 2 with n = 0, 1, 2, 3 or 4; (C 6 H 4 )-SO 3 H; (C 6 H 4 )-PO 3 H 2 , (C 6 H 4 )-OPO 3 H 2 and / or (CmH 2m ) e -O-(A'O) u -R 16< with m = 0, 1, 2, 3 or 4, e = 0, 1, 2, 3 or 4, A' = C x' H 2x' with x' = 2, 3, 4 or 5, u = an integer from 1 to 350 and R 16< are identical or different and are represented by an unbranched or branched C 1 -C 4 alkyl group.

[0049] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), the monomers of component d) are, in a further particularly preferred embodiment of the invention, selected from the monomers of the formulas (IX) and / or (X).

[0050] The monomers of formula (X) may also be present in salt form, preferably as NH 4 +< -, alkali or alkaline earth salt and particularly preferably as NH 4 +< - or as Na +< -salt.

[0051] Among the monomers of formulas (IX) and (X), preferred are those selected from the group consisting of maleic anhydride, maleic acid and the salts of maleic acid.

[0052] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), in a further particularly preferred embodiment of the invention at least one of the monomers of component d) is selected from the group consisting of the monomers of the following general formula (VII): wherein S is the same or different and is represented by -COOM k, R 1< is the same or different and is represented by H and / or a straight or branched C 1 -C 4 alkyl group and is preferably represented by H or methyl; and M is a cation selected from the group consisting of hydrogen ion, alkali ion, alkaline earth ion and alkaline earth ion, with k = valence.

[0053] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), the monomers of component d) are, in a further particularly preferred embodiment of the invention, selected from the monomers of the formula (VII).

[0054] Among the monomers of formula (VII), those selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid, sodium methacrylate and potassium methacrylate are preferred.

[0055] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), in a further particularly preferred embodiment of the invention at least one of the monomers of component d) is selected from the group consisting of the monomers of the following general formulas (Va), (Vb) and / or (Vc): wherein R 11< is the same or different and is represented by H and / or methyl; W is the same or different and is represented by O; R 12< is the same or different and is represented by a branched or unbranched C 1 -C 5 monohydroxyalkyl group wherein R 11< is the same or different and is represented by H and / or methyl; X is the same or different and is represented by O-(C n H 2n ) with n = 1, 2, 3 or 4; R 13< is the same or different and is represented by OH, SO 3 H, PO 3 H 2 , O-PO 3 H 2 and / or para-substituted C 6 H 4 -SO 3 H wherein R 14< , R 15< and R 16< are each the same or different and are each independently represented by H and / or a straight or branched C 1 -C 4 alkyl group; n is the same or different and is represented by 0, 1, 2, 3 and / or 4; R 17< is the same or different and is represented by (C 6 H 5 ), OH, OR y< , where R y< is an alkyl group having 1 to 8 and preferably 4 carbon atoms, and / or -OOCCH 3 .

[0056] If the copolymers according to the invention are obtainable from the radical copolymerization of the monomers of components a), b), c) and additionally one or more monomers of a component d) which are different from the monomers of components a), b) and c), the monomers of component d) are, in a further particularly preferred embodiment of the invention, selected from the monomers of the formulas (Va), (Vb) and / or (Vc).

[0057] The groups SO 3 H, PO 3 H 2 , O-PO 3 H 2 and para-substituted C 6 H 4 -SO 3 H in the monomers of the formula (Vb) can also be present in salt form, preferably as NH 4 +< -, alkali or alkaline earth salt and particularly preferably as NH 4 +< - or as Na +< -salt.

[0058] Among the monomers of formula (Vc), preferred are those selected from the group consisting of vinyl butyl ether and vinyl acetate.

[0059] In a particularly preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of components a), b), c) and additionally one or more monomers of component d), which is different from components a), b) and c), wherein in the copolymerization Component a) is used in an amount of 25.0 to 80.0 mol%, component b) is used in an amount of 1.0 to 50.0 mol% and preferably in an amount of 1.0 to 10.0 mol%, component c) is used in an amount of 15.0 to 73.9 mol% and preferably in an amount of 15.6 to 73.9 mol%, and component d) is used in an amount of 0.1 to 40.0 mol% and preferably in an amount of 0.1 to 30.0 mol%.

[0060] In a preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of only components a), b), c) and d), ie in this preferred embodiment of the invention no further monomer which is different from the monomers of components a), b), c) and d) is used to prepare the copolymers according to the invention.

[0061] Preferably, the structural units of the copolymers according to the invention resulting from the polymerization of the monomers a), b) and c) and optionally d) and optionally further monomers are present in a random, block-shaped, alternating or gradient-like distribution in the copolymer.

[0062] The weight-average molecular weight M w of the copolymers according to the invention is preferably from 10,000 to 250,000 g / mol, particularly preferably from 15,000 to 200,000 g / mol and especially preferably from 20,000 to 150,000 g / mol.

[0063] The copolymers of the invention can be prepared by methods familiar to the person skilled in the art. The copolymers of the invention can particularly preferably be prepared by free-radical solvent polymerization. Common solvents can be, for example, polar solvents such as alcohols or water, as well as alcohol-water mixtures. The polymerization is initiated by free-radical sources such as, for example, inorganic persulfates, organic azo compounds, peroxides, inorganic redox systems, or UV light. Chain transfer regulators that form less reactive radicals can also be used to control the molecular weight of the copolymers. Such chain transfer regulators include, for example, phenols, thiols, for example, sodium 2-mercaptoethanesulfonate, or sodium hypophosphite.In an exemplary procedure, the monomers for preparing the copolymers according to the invention and, if appropriate, a chain transfer regulator are dissolved in the solvent, oxygen is expelled, the temperature is then raised, and the free-radical initiator is added. The copolymerization is then carried out at the desired temperature for the desired time. The reaction mixture is then cooled, if appropriate, and the resulting copolymer is either further processed in solution or worked up. For example, the solution containing the copolymer can be concentrated by partial evaporation of the solvent, optionally under reduced pressure, or the solvent can be completely removed by evaporation, or the copolymer can be isolated by other means, for example by freeze-drying or precipitation.

[0064] The copolymers according to the invention are preferably obtainable from the radical copolymerization of at least components a), b) and c) in a solvent selected from the group consisting of water, one or more alcohols and mixtures thereof, wherein the one or more alcohols are preferably selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, tert-butanol, ethylene glycol, propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether and mixtures thereof. More preferably, the solvent is selected from the group consisting of water, ethanol, isopropanol, propylene glycol, tert-butanol, propylene glycol monobutyl ether and mixtures thereof, and most preferably, the solvent is selected from the group consisting of water, isopropanol, tert-butanol, propylene glycol and mixtures thereof.

[0065] The copolymers according to the invention are preferably obtainable from the radical copolymerization of at least components a), b) and c) at temperatures in the range from 20 to 200 °C, particularly preferably in the range from 20 to 100 °C and especially preferably in the range from 40 to 80 °C.

[0066] The copolymers according to the invention are preferably obtainable from the radical copolymerization of at least components a), b) and c), wherein the radical copolymerization is initiated by heating, irradiation with light or by addition of a radical initiator and particularly preferably is initiated by addition of a radical initiator, wherein the radical initiator is particularly preferably selected from the group consisting of peroxides, preferably dialkyl peroxides, hydroperoxides, peroxyketals, peroxyesters, peroxydicarbonates and / or diacyl peroxides;Azo compounds, preferably 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-Azobis(4-cyanovaleric acid), 2,2'-Azobis(isobutyronitrile), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile) and / or 2,2'-azobis(N-butyl-2-methylpropionamide); and persulfate initiators, preferably ammonium persulfate, sodium persulfate and / or potassium persulfate.;

[0067] The copolymers according to the invention are extremely preferably obtainable from the radical copolymerization of at least components a), b) and c), wherein the radical copolymerization is initiated by adding a radical initiator selected from the group consisting of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanovaleric acid), ammonium persulfate, sodium persulfate and potassium persulfate and preferably by adding a radical initiator selected from the group consisting of ammonium persulfate, sodium persulfate and 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride is initiated.

[0068] In a preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of at least components a), b) and c), wherein the radical copolymerization is carried out in the presence of a chain transfer agent selected from the group consisting of mercaptans, preferably octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol and 2-mercaptoethanesulfonate sodium; halogenated compounds; thiosalicylic acid; mercaptoacetic acid; buten-1-ol; dimeric α-methylstyrene and hypophosphite derivatives, preferably sodium hypophosphite.In a particularly preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of at least components a), b), and c), wherein the radical copolymerization is carried out in the presence of a chain transfer agent selected from the group consisting of mercaptans, preferably sodium 2-mercaptoethanesulfonate, and sodium hypophosphite. In a particularly preferred embodiment of the invention, the copolymers according to the invention are obtainable from the radical copolymerization of at least components a), b), and c), wherein the radical copolymerization is carried out in the presence of sodium hypophosphite as a chain transfer agent.

[0069] As already mentioned, the copolymers according to the invention can be advantageously used in cleaning compositions. In the cleaning compositions, the copolymers according to the invention represent component Z1). These cleaning compositions are described in more detail below.

[0070] The cleaning compositions preferably contain one or more copolymers of component Z1) in an amount of 0.005 to 10 wt.%, particularly preferably in an amount of 0.01 to 5 wt.% and especially preferably in an amount of 0.1 to 0.5 wt.%, in each case based on the total weight of the cleaning composition. Component Z2)

[0071] The cleaning agent compositions contain one or more surfactants as component Z2).

[0072] Preferably, the one or more surfactants of component Z2) of the cleaning compositions are selected from the group consisting of anionic, non-ionic, amphoteric and cationic surfactants.

[0073] The cleaning compositions may optionally contain anionic surfactants, e.g., alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates, and / or acylglutamates. The alkyl chains of said surfactants may be of synthetic or natural origin and consist of 8 to 30, preferably 8 to 18, and particularly preferably 12 to 14, carbon atoms in a linear or branched arrangement.

[0074] Anionic surfactants used according to the invention are preferably aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ethersulfonates, n-alkyl ether sulfonates, estersulfonates, and ligninsulfonates. Also usable within the scope of the present invention are alkylbenzenesulfonates, fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ethercarboxylic acids, and alkyl (ether) phosphates, as well as [alpha]-sulfofatty acid salts, acylglutamates, monoglyceride disulfates, and alkyl ethers of glycerol disulfate.

[0075] Preferred among these are fatty alcohol sulfates and / or fatty alcohol ether sulfates, especially fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. Those skilled in the art generally understand alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably with longer-chain alcohols in the context of the present invention. Depending on the reaction conditions, n moles of ethylene oxide and one mole of alcohol generally form a complex mixture of addition products with varying degrees of ethoxylation. Another embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably a mixture of ethylene oxide and propylene oxide.Preferred fatty alcohol ether sulfates are the sulfates of low-ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.

[0076] Particularly preferred are alkylbenzenesulfonate, alkanesulfonate, alkyl ether sulfate or alkyl sulfate.

[0077] Anionic surfactants are typically used as salts, but also as acids. The salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts, and mono-, di-, or trialkanolammonium salts, for example mono-, di-, or triethanolammonium salts, in particular lithium, sodium, potassium, or ammonium salts, particularly preferably sodium or potassium salts, especially preferably sodium salts.

[0078] Other surfactants can be non-ionic, amphoteric and / or cationic surfactants, for example betaines, amidobetaines, amine oxides, amidoamine oxides, fatty alcohol polyglycol ethers, alkyl polyglycosides or quaternary ammonium compounds.

[0079] Other nonionic surfactants can be, for example, alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers (fatty alcohol alkoxylates), alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers, and fatty acid polyglycol esters. Ethylene oxide-propylene oxide block copolymers and fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants that can be used according to the invention are polyol surfactants, particularly glycosurfactants, such as alkyl polyglycosides, especially alkyl polyglucosides.

[0080] Suitable fatty alcohol polyglycol ethers are unbranched or branched, saturated or unsaturated C 8 -C 22 alcohols alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated C 13 -C 18 fatty alcohols having a degree of ethoxylation of less than 30, particularly preferably 1 to 20, especially preferably 1 to 12 and extraordinarily preferably 1 to 8, for example C 12 -C 14 fatty alcohol ethoxylates with 8 EO.

[0081] Alkyl polyglycosides are surfactants that can be obtained by the reaction of sugars and alcohols using the relevant processes of preparative organic chemistry, resulting in a mixture of monoalkylated, oligomeric, or polymeric sugars, depending on the type of preparation. Preferred alkyl polyglycosides are alkyl polyglucosides, where the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 - to C 18 -alkyl chains, and the degree of oligomerization (DP) of the sugar is from 1 to 10, preferably from 1 to 6, particularly preferably from 1.1 to 3, and especially preferably from 1.1 to 1.7, for example C 8 -C 10 -alkyl-1,5-glucoside (DP of 1.5).

[0082] The amphoteric surfactants (zwitterionic surfactants) that can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids and biosurfactants.

[0083] Suitable betaines are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI sultaines) and the amidosulfobetaines as well as the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotamidopropylbetaine, Avocadamidopropylbetaine, Babassuamidopropylbetaine, Behenamidopropylbetaine, Behenylbetaine, Betaine, Canolamidopropylbetaine, Capryl / Capramidopropylbetaine, Carnitine, Cetylbetaine, Cocamidoethylbetaine, Cocamidopropylbetaine, Cocamidopropylhydroxysultaine, Cocobetaine, Cocohydroxysultaine, Coco / Oleamidopropylbetaine, Coco-Sultaine, Decylbetaine, Dihydroxyethyloleylglycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethylstearylglycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropylhydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl betaines, lauramidopropyl betaines, lauryl betaines, lauryl hydroxysultaines,Lauryl sultaine, milkamidopropyl betaine, minkamidopropyl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernel elamidopropyl betaine, polytetrafluoroethylene Acetoxypropyl betaine, ricinoleamidopropyl betaine, sesamidopropyl betaine, soyamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallowamidopropyl hydroxysultaine, tallow betaine, tallowdihydroxyethyl betaine, undecylenamidopropyl betaine and wheat germamidopropyl betaine.

[0084] The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.

[0085] Beispiele geeigneter Aminoxide sind die folgenden gemäß INCI benannten Verbindungen: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C 8 -C 10 Alkoxypropylamine Oxide, Dihydroxyethyl C 9 -C 11 Alkoxypropylamine Oxide, Dihydroxyethyl C 12 -C 15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C 12 -C 15 Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide,Myristyl / Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Undecylenamidopropylamine Oxide und Wheat Germamidopropylamine Oxide.,

[0086] Beispielhafte Alkylamidoalkylamine sind die folgenden gemäß INCI benannten Verbindungen: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate,Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate und Trisodium Lauroampho PG-Acetate Chloride Phosphate.,

[0087] Examples of alkyl-substituted amino acids are the following compounds named according to INCI: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA-Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C 12 -C 15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA-Lauraminopropionate and TEA-Myristaminopropionate.

[0088] Particularly preferably, the one or more surfactants of component Z2) of the cleaning compositions are selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates and quaternary ammonium compounds.

[0089] The proportion of the one or more surfactants of component Z2) in the cleaning composition is preferably from 0.1 to 20% by weight and particularly preferably from 0.1 to 6.0% by weight, in each case based on the total weight of the cleaning composition. Component Z3)

[0090] The cleaning agent compositions contain water as component Z3).

[0091] The proportion of water in the cleaning agent compositions is preferably from 10.00 to 99.89 wt.%, particularly preferably from 40.00 to 98.00 wt.% and especially preferably from 70 to 97.00 wt.%, in each case based on the total weight of the cleaning agent compositions.

[0092] Preferably, the cleaning compositions contain, in addition to the one or more copolymers of component Z1), the one or more surfactants of component Z2) and water of component Z3), one or more further substances selected from components Z4), Z5), Z6) and / or Z7): Z4) one or more inorganic or organic acids as component Z4), Z5) one or more complexing agents as component Z5), Z6) one or more solvents other than water as component Z6), Z7) one or more further additives, preferably selected from the group consisting of viscosity regulators, enzymes, bleaching agents, preservatives, fragrances and dyes, as component Z7), and the pH of the cleaning composition is preferably from 1 to 14 and particularly preferably from 3 to 11. Component Z4)

[0093] The acids can be inorganic acids, e.g. hydrochloric acid, sulfuric acid, nitric acid, amidosulfonic acid and / or phosphoric acid.

[0094] In a preferred embodiment of the invention, the acids present are organic acids, particularly preferably non-complexing acids such as lactic acid, formic acid, acetic acid, glycolic acid, and / or gluconic acid. Other preferred acids are malic acid, citric acid, tartaric acid, adipic acid, and / or succinic acid. In a preferred embodiment, the cleaning compositions contain one acid. In a further preferred embodiment of the invention, the cleaning compositions contain a mixture of two or more acids.

[0095] The amount of acid used, if different from 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.2 to 5% by weight and especially preferably from 1 to 3% by weight, in each case based on the total weight of the cleaning composition.

[0096] In a further preferred embodiment of the invention, a salt of an acid can also be added to buffer the pH, in particular the sodium, potassium, or magnesium salt, but also other alkali or alkaline earth salts or ammonium salts, in particular volatile amines such as monoethanolamine, ammonia, diethanolamines, but also triethanolamine. In a particularly preferred embodiment of the invention, the salt or salts of the acid or acids already present are used. Component Z5)

[0097] Suitable complexing agents are known to the person skilled in the art and are described by way of example in DE-A-10 2009 001 559.

[0098] Chelating agents (INCI: chelating agents), also known as sequestering agents, are ingredients that can complex and inactivate metal ions to prevent their adverse effects on the stability or appearance of the product, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions that cause water hardness, which are incompatible with many ingredients. On the other hand, complexing the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished product. Furthermore, the complexing agents support the cleaning effect.

[0099] Geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Komplexbildner: Aminotrimethylene, Phosphonsäure, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate,Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

[0100] The proportion of component Z5) in the cleaning agent composition, if it is different from 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 3.0% by weight and especially preferably from 0.1 to 1.0% by weight, in each case based on the total weight of the cleaning agent composition. Component Z6)

[0101] Suitable water-soluble solvents are known to the person skilled in the art and are described, for example, in US 2005 / 0239674. Alcohols, glycerol, glycols, and glycol ethers are preferably used, preferably lower alcohols such as ethanol, isopropanol, butanol, isobutanol, or alkylene glycols, e.g., propylene glycol, as well as glycol ethers, e.g., ethylene glycol n-butyl ether or propylene glycol n-butyl ether.

[0102] In a preferred embodiment, mixtures of several solvents are used.

[0103] The proportion of component Z6) in the cleaning agent composition, if it is different from 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 3% by weight and especially preferably from 0.5 to 1.5% by weight, based on the total weight of the cleaning agent composition. Component Z7)

[0104] Suitable additives include other common ingredients of cleaning agents, such as disinfectants, pH adjusters, dyes, fragrances, buffers, viscosity regulators, corrosion inhibitors, organic and inorganic salts, optical brighteners, bleaching agents, antioxidants, opacifiers, hydrotropes, abrasives, preservatives, oxidizing agents, and / or insecticides. These additives are well known to those skilled in the art and are described by way of example in DE-A-10 2009 001 559.

[0105] According to the invention, bleaching agents can be added to the cleaning composition. Suitable bleaching agents include peroxides, peracids, and / or perborates; H 2 O 2 is particularly preferred.

[0106] The cleaning agent compositions may also contain enzymes, preferably proteases, lipases, amylases, hydrolases, and / or cellulases. They can be added to the cleaning agent compositions in any form established according to the state of the art. In the case of liquid or gel-like cleaning agent compositions, this includes, in particular, solutions of the enzymes, advantageously as concentrated as possible, with a low water content, and / or containing stabilizers. Alternatively, the enzymes can be encapsulated, for example, by spray-drying or extrusion of the enzyme solution together with a polymer, preferably a natural one, or in the form of capsules, for example, those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals.Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using conventional methods, for example, by shaking or rolling granulation or in fluid-bed processes. Such granules, for example, through the application of polymeric film-forming agents, are advantageously low in dust and, thanks to the coating, are stable during storage.

[0107] Furthermore, enzyme stabilizers may be present in enzyme-containing cleaning compositions in order to protect an enzyme contained in a cleaning composition from damage such as inactivation, denaturation or degradation due to physical influences, oxidation or proteolytic cleavage.Particularly suitable enzyme stabilizers, depending on the enzyme used, are: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof; aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known from the prior art.

[0108] Preferably, combinations of stabilizers are used, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

[0109] Suitable as disinfectants and / or preservatives according to the invention are, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate, iodine, iodophores and peroxides.Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine) dihydrochloride, N,N'-Bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines. Preferred antimicrobial quaternary surfactants contain an ammonium, sulfonium, phosphonium, iodonium, or arsonium group, as described, for example, by KH Wallhäusser in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th edition).Edition - Stuttgart; New York: Thieme, 1995).

[0110] The terms disinfection, sanitation, antimicrobial effect, and antimicrobial agent have the usual technical meaning in the context of this invention, as described, for example, by KH Wallhäusser in "Praxis der Sterilisation, Desinfektion - Konservierung: Keimidentifizierung - Betriebshygiene" (Praxis of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene) (5th edition - Stuttgart; New York: Thieme, 1995). While disinfection in the narrower sense of medical practice means the killing of – theoretically all – infectious germs, sanitation is understood to mean the elimination of all germs as far as possible, including saprophytic germs that are normally harmless to humans.

[0111] Polyacrylic and polymethacrylic compounds include, for example, the high-molecular-weight homopolymers of acrylic acid (INCI name according to the International Dictionary of Cosmetic Ingredients of the Cosmetic, Toiletry, and Fragrance Association (CTFA): carbomer) cross-linked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol, or propylene, which are also known as carboxyvinyl polymers. Such polyacrylic acids are available, among others, from 3V Sigma under the trade name Polygel ®<, e.g., Polygel ®< DA, and from BFGoodrich under the trade name Carbopol ®<, e.g., Carbopol ®< 940 (molecular weight approx. 4,000,000), Carbopol ®< 941 (molecular weight approx. 1,250,000), or Carbopol ®< 934 (molecular weight approx. 3,000,000). The following acrylic acid copolymers are also included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates Copolymer), which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn ®< and Acusol ®< and from Degussa (Goldschmidt) under the trade name Tego ®< Polymer, e.g.the anionic non-associative polymers Aculyn ®< 22, Aculyn ®< 28, Aculyn ®< 33 (crosslinked), Acusol ®< 810, Acusol ®< 823 and Acusol ®< 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, which include, for example, copolymers of C 10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1 -C 4 alkanols (INCI Acrylates / C 10 -C 30 Alkyl Acrylate Crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopol ®<, e.g. E.g. the hydrophobic Carbopol ®< ETD 2623 and Carbopol ®< 1382 (INCI Acrylates / C 10-30 Alkyl Acrylate Grosspolymer) as well as Carbopol ®< AQUA 30 (formerly Carbopol ®< EX 473).

[0112] Other thickeners include polysaccharides and heteropolysaccharides, especially polysaccharide gums, such as gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan gum, ramsan, dextran, or xanthan gum and their derivatives, e.g., propoxylated guar gum, as well as mixtures thereof. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition, to a polysaccharide gum. These include starches of various origins and starch derivatives, e.g., hydroxyethyl starch, starch phosphate esters, or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl, or hydroxyethylmethylcellulose, or cellulose acetate.

[0113] A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 - 15 x 10 6< and is available, for example, from Kelco under the trade names Keltrol ®< and Kelzan ®< or from Rhodia under the trade name Rhodopol ®<.

[0114] Phyllosilicates can also be used as thickeners. These include, for example, the magnesium or sodium-magnesium phyllosilicates from Solvay Alkali, available under the trade name Laponite ®<, particularly Laponite ®< RD or Laponite ®< RDS, as well as the magnesium silicates from Süd-Chemie, especially Optigel ®< SH.

[0115] The amount of viscosity regulator, if different from 0%, is preferably up to 0.5% by weight, more preferably from 0.001 to 0.3% by weight, especially preferably from 0.01 to 0.2% by weight, and extremely preferably from 0.01 to 0.15% by weight, in each case based on the total weight of the cleaning composition. The viscosity of the cleaning composition is preferably from 0.4 to 400 mPas.

[0116] Furthermore, the cleaning compositions may contain one or more corrosion inhibitors.

[0117] Geeignete Korrosionsinhibitoren (INCI Corrosion Inhibitors) sind beispielsweise folgende gemäß INCI benannte Substanzen: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate und Triisopropanolamine.

[0118] Individual fragrance compounds, such as synthetic esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons, can be used as fragrances. Examples of fragrance compounds of the ester type include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl propionate, styrallyl propionate, and benzyl salicylate. Ethers include, for example, benzyl ethyl ether; aldehydes include, for example, the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, hydroxycitronellal, lilial, and bourgeonal; and ketones include, for example, benzyl ethyl ether. The alcohols include anethole, citronellol, eugenol, geranion, linalol, phenylethyl alcohol and terpineol, and the hydrocarbons mainly include terpenes and balsams.Mixtures of different fragrances are preferred, which together create an appealing scent.

[0119] Natural fragrance mixtures obtained from plant or animal sources can also be used as fragrances, such as pine, citrus, jasmine, lily, rose, or ylang-ylang oil. Essential oils of lower volatility, which are usually used as aroma components, are also suitable as perfume oils, such as sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, and labdanum oil.

[0120] The amount of fragrances in the cleaning compositions, if different from 0%, is preferably from 0.001 to 2% by weight and particularly preferably from 0.01 to 2% by weight, in each case based on the total weight of the cleaning compositions.

[0121] Any dyes and pigments contained in the cleaning agent compositions, both organic and inorganic, can be selected from the corresponding positive list of the Cosmetics Regulation or the EC list of cosmetic colorants. Pearlescent pigments, e.g., nacre (guanine / hypoxanthine mixed crystals from fish scales) and mother-of-pearl (ground mussel shells), monocrystalline pearlescent pigments such as bismuth oxychloride (BiOCl), and layered substrate pigments, e.g., are also advantageous. B. Mica / metal oxide, silver-white pearlescent pigments made of TiO 2 , interference pigments (TiO 2 , different layer thicknesses), colored luster pigments (Fe 2 O 3 ) and combination pigments (TiO 2 / Fe 2 O 3 , TiO 2 / Cr 2 O 3 , TiO 2 / Prussian Blue, TiO 2 / carmine).

[0122] The amount of dyes and pigments in the cleaning compositions, if different from 0%, is preferably from 0.01 to 1.0% by weight, based on the total weight of the cleaning compositions.

[0123] The proportion of component Z7) in the cleaning agent compositions, if it is different from 0%, is preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 1% by weight and especially preferably from 0.1 to 0.5% by weight, in each case based on the total weight of the cleaning agent compositions.

[0124] Preferably, the cleaning compositions contain Z1) 0.005 to 10.00 wt.% of component Z1), Z2) 0.10 to 20.00 wt.% of component Z2), Z3) 10.00 to 99.8 wt.% of component Z3), Z4) 0 to 10 wt.% of component Z4), Z5) 0 to 10 wt.% of component Z5), Z6) 0 to 10 wt.% of component Z6), and Z7) 0 to 10 wt.% of component Z7), each based on the total weight of the cleaning agent compositions.

[0125] The present invention also relates to cleaning compositions which contain one or more copolymers according to the invention.

[0126] The copolymers according to the invention and the cleaning compositions according to the invention are advantageously suitable for producing shine on hard surfaces, preferably on hard surfaces made of plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum or metal such as stainless steel.

[0127] The present invention therefore further relates to the use of one or more copolymers according to the invention, preferably in a cleaning agent composition according to the invention, or a cleaning agent composition according to the invention for producing shine on hard surfaces, preferably on hard surfaces made of plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum or metal such as stainless steel.

[0128] The copolymers according to the invention and the cleaning compositions according to the invention are also advantageously suitable for hydrophilizing hard surfaces, preferably hard surfaces made of plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum or metal such as stainless steel.

[0129] The present invention therefore further relates to the use of one or more copolymers according to the invention, preferably in a cleaning agent composition according to the invention, or a cleaning agent composition according to the invention for hydrophilizing a hard surface, preferably a hard surface made of plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum or metal such as stainless steel.

[0130] The copolymers according to the invention and the cleaning compositions according to the invention are furthermore advantageously suitable for achieving a repair effect on hard surfaces, preferably on hard surfaces made of plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum or metal such as stainless steel.

[0131] The present invention therefore further relates to the use of one or more copolymers according to the invention, preferably in a cleaning agent composition according to the invention, or a cleaning agent composition according to the invention for achieving a repair effect on a hard surface, preferably on a hard surface made of plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum or metal such as stainless steel.

[0132] The preferred embodiments given above for the copolymers according to the invention also apply correspondingly to the cleaning compositions according to the invention and to the inventive use of the copolymers according to the invention or the cleaning compositions according to the invention, in particular for producing shine on hard surfaces, for hydrophilizing hard surfaces and for achieving a repair effect on hard surfaces.

[0133] The invention is illustrated below by examples without being limited thereto. Unless explicitly stated otherwise in the examples, the percentages in the examples are to be understood as weight percent (wt%). Examples

[0134] The following abbreviations are used: AAPTAC [3-(Acryloylamino)-propyl]-trimethylammonium chloride (75 wt.% active in aqueous solution) DADMAC Diallyldimethylammonium chloride (65 wt.% active in aqueous solution) DMAA N,N-Dimethylacrylamide (100% active) MAPTAC [3-(Methacryloylamino)-propyl]-trimethylammonium chloride (50 wt.% active in aqueous solution) MESNA 2-Mercaptoethanesulfonate sodium (100% active) Meth 5000 Polyethylene glycol-co-polypropylene glycol methacrylate 5000 g / mol, 4-5 propylene glycol units (50 wt% active in aqueous solution) NIPAM N-Isopropylacrylamide (100% active) VA-44 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (100% active) V-PEG 1100 Polyethylene glycol vinyloxy butyl ether 1100 g / mol (100% active) V-PEG 5000 Polyethylene glycol vinyloxy butyl ether 5000 g / mol (100% active) Preparation of copolymers according to the invention

[0135] General instructions for the preparation of copolymers according to the invention In a multi-neck flask equipped with a KPG stirrer, reflux condenser and N 2 connection, the specified amounts of chemicals (excluding the initiator) are dissolved in the specified amount of distilled water under nitrogen (5 liters / hour) for the examples for the preparation of copolymers according to the invention given in Table 1. It should be noted that some of the substances used to prepare the copolymers according to the invention are employed in aqueous form (see the information on the substances used to prepare the copolymers according to the invention). The distilled water specified in the table is added in addition to the water introduced via these substances. In the case of acidic monomers, these are pre-neutralized with a base such as an alkali metal carbonate, for example potassium carbonate.The aqueous solution is then purged with nitrogen for 30 minutes and heated to 60°C. In the next step, the amount of initiator (VA-44) specified in Table 1 is dissolved in 10 g of distilled water and added over a period of 90 minutes. After the addition is complete, stirring is continued for a further hour at an internal temperature of 60°C. The conversion of the reaction is checked by subsequent analysis of the solid, and any unreacted monomers are reacted, if necessary, by adding a small amount of a 10 wt. % aqueous solution of the previously used initiator until complete conversion is achieved. The reaction mixture is then cooled to room temperature (20-23°C).

[0136] Synthesis examples are listed in Table 1. Copolymers 19-21 are not according to the invention. Table 1: Substances used to produce the copolymers Copolymer No. V-PEG 1100 V-PEG 5000 Meth 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC Na hypophosphite MESNA VA-44 distilled H 2 O Mw [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [g] [g] [g] [g] [g / mol] 1 - 4,816 - 32,985 80,064 - - - 0,120 - 1,560 149,450 39284 2 - 4,816 - 32,985 - 91,395 - - 0,120 - 1,560 149,450 3 - 4,816 - - - 22,899 83,755 - - - 1,560 142,250 6 - 4,816 - - - 57,198 - 46,163 - - 1,560 139,500 7 - 4,816 - - 80,064 - - 30,760 0,120 - 1,560 144,860 35849 8 - 4,816 - - - 57,198 - 46,163 - - 1,560 139,500 102330 10 - 4,816 - - 50,000 - - 46,000 - - 1,560 697,500 91934 11 - 4,816 - - 80,064 - - 30,760 - - 1,560 724,300 118920 14 29,809 - - - 14,758 - - 25,777 0,120 - 1,560 80,000 15 29,809 - - - 14,758 - - 25,777 - - 1,560 149,500 19 - - 4,816 - 80,064 - 42,015 - - 0,180 1,560 99,070 20 - - 4,816 - 80,064 - 42,015 - - 0,360 1,560 99,070 21 - - 4,816 - 80,064 - 42,015 - - 0,540 1,560 99,070 22 - 4,816 - - - 22,899 - 61,294 - - 1,560 136,000 42261 23 - 4,816 - - 20,060 - - 61,294 - - 1,560 136,000

[0137] The amounts given in Table 1 refer to the active ingredient. Table 1a: Relative amounts according to Table 1 Copolymer No. Total amount of monomers used [mmol] Structural units (A) [mol-%] Structural units (B) [mol-%] Structural units (C) [mol-%] 1 117,865 28,0 4,1 67,9 2 129,196 25,5 3,7 70,7 3 111,470 75,1 4,3 20,5 6 108,177 42,7 4,5 52,9 7 115,640 26,6 4,2 69,2 8 108,177 42,7 4,5 52,9 10 100,816 45,6 4,8 49,6 11 115,640 26,6 4,2 69,2 14 70,344 36,6 42,4 21,0 15 70,344 36,6 42,4 21,0 19 126,895 33,1 3,8 63,1 20 126,895 33,1 3,8 63,1 21 126,895 33,1 3,8 63,1 22 89,009 68,9 5,4 25,7 23 86,170 71,1 5,6 23,3

[0138] Determination of the weight-average molecular weights M w by GPC Method description

[0139] Column: PSS NOVEMA MAX Guard, 1x30Å & 2x1000Å 10 µm, 300 mm x 8 mm Detector: RI Oven temperature: 25 °C Flow: 1 ml / min Injection volume: 50 µl Eluent: 79.7 vol% 0.1M NaCl + 0.3 vol% TFA (trifluoroacetic acid) + 20 vol% ACN (acetonitrile) Calibration method: conventional calibration Standards: Poly(2-vinylpyridine) in the range of 1110 to 1 060 000 Dalton

[0140] Measured weight-average molecular weights M w for copolymers according to the invention are given in Table 1. Shining power

[0141] Black, glossy ceramic tiles (10 x 10 cm) are pre-cleaned, and then approximately 10 drops of the cleaning compound are applied to the center of the tiles. The cleaning compound is evenly distributed over the tile using a folded cellulose kitchen towel. After the tiles have dried vertically for at least 30 minutes, they are visually rated (1-10), with 1 being considered the best and 10 the worst.

[0142] Example formulations with and without the inventive copolymer were prepared, and gloss tests were conducted with these formulations. The example formulations and gloss results are shown in Table 2. Table 2 Example formulations and gloss results Cleaning agent composition A B C D E F G H C11 alcohol ethoxylate [wt.%] 4,0 2,5 4,5 4,0 2,5 4,5 1,0 - Propylene glycol butyl ether [wt.%] 1,0 0,6 0,5 1,0 0,6 0,5 - - Alkylpolyglucoside [wt.%] - 1,0 - - 1,0 - - - Sodium alkyl benzene sulfonate [wt.%] - - - - - - 2,0 0,5 Lactic acid [wt.%] - - - - - - 1,5 - Dipropylene glycol monobutyl ether [wt.%] - - - - - - - 0,25 Ammonium hydroxide [wt.%] - - - - - - - 0,3 Benzalkonium chloride [wt.%] - 0,4 - - 0,4 - - - Isopropanol [wt.%] - - - - - - - 7,0 Water [wt%] to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 pH (adjusted with NaOH or citric acid) 7 7 7 10 10 10 3,4 11,3 Visual assessment Without additives 6,3 2,5 10,0 9,2 3,0 10,0 10,0 7,0 + 0.2 wt.% copolymer 1 2,0 2,0 2,0 1,7 2,0 2,0 + 0.2 wt.% copolymer 2 2,0 2,7 + 0.2 wt.% copolymer 22 3,0 3,0 + 0.2 wt.% copolymer 3 3,3 2,3 1,3 + 0.2 wt.% copolymer 23 2,0 2,7 + 0.2 wt.% copolymer 6 3,7 2,0

[0143] The results in Table 2 show that better gloss results can be achieved by using the copolymers according to the invention in the example formulations compared to the corresponding example formulations without the copolymer according to the invention.

[0144] Market cleaners were mixed with copolymers according to the invention, and gloss tests were conducted with the market cleaners with and without the copolymer according to the invention. The results are presented in Table 3. Table 3 Use of copolymers in market cleaners cleaner Market Cleaner 1 Spray All-Purpose Cleaner Market Cleaner 2 Spray Bathroom Cleaner Market Cleaner 3 Spray Cleaner pH 11 2,9 2,5 Without additives 10 6,3 5,3 + 0.2 wt.% copolymer 6 2,0 1,0 1,0 + 0.2 wt.% copolymer 3 2,0 1,0 2,7

[0145] The results in Table 3 show that the use of the copolymers according to the invention in market cleaners allows better shine results to be achieved compared to the corresponding market cleaners without the addition of a copolymer according to the invention. Adsorption tests on hard surfaces

[0146] The experiments were conducted using the QCM-D quartz crystal microbalance (Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Västra Frölinda, Sweden). The method is based on the change in the natural frequency of a piezoelectric quartz crystal when it is loaded with a mass. The surface of the quartz crystal can be modified by spin coating or vapor deposition. The oscillating quartz crystal is located in a measuring cell. The measuring cell is a flow cell, into which the solution to be tested is pumped from storage vessels. The pumping speed is kept constant throughout the measurement. Typical pumping speeds are between 50–250 µl / minute. During a measurement, care must be taken to ensure that the tubing and measuring cell are free of air bubbles. Each measurement begins with the recording of the baseline, to which all frequency and dissipation measurements are set as the zero point.In this example, commercially available quartz crystals with a 50 nm thick silicon dioxide coating (QSX303, Q-Sense, Västra Frölinda, Sweden) and quartz crystals with a 50 nm thick stainless steel (SS2343) coating (QSX304 Q-Sense, Västra Frölinda, Sweden) were used.

[0147] Aqueous solutions of the copolymers according to the invention with an active content of 2000 ppm were tested. Tap water with a hardness of 20° German hardness (dH) was used as the water. The pH was adjusted to 10 with NaOH or citric acid. Table 4 Adsorption of the copolymers on silica: Copolymer No. Adsorbed mass [ng / cm 2< ] 23 264,4 22 275,9 8 355,8 3 142,5 7 348,0 Table 5 Adsorption of copolymers on stainless steel: Copolymer No. Adsorbed mass [ng / cm 2< ] 23 129,7 22 153,6

[0148] The results of Tables 4 and 5 show that the copolymers according to the invention are suitable for application on hard surfaces, since they adsorb on the inorganic surfaces investigated. Contact angle test

[0149] The contact angles were measured on various surfaces (ceramic, glass, stainless steel) by modifying the surfaces using the following method: The surfaces were immersed three times for 2 minutes in fresh deionized water (DI water) and then immersed in the respective aqueous copolymer solution for 20 minutes at room temperature while stirring. The surfaces were then dried with a gentle stream of nitrogen. The contact angles on the prepared surfaces were measured using DI water (equipment: drop analyzer from Krüss, Hamburg, Model DSA 100).

[0150] The contact angle of a water droplet on a surface is a measure of its hydrophilicity. A very hydrophilic surface is completely wetted by a water droplet. This phenomenon is also known as droplet spreading.

[0151] Copolymers according to the invention were tested as an aqueous solution with an active content of 2000 ppm. Tap water with a hardness of 20° German hardness (dH) was used as the water. The pH was adjusted to 10 with NaOH or citric acid. Table 6 Contact angle on black ceramic tile Copolymer No. Contact angle of water Untreated 18° 23 8° 22 Drop spreads 8 4,2° 3 15° 7 5° Table 7 Contact angle on glass Copolymer No. Contact angle of water Untreated 39° 8 Drop spreads 3 Drop spreads 7 Drop spreads Table 8 Contact angle on steel Copolymer No. Contact angle of water Untreated 15° 23 Drop spreads 22 Drop spreads

[0152] The results of Tables 6, 7 and 8 show that the copolymers of the invention are suitable for reducing the contact angle of water on inorganic surfaces (ie, for hydrophilizing inorganic surfaces). Repair effect

[0153] The topography of the surface of a damaged black tile was determined before and after treatment with aqueous solutions of the inventive copolymers with an active content of 2000 ppm (equipment: contact-free optical 3D surface characterization from Sensofar, Barcelona, ​​Model S neox). Using the MountainsMap software (Digital Surf SARL, Besançon, France), various 3D parameters can be calculated by segmenting the surface topography into area elements. These parameters provide information on, among other things, height (calculated according to ISO 25178) and roughness (calculated according to ISO 4287). Table 9 Roughness of a black damaged tile before and after copolymer treatment Copolymer No. Roughness untreated [nm] Roughness after treatment [nm] 22 71* 36* 8 140 94,6 3 110 108 7 86 85 * Changing the roughness of a black tile

[0154] The investigations clearly demonstrate the repair effect of the copolymers according to the invention.

Claims

1. Copolymer obtainable from the free-radical copolymerization at least of components a), b) and c) a) 25.0 to 80.0 mol% of one or more cationic monomers selected from the group consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, and b) 1.0 to 50.0 mol% and preferably 1.0 to 10.0 mol% of one or more polyethylene glycol macromonomers, and c) 15.0 to 74.0 mol% of one or more uncharged acrylamide monomers, characterized in that the one or more polyethylene glycol macromonomers of component b) is / are selected from monomers of the formula (IV)         H2C=CRx-Z-O-(C3H6O)l- (CH2CH2O)p-H     (IV) in which Rx is H or methyl, Z is O(CH2)4, l on molar average is a number from 0 to 7 and preferably from 0 to 6, and p on molar average is a number from 1 to 150, preferably from 11 to 150 and more preferably from 12 to 150.

2. Copolymer according to Claim 1, characterized in that the one or more cationic (meth)acrylamide monomers of component a) is / are selected from monomers of the formula (I) in which R1 is hydrogen or methyl.

3. Copolymer according to Claim 1 or 2, characterized in that the one or more cationic monomers of component a) is / are selected from the group consisting of diallyldimethylammomium chloride and (3-methacrylamidopropyl)trimethylammonium chloride.

4. Copolymer according to one or more of Claims 1 to 3, characterized in that in formula (IV), Rx is H, l = 0 and p on molar average is a number from 1 to 150, preferably from 11 to 150 and more preferably from 12 to 150.

5. Copolymer according to one or more of Claims 1 to 4, characterized in that the one or more polyethylene glycol macromonomers of component b) is / are selected from the group consisting of monomers of the formula (IV-A) in which pA on molar average is a number from 1 to 150, preferably from 1 to 120, more preferably from 11 to 120 and especially preferably from 22 to 120.

6. Copolymer according to one or more of Claims 1 to 5, characterized in that the one or more uncharged acrylamide monomers of component c) is / are selected from the monomers of the formula (III) in which R2 and R3 may each be the same or different and are each independently hydrogen and / or an aliphatic hydrocarbyl radical having 1 to 20 and preferably having 1 to 4 carbon atoms.

7. Copolymer according to one or more of Claims 1 to 6, characterized in that the one or more uncharged acrylamide monomers of component c) is / are selected from the group consisting of acrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide and N-isopropylacrylamide and are preferably selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide.

8. Copolymer according to one or more of Claims 1 to 7, characterized in that it is obtainable from the free-radical copolymerization at least of components a), b) and c), where component a) is used in the copolymerization in an amount of 25.0 to 80.0 mol%, component b) in an amount of 1.0 to 4.4 mol%, and component c) in an amount of 15.6 to 74.0 mol%.

9. Copolymer according to one or more of Claims 1 to 8, characterized in that the structural units originating from the polymerization of monomers a), b), c) and optionally of further monomers are present in the copolymer in a random, blockwise, alternating or gradient distribution.

10. Copolymer according to one or more of Claims 1 to 9, characterized in that it has a weight-average molecular weight Mw of from 10 000 to 250 000 g / mol, preferably from 15 000 to 200 000 g / mol and more preferably from 20 000 to 150 000 g / mol, when the weight-average molecular weight Mw is measured by GPC (gel permeation chromatography) with the poly(2-vinyl-pyridine) calibration standard having molecular weights Mw in the range from 1110 to 1 060 000 g / mol.

11. Detergent composition, characterized in that it comprises one or more copolymers according to one or more of Claims 1 to 10.

12. Use of one or more copolymers according to one or more of Claims 1 to 10 or of a detergent composition according to Claim 11 for producing shine on hard surfaces, preferably on hard surfaces of plastic, ceramic, stone, for example natural stone, porcelain, glass, wood, linoleum or metal, for example stainless steel.

13. Use of one or more copolymers according to one or more of Claims 1 to 10 or of a detergent composition according to Claim 11 for hydrophilization of a hard surface, preferably a hard surface of plastic, ceramic, stone, for example natural stone, porcelain, glass, wood, linoleum or metal, for example stainless steel.

14. Use of one or more copolymers according to one or more of Claims 1 to 10 or of a detergent composition according to Claim 11 for achieving a repair effect on a hard surface, preferably on a hard surface of plastic, ceramic, stone, for example natural stone, porcelain, glass, wood, linoleum or metal, for example stainless steel.