Copolymers and the use of same in cleaning agent compositions

Abstract

What are described are copolymers containing cationic structural units and macromonomeric structural units. The copolymers are, for example, advantageously suitable for use in detergent compositions and lead to advantageous shine results, for example, after application on hard surfaces.

Claims

1. A copolymer containing a) 15.0 to 84.5 mol % of at least one cationic structural unit (A), b) 1.0 to 4.5 mol % of at least one macromonomeric structural unit (B), and c) at least one structural unit (C), other than 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), and X.sub.1 is a halogen atom, C.sub.1- to C.sub.4-alkylsulfate or C.sub.1- to C.sub.4-alkylsulfonate, 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 the at least one structural unit (C) is/are 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.

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

3. The copolymer as claimed in claim 1, wherein the at least one macromonomeric structural unit (B) of the formula (III) is the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether in which l on molar average is a number from 1 to 7.

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

5. The copolymer as claimed in claim 1, which contains 0.1 to 74.0 mol % of at least one structural unit (C) other than the structural units (A) and (B).

6. The copolymer as claimed in claim 1, which contains the at least one cationic structural unit (A) in proportions of 23.0 to 79.0 mol %, the at least one macromonomeric structural unit (B) in proportions of 1.0 to 4.4 mol %, and the at least one structural unit (C) in proportions of 20.0 to 74.0 mol %.

7. The copolymer as claimed in claim 1, wherein the at least one structural unit (C) is/are 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, 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.

8. The copolymer as claimed in claim 7, wherein the at least one structural unit (C) is/are selected from the structural units of the formula (IV).

9. The copolymer as claimed in claim 1, wherein the at least one structural unit (C) is/are 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.

10. The copolymer as claimed in claim 1, which contains, in addition to the structural units (A), (B) and (C), at least one structural unit (D) other than the structural units (A), (B) and (C).

11. The copolymer as claimed in claim 10, which contains at least one structural unit (D) selected from the group consisting of the 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 O 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 O 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, where the structural units of the formula (X) may also be in salt form.

12. The copolymer as claimed in claim 1, wherein the structural units (A), (B) and (C) are present in the copolymer in a random, blockwise, alternating or gradient distribution.

13. The copolymer as claimed in claim 1, having a weight-average molecular weight M.sub.w, determined by means of GPC with poly(2-vinylpyridine) as standard, of from 10 000 to 250 000 g/mol.

14. A detergent composition, which comprises at least one copolymer as claimed in claim 1.

15. A method for producing shine on hard surfaces, comprising the step of contacting the hard surface with at least one composition comprising at least one copolymer as claimed in claim 1.

16. A method comprising the step of contacting the hard surface with at least one composition comprising at least one copolymer as claimed in claim 1.

17. The copolymer as claimed in claim 10, wherein the structural units (A), (B), (C) and (D) are present in the copolymer in a random, blockwise, alternating or gradient distribution.

18. The copolymer as claimed in claim 8, wherein p is in the range of 12-150.

19. The copolymer as claimed in claim 18, wherein R.sup.1b is methyl.

20. A copolymer consisting of: a) 15.0 to 84.5 mol % of at least one cationic structural unit (A), b) 1.0 to 4.5 mol % of at least one macromonomeric structural unit (B), and c) at least one structural unit (C), other than 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 is 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, and 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, 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, l on molar average is a number from 0 to 7, and p on molar average is a number from 1 to 150, and the at least one structural unit (C) is/are 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.

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) 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 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, sodium 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 5000 polyethylene glycol vinyloxybutyl ether 5000 g/mol (100% active)
Preparation of the Copolymers of the Invention

(3) General method for preparation of the copolymers of the invention: 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 the invention, 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 the invention are used in aqueous form (see the details given for the substances used for the preparation of the copolymers of the invention). 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. In the next step, the amount of initiator specified in table 1 (VA-44) 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 at an internal temperature of 60° C. for a further hour. 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 of copolymers of the invention.

(5) TABLE-US-00002 TABLE 1 Substances used for preparation of the copolymers Na Co- hypo- poly- V-PEG Meth MA Na phos- dist. mer 5000 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC NVP salt phite MESNA VA-44 H.sub.2O Mw No. [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [g] [g] [g] [g] [g/mol] 1 4.816 — 32.985 80.064 — — — — — 0.120 — 1.560 149.450 39284 2 4.816 — 32.985 — 91.395 — — — — 0.120 — 1.560 149.450 3 4.816 — — — 22.899 83.755 — — — — — 1.560 142.250 6 4.816 — — — 57.198 — 46.163 — — — — 1.560 139.500 7 4.816 — — 80.064 — — 30.760 — — 0.120 — 1.560 144.860 35849 11 4.816 — — 80.064 — — 30.760 — — — — 1.560 724.300 118920 16 — 6.875 15.146 69.017 — — — 154.580 — — 0.540 1.560 142.100 18 — 6.874 30.328 55.232 — — — 140.543 — — 0.540 1.560 141.060 19 — 4.816 — 80.064 — 42.015 — — — — 0.180 1.560 99.070 20 — 4.816 — 80.064 — 42.015 — — — — 0.360 1.560 99.070 21 — 4.816 — 80.064 — 42.015 — — — — 0.540 1.560 99.070 22 4.816 — — — 91.395 — 30.760 — — 0.120 — 1.560 149.450 23 4.816 — — — 91.395 — 30.760 — 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 Co- of the Structural Structural Structural Structural polymer monomers used units (A) units (B) units (C) units (D) No. [mmol] [mol %] [mol %] [mol %] [mol %] 1 117.865 28.0 4.1 67.9 — 2 129.196 25.5 3.7 70.7 — 3 111.470 75.1 4.3 20.5 — 6 108.177 42.7 4.5 52.9 — 7 115.640 26.6 4.2 69.2 — 11 115.640 26.6 4.2 69.2 — 16 245.618 6.2 2.8 91.0 — 18 232.977 13.0 3.0 84.0 — 19 126.895 33.1 3.8 63.1 — 20 126.895 33.1 3.8 63.1 — 21 126.895 33.1 3.8 63.1 — 22 126.971 24.2 3.8 72.0 — 23 128.061 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 M.sub.w for copolymers 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 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 Cleaning product 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 alkylbenzenesulfonate — — — — — — 2.0 0.5 [% by wt.] Lactic acid [% by wt.] — — — — — — 1.5 — Dipropylene glycol monobutyl — — — — — — —  0.25 ether [% by wt.] Ammonium hydroxide — — — — — — — 0.3 [% by wt.] Benzalkonium chloride — 0.4 — — 0.4 — — — [% by wt.] Isopropanol [% by wt.] — — — — — — — 7.0 Water [% by wt.] ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 pH (adjusted with NaOH or 7   7   7   10   10   10   3.4 11.3  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 copolymer 1 2.0 2.0 2.0 1.7 2.0 2.0 +0.2% by wt. of copolymer 2 2.0 2.7 +0.2% by wt. of copolymer 3 3.3 2.3 1.3 +0.2% by wt. of copolymer 6 3.7 2.0

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

(14) Copolymers 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.

(15) 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 weight of 2.0 1.0 1.0 copolymer 6 +0.2% by weight of 2.0 1.0 2.7 copolymer 3

(16) Table 3 shows that the use of the copolymers 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 the invention.

(17) Adsorption Tests on Hard Surfaces

(18) The tests were effected with the QCM-D Quartz 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.

(19) 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 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] 6 355.8 3 142.5 7 348.0 22 102.7 23 330.4

(22) TABLE-US-00008 TABLE 5 Adsorption of the copolymers on stainless steel Copolymer No. Mass adsorbed [ng/cm.sup.2] 22 121.0 23 156.6

(23) The results of tables 4 and 5 show that the copolymers 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 the invention were examined in the form of an aqueous solution having 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° 6 4.2°  3 15° 7  5° 22  droplet spreads 23  droplet spreads

(29) TABLE-US-00010 TABLE 7 Contact angle on glass Copolymer No. Contact angle of water Untreated 39° 6 droplet spreads 3 droplet spreads 7 droplet spreads

(30) TABLE-US-00011 TABLE 8 Contact angle on steel Copolymer No. Contact angle of water untreated 15° 22  8° 23 13°

(31) The results from tables 6, 7 and 8 show that the copolymers of the invention are suitable for reducing the contact angle of water on inorganic surfaces (i.e. suitable for 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 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 indices 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 after Roughness untreated treatment Copolymer No. [nm] [nm] 6 140 94.6 3 110 108 7 86 85 * Change in the roughness of a black tile

(35) The studies clearly show the repair effect of the copolymers of the invention.