Cleaning agent compositions containing copolymer

Abstract

What are described are detergent compositions comprising one or more copolymers containing cationic structural units and macromonomeric structural units, and also one or more surfactants and water. The detergent compositions are especially suitable, in an advantageous manner, for producing shine on and imparting hydrophilic properties to the surface which has been treated with the detergent compositions.

Claims

1. A detergent composition comprising Z1) at least one copolymer containing a) 25.0 to 99.8 mol % of at least one cationic structural unit (A), b) 0.1 to 13.8 mol % of at least one macromonomeric structural unit (B), and c) at least one structural unit (C) which differs from the structural units (A) and (B), wherein the at least one cationic structural unit (A) is represented by the following formula (I): ##STR00016## in which R.sup.1a is hydrogen or a methyl radical, R.sup.1b is hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms or polyethylene glycol (PEG), X.sub.1 is a halogen atom, C.sub.1- to C.sub.4-alkylsulfate or C.sub.1- to C.sub.4-alkylsulfonate, and the at least one macromonomeric structural unit (B) is represented by the formula (III): ##STR00017## in which R.sup.x is the same or different and is represented by H and/or methyl, Z is O(CH.sub.2).sub.4, l on molar average is a number from 0 to 7, and p on molar average is a number from 1 to 150, and wherein the at least one structural unit (C) is the polymerization product of at least one monomer species selected from the group consisting of noncationic acrylamides, noncationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms and Z2) one or more surfactants and Z3) water, wherein the detergent composition comprises the at least one copolymer of component Z1) in an amount of 0.005% to 10% by weight, based in each case on the total weight of the detergent composition.

2. The detergent composition as claimed in claim 1, wherein the at least one cationic structural unit (A) of the at least one copolymer of component Z1) is the polymerization product of diallyldimethylammonium chloride (DADMAC).

3. The detergent composition as claimed in claim 1, wherein the at least one macromonomeric structural unit (B) of the formula (III) of the at least one copolymer of component Z1) is the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether and polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether.

4. The detergent composition as claimed in claim 1, wherein, in the at least one macromonomeric structural unit (B) of the formula (III) of the at least one copolymer of component Z1), R.sup.x is H, l=0 and p on molar average is a number from 1 to 150.

5. The detergent composition as claimed in claim 1, wherein the at least one copolymer of component Z1) contains 0.1 to 74.6 mol % of the at least one structural unit (C).

6. The detergent composition as claimed in claim 1, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) is selected from the group consisting of the polymerization product of at least one N-vinyl-substituted lactam having 5 to 7 ring atoms and the structural units of the following formulae (IV) and/or (V): ##STR00018## in which R.sup.1 is the same or different and is hydrogen and/or methyl, and R.sup.3 and R.sup.4 are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms, an alkylaryl radical having 7 to 14 carbon atoms, a branched or unbranched C.sub.1-C.sub.5-monohydroxyalkyl group and/or polyethylene glycol (PEG), ##STR00019## in which R.sup.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.sub.nH.sub.2n) with n=1, 2, 3 or 4; and R.sup.13 is the same or different and is represented by OH, N(CH.sub.3).sub.2, SO.sub.3H, PO.sub.3H.sub.2, O—PO.sub.3H.sub.2 and/or para-substituted C.sub.6H.sub.4—SO.sub.3H.

7. The detergent composition as claimed in claim 6, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) is selected from the structural units of the formula (IV).

8. The detergent composition as claimed in claim 1, wherein the at least one structural unit (C) of the at least one copolymer of component Z1) is the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tert-butylacrylamide.

9. The detergent composition as claimed in claim 1, wherein the at least one copolymer of component Z1), in addition to the structural units (A), (B) and (C), further contains at least one structural unit (D) which differs from the structural units (A), (B) and (C), and where the at least one copolymer contains 25.0 to 99.7 mol % of the at least one structural unit (A), 0.1 to 4.5 mol % of the at least one structural unit (B), 0.1 to 74.6 mol % of the at least one structural unit (C) and 0.1 to 24.6 mol % of the at least one structural unit (D).

10. The detergent composition as claimed in claim 9, wherein the at least one copolymer of component Z1) contains at least one structural unit (D) selected from the group consisting of structural units of the following formulae (IX) and/or (X): ##STR00020## in which R.sup.11 is the same or different and is represented by H and/or methyl; Z is the same or different and is represented by 0 and/or NH; ##STR00021## in which R.sup.11 is the same or different and is represented by H and/or methyl; Q is the same or different and is represented by 0 and/or NH; and R.sup.15 is the same or different and is represented by H, (C.sub.nH.sub.2n)—SO.sub.3H with n=0, 1, 2, 3 or 4; (C.sub.nH.sub.2n)—OH with n=0, 1, 2, 3 or 4; (C.sub.nH.sub.2n)—PO.sub.3H.sub.2 with n=0, 1, 2, 3 or 4; (C.sub.nH.sub.2n)—OPO.sub.3H.sub.2 with n=0, 1, 2, 3 or 4; (C.sub.6H.sub.4)—SO.sub.3H; (C.sub.6H.sub.4)—PO.sub.3H.sub.2; (C.sub.6H.sub.4)—OPO.sub.3H.sub.2 and/or (C.sub.mH.sub.2m).sub.e—O-(A′O).sub.u—R.sup.16 with m=0, 1, 2, 3 or 4, e=0, 1, 2, 3 or 4, A′=C.sub.x′H.sub.2x′ with x′=2, 3, 4 or 5, u=an integer from 1 to 350 and R.sup.16 is the same or different and is represented by an unbranched or branched C.sub.1-C.sub.4-alkyl group.

11. The detergent composition as claimed in claim 1, wherein the structural units (A), (B) and (C) of the at least one copolymer of component Z1) are present in the copolymer in a random, blockwise, alternating or gradient distribution.

12. The detergent composition as claimed in claim 1, wherein the weight average molecular weight M.sub.w of the at least one copolymer of component Z1) is from 10 000 to 250 000 g/mol.

13. The detergent composition as claimed in claim 1, which comprises the at least one copolymer of component Z1) in an amount of 0.01% to 5% by weight, based in each case on the total weight of the detergent composition.

14. The detergent composition as claimed in claim 1, wherein the at least one surfactant of component Z2) is selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants.

15. The detergent composition as claimed in claim 14, wherein the at least one surfactant of component Z2) is selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates and quaternary ammonium compounds.

16. The detergent composition as claimed in claim 1, wherein the proportion of the at least one surfactant of component Z2) in the detergent composition is from 0.1% to 20% by weight, based in each case on the total weight of the detergent composition.

17. The detergent composition as claimed in claim 1, which further comprises, at least one substance selected from the group consisting of components Z4), Z5), Z6) and/or Z7): Z4) at least one inorganic or organic acid as component Z4), Z5) at least one complexing agent as component Z5), Z6) at least one solvent other than water as component Z6), Z7) at least one further additive, and wherein the pH of the detergent composition is from 1 to 14.

18. The detergent composition as claimed in claim 17, which comprises 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), based in each case on the total weight of the detergent composition.

19. A method for treatment of a hard surface, comprising the step of contacting the hard surface with a detergent composition as claimed in claim 1.

20. The method as claimed in claim 19, wherein the contacting the hard surface with the detergent composition imparts hydrophilic properties to the hard surface.

21. The method as claimed in claim 19, wherein the contacting the hard surface with the detergent composition produces shine on the hard surface.

22. The method as claimed in claim 19, wherein the contacting the hard surface with the detergent composition decreases a surface roughness of the hard surface.

23. A method of treating or cleaning a hard surface, which comprises the step of contacting the hard surface with at least one copolymer as defined in claim 1.

24. The detergent composition as claimed in claim 1, wherein the at least one copolymer of component Z1) contains b) 0.1 to 4.5 mol % of the at least one macromonomeric structural unit (B).

25. The detergent composition as claimed in claim 1, wherein the at least one copolymer of component Z1) contains a) 25.0 to 80.0 mol % of the at least one cationic structural unit (A), b) 0.4 to 4.5 mol % of the at least one macromonomeric structural unit (B), and c) 15.5 to 74.6 mol % of the at least one structural unit (C).

26. A detergent composition comprising Z1) at least one copolymer consisting of a) 25.0 to 99.8 mol % of at least one cationic structural unit (A), b) 0.1 to 13.8 mol % of at least one macromonomeric structural unit (B), and c) at least one structural unit (C) which differs from the structural units (A) and (B), wherein the at least one cationic structural unit (A) is represented by the following formulae (I) and/or (II): ##STR00022## in which R.sup.1 and R.sup.1a are each the same or different and are each independently hydrogen and/or a methyl radical, R.sup.1b, R.sup.3, R.sup.4 and R.sup.5 are each the same or different and are each independently represented by hydrogen, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbyl radical having 5 to 20 carbon atoms, an aryl radical having 6 to 14 carbon atoms and/or polyethylene glycol (PEG), Y is the same or different and is represented by oxygen, NH and/or NR.sup.3, V is the same or different and is represented by —(CH.sub.2).sub.x—, ##STR00023## x is the same or different and is represented by an integer from 1 to 6, X and X.sub.1 are each the same or different and are each independently represented by a halogen atom, C.sub.1- to C.sub.4-alkylsulfate and/or C.sub.1- to C.sub.4-alkylsulfonate, and the at least one macromonomeric structural unit (B) is represented by the formula (III): ##STR00024## in which R.sup.x is the same or different and is represented by H and/or methyl, Z is O(CH.sub.2).sub.4, on molar average is a number from 0 to 7, and p on molar average is a number from 1 to 150, and wherein the at least one structural unit (C) is the polymerization product of at least one monomer species selected from the group consisting of noncationic acrylamides, noncationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms and Z2) one or more surfactants and Z3) water, wherein the detergent composition comprises the at least one copolymer of component Z1) in an amount of 0.005% to 10% by weight, based in each case on the total weight of the detergent composition.

27. The detergent composition as claimed in claim 26, wherein the at least one copolymer of component Z1) contains b) 0.1 to 4.5 mol % of the at least one macromonomeric structural unit (B).

28. The detergent composition as claimed in claim 26, wherein the at least one copolymer of component Z1) contains a) 25.0 to 80.0 mol % of the at least one cationic structural unit (A), b) 0.4 to 4.5 mol % of the at least one macromonomeric structural unit (B), and c) 15.5 to 74.6 mol % of the at least one structural unit (C).

Description

EXAMPLES

(1) The following abbreviations are used:

(2) TABLE-US-00001 AAPTAC [3-(acryloylamino)propyl]trimethylammonium chloride (75% by weight active in aqueous solution) AMPS Na salt 2-acryloylamino-2-methylpropanesulfonic acid, Na salt (50% by weight active in aqueous solution) DADMAC diallyldimethylammonium chloride (65% by weight active in aqueous solution) DMAA N,N-dimethylacrylamide (100% active) MAPTAC [3-(methacryloylamino)propyl]trimethylammonium chloride (50% by weight active in aqueous solution) MESNA sodium 2-mercaptoethanesulfonate (100% active) Meth 1000 polyethylene glycol-co-polypropylene glycol methacrylate, 1000 g/mol, 4-5 propylene glycol units (70% by weight active in aqueous solution) Meth 5000 polyethylene glycol-co-polypropylene glycol methacrylate, 5000 g/mol, 4-5 propylene glycol units (50% by weight active in aqueous solution) MA Na salt maleic acid, Na salt (100% active) NIPAM N-isopropylacrylamide (100% active) NVP N-vinylpyrrolidone (100% active) VA-44 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (100% active) V-PEG 1100 polyethylene glycol vinyloxybutyl ether, 1100 g/mol (100% active) V-PEG 5000 polyethylene glycol vinyloxybutyl ether, 5000 g/mol (100% active)
Preparation of the Copolymers
General Method for Preparation of the Copolymers

(3) In a multineck flask equipped with a precision glass stirrer, reflux condenser and N.sub.2 connection, under nitrogen (5 liters/hour), for the examples cited in table 1 for preparation of copolymers of component Z1), the stated amounts of chemicals (excluding the initiator) are dissolved in the stated amount of distilled water. It should be noted that some of the substances used for preparation of the copolymers of component Z1) are used in aqueous form (see the details given for the substances used for the preparation of the copolymers of component Z1)). The distilled water specified in table 1 is added in addition to the water introduced via these substances. In the case of acidic monomers, these are pre-neutralized with base, for example alkali metal carbonate, e.g. potassium carbonate. Subsequently, the aqueous solution is purged with nitrogen for 30 minutes and heated to 60° C. if VA-44 is used as initiator, or to 80° C. if Na.sub.2S.sub.2O.sub.8 is used as initiator. In the next step, the amount of initiator specified in table 1 (VA-44 or Na.sub.2S.sub.2O.sub.8) is dissolved in 10 g of distilled water and metered in over a period of 90 minutes. After the metered addition has ended, stirring is continued for a further hour at an internal temperature of 60° C. if VA-44 is used as initiator, or at an internal temperature of 80° C. if Na.sub.2S.sub.2O.sub.8 is used as initiator. The conversion of the reaction is checked by a subsequent analysis of the solids, and any unconverted monomers, if necessary, are reacted via a small addition of a 10% by weight aqueous solution of the initiator already used beforehand until full conversion has been attained. Thereafter, the reaction mixture is cooled down to room temperature (20-23° C.).

(4) Table 1 lists synthesis examples for copolymers of component Z1) of the detergent compositions of the invention.

(5) TABLE-US-00002 TABLE 1 Substances used for preparation of the copolymers Co- V-PEG V-PEG Meth Meth polymer 1100 5000 1000 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC No. [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] 1 — 4.816 — — 32.985 80.064 — — — 2 — 4.816 — — 32.985 — 91.395 — — 3 — 4.816 — — — — 22.899 — 61.294 4 — 4.816 — — — — 22.899 83.755 — 5 — 4.816 — — — 20.060 — — 61.294 6 — 4.816 — — — — 57.198 — 46.163 7 — 4.816 — — — 80.064 — — 30.760 10 — 4.816 — — — 50.000 — — 46.000 11 — 4.816 — — — 80.064 — — 30.760 12 29.809 — — — — 14.758 — — 25.777 13 29.809 — — — — 14.758 — — 25.777 14 — — —  8.750 30.328 55.232 — — — 15 — — 34.370 — 30.328 55.232 — — — 16 — — 49.994 — 27.670 14.758 — — — 17 — — — 10.000 28.034 — — — — 18 — — —  6.794 27.670 14.758 — — — 19 — 4.816 — — — — 91.395 — 30.760 20 — 4.816 — — — — 91.395 — 30.760 Co- AMPS MA Na Na hypo- polymer NVP Na salt salt phosphite MESNA VA-44 Na.sub.2S.sub.2O.sub.8 dist. H.sub.2O M.sub.w No. [mmol] [mmol] [mmol] [g] [g] [g] [g] [g] [g/mol] 1 — — — 0.120 — 1.560 — 149.450 39284 2 — — — 0.120 — 1.560 — 149.450 36396 3 — — — — — 1.560 — 136.000 42261 4 — — — — — 1.560 — 142.250 10934 5 — — — — — 1.560 — 136.000 6 — — — — — 1.560 — 139.500 102330 7 — — — 0.120 — 1.560 — 144.860 35849 10 — — — — — 1.560 — 697.500 91934 11 — — — — — 1.560 — 724.300 12 — — — 0.120 — 1.560 — 80.000 13 — — — — — 1.560 — 149.500 14  56.235 — — — 0.180 1.560 — 131.670 15 140.543 — — — 0.540 1.560 — 160.700 16 — — — — 0.180 1.560 — 138.780 17 — 9.989 — — 0.180 1.560 — 105.000 18 — — — — 0.180 — 1.150 162.790 19 — — — 0.120 — 1.560 — 149.450 20 — — 1.090 — — 1.560 — 149.450 The amounts stated in table 1 are based on the active substance.

(6) TABLE-US-00003 TABLE 1a Relative amounts according to table 1 Total amount of the Structural Structural Structural Structural Copoly- monomers used units (A) units (B) units (C) units (D) mer No. [mmol] [mol %] [mol %] [mol %] [mol %] 1 117.865 28.0 4.1 67.9 — 2 129.196 25.5 3.7 70.7 — 3 89.009 68.9 5.4 25.7 — 4 111.470 75.1 4.3 20.5 — 5 86.170 71.1 5.6 23.3 — 6 108.177 42.7 4.5 52.9 — 7 115.640 26.6 4.2 69.2 — 10 100.816 45.6 4.8 49.6 — 11 115.640 26.6 4.2 69.2 — 12 70.344 36.6 42.4 21.0 — 13 70.344 36.6 42.4 21.0 — 14 150.545 20.1 5.8 74.0 — 15 260.473 11.6 13.2 75.2 — 16 92.422 29.9 54.1 16.0 — 17 48.023 58.4 20.8 20.8 — 18 49.222 56.2 13.8 30.0 — 19 126.971 24.2 3.8 72.0 — 20 128.061 24.0 3.8 71.4 0.9
Determination of the weight-average molecular weights M.sub.w by GPC:
Method description:

(7) TABLE-US-00004 Column: PSS NOVEMA MAX Guard, 1 × 30 Å & 2 × 1000 Å 10 μm, 300 mm × 8 mm Detector: RI Oven temperature: 25° C. Flow rate: 1 mL/minute Injection volume: 50 μL Eluent: 79.7% by vol. of 0.1M NaCl + 0.3% by vol. of TFA (trifluoroacetic acid) + 20.0% by vol. of ACN (acetonitrile) Calibration method: conventional calibration Standards: poly(2-vinylpyridine) in the range from 1110 to 1 060 000 daltons

(8) Measured weight-average molecular weights for copolymers of component Z1) of the detergent compositions of the invention are reported in table 1.

(9) Shining Capacity

(10) Black, shiny ceramic tiles (10×10 cm) are subjected to preliminary cleaning and then about 10 drops of the detergent composition are applied to the middle of the tiles. The detergent composition is distributed homogeneously on the tile with the aid of a folded cellulose kitchen towel. Once the tiles have dried vertically for at least 30 minutes, a visual assessment of the tiles is made with grades from 1 to 10, with 1 being the best and 10 the worst grade.

(11) Example formulations were produced with and without copolymer of component Z1) of the detergent compositions of the invention and these formulations were used to conduct shine tests. The example formulations and shine results are shown in table 2.

(12) TABLE-US-00005 TABLE 2 Example formulations and shine results Detergent composition A B C D E F G H C11 alcohol ethoxylate 4.0 2.5 4.5 4.0 2.5 4.5 1.0 — [% by wt.] Propylene glycol butyl 1.0 0.6 0.5 1.0 0.6 0.5 — — ether [% by wt.] Alkyl polyglucoside — 1.0 — — 1.0 — — — [% by wt.] Sodium — — — — — — 2.0 0.5 alkylbenzenesulfonate [% by wt.] Lactic acid — — — — — — 1.5 — [% by wt.] Dipropylene glycol — — — — — — —  0.25 monobutyl ether [% by wt.] Ammonium hydroxide — — — — — — — 0.3 [% by wt.] Benzalkonium chloride — 0.4 — — 0.4 — — — [% by wt.] Isopropanol — — — — — — — 7.0 [% by wt.] Water ad ad ad ad ad ad ad ad [% by wt.] 100 100 100 100 100 100 100 100 pH (adjusted with 7   7   7   10   10   10   3.4 11.3  NaOH or citric acid) Visual assessment No additive 6.3 2.5 10.0  9.2 3.0 10.0  10.0  7.0 +0.2% by wt. of 2.0 2.0 2.0 1.7 2.0 2.0 — — copolymer 1 +0.2% by wt. of 2.0 — — 2.7 — — — — copolymer 2 +0.2% by wt. of 3.0 — — 3.0 — — — — copolymer 3 +0.2% by wt. of 3.3 — — 2.3 — — — 1.3 copolymer 4 +0.2% by wt. of 2.0 — — 2.7 — — — — copolymer 5 +0.2% by wt. of — — — — — — 3.7 2.0 copolymer 6

(13) The results in table 2 show that the use of the copolymers of component Z1) in the example formulations achieves better shine results compared to the corresponding example formulations without copolymer of component Z1).

(14) Copolymers 7 and 10-20 were used to produce detergent compositions in an analogous manner.

(15) Copolymers of component Z1) of the detergent compositions of the invention were added to commercially available cleaning products, and shine tests were conducted with the commercially available cleaning products with and without copolymer. The results are shown in Table 3.

(16) TABLE-US-00006 TABLE 3 Use of copolymers in commercially available cleaning products Commercially Commercially Commercially available available available cleaning cleaning cleaning product 1 product 2 product 3 All-purpose Bathroom Cleaning Cleaning product cleaning spray cleaning spray spray pH 11 2.9 2.5 No additive 10 6.3 5.3 +0.2% by wt. of 2.0 1.0 1.0 copolymer 6 +0.2% by wt. of 2.0 1.0 2.7 copolymer 4

(17) Table 3 shows that the use of the copolymers of component Z1) of the detergent compositions of the invention in commercially available cleaning products can achieve better shine results compared to the corresponding commercially available cleaning products without addition of a copolymer of component Z1).

(18) Adsorption Tests on Hard Surfaces

(19) The tests were effected with the QCM-D Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Västra Frölinda, Sweden. The method is based on the change in the intrinsic frequency of a piezoelectric quartz crystal as soon as it is loaded with a mass. The surface of the crystal may be modified by spin-coating or vapor deposition. The crystal oscillator is within a test cell. The test cell used is a flow cell into which the solution to be examined is pumped from reservoir vessels. The pumping rate is kept constant during the measurement time. Typical pumping rates are between 50-250 μL/minute. During a measurement, it should be ensured that the hoses and test cell are free of air bubbles. Each measurement begins with the recording of the baseline, which is set as the zero point for all frequency and dissipation measurements. In this example, commercially available crystal oscillators having a 50 nm-thick silicon dioxide coating (QSX303, Q-Sense, Västra Frölinda, Sweden) and crystal oscillators having a 50 nm-thick stainless steel (SS2343) coating (QSX304, Q-Sense, Västra Frölinda, Sweden) were used.

(20) Aqueous solutions of the copolymers of component Z1) of the detergent compositions of the invention with an active content of 2000 ppm were examined. The water used was tapwater of 20° dH (German hardness). The pH was adjusted to pH 10 with NaOH or citric acid.

(21) TABLE-US-00007 TABLE 4 Adsorption of the copolymers on silica: Copolymer No. Mass adsorbed [ng/cm.sup.2] 5 264.4 3 275.9 6 355.8 4 142.5 7 348.0 19 102.7 20 330.4

(22) TABLE-US-00008 TABLE 5 Adsorption of the copolymers on stainless steel: Copolymer No. Mass adsorbed [ng/cm.sup.2] 5 129.7 3 153.6 19 121.0 20 156.6

(23) The results of tables 4 and 5 show that the copolymers of component Z1) of the detergent compositions of the invention are suitable for use on hard surfaces, since these are adsorbed on the inorganic surfaces examined.

(24) Contact Angle Test

(25) The contact angles were measured on various surfaces (ceramic, glass, stainless steel) by modifying the surfaces by the following method: The surfaces were immersed three times into fresh demineralized water (DM water) for 2 minutes and then, for modification, immersed into the particular aqueous copolymer solution at room temperature while stirring for 20 minutes. Thereafter, the surfaces were dried with a gentle nitrogen stream. The contact angle was measured on the surfaces thus prepared with DM water (apparatus: DSA 100 droplet analyzer from Krüss, Hamburg).

(26) The magnitude of the contact angle of a water droplet on a surface is a measure of the hydrophilization thereof. A very hydrophilic surface is fully wetted by a water droplet. This phenomenon is also referred to as spreading of the droplet.

(27) Copolymers of component Z1) of the detergent compositions of the invention were examined in the form of an aqueous solution with an active content of 2000 ppm. The water used was tapwater of 20° dH (German hardness). The pH was adjusted to pH 10 with NaOH or citric acid.

(28) TABLE-US-00009 TABLE 6 Contact angle on black ceramic tiles Copolymer No. Contact angle of water Untreated 18°  5 8° 3 droplet spreads 6   4.2° 4 15°  7 5° 19 droplet spreads 20 droplet spreads

(29) TABLE-US-00010 TABLE 7 Contact angle on glass Copolymer No. Contact angle of water Untreated 39° 6 droplet spreads 4 droplet spreads 7 droplet spreads

(30) TABLE-US-00011 TABLE 8 Contact angle on steel Copolymer No. Contact angle of water untreated 15° 5 droplet spreads 3 droplet spreads 19  8° 20 13°

(31) The results from tables 6, 7 and 8 show that the copolymers of component Z1) of the detergent compositions of the invention are suitable for reducing the contact angle of water on inorganic surfaces (i.e. of hydrophilizing inorganic surfaces).

(32) Repair Effect

(33) The topography of the surface of a damaged black tile was determined before and after treatment with aqueous solutions of the copolymers of component Z1) of the detergent compositions of the invention having an active content of 2000 ppm (apparatus: contactless optical 3D surface characterization system from Sensofar, Barcelona, model: S neox). With the aid of the MountainsMap software (Digital Surf SARL, Besancon, France), by segmentation of the topography of a surface into area elements, various 3D parameters can be calculated. These parameters give information about aspects including height information (calculation effected according to ISO 25178) and roughness (calculation effected according to ISO 4287).

(34) TABLE-US-00012 TABLE 9 Roughness of a black damaged tile before and after copolymer treatment Roughness untreated Roughness after treatment Copolymer No. [nm] [nm] 3  71*  36* 6 140   94.6 4 110 108  7  86 85 *Change in the roughness of a black tile

(35) The studies clearly show the repair effect of the copolymers of component Z1) of the detergent compositions of the invention.