PROCESS FOR PREPARING STABLE POLYMERS CONTAINING VINYLIMIDAZOLE

Abstract

Described herein are aqueous mixtures including water, 1-vinylimidazole-containing polymer(s) (P) and quaternary ammonium salts (QA). Also described herein are methods of production and use of same.

Claims

1. A process for producing an aqueous mixture comprising water, at least one 1-vinylimidazole-containing polymer (P) and at least one quaternary ammonium salt (QA), the process comprising adding an aqueous solution of at least one quaternary ammonium salt (QA) to an aqueous solution of at least one 1-vinylimidazole-containing polymer (P) and subsequent mixing.

2. The process for producing an aqueous mixture according to claim 1, wherein the proportion of water is greater than 10% by weight based on the total mixture.

3. The process for producing an aqueous mixture according to claim 1, wherein the 1-vinylimidazole-containing polymers (P) are selected from the group consisting of polymers having a proportion of vinylimidazole of greater than or equal to 5% by weight based on the polymer (P).

4. The process for producing an aqueous mixture according to claim 1, wherein the 1-vinylimidazole-containing polymers (P) are homopolymers of 1-vinylimidazole.

5. The process for producing an aqueous mixture according to claim 1, wherein the 1-vinylimidazole-containing polymers (P) are selected from the group consisting of copolymers of 1-vinylimidazole with at least one further monomer (A).

6. The process for producing an aqueous mixture according to claim 5, wherein the 1-vinylimidazole-containing polymers (P) are selected from the group consisting of copolymers of 1-vinylimidazole with at least one further monomer (A) and wherein the at least one further monomer (A) is selected from the group consisting of vinylpiperidone, vinylcaprolactam, 1-vinyloxazolidinone, 4-vinylpyridine N-oxide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methyl acetamide, acrylamide, basic monomers and their quaternized variants, isoprenol, styrene, 1-alkenes, vinyl esters, vinyl ethers, alkyl (meth)acrylates, alkyl maleates, N,N′-dialkylacrylamides, (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid and its alkali metal salts, monomers containing alkylene oxide groups, and mixtures thereof.

7. The process for producing an aqueous mixture according to claim 5, wherein the monomer (A) is 1-vinylpyrrolidone.

8. The process for producing an aqueous mixture according to claim 1, wherein the 1-vinylimidazole-containing polymers (P) are obtained by polymerizing 1-vinylimidazole and optionally monomer (A), optionally in the presence of up to 50% by weight of polyalkylene glycols, based on the monomers used.

9. The process for producing an aqueous mixture according to claim 1, wherein the 1-vinylimidazole-containing polymers (P) have a molecular weight Mw of 2000 to 200 000 g/mol.

10. The process for producing an aqueous mixture according to claim 1, wherein the quaternary ammonium salts (QA) are halide salts.

11. The process for producing an aqueous mixture according to claim 1, wherein the quaternary ammonium salts (QA) comprise at least one alkyl chain methylene group.

12. The process for producing an aqueous mixture according to claim 1, wherein the quaternary ammonium salts (QA) are selected from the group consisting of didecyldimethylammonium chloride, benzalkonium chloride, cetylalkonium chloride, cetylpyridinium chloride and mixtures thereof.

13. The process for producing an aqueous mixture according to claim 1, comprising quaternary ammonium salts (QA) in a proportion of at least 0.01% by weight to 2.0% by weight based on the total mixture.

14. The process for producing an aqueous mixture according to claim 1, comprising polymers (P) in a proportion of 5% to 90% by weight based on the total mixture.

15. A process for producing a liquid washing composition, by producing an aqueous mixture as described in claim 1, and adding at least one component selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, enzymes, optical brighteners, complexing agents, polymers, copolymers, soaps, silicone defoamers, solubilizers, short-chain alcohols, dyes, fragrances and mixtures thereof.

16. A process for stabilizing 1-vinylimidazole-containing polymers (P), the process comprising adding at least one quaternary ammonium salt (QA) to the 1-vinylimidazole-containing polymers (P).

17. A method of using at least one quaternary ammonium salt (QA), the method comprising using the at least one quaternary ammonium salt (QA) for stabilization of 1-vinylimidazole-containing polymers (P).

18. A method of using at least one quaternary ammonium salt (QA), the method comprising using the at least one quaternary ammonium salt (QA) for stabilization of liquid washing-composition formulations comprising 1-vinylimidazole-containing polymers (P).

19. An aqueous mixture comprising water, at least one 1-vinylimidazole-containing polymer (P) and at least one quaternary ammonium salt (QA), comprising (i) quaternary ammonium salts (QA) in a proportion of at least 0.01% by weight to 2.0% by weight based on the total mixture, and (ii) polymers (P) in a proportion of 5% to 90% by weight based on the total mixture.

20. The aqueous mixture according to claim 19, comprising (i) quaternary ammonium salts (QA) in a proportion of 0.01% by weight to 0.1% by weight, based on the total mixture, and (ii) polymers (P) in a proportion of 20% to 60% by weight based on the total mixture.

Description

EXAMPLES

[0210] Experimental examples illustrating some aspects of the present invention are described below.

[0211] The polymers as per Table 1 below were synthesized as follows.

Example P1

[0212] In a 1.5 L polymerization apparatus, a mixture of 15 g of 1-vinylpyrrolidone, 5 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62° C. under stirring and nitrogen blanketing. After this temperature has been reached, a mixture of 258 g of 1-vinylpyrrolidone, 12 g of 1-vinylimidazole, 2.9 g of mercaptoethanol and 485 g of water, as feed 1, and a solution of 5.8 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 100 g of water, as feed 2, are metered in within 3 hours. The reaction mixture is subsequently stirred at 62° C. for 30 minutes and then admixed with an aqueous solution of 1.5 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 10 g of water within 5 minutes and stirred at 62° C. for 2.5 hours. 980.5 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.3%.

Example P2

[0213] In a 1.5 L polymerization apparatus, a mixture of 15 g of 1-vinylpyrrolidone, 5 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62° C. under stirring and nitrogen blanketing. After this temperature has been reached, a mixture of 230 g of 1-vinylpyrrolidone, 40 g of 1-vinylimidazole, 2.9 g of mercaptoethanol and 485 g of water, as feed 1, and a solution of 5.8 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 100 g of water, as feed 2, are metered in within 3 hours. The reaction mixture is subsequently stirred at 62° C. for 30 minutes and then admixed with an aqueous solution of 1.5 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 10 g of water within 5 minutes and stirred at 62° C. for 2.5 hours. 989 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.4%.

Example P3

[0214] In a 1.5 L polymerization apparatus, a mixture of 10 g of 1-vinylpyrrolidone, 10 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62° C. under stirring and nitrogen blanketing. After this temperature has been reached, a mixture of 193 g of 1-vinylpyrrolidone, 77 g of 1-vinylimidazole, 2.2 g of mercaptoethanol and 485 g of water is as feed 1, and after a time delay of 5 minutes, the metering of feed 2 (a solution of 4.0 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propan] dihydrochloride in 100 g of water) is started, which is completed within 3 hours. The reaction mixture is subsequently stirred at 62° C. for 30 minutes and then admixed with an aqueous solution of 1.5 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 10 g of water within 5 minutes and stirred at 62° C. for 2.5 hours. 987.1 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.7%.

Example P4

[0215] In a 1.5 L polymerization apparatus, a mixture of 10 g of 1-vinylpyrrolidone, 10 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62° C. under stirring and nitrogen blanketing. After this temperature has been reached, a mixture of 193 g of 1-vinylpyrrolidone, 77 g of 1-vinylimidazole, 2.9 g of mercaptoethanol and 485 g of water, as feed 1, and a solution of 5.8 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 100 g of water, as feed 2, are metered in within 3 hours. The reaction mixture is subsequently stirred at 62° C. for 30 minutes and then admixed with an aqueous solution of 1.5 g of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride in 10 g of water within 5 minutes and stirred at 62° C. for 2.5 hours. 986.5 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.7%.

Example P5

[0216] 125 g of 1-vinylpyrrolidone, 125 g of 1-vinylimidzole and 500 g of water are initially charged in a 1.5 L stirred apparatus and heated to 75° C. under nitrogen blanketing and stirring. Once the reaction mixture has reached a temperature of 75° C., a solution of 5.0 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 50 ml of water is metered as feed 1 within 120 minutes and a solution of 6.0 g of mercaptoethanol in 50 ml of water is metered as feed 2 within 100 minutes. After the metering of the initiator has ended, the reaction mixture is stirred at a temperature of 75° C. for 30 minutes and subsequently admixed with 1.0 g of 2,2′-azobis(2-amidinopropane) dihydrochloride and stirred at 75° C. for a further 2 hours. 860.5 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.4%.

Example P6

[0217] Example P5 is repeated with the exception that a solution of 5.0 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 50 ml of water is metered in as feed 1 within 90 minutes and a solution of 10.0 g of mercaptoethanol in 50 ml of water is metered in as feed 2 within 60 minutes. 861.1 g of a yellow polymer solution are obtained. The solids content of the polymer solution is 30.5%.

Example P7

[0218] 19.5 kg of 1-vinylpyrrolidone and 19.5 kg of 1-vinylimidzole in 75 kg of water are initially charged in a 200 L stirred apparatus. The apparatus is evacuated (25 mbar) twice while stirring and pressurized with nitrogen while the solution is heated to 85° C. Once the reaction mixture has reached a temperature of 85° C., feed 1 (a solution of 375 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 9 L of water) is metered within 3 h. Feed 2 is started 30 minutes before feed 1 is ended, this being a solution of 450 g of mercaptoethanol in 9 L of water. Feed 2 is metered continuously within 2 h. Thereafter, the reaction mixture is additionally stirred at 85° C. for 30 minutes, followed by 1.5 L of a 10% solution of 2,2′-azobis(2-amidinopropane) dihydrochloride and a 2-hour stirring time at 75° C. 131.1 kg of a yellow, clear aqueous polymer solution is obtained. The solids content of the polymer solution is 30.5%.

Example P8

Polymerization of 1-vinylimidazole and 1-vinylpyrrolidone in the Presence of PEG

[0219] In a 200 L polymerization apparatus, a mixture of 16 kg of polyethylene glycol having a molar mass of 600 g/mol and 80 kg of water is heated to a temperature of 80° C. under stirring and nitrogen blanketing. After this temperature has been reached, 40 kg of 1-vinylpyrrolidone are started as feed 1, the metering rate being selected for metering within 3 h. After a delay of 20 minutes, what are started are feed 2 consisting of 20 kg of 1-vinylimidzole (metering within 3 h) and, in parallel, feed 3 consisting of a solution of 1200 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 22 kg of water, which is dosed within 3.5 hours. The reaction mixture is subsequently stirred at 80° C. for 30 minutes and then admixed with an aqueous solution of 120 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 2.2 kg of water within 5 minutes and stirred at 80° C. for 2.5 hours. A yellow, clear and low-odor aqueous polymer solution is obtained after cooling. The solids content of the polymer solution is 40.7%.

Example P9

Poly-1-vinylimidazole, Homopolymer

[0220] In a polymerization apparatus, a mixture of 300 g of 1-vinylimidazole and 400 g of water is heated to a temperature of 80° C. under stirring in a nitrogen atmosphere. After this temperature has been reached, a solution of 9 g of mercaptoethanol in 50 g of water is metered in as feed 1 within 2 hours and a solution of 7.5 g of azobis(2-methylbutyronitrile) in 70 g of isopropanol is metered in as feed 2 within 3 hours. Thereafter, the reaction mixture is stirred at a temperature of 80° C. for 1 hour and then admixed with a solution of 1.5 g of azobis(2-methylbutyronitrile) in a little isopropanol and the reaction mixture is stirred at 80° C. for a further 3 hours. The isopropanol is then removed from the reaction mixture with the aid of steam distillation. A yellow, clear and low-odor aqueous polymer solution is obtained. The homopolymer of the 1-vinylimidazole has a molecular weight of 25 300 g/mol. The solids content of the polymer solution is 41.6%.

[0221] The following polymers were used for the tests described below (Table 1):

TABLE-US-00001 VI [% VP [% Molar 3rd fraction of fraction of mass Mw % component polymer] polymer] GPC MW/Mn water PEG(EO) P1 5.8 94.2 16 300 3.2 69.6 — P2 15 85 23 850 3.8 69.7 — P3 30 70 49 480 5.4 69.3 — P4 30 70 25 180 3.7 69.3 — P5 50 50 35 860 4.9 69.6 — P6 50 50 19 100 3.8 69.5 — P7 50 50 63 550 6.7 69.5 — P8 26 53 76 000 7.8 59.3 21 P9 0 100 22 300 3.0 58.4 —

[0222] Molar mass determination by SEC (size-exclusion chromatography) was carried out under the following conditions.

[0223] The column (NOVEMA Max Ultrahigh) had a length of 30 cm with a diameter of 8 mm. The separation material used was a modified acrylate copolymer network.

[0224] The eluent used was 0.1% (w/w) trifluoroacetic acid/0.1 M NaCl in distilled water. The column temperature was 35° C. and the flow rate was 0.5 ml/min. 100 μl were injected at a concentration of 1.5 mg/ml. The sample solutions were filtered across a Sartorius Minisart RC 25 (0.2 μm). Samples are generally dissolved in the SEC eluent. The detector was a DRI Agilent 1100 UV GAT-LCD 503 [232 nm].

[0225] The calibration was carried out using narrow-distribution poly(2-vinylpyridine) standards from PSS, Germany, having molecular weights from M=620 to M=2 890 000. In addition, pyridine having a molecular weight of M=79 was used. Values outside this elution range were extrapolated.

[0226] Stability of Preservatives in VI-Containing Polymers:

[0227] The following stabilizers for VI-containing polymers (here: aqueous solution of a copolymer of vinylpyrrolidone and vinylimidazole) were tested.

[0228] (Selected) conventional stabilizers: [0229] MIT=methylisothiazolinone; methyl-4-isothiazolin-3-one [0230] BIT=benzisothiazolinone; 1,2-benzisothiazolin-3-one [0231] CMIT=chloromethylisothiazolinone; 5-chloro-N-methylisothiazolin-3-one [0232] OIT=octylisothiazolinone [0233] DCOIT=dichloroctylisothiazolinone

[0234] Selected stabilizers of the invention that are based on quaternary ammonium salts: [0235] DDAC=didecyldimethylammonium chloride [0236] BAC=benzalkonium chloride [0237] 16-BAC=cetylalkonium chloride [0238] CPC=cetylpyridinium chloride

[0239] Analysis of active substance: Results for active-substance concentration before and after storage at 40° C. (14 days, 28 days): [ppm]

[0240] MIT, BIT, CM IT, OIT, DCOIT and iodopropynyl butyl carbamate were determined by RP chromatography with UV detection after dilution of the sample to be tested. An RP18 column was used for this purpose, with an eluent composed of an acid-methanol mixture under isocratic conditions.

[0241] Quaternary ammonium salts, i.e. DDAC, BAC, 16-BAC and CPC, were determined by LC chromatography with a water/formic acid/ammonium formate eluent.

[0242] Iodine color number according to DIN 6162:2014-09

[0243] Physical stability; visual assessment according to:

[0244] ++=no discernible change with respect to color, turbidity or phase separation; +=marginal change in color number, somewhat increased Tyndall effect but no turbidity; 0=easily discernible increase in color number and moderate turbidity—no phase separation; −turbidity and change in color number readily discernible by visual assessment; −−strong color change with strong turbidity and incipient phase separation.

[0245] Before storage, all batches could be rated ++ (no turbidity or phase separation; no influence of the biocide on the color number of the product).

[0246] Microbiological results at the start (freshly formulated, i.e. 4-week test series is started immediately) and after 60 days of storage at 40° C. (i.e. the 4-week microbial testing is started with the sample stored at 40° C. for 60 days)

[0247] The test described below is carried out in order to ascertain the preserving effect of chemical preservatives in aqueous products and systems, the principle of the described method reflecting the efficacy of chemical preservatives with respect to pot-maintenance of aqueous products/systems under conditions corresponding to the use of laundry products/consumer products by the consumer. For this purpose, the preservatives to be tested are added in those concentrations which correspond to from the literature or to the manufacturer data from the suppliers (e.g.

[0248] Thor, Speyer). In said test, our orientation was toward the upper range, which, with the exception of VI-containing polymers, had always led to excellent results in the case of aqueous polymers for laundry.

[0249] A constant microorganism load is achieved by periodic inoculation of the test batches. Before the swabs of each batch made respectively immediately in parallel with the inoculation. The assessment is made on the basis of the microbial growth of the streaks. A preservative is more effective, the longer it takes until microbial growth first appears.

[0250] When carrying out said tests, 25 g of the polymer to be tested are weighed in each case into a vessel with a screw cap. The preservatives to be tested are each added in separate batches according to the specified use concentrations. An unpreserved product sample was used in each case for the growth control. Two days after the addition of the preservative, the samples are infected with 0.5 ml of inoculum (2% w/w). The titer of this inoculant solution is 10.sup.9 organisms per ml. The following microorganisms are the test organisms for the preservation test: [0251] Bacteria: [0252] Escherichia coli [0253] Staphylococcus aureus [0254] Pseudomonas aeruginosa [0255] Pseudomonas putida [0256] Burkholderia cepacia [0257] Alcaligenes faecalis [0258] Yeast: [0259] Candida albicans [0260] Candida valida [0261] Rhodotorula rura [0262] Saccharomyces cerevisiae

[0263] The test batches are inoculated four times altogether and once a week and are streaked on an agar plate once a week; the first streaking is done immediately before the new inoculation. Microbial growth on the agar surface is assessed after a three-day incubation at 25° C. As a pre-caution, negative swabs are additionally observed for a further three days and reassessed. The preserving effect is effected in a semiquantitative method via the growth of the individual streaks in accordance with the assessment from—via + to +++. The preservative result is repeatedly demonstrably robust, i.e. +++—defines the microbial growth.

[0264] When assessing the results, it is assumed that a preservative can be regarded as good if there are batches under the above-described laboratory conditions for a period of four weeks without microbial invasion of the sample, and that, even after the fourth inoculation, no microbial attacks occur growth can be identified. [0265] −−: no growth [0266] −: slight growth, max. 100 colonies [0267] 0: moderate growth, max. 400 colonies [0268] +: uniform growth with individual colonies still easily identifiable [0269] ++: strong growth; too many colonies to be counted, already some extensive growth

[0270] The test for ten weeks shows the surprising rise in activity of the preparations of the invention, i.e. extension of ten inoculation cycles.

[0271] The following tables provide an overview of the test results,

TABLE-US-00002 TABLE 2 a Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P5 (HP56) RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 151 119 94 3.6 8.7 − −− + −− ++ BIT 150 101 85 69 3.6 10.4 − −− ++ − ++ CMIT 150 94 81 59 3.5 9.0 −− −− + − ++ OIT 250 142 89 72 3.4 9.7 −− − ++ 0 ++ DCOIT 300 230 180 94 3.6 8.7 −− −− + − ++ Iodopropynyl 250 206 176 84 3.4 11.7 − −− + − + butyl carbamate DDAC 950 950 940 940 3.3 3.3 ++ −− −− −− −− BAC 1000 990 990 970 3.3 3.3 + −− −− −− −− 16-BAC 1000 960 960 940 3.4 3.3 + −− −− − − CPC 1000 940 940 910 3.4 3.4 + −− − − 0

TABLE-US-00003 TABLE 2 b Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P4 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 164 136 113 3.4 8.7 − −− + −− ++ BIT 150 117 93 82 3.4 9.2 − −− + − ++ CMIT 150 111 89 73 3.2 8.9 −− −− + − + OIT 250 165 114 90 3.3 9.7 −− − ++ 0 ++ DCOIT 300 246 198 123 3.4 8.9 − −− + − ++ Iodopropynyl 250 212 188 101 3.4 10.0 − −− 0 − ++ butyl carbamate DDAC 950 950 942 940 3.3 3.3 ++ −− −− −− −− BAC 1000 1000 991 977 3.2 3.3 + −− −− −− −− 16-BAC 1000 964 960 944 3.1 3.3 + −− − − − CPC 1000 948 938 914 3.1 3.2 + −− 0 − 0

TABLE-US-00004 TABLE 2 c Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P3 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 171 140 122 3.4 8.5 − − + −− ++ BIT 150 119 99 80 3.4 9.3 − − ++ − ++ CMIT 150 117 93 77 3.2 8.5 − −− + − ++ OIT 250 163 121 96 3.3 9.2 −− −− ++ 0 ++ DCOIT 300 232 183 112 3.4 9.1 −− −− + − ++ Iodopropynyl 250 221 190 107 3.4 10.4 − − + + butyl carbamate DDAC 950 950 940 930 3.3 3.3 ++ −− −− −− −− BAC 1000 970 973 967 3.2 3.3 ++ −− −− −− − 16-BAC 1000 975 968 952 3.1 3.3 + −− −− − − CPC 1000 960 949 936 3.1 3.4 + −− − − 0

TABLE-US-00005 TABLE 2 d Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P2 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 181 139 116 2.7 5.8 − − + −− + BIT 150 112 93 80 2.9 7.1 − − ++ −− ++ CMIT 150 108 89 66 3.1 8.6 −− −− + − + OIT 250 170 101 84 3.0 8.0 −− −− + − ++ DCOIT 300 244 195 109 3.1 8.1 −− −− + − + Iodopropynyl 250 225 183 122 2.8 8.0 − − + − + butyl carbamate DDAC 950 950 940 940 2.9 3.0 ++ −− −− −− −− BAC 1000 990 990 970 3.0 3.2 + −− −− −− − 16-BAC 1000 960 960 940 3.0 3.1 + −− −− − − CPC 1000 940 940 910 3.0 3.2 + −− − − −

TABLE-US-00006 TABLE 2 e Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P1 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 217 156 131 2.5 5.5 − − + −− 0 BIT 150 101 85 69 2.6 6.0 − − + −− + CMIT 150 94 81 59 2.8 6.2 −− −− 0 − + OIT 250 142 89 72 2.8 5.9 −− −− + − + DCOIT 300 244 183 94 3.0 6.2 −− −− 0 − + Iodopropynyl 250 206 176 84 2.8 7.5 − − 0 + butyl carbamate DDAC 950 950 940 940 2.9 2.9 ++ −− −− −− −− BAC 1000 990 990 970 2.6 2.8 + −− −− −− − 16-BAC 1000 960 960 940 2.6 2.7 + −− −− −− − CPC 1000 940 940 910 2.6 2.9 + −− − − −

TABLE-US-00007 TABLE 2 f Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P6 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 143 117 87 3.6 8.5 − −− + −− ++ BIT 150 99 83 66 3.6 10.0 − −− + − ++ CMIT 150 91 76 55 3.5 9.1 −− −− + − + OIT 250 135 88 68 3.4 9.7 −− − ++ 0 ++ DCOIT 300 222 184 98 3.6 8.4 −− −− + − + Iodopropynyl 250 201 174 80 3.4 11.0 − −− + − + butyl carbamate DDAC 950 950 950 943 3.3 3.3 ++ −− −− −− −− BAC 1000 990 981 976 3.3 3.4 + −− −− −− −− 16-BAC 1000 970 961 954 3.4 3.5 + −− −− − − CPC 1000 938 940 919 3.4 3.6 + −− − − 0

TABLE-US-00008 TABLE 2 g Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P7 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 149 123 91 3.6 8.5 − −− + −− ++ BIT 150 105 88 72 3.6 10.0 − −− ++ − ++ CMIT 150 96 80 64 3.5 9.1 − −− + − ++ OIT 250 139 92 73 3.4 9.7 −− − ++ 0 ++ DCOIT 300 228 189 106 3.6 8.4 −− −− + − ++ Iodopropynyl 250 207 178 87 3.4 11.0 − −− + − + butyl carbamate DDAC 950 947 945 938 3.3 3.3 ++ −− −− −− −− BAC 1000 988 985 979 3.3 3.4 ++ −− −− −− −− 16-BAC 1000 975 966 953 3.4 3.5 + −− −− − − CPC 1000 941 944 928 3.4 3.6 + −− − − 0

TABLE-US-00009 TABLE 2 h Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P8 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 151 119 94 3.5 8.6 − − + −− + BIT 150 101 85 69 3.4 10.4 −− − + −− + CMIT 150 94 81 59 3.3 9.3 −− −− 0 − 0 OIT 250 142 89 72 3.3 10.0 −− −− + − + DCOIT 300 230 180 94 3.4 8.9 −− −− + − 0 Iodopropynyl 250 206 176 84 3.4 11.4 − − + − + butyl carbamate DDAC 950 950 940 940 3.3 3.3 ++ −− −− −− −− BAC 1000 990 990 970 3.3 3.4 + −− −− −− −− 16-BAC 1000 960 960 940 3.2 3.5 + −− −− −− − CPC 1000 940 940 910 3.3 3.6 + −− − − 0

TABLE-US-00010 TABLE 2 i Start sample 60 d Start sample 60 d Iodine measurement, 40° C., measurement, 40° C., Iodine color Physical bact. bact. yeast yeast color number, stability, assess., assess., assess., assess., Polymer 0 d, 14 d, 28 d, 60 d, number, 60 d 60 d 4th 4th 4th 4th P9 RT 40° C. 40° C. 40° C. start 40° C. 40° C.* inoculation inoculation inoculation inoculation MIT 250 131 98 80 3.9 12.7 − −− + −− ++ BIT 150 97 78 60 4.0 12.8 − −− ++ − ++ CMIT 150 82 70 51 3.9 13.9 −− −− ++ − ++ OIT 250 128 76 62 4.0 15.5 −− −− ++ − ++ DCOIT 300 219 165 87 3.9 14.7 − −− ++ − ++ Iodopropynyl 250 191 160 78 3.9 16.9 − −− + + butyl carbamate DDAC 950 950 944 940 3.8 3.9 ++ −− −− −− −− BAC 1000 990 985 975 3.7 4.0 + −− − −− −− 16-BAC 1000 960 960 940 3.7 3.9 ++ −− −− −− − CPC 1000 940 940 910 3.9 4.2 + −− − − −

[0272] A good agreement between biocide stability/degradation, color number, and evaluation of physical stability is discerned. The sufficient stability of the inventive combination leads to a sustained microbiological stability as well. The strong interaction and the degradation of the isothiazolinones preferred by the person skilled in the art, but also iodopropynyl butyl carbamate, is surprising, whereas the stability of the quaternized systems is unexpectedly good and, in contrast to what is presumed by the person skilled in the art, it is also possible to prepare highly stable washing-composition formulations (see the description below).

[0273] Checking of the Stability of the Stabilized Vinylimidazole-Containing Polymers of the Invention in Washing-Composition Formulations

[0274] The mixtures of the invention were tested in exemplary liquid washing-composition formulations. As can be gathered from the data below, there was no apparent deterioration in (physical) stability when using the mixtures of the invention comprising VI polymers and quaternary ammonium salts, compared to using the VI polymers without stabilizer.

[0275] Composition of the Washing-Composition Formulations:

[0276] WM1: 5.5 g of linear alkylbenzenesulfonic acid, 2.4 g of coconut fatty acid K12-18, 7.7 g of C12-C14 alcohol+2 mol EO+sulfate, Na salt (C12-C14 ether sulfate), 2.2 g of KOH, 5.4 g of C13-C15 oxo alcohol+7 mol EO, 6.0 g of 1,2-propylene glycol, 2.0 g of ethanol and water to 90 g

[0277] WM2: 6.6 g of linear alkylbenzenesulfonic acid, 2.4 g of coconut fatty acid K12-18, 9.3 g of C12-C14 alcohol+2 mol EO+sulfate, Na salt (C12-C14 ether sulfate), 2.5 g of KOH, 3.3 g of C13-C15 oxo alcohol+7 mol EO, 6.0 g of 1,2-propylene glycol, 2.0 g of ethanol and water to 90 g

[0278] The VI polymers with and without the quaternary ammonium salt preservative were mixed into washing composition WM1 or WM2 under stirring (room temperature, 60 min). The stability and the appearance of the washing compositions were assessed immediately, after 7 days and after 28 days (storage at 25° C.).

TABLE-US-00011 TABLE 3 a Results of the stability tests with washing- composition formulations comprising VI polymers WM 1 + 1.0% polymer tel quel Appearance, Appearance, Appearance, immediately after 7 days after 28 days P1 without clear, clear, clear, preservative homogeneous homogeneous homogeneous P3 without clear, clear, clear, preservative homogeneous homogeneous homogeneous P5 without clear, clear, clear, preservative homogeneous homogeneous homogeneous P1 with clear, clear, clear, preservative homogeneous homogeneous homogeneous P3 with clear, clear, clear, preservative homogeneous homogeneous homogeneous P5 with clear, clear, clear, preservative homogeneous homogeneous homogeneous

TABLE-US-00012 TABLE 3 b Results of the stability tests with washing- composition formulations comprising VI polymers WM 2 + 0.8% polymer tel quel Appearance, Appearance, Appearance, immediately after 7 days after 28 days P1 without clear, clear, clear, preservative homogeneous homogeneous homogeneous P3 without clear, clear, clear, preservative homogeneous homogeneous homogeneous P5 without clear, clear, clear, preservative homogeneous homogeneous homogeneous P1 with clear, clear, clear, preservative homogeneous homogeneous homogeneous P3 with clear, clear, clear, preservative homogeneous homogeneous homogeneous P5 with clear, clear, clear, preservative homogeneous homogeneous homogeneous

[0279] In summary, the present invention comprises, inter alia, the following variants. [0280] 1. An aqueous mixture comprising or consisting of water, at least one 1-vinylimidazole-containing polymer (P) and at least one quaternary ammonium salt (QA). [0281] 2. The mixture according to variant 1, wherein the proportion of water is greater than 10% by weight, preferably greater than 20% by weight, further preferably at least 25% by weight, based on the total mixture. [0282] 3. The mixture according to variant 1 or 2, wherein the 1-vinylimidazole-containing polymers (P) are selected from polymers having a proportion of vinylimidazole of greater than or equal to 5% by weight, preferably greater than or equal to 10% by weight, further preferably greater than or equal to 15% by weight, based on the polymer (P). [0283] 4. The mixture according to any of the preceding variants, wherein the 1-vinylimidazole-containing polymers (P) are homopolymers of 1-vinylimidazole. [0284] 5. The mixture according to any of preceding variants 1 to 3, wherein the 1-vinylimidazole-containing polymers (P) are selected from copolymers of 1-vinylimidazole with at least one further monomer (A). [0285] 6. The mixture according to variant 5, wherein the 1-vinylimidazole-containing polymers (P) are selected from copolymers of 1-vinylimidazole with at least one further monomer (A) and wherein the at least one further monomer (A) is selected from the list consisting of vinylpi-peridone, vinylcaprolactam, 1-vinyloxazolidinone, 4-vinylpyridine N-oxide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, acrylamide, basic monomers and their quaternized variants, isoprenol, styrene, 1-alkenes, vinyl esters, vinyl ethers, alkyl (meth)acrylates, alkyl maleates, N,N′-dialkylacrylamides, (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid and its alkali metal salts, monomers containing alkylene oxide groups, and mixtures thereof. [0286] 7. The mixture according to variant 5, wherein the monomer (A) is 1-vinylpyrrolidone. [0287] 8. The mixture according to any of the preceding variants, wherein the 1-vinylimidazole-containing polymers (P) are obtained by polymerizing 1-vinylimidazole and optionally monomer (A), optionally in the presence of up to 50% by weight, preferably up to 30% by weight, of polyalkylene glycols, based on the monomers used. [0288] 9. The mixture according to any of the preceding variants, wherein the 1-vinylimidazole-containing polymers (P) have a molecular weight Mw of 2000 to 200 000 g/mol, preferably 3000 to 100 000 g/mol, further preferably 5000 to 80 000 g/mol. [0289] 10. The mixture according to any of the preceding variants, wherein the quaternary ammonium salts (QA) are halide salts, preferably selected from the list consisting of bromide salts and chloride salts. [0290] 11. The mixture according to any of the preceding variants, wherein the quaternary ammonium salts (QA) comprise at least one alkyl chain, preferably each comprising 2 to 20, more preferably 4 to 18, methylene groups. [0291] 12. The mixture according to any of the preceding variants, wherein the quaternary ammonium salts (QA) are selected from the list consisting of didecyldimethylammonium chloride, benzalkonium chloride, cetylalkonium chloride, cetylpyridinium chloride and mixtures thereof. [0292] 13. The mixture according to any of the preceding variants, comprising quaternary ammonium salts (QA) in a proportion of at least 0.01% by weight to 2.0% by weight, preferably 0.01% by weight to 1.0% by weight, further preferably 0.03% to 0.3% by weight, particularly preferably 0.05% to 0.1% by weight, based on the total mixture. [0293] 14. The mixture according to any of the preceding variants, comprising polymers (P) in a proportion of 5% to 90% by weight, preferably 20% to 60% by weight, based on the total mixture. [0294] 15. A liquid washing composition comprising the mixture according to any of the preceding variants and additionally at least one component selected from the list comprising or consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, enzymes, optical brighteners, complexing agents, polymers, copolymers, soaps, silicone defoamers, solubilizers, short-chain alcohols, dyes, fragrances and mixtures thereof. [0295] 16. A process for producing a mixture according to any of preceding variants 1 to 14, by adding an aqueous solution of at least one quaternary ammonium salt (QA) to an aqueous solution of at least one 1-vinylimidazole-containing polymer (P) and subsequent mixing. [0296] 17. A process for stabilizing 1-vinylimidazole-containing polymers (P) by adding at least one quaternary ammonium salt (QA). [0297] 18. The use of at least one quaternary ammonium salt (QA) for stabilization of 1-vinylimidazole-containing polymers (P). [0298] 19. The use of at least one quaternary ammonium salt (QA) for stabilization of liquid washing-composition formulations comprising 1-vinylimidazole-containing polymers (P).