COPOLYMERS AND USE THEREOF IN CLEANING-AGENT COMPOSITIONS

Abstract

What are described are copolymers obtainable from the free-radical copolymerization at least of 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) uncharged acrylamide monomers.

The copolymers are advantageously suitable, for example, for use in detergent compositions and lead to advantageous shine results, for example, after application on hard surfaces.

Claims

1. A copolymer obtainable from the free-radical copolymerization at least of components a), b) and c) a) 25.0 to 80.0 mol % of at least one cationic monomer selected from the group consisting of cationic (meth)acrylamide monomers and diallyldimethylammonium chloride, and b) 0.1 to 50.0 mol % of at least one polyethylene glycol macromonomer, and c) 15.0 to 74.9 mol % of at least one uncharged acrylamide monomer.

2. The copolymer as claimed in claim 1, wherein the at least one cationic (meth)acrylamide monomer of component a) is/are selected from the group consisting of monomers of the formula (I) ##STR00013## in which R1 is hydrogen or methyl.

3. The copolymer as claimed in claim 1, wherein the at least one cationic monomer of component a) is/are selected from the group consisting of diallyldimethylammomium chloride and (3-methacrylamidopropyl)trimethylammonium chloride.

4. The copolymer as claimed in claim 1, wherein the at least one polyethylene glycol macromonomer of component b) is/are selected from the group consisting of monomers of the formula (IV)
H.sub.2CCR.sup.xZO(C.sub.3H.sub.6O).sub.I(CH.sub.2CH.sub.2O).sub.pH (IV) in which R.sup.x is H or methyl, Z is CO or O(CH.sub.2).sub.4, I on molar average is a number from 0 to 7, and p on molar average is a number from 1 to 150.

5. The copolymer as claimed in claim 4, wherein in formula (IV) i) R.sup.x is H, IO and p on molar average is a number from 1 to 150 when Z is O(CH.sub.2).sub.4 or ii) R.sup.x is H or methyl, I on molar average is a number from 1 to 7, and p on molar average is a number from 1 to 150 when Z is CO.

6. The copolymer as claimed in claim 1, wherein the at least one polyethylene glycol macromonomer of component b) is/are selected from the group consisting of monomers of the formula (IV-A) ##STR00014## in which pA on molar average is a number from 1 to 150, and monomers of the formula (IV-B) ##STR00015## in which IB on molar average is a number from 1 to 7 and pB on molar average is a number from 1 to 150.

7. The copolymer as claimed in claim 1, wherein the at least one uncharged acrylamide monomer of component c) is/are selected from the group consisting of the monomers of the formula (III) ##STR00016## in which R2 and R3 may each be the same or different and are each independently hydrogen and/or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms.

8. The copolymer as claimed in claim 1, wherein the at least one uncharged acrylamide monomer of component c) is/are selected from the group consisting of acrylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N-tert-butylacrylamide and N-isopropylacrylamide.

9. The copolymer as claimed in claim 1, which is obtainable from the free-radical copolymerization at least of components a), b) and c), where component a) is used in the copolymerization in an amount of 25.0 to 80.0 mol %, component b) in an amount of 0.1 to 4.4 mol %, and component c) in an amount of 15.6 to 74.9 mol %.

10. The copolymer as claimed in claim 1, wherein the structural units originating from the polymerization of monomers a), b), c) and optionally d) and optionally of further monomers are present in the copolymer in a random, blockwise, alternating or gradient distribution.

11. The copolymer as claimed in claim 1, having a weight-average molecular weight M.sub.w of from 10 000 to 250 000 g/mol.

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

13. A method The usc of onc or morc copolymcrs as claimcd for producing shine on a hard surface, comprising the step of contacting the hard surface with at least one composition comprising at least one copolymer as claimed in claim 1.

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

15. A method for achieving a repair effect on a hard surface comprising the step of contacting the hard surface with at least one composition comprising at least one copolymer as claimed in claim 1.

Description

EXAMPLES

[0222] The following abbreviations are used:

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) NIPAM N-isopropylacrylamide (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)

[0223] Preparation of Copolymers of the Invention

[0224] General Method for Preparation of the Copolymers of the Invention

[0225] 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 the 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 the table 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.).

[0226] Table 1 lists synthesis examples.

TABLE-US-00002 TABLE 1 Substances used for preparation of the copolymers Co- V-PEG V-PEG Meth Na hypo- VA- dist. polymer 1100 5000 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC phosphite MESNA 44 H.sub.2O Mw No. [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [mmol] [g] [g] [g] [g] [g/mol] 1 4.816 32.985 80.064 0.120 1.560 149.450 39284 2 4.816 32.985 91.395 0.120 1.560 149.450 3 4.816 22.899 83.755 1.560 142.250 6 4.816 57.198 46.163 1.560 139.500 7 4.816 80.064 30.760 0.120 1.560 144.860 35849 8 4.816 57.198 46.163 1.560 139.500 102330 10 4.816 50.000 46.000 1.560 697.500 91934 11 4.816 80.064 30.760 1.560 724.300 118920 14 29.809 14.758 25.777 0.120 1.560 80.000 15 29.809 14.758 25.777 1.560 149.500 19 4.816 80.064 42.015 0.180 1.560 99.070 20 4.816 80.064 42.015 0.360 1.560 99.070 21 4.816 80.064 42.015 0.540 1.560 99.070 22 4.816 22.899 61.294 1.560 136.000 42261 23 4.816 20.060 61.294 1.560 136.000 The amounts stated in table 1 are based on the active substance.

TABLE-US-00003 TABLE 1a Relative amounts according to table 1 Total amount of the Structural Structural Structural Copolymer monomers used units (A) units (B) units (C) No. [mmol] [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 8 108.177 42.7 4.5 52.9 10 100.816 45.6 4.8 49.6 11 115.640 26.6 4.2 69.2 14 70.344 36.6 42.4 21.0 15 70.344 36.6 42.4 21.0 19 126.895 33.1 3.8 63.1 20 126.895 33.1 3.8 63.1 21 126.895 33.1 3.8 63.1 22 89.009 68.9 5.4 25.7 23 86.170 71.1 5.6 23.3

[0227] Determination of the weight-average molecular weights M.sub.w by GPC

[0228] Method description

TABLE-US-00004 Column: PSS NOVEMA MAX Guard, 1 30 & 2 1000 10 m, 300 mm 8 mm Detector: RI Oven temperature: 25 C. Flow rate: 1 ml/min Injection volume: 50 l Eluent: 79.7% by vol. of 0.1M NaCl + 0.3% by vol. of TFA (trifluoroacetic acid) + 20% by vol. of ACN (acetonitrile) Calibration method: conventional calibration Standards: poly(2-vinylpyridine) in the range from 1110 to 1 060 000 daltons

[0229] Measured weight-average molecular weights Mw for copolymers of the invention are reported in table 1.

[0230] Shining Capacity

[0231] Black, shiny ceramic tiles (1010 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.

[0232] 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.

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 ether 1.0 0.6 0.5 1.0 0.6 0.5 [% 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 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 2.0 2.0 2.0 1.7 2.0 2.0 1 +0.2% by wt. of copolymer 2.0 2.7 2 +0.2% by wt. of copolymer 3.0 3.0 22 +0.2% by wt. of copolymer 3.3 2.3 1.3 3 +0.2% by wt. of copolymer 2.0 2.7 23 +0.2% by wt. of copolymer 3.7 2.0 6

[0233] The results in table 2 show that the use of the copolymers of the invention in the example formulations achieves better shine results compared to the corresponding example formulations without copolymer of the invention.

[0234] 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 of the invention. The results are shown in Table 3.

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

[0235] The results in table 3 show 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.

[0236] Adsorption Tests on Hard Surfaces

[0237] The tests were effected with the QCM-D Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Vstra Frlinda, 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 L/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, Vstra Frlinda, Sweden) and crystal oscillators having a 50 nm-thick stainless steel (SS2343) coating (QSX304, Q-Sense, Vstra Frlinda, Sweden) were used.

[0238] 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.

TABLE-US-00007 TABLE 4 Adsorption of the copolymers on silica: Copolymer No. Mass adsorbed [ng/cm.sup.2] 23 264.4 22 275.9 8 355.8 3 142.5 7 348.0

TABLE-US-00008 TABLE 5 Adsorption of the copolymers on stainless steel: Copolymer No. Mass adsorbed [ng/cm.sup.2] 23 129.7 22 153.6

[0239] 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.

[0240] Contact Angle Test

[0241] 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 dem ineralized 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 Krss, Hamburg).

[0242] 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.

[0243] 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.

TABLE-US-00009 TABLE 6 Contact angle on black ceramic tiles Copolymer No. Contact angle of water Untreated 18 23 8 22 droplet spreads 8 4.2 3 15 7 5

TABLE-US-00010 TABLE 7 Contact angle on glass Copolymer No. Contact angle of water Untreated 39 8 droplet spreads 3 droplet spreads 7 droplet spreads

TABLE-US-00011 TABLE 8 Contact angle on steel Copolymer No. Contact angle of water Untreated 15 23 droplet spreads 22 droplet spreads

[0244] 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. of hydrophilizing inorganic surfaces).

[0245] Repair Effect

[0246] 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).

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] 22 71* 36* 8 140 94.6 3 110 108 7 86 85 *Change in the roughness of a black tile

[0247] The studies clearly show the repair effect of the copolymers of the invention.