CLEANING COMPOSITIONS COMPRISING COPOLYMERS AND THEIR USE

Abstract

Cleaning compositions e.g. containing one or more copolymers comprising structural units a) derived from one or more monomers comprising a sulfonic acid group or a sulfonate group, and structural units b) derived from one or more monomers comprising a carboxylic acid group or a carboxylate group and structural units c) derived from one or more cationic monomers are disclosed.

The cleaning compositions are e.g. suited to be used for the treatment of hard surfaces, for easier next time cleaning of hard surfaces and for preventing the build-up of limescale on hard surfaces.

Claims

1. A cleaning composition comprising Z1) one or more copolymers comprising components a), b) and c) a) one or more structural units derived from one or more monomers comprising a sulfonic acid group or a sulfonate group, and b) one or more structural units derived from one or more monomers comprising a carboxylic acid group or a carboxylate group, and c) one or more structural units derived from one or more cationic monomers, Z2) one or more surfactants, and Z3) water.

2. The cleaning composition according to claim 1, characterized in that the one or more structural units of component a) are derived from one or more monomers selected from the group consisting of vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, their corresponding sulfonates, and mixtures thereof.

3. The cleaning composition according to claim 1, characterized in that the one or more structural units of component b) are derived from one or more monomers selected from the group consisting of itaconic acid, methacrylic acid, acrylic acid, maleic acid, methyl maleic acid, their corresponding carboxylates, and mixtures thereof.

4. The cleaning composition according to claim 1, characterized in that the one or more structural units of component c) are derived from one or more cationic monomers selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium salts, [2-(methacryloyloxy)ethyl]trimethylammonium salts, [2-(acryloylamino)ethyl]trimethylammonium salts, [2-(methacryloylamino)ethyl]trimethylammonium salts, [3-(acryloylamino)propyl]trimethylammonium salts, [3-(methacryloylamino)propyl]trimethylammonium salts, diallyldimethylammonium salts, and mixtures thereof.

5. The cleaning composition according to claim 1, characterized in that the one or more copolymers of component Z1) comprise a) from 0.1 to 99 mol-% of one or more structural units of component a), b) from 0.1 to 99 mol-% of one or more structural units of component b), and c) from 0.1 to 99 mol-% of one or more structural units of component c), the mole percentages mentioned for components a), b) and c) in each case are based on the sum of the moles of the components a), b) and c) of the copolymer.

6. The cleaning composition according to claim 1, characterized in that the one or more copolymers of component Z1) consist of components a), b) and c) a) 15 to 30 mol-% of structural units derived from one monomer comprising a sulfonic acid group or a sulfonate group, b) 60 to 80 mol-% of structural units derived from one monomer comprising a carboxylic acid group or a carboxylate group, c) 0.5 to 15 mol-% of structural units derived from one monomer selected from the group consisting of diallyl dimethyl ammonium salts, (3-acrylamidopropyl)trimethylammonium salts, and [3-(methacryloylamino)propyl]trimethylammonium salts, the mole percentages mentioned for components a), b) and c) in each case are based on the sum of the moles of the components a), b) and c) of the copolymer, with the proviso that if the copolymer comprises structural units that only differ in the counterion of the sulfonic acid group or the sulfonate group of component a), or only differ in the counterion of the carboxylic acid group or the carboxylate group of component b), or only differ in the counterion of the ammonium salts of component c), the respective structural units in each of the three cases are considered as being derived from only one monomer.

7. The cleaning composition according to claim 1, characterized in that the one or more copolymers of component Z1) consist of components a), b) and c) a) 15 to 30 mol-% of structural units derived from 2-acrylamido-2-methylpropane sulfonic acid and/or one or more of its salts, b) 60 to 80 mol-% of structural units derived from acrylic acid and/or one or more of its salts, and c) 0.5 to 15 mol-% of structural units derived from one or more diallyl dimethyl ammonium salts, the mole percentages mentioned for components a), b) and c) in each case are based on the sum of the moles of the components a), b) and c) of the copolymer.

8. The cleaning composition according to claim 1, characterized in that the structural units of components a), b), c), and, if present, a further component d) of the one or more copolymers of component Z1) are present in the copolymer in a random, blockwise, alternating or gradient distribution.

9. The cleaning composition according to claim 1, characterized in that the weight average molecular weight M.sub.w of the one or more copolymers of component Z1) is from 10 000 to 250 000 g/mol.

10. The cleaning composition according to claim 1, characterized in that it comprises the one or more copolymers of component Z1) in an amount from 0.001 to 10% by weight, in each case based on the total weight of the cleaning composition.

11. The cleaning composition according to claim 1, characterized in that the one or more surfactants of component Z2) are selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof.

12. The cleaning composition according to claim 1, characterized in that the one or more surfactants of component Z2) are selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates, N-acylglucamines, preferably N-acyl-N-methylglucamines, quaternary ammonium compounds, and mixtures thereof.

13. The cleaning composition according to claim 1, characterized in that the amount of the one or more surfactants of component Z2) is from 0.1 to 20% by weight based on the total weight of the cleaning composition.

14. The cleaning composition according to claim 1, characterized in that it comprises hypochlorite.

15. A method of treatment of a hard surface comprising the step of contacting the hard surface with a cleaning composition comprising Z1) one or more copolymers comprising components a), b) and c) a) one or more structural units derived from one or more monomers comprising a sulfonic acid group or a sulfonate group, and b) one or more structural units derived from one or more monomers comprising a carboxylic acid group or a carboxylate group, and c) one or more structural units derived from one or more cationic monomers, Z2) one or more surfactants, and Z3) water.

16. The method according to claim 15, wherein the treatment of the hard surface is cleaning the hard surface.

17. The method according to claim 15, wherein the treatment of the hard surface is for preventing the build-up of limescale on the hard surface.

18. The method according to claim 15, wherein the treatment of the hard surface is preventing the build-up of limescale in a toilet.

19. (canceled)

20. A copolymer consisting of components a), b) and c), wherein a) is 15 to 30 mol-%, of structural units derived from one monomer comprising a sulfonic acid group or a sulfonate group, b) is 60 to 80 mol-% of structural units derived from one monomer comprising a carboxylic acid group or a carboxylate group, and c) is 0.5 to 15 mol-%, of structural units derived from one monomer selected from the group consisting of diallyl dimethyl ammonium salts, (3-acrylamidopropyl)trimethylammonium salts, and [3-(methacryloylamino)propyl]trimethylammonium salts, the mole percentages mentioned for components a), b) and c) in each case are based on the sum of the moles of the components a), b) and c) of the copolymer, with the proviso that if the copolymer comprises structural units that only differ in the counterion of the sulfonic acid group or the sulfonate group of component a), or only differ in the counterion of the carboxylic acid group or the carboxylate group of component b), or only differ in the counterion of the ammonium salts of component c), the respective structural units in each of the three cases are considered as being derived from only one monomer.

21. The copolymer according to claim 20, characterized in that it consists of a) 15 to 30 mol-%, of structural units derived from 2-acrylamido-2-methylpropane sulfonic acid and/or one or more of its salts, b) 60 to 80 mol-%, of structural units derived from acrylic acid and/or one or more of its salts, and c) 0.5 to 15 mol-%, of structural units derived from one or more diallyl dimethyl ammonium salts.

22. The copolymer according to claim 20, characterized in that the structural units of components a), b) and c) are present in the copolymer in a random, blockwise, alternating or gradient distribution.

23. The copolymer according to claim 20, characterized in that its weight average molecular weight M.sub.w is from 10 000 to 250 000 g/mol.

Description

EXAMPLE 1—SYNTHESIS OF COPOLYMER 1

[0289] A monomer solution consisting of 2-acrylamido-2-methylpropane sulfonic acid (93.5 g, 0.45 mol), acrylic acid (97.5 g, 1.35 mol) and demineralized water (100 g) was prepared in a flask. Demineralized water (93 g) and diallyl dimethyl ammonium chloride (31.5 g, 65 wt.-% aqueous solution, 0.13 mol) were charged into a polymerization reactor. The polymerization reactor was heated to reflux (103° C.). At reflux and stirring, the monomer solution from the flask was dosed into the polymerization reactor within a period of 4 h. In parallel, within 4 h 15 min, a 20 wt.-% sodium persulfate aqueous solution (100 g) was dosed. After additional 2 h of reflux of the reaction mixture, the reaction mixture was cooled and neutralized to pH 7-9 with a 50 wt.-% aqueous NaOH solution. Copolymer 1 was obtained as a 43 wt.-% aqueous solution.

[0290] Copolymer 1 consists of 23.4 mol-% of structural units derived from 2-acrylamido-2-methylpropane sulfonic acid, 70.1 mol-% of structural units derived from acrylic acid and 6.6 mol-% of structural units derived from diallyl dimethyl ammonium chloride.

EXAMPLE 2—SYNTHESIS OF COPOLYMER 2

[0291] A monomer solution consisting of 2-acrylamido-2-methylpropane sulfonic acid (95.9 g, 0.46 mol), acrylic acid (100.1 g, 1.39 mol) and demineralized water (506 g) was prepared in a flask and the pH of the solution was adjusted to 5 with 50 wt.-% aqueous NaOH solution. Demineralized water (112 g) and (3-acrylamidopropyl)trimethylammonium chloride (20.8 g, 75 wt.-% aqueous solution, 0.08 mol) were charged into a polymerization reactor. The polymerization reactor was heated to reflux (103° C.). At reflux and stirring, the monomer solution from the flask was dosed into the polymerization reactor within a period of 4 h. In parallel, within 4 h 15 min, a 20 wt.-% sodium persulfate aqueous solution (100 g) was dosed into the polymerization reactor. After additional 2 h of reflux of the reaction mixture, the reaction mixture was cooled and neutralized with 50 wt.-% aqueous NaOH solution (approximately 100 g). Copolymer 2 was obtained as a 28 wt.-% aqueous solution.

[0292] Copolymer 2 consists of 24.0 mol-% of structural units derived from 2-acrylamido-2-methylpropane sulfonic acid, 72.1 mol-% of structural units derived from acrylic acid and 3.9 mol-% of structural units derived from (3-acrylamidopropyl)trimethylammonium chloride.

EXAMPLE 3—SYNTHESIS OF COPOLYMER 3

[0293] A monomer solution consisting of 2-acrylamido-2-methylpropane sulfonic acid (98.5 g, 0.48 mol), acrylic acid (102.7 g, 1.43 mol) and demineralized water (100 g) was prepared in a flask. Demineralized water (108 g) and diallyl dimethyl ammonium chloride (16.2 g, 65 wt.-% aqueous solution, 0.07 mol) were charged into a polymerization reactor. The polymerization reactor was heated to reflux (103° C.). At reflux and stirring, the monomer solution from the flask was dosed into the polymerization reactor within a period of 4 h. In parallel, within 4 h 15 min, 100 g of a 20 wt.-% sodium persulfate aqueous solution was dosed. After additional 2 h of reflux of the reaction mixture, the reaction mixture was cooled and neutralized to pH 7-9 with a 50 wt.-% aqueous NaOH solution. Copolymer 3 was obtained as a 43 wt.-% aqueous solution.

[0294] Copolymer 3 consists of 24.2 mol-% of structural units derived from 2-acrylamido-2-methylpropane sulfonic acid, 72.5 mol-% of structural units derived from acrylic acid and 3.3 mol-% of structural units derived from diallyl dimethyl ammonium chloride.

EXAMPLE 4—SYNTHESIS OF COPOLYMER 4

[0295] A monomer solution consisting of 2-acrylamido-2-methylpropane sulfonic acid (98.4 g, 0.47 mol), acrylic acid (102.8 g, 1.43 mol) and demineralized water (306 g) was prepared in a flask and the pH of the solution was adjusted to 5 with 50 wt.-% aqueous NaOH solution. Demineralized water (112 g) and (3-acrylamidopropyl)trimethylammonium chloride (13.9 g, 75 wt.-% aqueous solution, 0.05 mol) were charged into a polymerization reactor. The polymerization reactor was heated to reflux (103° C.). At reflux and stirring, the monomer solution from the flask was dosed into the polymerization reactor within a period of 4 h. In parallel, within 4 h 15 min, a 20 wt.-% sodium persulfate aqueous solution (100 g) was dosed into the polymerization reactor. After additional 2 h of reflux of the reaction mixture, the reaction mixture was cooled and neutralized with 50 wt.-% aqueous NaOH solution (approximately 100 g). Copolymer 4 was obtained as a 33 wt.-% aqueous solution.

[0296] Copolymer 4 consists of 24.3 mol-% of structural units derived from 2-acrylamido-2-methylpropane sulfonic acid, 73.1 mol-% of structural units derived from acrylic acid and 2.6 mol-% of structural units derived from (3-acrylamidopropyl)trimethylammonium chloride.

EXAMPLE 5—SYNTHESIS OF POLYMER 5 (COMPARATIVE EXAMPLE)

[0297] A taurine modified polyacrylic acid polymer 5 according to DE 10 2004 040 848 A1 was prepared to be compared with the inventive copolymers.

[0298] Taurine (35.1 g) was dissolved in water (250 g). The pH of the solution was adjusted to 8.75 by adding sodium hydroxide. Polyacrylic acid polymer (20 g) was then added to the solution. The mixture was put into a microwave reactor and heated to 190° C. for 30 min. Polymer 5 was obtained as a 20 wt.-% aqueous solution.

EXAMPLE 6—PREPARATION OF A HYPOCHLORITE-BASED TOILET CLEANER

[0299] The toilet cleaner used for examples 7 to 9 was formulated as follows:

TABLE-US-00001 Substance Amount GENAMINOX LA 1.0 wt.-% active (lauramine oxide) Lauric acid 0.6 wt.-% active Sodium hypochlorite ca. 5 wt.-% active Sodium hydroxide Adjust the pH of the finished formulation to 13 Demineralized water Added up to 100 wt.-%

EXAMPLE 7—STABILITY TEST IN HYPOCHLORITE-BASED TOILET CLEANER

[0300] Toilet cleaners with 0.2 wt.-% of copolymer 1, 2 and polymer 5 respectively were prepared at room temperature. 50 g of each solution, including a solution of hypochlorite-based toilet cleaner without any further additives as a blank, were then stored in an oven at 50° C. for 14 days. The active chlorine value was measured at day 0, 3, 7 and 14, and listed below.

TABLE-US-00002 Active chlorine (wt.-%) Test Solution Day 0 Day 3 Day 7 Day 14 Blank 2.3 2.2 1.8 0.9 (only cleaner) Cleaner + 2.3 2.2 2.0 1.1 copolymer 1 Cleaner + 2.3 2.1 1.8 0.5 copolymer 2 Cleaner + 2.2 1.9 1.1 <0.1 polymer 5

[0301] Inventive copolymers 1 and 2 are stable in the hypochlorite-based toilet cleaner. However, comparative polymer 5 is not stable in the hypochlorite-based toilet cleaner.

EXAMPLE 8—LIMESCALE BUILD-UP PREVENTION

[0302] In this test, standard northern European toilets with standard flush (each flush using ca. 7 liters of water) mechanism were used. Each toilet was connected to tap water (with water hardness 15-20° dH) and was also connected to a waste water pipe to drain flushed water.

[0303] The toilet bowls were thoroughly cleaned with 10 wt.-% aqueous citric acid solution, flushed 3 times and dried for at least 3 h before each test. 80 g of a test cleaner was distributed evenly onto the surface of the toilet bowls and the test cleaner was allowed to run down to the waterline. The treated toilet bowls were left for 1 h and 5 flushes were then applied to remove the cleaner residue from the toilet bowls. After that, the toilets were flushed in total 12 times a day for 5 days. The limescale build-up was then evaluated visually after 1, 3 and 5 days and given a score from 0 to 4 (0—no limescale; 4—severe limescale build-up). The results are listed below. The hypochlorite-based cleaner, the cleaner+copolymer 1 and the cleaner+copolymer 2 mentioned in the table below are the compositions as described in examples 6 and 7.

TABLE-US-00003 Test Cleaner Day 1 Day 3 Day 5 Only hypochlorite-based 1 3 4 cleaner Cleaner + copolymer 1 0 0 0 Cleaner + copolymer 2 0 1 1

[0304] According to the results, the inventive copolymers deliver significant limescale build-up inhibition performance.

EXAMPLE 9—EASIER NEXT TIME CLEANING

[0305] In this test, toilets were cleaned and treated with test cleaners in the same way as described in example 8. After being flushed to remove the cleaner residue, the toilet was left to dry for at least 1 h. An artificial soil (sunflower oil+fat black) was then applied to the surface of the toilet bowl via pipette. The soil was left on the surface for 15 min and the toilets were then flushed (with standard flushes and 15 min interval between two flushes) until the soil was completely removed.

[0306] The toilet treated with only the hypochlorite-based cleaner took more than 6 flushes to remove all soil. However, the toilet treated with cleaner+copolymer 1 took only 2 flushes, in which after the first flush, most of the soil was already removed.