BR112019009247B1 - COPOLYMERS, CLEANING AGENT COMPOSITION COMPRISING THEM, AND USES THEREOF - Google Patents

Abstract

The present invention relates to copolymers, which can be obtained from the radical copolymerization of at least the following components: a) cationic monomers, selected from the group, consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, b) polyethylene glycol macromonomers and c) neutral acrylamide monomers. The copolymers are, for example, advantageously suitable for use in cleaning agent compositions and after application to hard surfaces lead, for example, to advantageous gloss results.

Description

[001] The present invention relates to copolymers, which can be obtained from the radical copolymerization of at least the following components: cationic monomers, selected from the group consisting of cationic (meth) acrylamide monomers and chloride diallyldimethylammonium, polyethylene glycol macromonomers and neutral acrylamide monomers, cleaning agent compositions containing such copolymers, as well as the use of the copolymers or cleaning agent compositions, in particular, to produce shine on hard surfaces, for the hydrophilization of hard surfaces and to achieve a repair effect on hard surfaces.

[002] Commercial cleaning formulations allow efficient cleaning of hard surfaces in industry, the home or common places. These generally consist of an aqueous solution of surfactants, in particular, non-ionic and anionic surfactants, alcohol (alcohols) to facilitate drying, bases to adjust the pH value and optionally quaternary amines as disinfectants.

[003] Documents WO 2013/170001 and WO 2013/170002 describe cleaning formulations, which contain alkoxylated polyethylenimine polymers and lead to improved gloss on hard surfaces.

[004] Document WO 2009/156067 describes cleaning formulations, which contain saccharide graft copolymers and can be used to improve the gloss of hard surfaces and/or have hydrophilic properties.

[005] Document WO 2003/031546 describes aqueous antimicrobial cleaning compositions for treating hard surfaces, with the result of obtaining a shine or improving the shine of hard surfaces.

[006] Document WO 98/49263 describes aqueous acid surface cleaners, which contain a polymeric additive and obtain a better surface shine.

[007] Document US 2014/0005095 describes cleaning compositions for hard surfaces, which obtain a shiny, scratch-free surface.

[008] Document EP 1196523 B1 describes cleaning agent compositions, which are intended for the treatment of hard surfaces in industry, the home or also in common places and aim, in particular, to provide hydrophilic properties, as well as water-repellent properties. protection to these surfaces.

[009] Although good results are already obtained with known systems, there remains, however, ample room for improvement. An essential shortcoming of these cleaning formulations often consists in the fact that on the hard surface, after drying, residues of the cleaning formulation can be seen in the form of scratches, streaks or stains and thus the surface shine is minimized.

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

[0011] Surprisingly, it was found that this objective can be solved by copolymers, which can be obtained from the radical copolymerization of at least components a), b) and c) (a) 25.0 to 80.0% in mol, of one or more cationic monomers, selected from the group, consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride and (b) 0.1 to 50.0 mol%, preferably 0.5 to 50.0 mol%, particularly preferably 1.0 to 50.0 mol%, and in particular preferably 1.0 to 10.0 mol%, of one or more polyethylene glycol macromonomers and ( c) 15.0 to 74.9 mol%, preferably 15.0 to 74.5 mol% and, in particular, preferably 15.0 to 74.0 mol%, of one or more neutral acrylamide monomers.

[0012] The object of the present invention is, therefore, copolymers, which can be obtained 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) 0.1 to 50.0 mol%, preferably 0.5 to 50.0 mol%, particularly preferably 1.0 to 50.0 mol%, and in particular preferably 1.0 to 10.0 mol%, of one or more polyethylene glycol macromonomers and (c) 15.0 to 74.0% by weight, preferably 15.0 to 74.5% by weight and particularly preferably, 15.0 to 74.0% by weight, of one or more neutral acrylamide monomers.

[0013] In the context of the present invention, the expression “(meth)acryl” comprises both the corresponding acryl compound and the corresponding methacryl compound.

[0014] The term “hard surface” means, in the sense of the invention, a surface made of shape-resistant materials, for example, from plastic, ceramic, stone, such as, for example, natural stone, porcelain, glass, wood, linoleum and metal, such as, for example, stainless steel, surfaces typically in the kitchen and sanitary area, for example, in kitchens, bathrooms and toilets, in the home, but also in the industrial area, for example, in butchers, slaughterhouses, in dairies, storage tanks for food or industrial products, as well as in public areas, such as, for example, on building facades, in swimming pools or in railway stations.

[0015] Document WO 2012/076365 A1 publishes cationic copolymers containing cationic structural units and macromonomer structural units, as well as their use as an additive for construction material systems, in particular, based on calcium sulfate.

[0016] Document WO 2008/049549 A2 describes hydrophobically modified cationic copolymers, which have at least three different structural units and of which one structural unit has a terminal phenyl group or a specially substituted phenyl group. With the help of copolymers it is possible to obtain, in particular, in combination with anionic surfactants, even in the case of high salt loads, a considerable improvement in water retention in construction material systems based on hydraulic adhesives, such as cement.

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

[0018] Document WO 2008/046652 A1 describes graft polymers, which can be obtained through the copolymerization of at least one specific macromonomer and at least one other monomer, which has a polymerizable ethylenically unsaturated double bond, as well as their use as an agent dispersion, for example in pigment concentrates.

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

[0020] In document JP 2008-056711 A, copolymers with a number-average molecular weight of 5000 to 1,000,000 are published, which contain structural units, which are formed through the polymerization of certain cationic monomers, polyoxyalkylene-modified monomers and cross-linkable monomers and which may additionally contain other structural units, which are formed through the polymerization of other monomers, which may be copolymerized with the monomers mentioned above. Copolymers can be used, for example, as antistatic agents for thermoplastic polymers.

[0021] An advantage of the invention is that the copolymers according to the invention can be added to cleaning agent compositions and these, when applied to a hard surface, can cause an advantageous cleaning effect.

[0022] Another advantage of the invention is that the copolymers according to the invention can be added to cleaning agent compositions and thus cause a shiny effect on the hard surface to which they were applied.

[0023] Another advantage of the invention is that the copolymers according to the invention can be added to cleaning agent 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 agent composition can be reduced. The presence of traces or stains, which are left on hard surfaces by water or aqueous compositions of cleaning agents, which have come into contact with them, is related to the phenomenon of contraction of water droplets or drops of aqueous compositions of cleaning agents. cleaning agents in contact with the hard surface, which upon subsequent drying leave traces on the surface. Furthermore, by reducing the contact angle between the treated surface and a water droplet, the drying speed of a surface can be improved.

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

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

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

[0027] Preferably, the various cationic (meth) acrylamide monomers of component a) is or are selected from monomers of formula (I) in which R1 represents hydrogen or methyl.

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

[0029] Preferably, one or more polyethylene glycol macromonomers of component b) are selected from monomers of formula (IV) in which Rx is H or methyl, Z is C=O or O(CH2)4 and preferably O(CH2)4, l on the molar average, is a number from 0 to 7 and preferably from 0 to 6 and p on the molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150. Preferably, in formula (IV) Rx is H, l = 0 and p, on the molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150, when Z represents O(CH2)4 or ii) Rx is H or methyl, l, on the molar average, is a number from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 6 and, on the molar average, is a number from 1 to 150, preferably from 11 to 150 and particularly preferably from 12 to 150, when Z represents C=O .

[0030] Particularly preferably, the one or more polyethylene glycol macromonomers of component b) are selected from the group consisting of monomers of formula (IV-A) in which pA on the molar average is a number from 1 to 150, preferably from 1 to 120, particularly preferably from 11 to 120 and, in particular, preferably from 22 to 120 and monomers of formula (IV-B) in which IB on the molar average, represents a number from 1 to 7, preferably from 2 to 6 and particularly preferably, from 3 to 6 pB on the molar average, represents a number from 1 to 150, preferably from 1 to 120, of particularly preferably, from 11 to 120 and, in particular, preferably from 12 to 120.

[0031] Preferably, the one or more neutral acrylamide monomers of component c) are selected from the monomers of formula (III) in which R2 and R3 each, may be the same or different and independently of each other, each represent hydrogen and/or an aliphatic hydrocarbon radical with 1 to 20 and preferably 1 to 4 carbon atoms.

[0032] 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, in particular, preferably the one or more neutral acrylamide monomers of component c) are selected from the group, which consists of N,N-dimethylacrylamide and N-isopropylacrylamide.

[0033] Preferably, the copolymers according to the invention can be obtained from the radical copolymerization of at least components a), b) and c), and 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 0.1 to 4.4 mol%, preferably in an amount of 0.5 to 4.4 mol% and particularly preferably, in an amount of 1.0 to 4.4% by weight and component c) is used in an amount of 15.6 to 74.9% by weight, preferably in an amount of 15.6 to 74.5% by weight. weight and particularly preferably in an amount of 15.6 to 74.0% by weight.

[0034] In a preferred embodiment of the invention, the copolymers according to the invention can be obtained from the radical copolymerization merely of components a), b) and c), that is, in this preferred embodiment of the invention it is not No other monomer is used, which is different from the monomers of components a), b) and c), for the production of the copolymers according to the invention.

[0035] In another preferred embodiment of the invention, the copolymers according to the invention can be obtained from the radical copolymerization of the monomers of components a), b), c) and additionally from one or more monomers of a component d), which are different from the monomers of components a), b) and c).

[0036] Since the copolymers according to the invention can be obtained 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 those 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 lactams substituted by N-vinyl with 5 to 7 ring atoms and monomers of the following general formula (V): in which R11 is the same or different and is represented by H and/or methyl; " -substituted.

[0037] Since the copolymers according to the invention can be obtained 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 those 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, which consists of lactams substituted by N-vinyl with 5 to 7 ring atoms and the monomers of the general formula (V).

[0038] Among lactams substituted by N-vinyl with 5 to 7 ring atoms, N-vinylpyrrolidone is preferred.

[0039] The para-substituted SO3H, PO3H2, O-PO3H2 and C6H4-SO3H groups in the monomers of formula (V) can also be present in salt form, preferably as NH4+ salt, alkali or alkaline earth metal salt and particularly preferably as an NH4+ salt or as a Na+ salt.

[0040] Among the monomers of formula (V), in which R13 is N(CH3)2, those monomers are preferred, which are selected from the group, consisting of [3-(methacryloylamino)-propyl]-dimethylamine ( R11 is methyl; n = 3 and R13 is N(CH3)2).

[0041] 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-acryoylamino-2-methylpropanesulfonic acid and those particularly preferred, which are selected from the group, consisting of 2-acryoylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid -acryoylamino-2-methylpropanesulfonic acid.

[0042] Since the copolymers according to the invention can be obtained 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 those 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, which consists of the monomers of the following general formula (VIII): in which W is the same or different and is represented by -CO-O-(CH2)x, x is an integer from 1 to 6, preferably 2 or 3, R1 is the same or different and represents hydrogen and/or methyl and R3 and R4 each are the same or different and independently of each other, are represented by hydrogen, an aliphatic hydrocarbon radical having 1 to 20, preferably 1 to 4 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 20, preferably 5 to 8 carbon atoms. carbon, an aryl radical with 6 to 14 carbon atoms and/or polyethylene glycol (PEG).

[0043] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), monomers of component d), in another particular, preferred embodiment of the invention, are selected from the monomers of formula (VIII).

[0044] Among the monomers of formula (VIII) those are preferred which are selected from the group consisting of [2-(methacryloyloxy)-ethyl]-dimethylamine, [2-(acryloyloxy)-ethyl]-dimethylamine, [2-(methacryloyloxy)-ethyl]-diethylamine and [2-(acryloyloxy)-ethyl]-diethylamine.

[0045] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), in another particularly preferred embodiment of the invention, at least one of the monomers of component d) is selected from the group, which consists of the monomers of the following general formulas (IX) and /or (X): in which R11 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; in which R11 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 R15 is the same or different and is represented by H, (CnH2n)-SO3H with n = 0, 1, 2, 3 or 4; (CnH2n)-OH with = 0, 1, 2, 3 or 4; (CnH2n)- PO3H2 with n = 0, 1, 2, 3 or 4; (CnH2n)-OPO3H2 with n = 0, 1, 2, 3 or 4; (C6H4)-SO3H; (C6H4)-PO3H2; (C6H4)-OPO3H2 and/or (CmH2m)eO-(A'O)u- R16 with m = 0, 1, 2, 3 or 4, e = 0, 1, 2, 3 or 4, A' = Cx 'H2x' with x' = 2, 3, 4 or 5, u = an integer from 1 to 350 and R16 is the same or different as well as represented by an unbranched or branched C1-C4-alkyl group.

[0046] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), the monomers of component d) in another, in particular, preferred embodiment of the invention, are selected from the monomers of formulas (IX) and/or (X).

[0047] The monomers of formula (X) may also be present in salt form, preferably as NH4+ salt, alkali or alkaline earth metal salt and particularly preferably as NH4+ salt or as Na+ salt.

[0048] Among the monomers of formulas (IX) and (X), those that are selected from the group consisting of maleic acid anhydride, maleic acid and maleic acid salts are preferred.

[0049] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), in another particularly preferred embodiment of the invention, at least one of the monomers of component d) is selected from the group, which consists of the monomers of the following general formula (VII): in which S is the same or different and is represented by -COOMk, R1 is the same or different and is represented by H and/or by an unbranched or branched C1-C4- alkyl group and is preferably represented by H or methyl; and M is a cation selected from the group, which consists of hydrogen ion, alkali metal ion, alkaline earth metal ion and alkaline earth metal ion, with k being the valence.

[0050] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), monomers of component d), in a particularly preferred embodiment of the invention, are selected from the monomers of formula (VII).

[0051] 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.

[0052] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), in another particularly preferred embodiment of the invention at least one of the monomers of component d) is selected from the group, which consists of the monomers of the following general formulas (Va), ( Vb) and/or (Vc): in which R11 is the same or different and is represented by H and/or methyl; W is the same or different and is represented by O; R12 is the same or different and is represented by a branched or unbranched C1-C5-monohydroxyalkyl group in which R11 is the same or different and is represented by H and/or methyl; X is the same or different and is represented by O-(CnH2n) with n = 1, 2, 3 or 4; R13 is the same or different and is represented by OH, SO3H, PO3H2, O-PO3H2 and/or para-substituted C6H4-SO3H in which R14, R15 and R16 are each the same or different and each independently of each other are represented by H and/or by an unbranched or branched C1-C4-alkyl group; n is the same or different and is represented by 0, 1, 2, 3 and/or 4; R17 is the same or different and is represented by (C6H5), OH, ORy, with Ry representing an alkyl group with 1 to 8 and preferably 4 carbon atoms and/or -OOCCH3.

[0053] Since the copolymers according to the invention can be obtained 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 those monomers of components a), b) and c), the monomers of component d), in a particularly preferred embodiment of the invention, are selected from the monomers of formulas (Va), (Vb) and/or ( You).

[0054] The para-substituted SO3H, PO3H2, O-PO3H2 and C6H4-SO3H groups in the monomers of formula (Vb) can also be present in salt form, preferably as NH4+ salt, alkali or alkaline earth metal salt and particularly preferably, as an NH4+ salt or as a Na+ salt.

[0055] Among the monomers of formula (Vc), those that are selected from the group consisting of vinyl butyric ether and vinyl acetate are preferred.

[0056] In a particularly preferred embodiment of the invention, the copolymers according to the invention can be obtained 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), and in the copolymerization

[0057] component a) is used in an amount of 25.0 to 80.0 mol%, component b) is used in an amount of 0.1 to 50.0 mol%, preferably in an amount of 0.5 to 50.0 mol%, particularly preferably in an amount of 1.0 to 50.0 mol%, and in particular preferably in an amount of 1.0 to 10.0 mol% , component c) is used in an amount of 15.0 to 74.4 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%.

[0058] In a particularly preferred embodiment of the present invention, the copolymers according to the invention can be obtained from the radical copolymerization of components a), b), c) and additionally one or more monomers of the component d), which is different from components a), b) and c), and in copolymerization component a) is used in an amount of 25.0 to 80.0 mol%, component b) is used in an amount of amount of 0.1 to 4.4 mol% and preferably in an amount of 0.5 to 4.4 mol%, component c) is used in an amount of 15.6 to 74.4 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%.

[0059] In a preferred embodiment of the invention, the copolymers according to the invention can be obtained from the radical copolymerization merely of components a), b), c) and d), that is, in this preferred embodiment of the In the invention, no other monomer is used, which is different from the monomers of components a), b), c) and d), for the production of the copolymers according to the invention.

[0060] Preferably, the structural units of the copolymers according to the invention arising from the polymerization of monomers a), b) and c) and optionally d) and optionally other monomers, are present in the copolymer in statistical distribution, in the form of blocks, alternating or gradient type.

[0061] Preferably, the average weight molecular weight Mw of the copolymers according to the invention is from 10,000 to 250,000 g/mol, particularly preferably from 15,000 to 200,000 g/mol and, in particular, preferably from 20,000 to 150,000 g/mol.

[0062] The copolymers according to the invention can be produced by methods, which are common to the person skilled in the art. Particularly preferably, the copolymers according to the invention can be produced by radical polymerization in solvent. Common solvents can be, for example, polar solvents, such as alcohols or water, as well as mixtures of alcohol and water. Polymerization is initiated via radical sources such as, for example, inorganic persulfates, organic azo compounds, peroxides, inorganic redox systems or ultraviolet light. Furthermore, chain transfer regulators, which form fewer reactive radicals, can be used to control the molecular weight of the copolymers. Such chain transfer regulators are, for example, phenols, thiols, for example, sodium 2-mercaptoethanesulfonate or sodium hypophosphite. In an exemplary embodiment, the monomers to produce the copolymers according to the invention and optionally a chain transfer regulator are dissolved in the solvent, the oxygen is extracted, then the temperature is increased and the radical initiator is added. The copolymerization is then carried out at the desired temperature for the desired period of time. Next, the reaction mixture is optionally cooled and the formed copolymer is either further solution processed or recovered, 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 also be isolated in another way, for example, by lyophilization or precipitation.

[0063] Preferably, the copolymers according to the invention can be obtained 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, one or more alcohols being preferably selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, tert.-butanol, ethylene glycol, propylene glycol, propylene glycolmonobutyl ether, ethylene glycolmonobutyl ether, propylene glycolmonomethyl ether, ethylene glycolmonomethyl ether and mixtures thereof. Particularly preferred, the solvent is selected from the group, consisting of water, ethanol, isopropanol, propylene glycol, tert.-butanol, propylene glycolmonobutyl ether and mixtures thereof, and in particular, the solvent is preferably selected from the group, which consists of water, isopropanol, tert.-butanol, propylene glycol and mixtures thereof.

[0064] Preferably, the copolymers according to the invention can be obtained from the radical copolymerization of at least components a), b) and c) at temperatures in the range of 20 to 200oC, particularly preferably, in the range of 20 to 100oC and, in particular, preferably in the range of 40 to 80oC.

[0065] Preferably, the copolymers according to the invention can be obtained from the radical copolymerization of at least components a), b) and c), with the radical copolymerization being initiated through heating, irradiation with light or through the addition of a radical initiator and particularly preferably by adding a radical initiator, the radical initiator being in particular preferably selected from the group consisting of

[0066] 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, 2,2'-azobis [2-(2-imidazolin-2-yl)propane], 2,2'- azobis [2-methyl-N-(2 -hydroxyethyl)propionamide], 4,4'-bis(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(cyclohexan-1-carbonitrile) and /or 2,2'-azobis(N-butyl-2-methylpropionamide); and persulfate initiators, preferably ammonium persulfate, sodium persulfate and/or potassium persulfate.

[0067] Copolymers according to the invention are extraordinarily preferred, which can be obtained from the radical copolymerization of at least components a), b) and c), with the radical copolymerization being initiated through the addition of a selected radical initiator from the group consisting of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis tetrahydrate [N-(2-carboxyethyl)-2-methylpropionamidine], 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 the addition of a radical initiator selected from the group consisting of ammonium persulfate, sodium persulfate and 2,2'-azobis dihydrochloride [2-(2 -imidazolin-2-yl)propane].

[0068] In a preferred embodiment of the invention, the copolymers according to the invention can be obtained from the radical copolymerization of at least components a), b) and c), with the radical copolymerization being carried out in the presence of a chain transfer agent selected from the group consisting of mercaptans, preferably octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, mercaptoethanol and sodium 2-mercaptoethanesulfonate; halogenated compounds; thiosalicylic acid, mercaptoacetic acid; buten-1-ol; dimeric a-methylstyrene and hypophosphite derivatives, preferably sodium hypophosphite. In a particularly preferred embodiment of the invention, the copolymers according to the invention can be obtained from the radical copolymerization of at least components a), b) and c), with the radical copolymerization being carried out in the presence of a dehydrating agent. chain transfer, 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 can be obtained from the radical copolymerization of at least components a), b) and c), with the radical copolymerization being 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 used advantageously in cleaning agent compositions. In cleaning agent compositions, the copolymers according to the invention represent component Z1). These cleaning agent compositions are described in detail below.

[0070] Preferably, the cleaning agent compositions contain one or more copolymers of component Z1) in an amount of 0.005 to 10% by weight, particularly preferably, in an amount of 0.01 to 5% by weight and, in particular, preferably in an amount of 0.1 to 0.5% by weight, each based on the total weight of the cleaning agent composition.

Z2 Component)

[0071] Cleaning agent compositions contain as component Z2) one or more surface-active agents.

[0072] Preferably, the one or more surfactants of component Z2) of the cleaning agent compositions are selected from the group, which consists of anionic, nonionic, amphoteric and cationic surfactants.

[0073] Cleaning agent compositions may optionally contain anionic surfactants, for example, alkyl benzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates and/or glutamates of acyl. The alkyl chains of the mentioned 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 linear or branched arrangement.

[0074] Anionic surfactants, which are 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 , olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and ligninsulfonates. Likewise, in the context of the present invention, alkyl benzenesulfonates, fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid ester), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates can be used. fatty acids, ethercarboxylic acids and alkyl(ether)phosphates, as well as [alpha]-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ether of glycerin disulfate.

[0075] Of these, fatty alcohol sulfates and/or fatty alcohol ether sulfates are preferred, in particular, fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions in corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions in alkoxylated alcohols. In this case, the specialist generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention, preferably with long-chain alcohols. As a rule, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products with different degrees of ethoxylation results. Another form of alkoxylation is to use mixtures of alkylene oxides, preferably a mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are low ethoxylated fatty alcohol sulfates with 1 to 4 ethylene oxide (EO) units, in particular, 1 to 2 EO, for example, 1.3 EO.

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

[0077] Anionic surfactants are generally used as salts, but also as acid. In the case of salts, these are preferably alkali metal salts, alkaline earth metal salts, ammonium salts, as well as mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular, of lithium, sodium, potassium or ammonium salts, particularly preferably of sodium or potassium salts, in particular preferably of sodium salts.

[0078] Other surfactants may be non-ionic, amphoteric and/or cationic surfactants, for example, betaine, amidobetaine, amidobetaine, amine oxides, amidoamine oxides, fatty alcohol polyglycolic ethers, alkyl polyglycosides or also ammonium compounds quaternary.

[0079] Other non-ionic surfactants may be, for example, alkoxylates, such as polyglycolic ethers, fatty alcohol polyglycolic ethers (fatty alcohol alkoxylates), alkylphenolpolyglycolic ethers, polyglycolic ethers closed at the terminal group, mixed ethers and mixed hydroxy ethers and fatty acid polyglycolic ester. Likewise, block copolymers of ethylene oxide-propylene oxide and fatty acid alkanolamides and fatty acid polyglycolic ethers can be used. Another important class of non-ionic surfactants, which can be employed according to the invention, are polyol surfactants and here particularly glycol surfactants, such as alkyl polyglycosides, in particular alkyl polyglucosides.

[0080] Suitable fatty alcohol polyglycolic ethers are C8-C22- alkoxylated alcohols, unbranched or branched, saturated or unsaturated with ethylene oxide (EO) and/or propylene oxide (PO) with a degree of alkoxylation of up to 30, preferably ethoxylated C10-C18 fatty alcohols with a degree of ethoxylation of less than 30, particularly preferably 1 to 20, in particular preferably 1 to 12 and extraordinarily preferably 1 to 8, for example C12 alcohol ethoxylates -C14-fat with 8 EO.

[0081] Alkyl polyglycosides are surface-active agents, which can be obtained through the reaction of sugars and alcohols according to the respective preparatory organic chemistry process, and depending on the type of production, a mixture of oligomeric or monoalkylated polymeric sugars results. Preferred alkyl polyglycosides are alkyl polyglucosides, with particularly preferred alcohol being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C8- to C18-alkyl chains and the degree oligomerization rate (DP) of the sugars is 1 to 10, preferably 1 to 6, particularly preferably 1.1 to 3, and in particular preferably 1.1 to 1.7, for example C8- C10-alkyl-1,5-glucoside (DP of 1.5).

[0082] Amphoteric surfactants (hybrid surfactants), which can be used according to the invention, include betaine, aminoxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biological surfactants.

[0083] Suitable betaines are alkyl betaines, alkylamidobetaines, imidazolium betaines, sulfobetaines (INCI Sultaines) and amidosulfobetaines, as well as phosphobetaines. Examples of suitable betaines and sulfobetaines are the following compounds mentioned according to the INCI nomenclature: almondamidopropyl betaine, apricotamidopropyl betaine, avocadoamidopropyl betaine, babassuamidopropyl betaine, behenamidopropyl betaine, behenyl betaine, betaine, canolamidopropyl betaine, capryl/capramidopropyl betaine, camitine, cetyl betaine , cocamidoethyl betaine, cocamido propyl betaine, cocamido propylhydroxysultaines, coco betaine, cocohydroxysultaine, coco/oleamidopropyl betaine, coco-sultaine, decyl betaine, dihydroxyethyl oleylglycinate, dihydroxyethyl soy glycinate, dihydroxyethylstearylglycinate, dihydroxyethyl tallow glycinate, propyl dimethicone PG-Betaine, Erucamopropil-Hydroxisultaino, Tallow Hydrogen Betaine, Isotera-Eopropil Betaine, Lauramopropil Betaine, Lauril Betaine, Lauril-hydroxisultine, laurylsultine, amidopropil Betaine, Milistile Betaine Milistopropil Betaine, Minitil Betaine, Minitil Betaine iam, oleamopropil betaine, oleamopropil hydroxisultine, oleil betaine, olivamidopropyl betaine, palm amidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernel amidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinolamidopropyl betaine, sesamidopropyl betaine, soy amidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallow amidopropyl betaine, tallowamidopropyl hydroxysultaine , tallow betaine, tallow dihydroxyethyl betaine, undecylenamidopropyl betaine and germanoamidopropyl betaine from wheat.

[0084] Suitable amine oxides according to the invention include alkylamine oxides, in particular, alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamide oxides.

[0085] Examples of suitable amine oxides are the following compounds mentioned according to the INCI nomenclature: almondamidopropylamine oxide, babassu amidopropylamine oxide, behenamine oxide, cocamidopropylamine oxide, cocamidopropylamine oxide, cocamine oxide, coconut oxide -morpholine, decylamine oxide, decyltetradecylamine oxide, diaminopyrimidine oxide, dihydroxyethyl C8-C10 alkoxypropylamine oxide, dihydroxyethyl C9-C11 alkoxypropylamine oxide, dihydroxyethyl C12-C15 alkoxypropylamine oxide, dihydroxyethyl oxide cocamine, dihydroxyethyl lauramine oxide, dihydroxyethyl stearamine oxide, dihydroxyethyl tallow amine oxide, hydrogenated palm kernel amine oxide, hydrogenated tallow amine oxide, hydroxyethyl hydroxypropyl C12-C15 alkoxypropylamine oxide, isostearamidopropylamine, isostearamidopropyl morpholine oxide, lauramidopropylamine oxide, lauramine oxide, methyl morpholine oxide, milk amidopropyl amine oxide, mink amidopropylamine oxide, myristamidopropylamine oxide, myristamine oxide, myristyl/cetyl amine oxide, oleamidopropylamine, oleamine oxide, olivamidopropylamine oxide, palmitamidopropylamine oxide, palmitamine oxide, PEG-3 lauramine oxide, potassium dihydroxyethyl cocamine oxide phosphate, potassium trisphosphonomethylamine oxide, sesamidopropylamine oxide, soy amidopropylamine oxide , stearamidopropylamine oxide, stearamine oxide, tallow amidopropylamine oxide, tallow amine oxide, undecylenamidopropylamine oxide and wheat germanoamidopropylamine oxide.

[0086] Exemplary alkylamidoalkylamines are the following compounds mentioned according to the INCI nomenclature: cocobetainamido amphopropionate acid, DEA-caproamphodiacetate disodium, disodium, capryloamphodiacetate disodium, disodium, cocoamphocarboxyethyl-disodium, cocoamphodiacetate disodium, disodium, isostearoamphodiacetate disodium sodium, disodium isostearoamphodipropionate, laureth- 5 disodium carboxyanphodiacetate, disodium lauroamphodiacetate, disodium lauroamphodipropionate, disodium oleoamphodipropionate, PPG-2-isodeceth-7 disodium carboxyanphodiacetate, disodium stearoamphodiacetate, tallow disodium amphodiacetate, disodium wheat germanphodiacetate, 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 , lauroampho PG-acetate sodium phosphate, lauroamphopropionate sodium, niristoamphoacetate sodium, oleoamphoacetate sodium, Sodium oleoamphohydroxypropylsulfonate, sodium oleoamphopropionate, sodium ricinoleoamphoacetate, sodium stearoamphoacetate, sodium stearoamphohydroxypropylsulfonate, sodium stearoamphopropionate, sodium tallanphopropionate, sodium tallow amphoacetate, sodium undecyleneamphoacetate, sodium undecyleneamphopropionate, sodium germane amphoacetate and lauroampho PG-acetate trisodium phosphate chloride.

[0087] Exemplary alkyl-substituted amino acids are the following compounds mentioned according to the INCI nomenclature: aminopropyl laurylglutamines, cocaminobutyric acid, cocaminopropionic acid, DEA-lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium lauriminodipropionate, disodium steariminodipropionate dico, disodium tallowiminodipropionate, lauraminopropionic acid, lauryl aminopropylglycine, lauryl diethylenediaminoglycine, myristaminopropionic acid, C12-C15 sodium 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 agent compositions are selected from the group consisting of fatty alcohol polyglycolic ethers, alkylpolyglycosides, alkyl benzenesulfonates, alkanesulfonates, sulfates of alkyl ether, alkyl sulfates and quaternary ammonium compounds.

[0089] The proportion of one or more surface-active agents of component Z2) in the cleaning agent composition is preferably 0.1 to 20% by weight and particularly preferably 0.1 to 6.0% by weight , each based on the total weight of the cleaning agent composition.

Z3 Component)

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

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

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

Component Z4)

[0093] In the case of acids, these may be inorganic acids, for example, hydrochloric acid, sulfuric acid, nitric acid, amidosulfonic acid and/or phosphoric acid.

[0094] In a preferred embodiment of the invention, the acids contained 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 agent compositions contain an acid. In another preferred embodiment of the invention, the cleaning agent compositions contain a mixture of two or more acids.

[0095] The amount of acid used, when this is other than 0%, is preferably from 0.1 to 10% by weight, particularly preferably from 0.2 to 5% by weight and, in particular, preferably from 1 to 3% by weight, each based on the total weight of the cleaning agent composition.

[0096] In another preferred embodiment of the invention, to buffer the pH value a salt of an acid can also be added, in particular, the sodium, potassium or magnesium salt, but also other metal salts alkalies or alkaline earths or also 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 contained are used.

Component Z5)

[0097] Suitable complex formers are known to the person skilled in the art and described, for example, in DE-A-10 2009 001 559.

[0098] Complex formers (INCI Chelating Agents), also referred to as sequestrants, are constitutive substances, which are capable of complexing and inactivating metal ions, in order to prevent their disadvantageous effects on the stability or appearance of the agents, e.g. , turbidities. On the one hand, in this case, it is important to complex the calcium and magnesium ions of incompatible water hardness with numerous constituent substances. The complexation of heavy metal ions, such as iron or copper, on the other hand, delays the oxidative decomposition of ready-made agents. Furthermore, complex formers support the cleansing effect.

[0099] Suitable, for example, are the following complex formers designated in accordance with the INCI nomenclature: aminotrimethylene, phosphonic acid, 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 ic, aminotrimethylene pentasodium phosphonate, ethylenediamine tetramethylene pentasodium phosphonate, pentasodium pentetate, pentasodium triphosphate, pentetic acid, phytic acid, potassium citrate, potassium EDTMP, potassium gluconate, potassium polyphosphate, potassium trisphosphonomethylamine oxide, ribonic acid, chitosan sodium methylene phosphonate, sodium citrate sodium, diethylenetriamine sodium pentamethylene phosphonate, sodium dihydroxyethyl glycinate, sodium EDTMP, sodium gluceptate, sodium gluconate, sodium glycereth-1 polyphosphate, sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium phytate, sodium polydmethylglycinophenolsulfonate, 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, triss NTA sodium and trisodium phosphate.

[00100] The proportion of component Z5) in the cleaning agent composition, when this is different from 0%, is preferably 0.1 to 10% by weight, particularly preferably, 0.1 to 3.0% by weight and, in particular, preferably from 0.1 to 1.0% by weight, each based on the total weight of the cleaning agent composition.

Component Z6)

[00101] Suitable water-soluble solvents are known to the specialist and described, for example, in document US 2005/0239674. Preferably, alcohols, glycerin, glycols and glycol ether are used, preferably lower alcohols, such as ethanol, isopropanol, butanol, isobutanol or alkylene glycols, for example propylene glycol, as well as glycol ether, for example ethylene glycol-n-butyl ether or ether n-butyl propylene glycol.

[00102] In a preferred embodiment, mixtures of various solvents are used.

[00103] The proportion of component Z6) in the cleaning agent composition, when this is different from 0%, is preferably 0.1 to 10% by weight, particularly preferably, 0.1 to 3% by weight and, in particular, preferably from 0.5 to 1.5% by weight, based on the total weight of the cleaning agent composition.

Component Z7)

[00104] Suitable additives are other common constituent substances of cleaning agents, for example, disinfectants, pH regulating agents, dyes, aromas, buffers, viscosity regulators, corrosion inhibitors, organic and inorganic salts, optical brighteners, bleaches, antioxidants , opacifiers, hydrotropes, abrasives, preservatives, oxidizing agents and/or insecticides. Such additives are well known to the skilled person and described, for example, in document DE-A-10 2009 001 559.

[00105] According to the invention, bleach can be added to the composition of the cleaning agent. Suitable bleaches comprise peroxides, peracids and/or perborates, H2O2 is particularly preferred.

[00106] Cleaning agent compositions may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. These can be added to cleaning agent compositions in any form established by the state of the art. Liquid or gel compositions of cleaning agents include, in particular, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers. Alternatively, the enzymes may be encapsulated, for example, by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those, in which the enzymes are enclosed as 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. Other active substances can be additionally applied to overlapping layers, for example, stabilizers, emulsifiers, pigments, bleaches or dyes. Such capsules are applied by per se known methods, for example, by stirring or roller granulation or in fluid bed processes. Advantageously, such granules, for example, through the application of polymeric film formers, are dust-poor and due to the coating, are storage stable.

[00107] Furthermore, in cleaning agent compositions containing enzymes, enzyme stabilizers may be present in order to protect an enzyme contained in a cleaning agent composition against damage, such as, for example, inactivation, denaturation or decomposition, for example. example, through physical influences, oxidation or proteolytic dissociation. As enzyme stabilizers, each depending on the enzyme employed, are suitable in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, mainly derivatives with aromatic groups, for example substituted phenylboronic acids, respectively their salts or esters, peptide aldehydes (reduced C-terminal oligopeptides), aminoalcohols such as mono-, di-triethanol and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the aforementioned acids; fatty acid amidalkoxylates; lower aliphatic alcohols and mainly polyols, for example, glycerin, 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.

[00108] 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.

[00109] Suitable disinfectants and/or preservatives according to the invention are, for example, antimicrobial active substances from the group of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, derivatives of phenol, diphenyls, diphenylalkanes, urea derivatives, acetals as well as oxygen formals, nitrogen, benzamides, isothiazoles and their derivatives, such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactant compounds, guanidines, antimicrobial amphoteric compounds , quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial active substances 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'-methylen-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-yliden)-bis-(1-octanamine) dihydrochloride, N,N'-bis-(4-chlorophenyl)-3,12-diimino-2,4,11, 13-tetraazatetradecandiimidamide, antimicrobial quaternary surfactant compounds, guanidines. Quaternary surfactant compounds with antimicrobial action contain an ammonium, sulphonium, phosphonium, iodonium or arsone group, as described, for example, by K. H. Wallhausser in “Praxis der Sterilisation, Disinfektion - Konservierung: Keimidentifizierung - Betriebshygiene” (5th edition - Stuttgart; New York: Thieme, 1995).

[00110] The terms disinfection, sanitation, antimicrobial effect and antimicrobial active substance have, in the context of the invention, the usual technical meaning, which is reported by K. H. Wallhausser in “Praxis der Sterilisation, Disinfektion - Konservierung: Keimidentifizierung - Betriebshygiene” (5th edition - Stuttgart; New York: Thieme, 1995). While disinfection in the narrowest sense of medical practice means the death of - theoretically all - infection germs, by sanitation is to be understood the broadest possible elimination of all germs - also saprophytes normally harmless to humans -.

[00111] Polyacryl and polymethacryl compounds include, for example, homopolymers of high molecular weight acrylic acid cross-linked with a polyalkenyl polyether, in particular, with an allyl ether of sucrose, pentaerythritol or propylene (INCI nomenclature denomination of according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA): carbomer), which are also designated as carboxyvinyl polymers. Such polyacrylic acids can be obtained, among others, from the company 3V Sigma under the trade name Polygel®, e.g. Polygel® DA and from the company BF Goodrich under the trade name Carbopol®, e.g. Carbopol® 940 (molecular weight about 4,000 ,000), Carbopol® 941 (molecular weight of about 1,250,000) or Carbopol® 934 (molecular weight of about 3,000,000). Additionally, the following acrylic acid copolymers are included:

[00112] copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and simple esters, preferably formed with C1-4-alkanols (INCI acrylate copolymer), to which belong, for example, methacrylic acid copolymers, butyl acrylate and methyl methacrylate (CAS designation according to the Chemical Abstracts Service: 25035-69-2) or from butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which can be obtained, e.g. , by the company Rohm & Haas under the trade name Aculyn® and Acusol®, as well as by the company Degussa (Goldschmidt) under the trade name Tego® Polymer, for example, the non-associative anionic polymers Aculyn® 22, Aculyn® 28, Aculyn® 33 ( crosslinked), Acusol® 810 and Acusol® 823 and Acusol® 830 CAS 25852-37-3);

[00113] high molecular weight cross-linked acrylic acid copolymers, to which belong, for example, copolymers of C10-30-acryl acrylates cross-linked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the acrylic acid group , methacrylic acid and its simple esters, preferably formed with C1-C4-alkanols (INCI acrylate/C10C30-alkyl acrylate cropolymer) and which can be obtained, for example, from BF Goodrich under the trade name Carbopol®, for example, the hydrophobated Carbopol® ETD 2623 and Carbopol® 1382 (INCI acrylate/C10C30-alkyl acrylate cropolymer), as well as Carbopol® AQUA 30 (formerly Carbopol® EX 473).

[00114] Other thickeners are polysaccharides and heteropolysaccharides, in particular, polysaccharide gums, for example, gum arabic, agar, alginates, carrageenans and their salts, guar, guarana, gum, gellan, ramsan, dextran or xanthan and their derivatives , for example, propoxylated guar, 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, for example, starches of the most different origin and starch derivatives, for example, hydroxyethyl starch, ester of starch phosphate or starch acetates or carboxymethylcellulose or its sodium salt, methyl-, ethyl-, hydroxyethyl-, hydroxypropyl-, hydroxypropylmethyl- or hydroxyethylmethylcellulose or cellulose acetate.

[00115] A particularly preferred 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 106 and which can be obtained, for example, from the company Kelco under the trade name Keltrol® and Kelzan® or also by the company Rhodia under the trade name Rhodopol®.

[00116] Other layer silicates can be used as thickeners. These include, for example, magnesium or sodium-magnesium layer silicates, which can be obtained under the commercial name Laponite® from the company Solvay Alkali, in particular, Laponite® RD or also Laponite® RDS, as well as silicates of magnesium from the company Süd-Chemie, mainly Optigel® SH.

[00117] The amount of viscosity regulator, when it is different from 0%, is preferably up to 0.5% by weight, particularly preferably from 0.001 to 0.3% by weight, in particular preferably 0. 01 to 0.2% by weight and most preferably from 0.01 to 0.15% by weight, each based on the total weight of the cleaning agent composition. The viscosity of the cleaning agent composition is preferably 0.4 to 400 m.Pas.

[00118] Furthermore, cleaning agent compositions may contain one or more corrosion inhibitors.

[00119] Suitable corrosion inhibitors (INCI Corrosion Inhibitors) are, for example, the following substances mentioned according to the INCI nomenclature: cyclohexylamine, diammonium phosphate, dilithium oxalate, dimethylamino methylpropanol, dipotassium oxalate, dipotassium phosphate, phosphate disodium, 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 and triisopropanolamine.

[00120] Individual odorizing compounds can be used as aromas, for example, synthetic products such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Odorizing compounds of the ester type are, for example, benzyl acetate, phenoxyethylisobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styralyl propionate and benzyl salicylate. Ethers include, for example, benzylethyl ethers; -isomethylionone and methylcedrylketone, to alcohols anethole, citronellol, eugenol, geranion, linalool, phenylethyl alcohol and terpineol, to hydrocarbons belong mainly terpenes and balms. Preferably, mixtures of various odorants are used, which together produce an attractive fragrance.

[00121] Natural odorizing mixtures can also be used as aromas, such as are available from plant or animal sources, for example, pine cone, citrus, jasmine, lily, rose or Ylang-Ylang oil. Ethereal oils of lower volatility, which are mostly used as aromatic components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, peppermint oil, rosemary leaf oil. cinnamon, linden oil, juniper berry oil, vetiver oil, frankincense oil, galbanum oil and labdanum oil.

[00122] The amount of aromas in the cleaning agent compositions, when it is different from 0%, is preferably from 0.001 to 2% by weight and particularly preferably from 0.01 to 2% by weight, each with based on the total weight of the cleaning agent compositions.

[00123] The dyes and pigments optionally contained in the cleaning agent compositions, both organic and inorganic dyes, can be selected from the corresponding positive list of cosmetic regulations or the EG list of cosmetic dyes. Advantageously, pearlescent pigments are also used, for example, pearl (mixed crystals of guaninehypoxanthine from fish scales) and mother-of-pearl (crushed shell shells), monocrystalline pearlescent pigments, such as, for example, bismuth oxychloride (BiOCl) , layer substrate pigment, e.g. mica/metal oxide, white silver pearl luster pigments from TiO2, interference pigments (TiO2, different layer thickness), color luster pigments (Fe2O3) and combination (TiO2/Fe2O3, TiO2/Cr2O3, TiO2/Berlin blue, TiO2/carmine).

[00124] The amount of dyes and pigments in the cleaning agent compositions, when it is different from 0%, is preferably 0.01 to 1.0% by weight, based on the total weight of the cleaning agent compositions.

[00125] The proportion of component Z7) in the cleaning agent compositions, when this is different from 0%, is preferably from 0.01 to 10% by weight, particularly preferably, from 0.1 to 1% by weight and, in particular, preferably from 0.1 to 0.5% by weight, each based on the total weight of the cleaning agent compositions.

[00126] Preferably, the cleaning agent compositions contain Z1) 0.005 to 10.00% by weight of component Z1), Z2) 0.10 to 20.00% by weight of component Z2), Z3) 10, 00 to 99.8% by weight of component Z3), Z4) 0 to 10% by weight of component Z4), Z5) 0 to 10% by weight of component Z5), Z6) 0 to 10% by weight , of component Z6) and Z7) 0 to 10% by weight, of component Z7), each based on the total weight of the cleaning agent compositions.

[00127] Another object of the present invention is also cleaning agent compositions, which contain one or more copolymers according to the invention.

[00128] The copolymers according to the invention and the cleaning agent compositions according to the invention are advantageously suitable for producing shine on hard surfaces, preferably on hard surfaces made of plastic, ceramic, stone, etc. such as natural stone, porcelain, glass, wood, linoleum or metal such as, for example, stainless steel.

[00129] Another object of the present invention is therefore the use of one or more copolymers according to the invention, preferably in a cleaning agent composition according to the invention or in a cleaning agent composition according to the invention, for producing gloss on hard surfaces, preferably on hard surfaces of plastic, ceramic, stone, such as, for example, natural stone, porcelain, glass, wood, linoleum or metal, such as, for example, stainless steel .

[00130] The copolymers according to the invention and the cleaning agent compositions are also advantageously suitable for hydrophilizing hard surfaces, preferably hard surfaces made of plastic, ceramics, stone, such as, for example , natural stone, porcelain, glass, wood, linoleum or metal, such as, for example, stainless steel.

[00131] Another object of the present invention is therefore the use of one or more copolymers according to the invention, preferably in a cleaning agent composition according to the invention or in a cleaning agent composition according to the invention for the hydrophilization of a hard surface, preferably a hard surface of plastic, ceramics, stone, such as, for example, natural stone, porcelain, glass, wood, linoleum or metal, such as, for example, stainless steel.

[00132] The copolymers according to the invention and the cleaning agent compositions are also advantageously suitable for obtaining a repair effect on hard surfaces, preferably on hard surfaces made of plastic, ceramics, stone, such as, for example, natural stone, porcelain, glass, wood, linoleum or metal, such as, for example, stainless steel.

[00133] Another object of the present invention is therefore the use of one or more copolymers according to the invention, preferably in a cleaning agent composition according to the invention or in a cleaning agent composition according to the invention for obtaining a repair effect on a hard surface, preferably on a hard surface made of plastic, ceramics, stone, such as, for example, natural stone, porcelain, glass, wood, linoleum or metal, such as, for example example, stainless steel.

[00134] The preferred embodiments indicated above for the copolymers according to the invention also apply correspondingly to the cleaning agent compositions according to the invention and for the use according to the invention of the copolymers of according to the invention or cleaning agent compositions according to the invention, in particular for producing a gloss on hard surfaces, for hydrophilizing hard surfaces and for obtaining a repairing effect on hard surfaces.

[00135] Below, the invention is explained in detail through examples, without limiting it to them. Unless otherwise explicitly stated in the examples, the percentage data in the examples are to be understood as percent by weight (% by weight).

Examples

[00136] The following abbreviations are used:

Production of copolymers according to the invention General prescription for the production of copolymers according to the invention

[00137] In a multitubular flask equipped with a KPG agitator, reflux condenser and N2 connection, dissolve under nitrogen (5 liters/hour) for the examples indicated in table 1, for the production of copolymers according to the invention, the indicated amounts of chemicals (except the starter) in the indicated amount of distilled water. It should be noted that some of the substances used for the production of the copolymers according to the invention are used in aqueous form (see the instructions for the substances used for the production of the copolymers according to the invention). The distilled water indicated in the table is additionally added to the water introduced through these substances. In the case of acidic monomers, these are pre-neutralized with base, such as, for example, alkali metal carbonate, e.g. potassium carbonate. Then, the aqueous solution is rinsed for 30 minutes with nitrogen and heated to 60oC. In the next step, the amount of initiator (VA-44) indicated in table 1 is dissolved in 10 g of distilled water and added in batches over a period of 90 minutes. After dosing is complete, the mixture is post-stirred for a further hour at an internal temperature of 60oC. Through a subsequent analysis of the solid, the conversion of the reaction is tested and any unreacted monomers are optionally brought into the reaction through a small addition of an aqueous solution at 10% by weight, of the previously used initiator, until complete conversion is achieved. . Next, the reaction mixture is cooled to room temperature (20-23oC).

[00138] In table 1 the following synthesis examples are listed. Table 1: Substances used for the production of copolymers

[00139] The quantities indicated in table 1 refer to the active substance. Table 1a: Relative quantities according to table 1

[00140] Determination of average weight molecular weights Mw using GPC Description of the method Average weight molecular weights Mw measured for copolymers according to the invention are indicated in table 1.

Brightness intensity

[00141] Glossy, black ceramic tiles (10 x 10 cm) are pre-cleaned, and then about 10 drops of the cleaning agent composition are applied to the center of the tile. The cleaning agent composition is evenly distributed on the tile with the help of a folded cellulose towel. After the tiles have been vertically dry for at least 30 minutes, a visual assessment (grade 1 - 10) of the tiles takes place, with 1 being considered the best and 10 the worst grade.

[00142] Exemplary formulations with and without copolymer according to the invention were prepared and gloss tests were carried out with these formulations. Exemplary formulations and gloss results are shown in Table 2. Table 2 Exemplary formulations and gloss results

[00143] The results in table 2 show that through the use of the copolymers according to the invention in the exemplary formulations, better gloss results can be obtained compared to the corresponding exemplary formulations without the copolymer according to the invention.

[00144] Commercial cleaners were mixed with the copolymers according to the invention and gloss tests were carried out with the commercial cleaners with and without the copolymer according to the invention. The results are shown in table 3.

[00145] The results in Table 3 show that by using the copolymers according to the invention in commercial cleaners, better gloss results can be obtained compared to the corresponding commercial cleaners without adding a copolymer according to the invention.

Adsorption tests on hard surfaces

[00146] The tests took place with the QCM-D quartz crystal microbalance (in English “Quartz Crystal Microbalance with Dissipation Monitoring”, Q-Sense, Vastra Frolinda, Sweden). The process is based on a change in the frequency of a piezoelectric quartz crystal, as soon as it is charged with a mass. The quartz surface can be modified by spin-coating or vaporization. The oscillating quartz is located in a measuring cell. A flow cell serves as a measuring cell, into which the solution to be examined is pumped from storage containers. The pumping speed is kept constant during the measurement time. Typical pumping speeds are between 50-250 µl/minute. During a measurement, make sure that the hoses and measuring cells are free of air bubbles. Each measurement begins with recording the baseline, relative to which all frequency and dissipation measurement values are set to zero point. In this example, commercially obtained oscillating quartz crystals with a silicon dioxide coating with a thickness of 50 nm (QSX303, Q-Sense, Vastra Frolinda, Sweden) and oscillating quartz crystals with a stainless steel coating with a 50 nm thickness (SS2343) (QSX304, Q-Sense, Vastra Frolinda, Sweden).

[00147] Aqueous solutions of the copolymers according to the invention were examined with an active content of 2000 ppm. Tap water with 20o dH was used as water. The pH value was adjusted to pH 10 with NaOH or citric acid. Table 4 Adsorption of copolymers on silica:

[00148] The results in tables 4 and 5 show that the copolymers according to the invention are suitable for application on hard surfaces, as they adsorb on the inorganic surfaces examined.

Contact Angle Test

[00149] The contact angles are measured on different surfaces (ceramic, glass, stainless steel), where the surfaces were modified according to the following method: the surfaces were immersed three times for 2 minutes in fresh demineralized water (VE water ) and then, for modification, immersed for 20 minutes at room temperature with stirring in the respective aqueous copolymeric solution. The surfaces were then dried with a gentle stream of nitrogen. The contact angle was measured on surfaces prepared in this way with VE water (device: droplet analyzer from Krüss, Hamburg, model DSA 100).

[00150] The height of the contact angle of a water droplet on a surface is a measure for its hydrophilization. A very hydrophilic surface is completely wetted by a drop of water. This phenomenon is also referred to as droplet spreading.

[00151] The copolymers according to the invention were examined as an aqueous solution with an active content of 2000 ppm. Tap water with 20o dH was used as water. The pH value was adjusted to pH 10 with NaOH or citric acid. Table 6 Contact Angle on Black Ceramic Tile

[00152] The results of tables 6, 7 and 8 show that the copolymers according to the invention are suitable for reducing the water contact angle on inorganic surfaces (that is, for hydrophilizing inorganic surfaces).

Repair effect:

[00153] From the surface of a damaged black tile, before and after treatment with solutions of the copolymers according to the invention with an active content of 2000 ppm, the topography was determined (apparatus: surface characterization in 3D optics free of contact of the company Sensofar, Barcelona, model S neox). With the help of the MountainsMap software (Digital Surf SARL, Besancon, France) it is possible to observe different characteristic values in 3D by segmenting the topography of a surface into flat elements. These characteristic values provide alerts, among others, about height information (calculation takes place in accordance with ISO 25178) and roughness (calculation takes place in accordance with ISO 4287). Table 9 Roughness of a damaged black tile before and after copolymer treatment * changing the roughness of a black tile

[00154] The examinations clearly show the repair effect of the copolymers according to the invention.

Claims (19)

1. Copolymer, characterized by the fact that it is obtained 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 from the group consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride and (b) 1.0 to 50.0 mol% of one or more polyethylene glycol macromonomers, and (c) 15.0 to 74.0% in moles of one or more neutral acrylamide monomers, wherein one or more polyethylene glycol macromonomers of component (b) is or are selected from monomers of formula (IV) in which Rx is H or methyl, Z is C=O or O(CH2)4, l in the molar average is a number from 0 to 7, and p in the molar average is a number from 1 to 150. 2. Copolymer according to claim 1, characterized by the fact that Z is O(CH2)4. 3. Copolymer according to claim 1 or 2, characterized by the fact that p, on the molar average, is a number from 11 to 150. 4. Copolymer according to any one of claims 1 to 3, characterized by the fact that the one or more cationic (meth) acrylamide monomers of component (a) is or are selected from monomers of formula (I ) in which R1 is hydrogen or methyl. 5. Copolymer according to any one of claims 1 to 4, characterized in that the one or more cationic monomers of component (a) is or are selected from the group consisting of diallyldimethylammonium chloride and chloride of (3-methylamidopropyl)-trimethylammonium. 6. Copolymer according to any one of claims 1, 2, 4 and 5, characterized in that in formula (IV) (i) Rx is H, l = 0 and p, in the molar average, is a number from 1 to 150, when Z represents O(CH2)4, or (ii) Rx is H or methyl, l, in molar average, is a number from 1 to 7, and p, in molar average, is a number from 1 to 150, when Z represents C=O. 7. Copolymer according to any one of claims 1, 2, 4, 5 and 6, characterized in that the one or more polyethylene glycol macromonomers of component (b) is or are selected from the group consisting in monomers of formula (IV-A) in which pA in the molar average is a number from 1 to 150 and monomers of the formula (IV-B) in which B in the molar average represents a number from 1 to 7 and pB in the molar average represents a number from 1 to 150. 8. Copolymer according to claim 7, characterized in that pA, in the molar average, is a number from 11 to 120 and pB, in the molar average, is a number from 11 to 120. 9. Copolymer according to any one of claims 1 to 8, characterized in that the one or more neutral acrylamide monomers of component (c) is or are selected from the monomers of formula (III) in which R2 and R3 each may be the same or different and are each independently hydrogen and/or an aliphatic hydrocarbon radical with 1 to 20 carbon atoms. 10. Copolymer according to any one of claims 1 to 9, characterized in that the one or more neutral acrylamide monomers of component (c) is or are selected from the group consisting of acrylamide, N- ethylacrylamide, N,N-dimethylacrylamide, N-tert.-butylacrylamide and N-isopropylacrylamide. 11. Copolymer according to any one of claims 1 to 10, characterized in that the one or more neutral acrylamide monomers of component (c) is or are selected from the group consisting of N,N- dimethylacrylamide and N-isopropylacrylamide. 12. Copolymer according to any one of claims 1 to 11, characterized in that it is obtained from the radical copolymerization of at least components (a), (b) and (c), and in the copolymerization the component (a ) is used in an amount of 25.0 to 80.0% by mol, component (b) in an amount of 1.0 to 4.4% by mol, and component (c) in an amount of 15. 6 to 74.0 mol%. 13. Copolymer according to any one of claims 1 to 12, characterized in that the structural units from the polymerization of monomers (a), (b) and (c) and optionally from other monomers, are present in the copolymer in distribution statistical, block, alternative or gradient type. 14. Copolymer according to any one of claims 1 to 13, characterized by the fact that its average molecular weight Mw is 10,000 to 250,00 g/mol. 15. Cleaning agent composition, characterized by the fact that it comprises one or more copolymers as defined in any one of claims 1 to 14. 16. Use of one or more copolymers as defined in any one of claims 1 to 14, or of a cleaning agent composition as defined in claim 15, characterized in that it is for producing shine on hard surfaces. 17. Use of one or more copolymers as defined in any one of claims 1 to 14, or of a cleaning agent composition as defined in claim 15, characterized in that it is for the hydrophilization of a hard surface. 18. Use of one or more copolymers as defined in any one of claims 1 to 14, or of a cleaning agent composition as defined in claim 15, characterized in that it is for obtaining a repair effect on a hard surface . 19. Use according to any one of claims 16 to 18, characterized by the fact that hard surface is a hard surface of plastic, ceramic, stone, porcelain, glass, wood, linoleum or metal.