Compositions of Dibromomalonamide And

(19) TZZ ¥_T

(11) EP 2 582 238 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C02F 1/50 (2006.01) C02F 103/02 (2006.01) 04.06.2014 Bulletin 2014/23 A01N 37/30 (2006.01) A01N 59/16 (2006.01) A01N 59/20 (2006.01) A01P 1/00 (2006.01) (21) Application number: 11746373.7 (86) International application number: (22) Date of filing: 03.08.2011 PCT/US2011/046346

(87) International publication number: WO 2012/021340 (16.02.2012 Gazette 2012/07)

(54) COMPOSITIONS OF DIBROMOMALONAMIDE AND THEIR USE AS BIOCIDES ZUSAMMENSETZUNGEN ENTHALTEND DIBROMOMALOMAMID UND IHRE VERWENDUNG ALS BIOZIDE COMPOSITIONS CONTENANT DU DIBROMOMALONAMIDE ET LEUR UTILISATION COMME BIOCIDE

(84) Designated Contracting States: (56) References cited: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB US-A- 4 232 041 GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR • DATABASECA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; (30) Priority: 09.08.2010 US 371906 P PODDUBNAYA,N. A. ET AL: "Spectrophotometry of biuret complexes as a method for studying (43) Date of publication of application: proteins. VI. Absorption spectra of solutions of 24.04.2013 Bulletin 2013/17 copper complexes of some amides", XP002660142, retrieved from STN Database (73) Proprietors: accession no. 1949:34384 -& PODDUBNAYA: • Dow Global Technologies LLC "Spectrophotometry of biuret complexes as a Midland, MI 48674 (US) method for studying proteins. VI. Absorption • Rohm and Haas Company spectra of solutions of copper complexes of Philadelphia, PA 19106 (US) some amides", ZHURNAL OBSHCHEI KHIMII, NAUKA, MOSCOW, RU, vol. 18, 1 January 1948 (72) Inventors: (1948-01-01), pages 1848-1859, XP009152637, • SINGLETON, Freddie L. ISSN: 0044-460X Vernon Hills, IL 60061 (US) • SILVA MARTINEZ S ET AL: "Electrolytically • GHOSH, Tirthankar generated silver and copper ions to treat cooling Oreland, PA 19075 (US) water: an environmentally friendly novel • CAGLE, Kimberly S. alternative", INTERNATIONAL JOURNAL OF Schaumburg, IL 60101 (US) HYDROGEN ENERGY, ELSEVIER SCIENCE PUBLISHERS B.V., BARKING, GB, vol. 29, no. 9, (74) Representative: Buckley, Guy Julian 1 August 2004 (2004-08-01) , pages 921-932, Patent Outsourcing Limited XP004502832, ISSN: 0360-3199, DOI: 1 King Street 10.1016/J.IJHYDENE.2003.06.002 Bakewell Derbyshire DE45 1DZ (GB)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 582 238 B1

Printed by Jouve, 75001 PARIS (FR) EP 2 582 238 B1

Description

Field of the Invention

5 [0001] The invention relates to biocidal compositions comprising 2,2-dibromomalonamide and silver and methods for the control of microorganisms in aqueous and water-containing systems using compositions comprising 2,2-dibromomalonamide and a metal selected from silver, copper, and mixtures thereof.

Background of the Invention 10 [0002] Water systems provide fertile breeding grounds for algae, bacteria, viruses, and fungi some of which can be pathogenic. Such microorganism contamination can create a variety of problems, including aesthetic unpleasantries such as slimy green water, serious health risks such as fungal, bacterial, or viral infections, and mechanical problems including plugging, corrosion of equipment, and reduction of heat transfer. 15 [0003] Biocides are commonly used to disinfect and control the growth of microorganisms in aqueous and water containing systems. However, not all biocides are effective against a wide range of microorganisms and/or temperatures, and some are incompatible with other chemical treatment additives. In addition, some biocides do not provide microbial control over long enough time periods. [0004] While some of these shortcomings can be overcome through use of larger amounts of the biocide, this option 20 creates its own problems, including increased cost, increased waste, and increased likelihood that the biocide will interfere with the desirable properties of the treated medium. In addition, even with use of larger amounts of the biocide, many commercial biocidal compounds cannot provide effective control due to weak activity against certain types of microorganisms or resistance of the microorganisms to those compounds. [0005] It would be a significant advance in the art to provide biocide compositions for treatment of water systems that 25 provide one or more of the following advantages: increased efficacy at lower concentrations, compatibility with physical conditions and other additives in the treated medium, effectiveness against a broad spectrum of microorganisms, and/or ability to provide both short term and long term control of microorganisms.

BRIEF SUMMARY OF THE INVENTION 30 [0006] The present invention, in its various aspects, is as set out in the accompanying claims. [0007] In one aspect, the invention provides a biocidal composition. The composition is useful for controlling microorganisms in aqueous or water containing systems. The composition comprises: 2,2-dibromomalonamide and a metal comprising silver. 35 [0008] In a second aspect, the invention provides a method for controlling microorganisms in aqueous or water containing systems. The method comprises treating the system with an effective amount of a biocidal composition as described herein.

DETAILED DESCRIPTION OF THE INVENTION 40 [0009] As noted above, the invention provides a biocidal composition comprising 2,2-dibromomalonamide and silver and methods of using compositions comprising: 2,2-dibromomalonamide and a metal selected from silver, copper, and mixtures thereof in the control of microorganisms. It has surprisingly been discovered that combinations of 2,2-dibromomalonamide and the metal as described herein, at certain weight ratios, are synergistic when used for microorganism 45 control in aqueous or water containing media. That is, the combined materials result in improved biocidal properties than would otherwise be expected based on their individual performance. The synergy permits reduced amounts of the materials to be used to achieve the desired biocidal performance, thus reducing problems caused by growth of microorganisms in industrial process waters while potentially reducing environmental impact and materials cost. [0010] For the purposes of this specification, the meaning of "microorganism" includes, but is not limited to, bacteria, 50 fungi, algae, and viruses. The words "control" and "controlling" should be broadly construed to include within their meaning, and without being limited thereto, inhibiting the growth or propagation of microorganisms, killing microorganisms, disinfection, and/or preservation. In some preferred embodiments, "control" and "controlling" mean inhibiting the growth or propagation of microorganisms. In further embodiments, "control" and "controlling" mean the killing of microorganisms. 55 [0011] The terms "2,2-dibromomalonamide," "dibromomalonamide," and "DBMAL" mean a compound represented by the following formula:

2 EP 2 582 238 B1

[0012] In some embodiments of the invention, the weight ratio of 2,2-dibromomalonamide to the metal is between 1000:1 and 1:100, alternatively between 800:1 and 1:1. The 2,2-dibromomalonamide is commercially available and/or may be readily prepared by those skilled in the art using well known techniques. 10 [0013] In some embodiment, the composition of the invention comprises 2,2-dibromomalonamide and silver. The silver may be in any ionic or non-ionic form that is capable of reacting with a cellular component of a microorganism. The silver is preferably obtained from an inorganic or organic source or by electrolytic generation of silver ions. Examples include, but are not limited to one or more of the following: silver acetate, silver acetylacetonate , silver arsenate, silver benzoate, silver bromate, silver bromide, silver carbonate, silver chlorate, silver chloride, silver chromate, silver citrate hydrate, 15 silver cyanate, silver cyclohexanebutyrate, silver fluoride, silver heptafluorobutyrate, silver hexafluoroantimonate, silver hexafluoroarsenate, silver hexafluorophosphate, silver hydrogen fluoride, silver iodate, silver iodide, silver lactate, silver metavanadate, silver methanesulfonate, silver methenamine, silver molybdate, silver nitrate, silver nitrite, silver oxide, silver pentafluoropropionate, silver perchlorate hydrate, silver perchlorate monohydrate, silver perchlorate, silver phosphate, silver phthalocyanine, silver picolinate, silver protein, silver proteinate, silver p-toluenesulfonate, silver selenide, 20 silver sulfadiazine, silver sulfate, silver sulfide, silver sulfite, silver telluride, silver tetrafluoroborate, silver thiocyanate, silver trifluoroacetate, silver trifluoromethanesulfonate, or silver tungstate. A preferred source is silver nitrate. The silve r can also be obtained from a formulation designed to control the release of silver. Examples of controlled release formulations of silver include those based on organic polymers, zeolites, glass, calcium phosphate, titanium dioxide and zinc oxide. These formulations can employ the various inorganic or organic silver forms mentioned above. 25 [0014] In some embodiments, the weight ratio of 2,2-dibromomalonamide to silver is between 800:1 and 1:1, alternatively between between 800:1 and 6:1, alternatively between 800:1 and 12.5:1, or alternatively between 400:1 and 6:1. [0015] In some embodiment, the composition used in the method of the invention comprises 2,2 dibromomalonamide and copper. The copper may be in any ionic or non-ionic form that is capable of reacting with a cellular component of a microorganism. The copper is preferably obtained from an inorganic or organic source or by electrolytic generation of 30 copper ions. Examples include, but are not limited to one or more of the following: copper acetate; copper acetylacetonate; copper bromide; copper carbonate; copper chloride; copper chromite; copper cyanide; copper cyclohexanebutyrate; copper D-gluconate; copper fluoride; copper formate hydrate; copper hexafluoroacetylacetonate hydrate; copper hydroxide; copper iodide; copper iodide dimethyl sulfide complex; copper iodide trimethylphosphite complex; copper methoxide; copper molybdate; copper nitrate; copper oxide; copper oxychloride; copper perchlorate hexahydrate; copper 35 pyrophosphate hydrate; copper selenide; copper selenite; copper sulfate; copper sulfide; copper tartrate hydrate; copper telluride; copper thiocyanate; copper thiophene-2-carboxylate; copper thiophenolate; copper trifluoroacetylacetonate; copper 1-butanethiolate; copper 2-ethylhexanoate; copper 3-methylsalicylate; or copper trifluoromethanesulfonate. A preferred source is copper sulfate. The copper can also be obtained from a formulation designed to control the release of copper. Examples of controlled release formulations of copper include those based on organic polymers, zeolites, 40 glass, calcium phosphate, titanium dioxide and zinc oxide. These formulations can employ the various inorganic or organic copper forms mentioned above. [0016] In some embodiments, the weight ratio of 2,2-dibromomalonamide to copper is between 100:1 and 1:1, alternatively between 70:1 and 1:1, alternatively 40:1 and 1:1, alternatively between 32:1 and 1:1, or alternatively between 16:1 and 1:1 or 16:1 and 2:1. 45 [0017] The foregoing ratios are based on the amount of the metal in the composition, even though the metal may have been delivered, e.g., as an inorganic or organic compound. [0018] The composition of the invention is useful for controlling microorganisms in a variety of aqueous and water containing systems. Examples of such systems include, but are not limited to, paints and coatings, aqueous emulsions, latexes, adhesives, inks, pigment dispersions, household and industrial cleaners, detergents, dish detergents, mineral 50 slurries polymer emulsions, caulks and adhesives, tape joint compounds, disinfectants, sanitizers, metalworking fluids, construction products, personal care products, textile fluids such as spin finishes, industrial process water (e.g. oilfield water, pulp and paper water, cooling water), oilfield functional fluids such as drilling muds and fracturing fluids, fuels, air washers, wastewater, ballast water, filtration systems, and swimming pool and spa water. Preferred aqueous systems are metal working fluids, personal care, household and industrial cleaners, industrial process water, and paints and 55 coatings. Particularly preferred are industrial process water, paints and coatings, metal working fluids, and textile fluids such as spin finishes. [0019] A person of ordinary skill in the art can readily determine, without undue experimentation, the effective amount of the composition that should be used in any particular application to provide microorganism control. By way of illustration,

3 EP 2 582 238 B1

a suitable actives concentration (total for both 2,2-dibromomalonamide and metal) is typically at least 0.001 weight percent, alternatively at least 0.01 weight percent, based on the total weight of the aqueous or water containing system including the biocide composition. In some embodiments, a suitable upper limit for the actives concentration is 5 weight percent or less, alternatively 1 weight percent, or alternatively 0.1 weight percent, based on the total weight of the 5 aqueous or water containing system. [0020] The components of the composition may be added to the aqueous or water containing system separately, or preblended prior to addition. A person of ordinary skill in the art can easily determine the appropriate method of addition. The composition may be used in the system with other additives such as, but not limited to, surfactants, ionic/nonionic polymers and scale and corrosion inhibitors, oxygen scavengers, and/or additional biocides. 10 [0021] The following examples are illustrative of the invention. Unless otherwise indicated, the ratios, percentages, parts, and the like used herein are by weight.

EXAMPLES

15 [0022] The results provided in the Examples are generated using a growth inhibition assay. Details of each assay are provided below. [0023] Growth Inhibition Assay. The growth inhibition assay used in the Examples measures inhibition of growth (or lack thereof) of a microbial consortium. Inhibition of growth can be the result of killing of the cells (so no growth occurs), killing of a significant portion of the populations of cells so that regrowth requires a prolonged time, or inhibition of growt h 20 without killing (stasis). Regardless of the mechanism of action, the impact of a biocide (or combination of biocides) can be measured over time on the basis of an increase in the size of the community. [0024] The assay measures the efficacy of one or more biocides at preventing growth of a consortium of bacteria in

a dilute mineral salts medium. The medium contains (in mg/l) the following components: FeCl3.6H2O (1); CaCl2.2H2O (10); MgSO4.7H2O (22.5); (NH4)2SO4 (40); KH2PO4 (10); K2HPO4 (25.5); Yeast Extract (10); and glucose (100). After 25 all components are added to deionized water, the pH of the medium is adjusted to 7.5. Following filter sterilization, aliquots are dispensed in 100 ml quantities to sterile microtiter plate wells. Dilutions of 2,2-dibromomalonamide ("DBMAL") and/or "Biocide B" are then added to the microtiter plate. After preparing the combinations of actives as illustrated below, each well is inoculated with 100 ul of a cell suspension containing ca. 1 x 10 6 cells per milliliter of a mixture of Pseudomonas aeruginosa, Klebsiella pneumoniae, Staphylococcus aureus, and Bacillus subtilis. The final total volume of medium in 30 each well is 300 ml. Once prepared as described herein, the concentration of each active ranged from 25 ppm to 0.195 ppm as illustrated in Table 1. The resulting matrix allows testing of eight concentrations of each active and 64 combinations of actives in the ratios (of actives).

Controls (not shown) contain the medium with no biocide added. [0025] Immediately after the microtiter plates are prepared, the optical density (OD) readings for each well is measured 50 at 580 nm and the plates are then incubated at 37 °C for 24 hr. After the incubation period, the plates are gently agitated before OD580 values are collected. The OD 580 values at To are subtracted from T 24 values to determine the total amount of growth (or lack thereof) that occurs. These values are used to calculate the percent inhibition of growth caused by

the presence of each biocide and each of the 64 combinations. A 90% inhibition of growth90 (I) value is used as a threshold for calculating synergy index (SI) values with the following equation: 55

4 EP 2 582 238 B1

where

CDBMAL: Concentration of DBMAL required to inhibit at least 90% of bacterial growth when used alone CB: Concentration of biocide (B) required to inhibit at least 90% of bacterial growth when used alone. 5 MDBMAL: Concentration of DBMAL required to inhibit at least 90% of bacterial growth when used in combination with biocide (B).

MB: Concentration of biocide (B) required to inhibit at least 90% of bacterial growth when used in combination with DBMAL

10 [0026] The SI values are interpreted as follows:

SI <1 : Synergistic combination SI = 1 : Additive combination SI >1 : Antagonistic combination 15 [0027] In the Examples below, the amounts of biocides in the solution are measured in mg per liter of solution (mg/l). Since solution densities are approximately 1.00, the mg/l measurement corresponds to weight and can be expressed as parts per million (ppm). Both units may therefore be used interchangeably in the Examples. [0028] Silver(Ag) and copper (Cu) are evaluated.For eachmetal, twoseparate experiments arecarried out todetermine 20 if synergy can be detected when used in combination with DBMAL. Results of the experiments are presented in the following sections.

Example 1

25 DBMAL and Silver

Experiment 1

[0029] Although the Ag is added to the cell suspensions as AgNO3, the indicated concentrations are for Ag in mg/l. 30 DBMAL and Ag are tested individually and in selected ratios from 1:64 to 64:1 (DBMAL to Ag). The I 90 values for DBMAL and Ag are 12.5 mg/l and 0.063 mg/l, respectively. In the subsequent experiment, the90 I value for Ag is 0.125 ppm. Regardless, in both studies, several synergistic combinations were detected. Table 2 contains ratios and synergy index values for the synergistic combinations

35 Table 2. DBMAL (mg/l) Ag (mg/l) SI Ratio (DBMAL:Ag) 6.25 0.0156 0.75 400:1 6.25 0.0078 0.63 800:1 40 3.13 0.0313 0.75 100:1 3.13 0.0156 0.50 200:1 3.13 0.0078 0.37 400:1

45 1.56 0.0313 0.62 50:1 1.56 0.0156 0.38 100:1 1.56 0.0078 0.25 200:1 0.78 0.0313 0.55 25:1 50 0.78 0.0156 0.32 50:1 0.39 0.0313 0.52 12.5:1

55 [0030] As can be seen from the Table, a wide range of ratios of the two actives exhibit SI values

5 EP 2 582 238 B1

<1, indicating a synergistic effect.

Experiment 2

5 [0031] As illustrated in Table 3, the results presented in Table 2 (Experiment 1) are reproducible and show a pattern of inhibition that is very similar to that obtained in Experiment 1.

Table 3 DBMAL (mg/l) Ag (mg/l) SI Ratio (DBMAL:Ag) 10 6.25 0.0313 0.75 200:1 6.25 0.0156 0.63 400:1 3.125 0.0625 0.75 50:1 15 3.125 0.0313 0.50 100:1 3.125 0.0156 0.38 200:1 3.125 0.0078 0.31 400:1 1.563 0.0625 0.63 200:1 20 1.563 0.0313 0.37 50:1 1.563 0.0156 0.25 100:1 1.563 0.0078 0.19 200:1 25 0.781 0.0625 0.57 12.5:1 0.781 0.0313 0.31 25:1 0.391 0.0625 0.54 6.25:1 0.391 0.0313 0.28 12.5:1 30

Example 2

DBMAL and Copper 35 [0032] Table 6 shows inhibition growth assay results for DBMAL, Cu, and combinations thereof. 0.78 mg/l Cu is required for at least 90 % inhibition of growth of the test organisms and, as previously detected, 12.5 mg/l DBMAL is needed to achieve the same effect. In the presence of some concentrations of the two actives that are less than the I 90 concentrations, the effect is observed to be synergistic. Data is shown in Table 4. 40 Table 4 DBMAL (mg/l) Cu (mg/l) SI Ratio (DBMAL:Cu) 6.25 0.195 0.75 32:1 45 3.125 0.39 0.752 8:1 3.125 0.195 0.50 16:1 1.563 0.39 0.62 4:1

50 1.563 0.195 0.37 8:1 0.780 0.39 0.56 2:1 0.780 0.195 0.31 4:1 0.391 0.391 0.53 1:1 55 0.391 0.195 0.28 2:1

Experiment 2

[0033] In this experiment, similar results to Experiment 1 are obtained (see Table 5).

6 EP 2 582 238 B1

Table 5 DBMAL (mg/l) Cu (mg/l) SI Ratio (DBMAL:Cu)

5 6.25 0.20 0.75 32:1 3.13 0.39 0.75 8:1 3.13 0.20 0.50 16:1 1.56 0.39 0.62 4:1 10 1.56 0.20 0.37 8:1 0.78 0.39 0.56 2:1 0.78 0.20 0.31 4:1

15 Example 3

[0034] Table 10 shows results of assays on DBMAL and zinc (Zn). No synergy was detected between these materials.

7 EP 2 582 238 B1

15 Zn (mg/l) Zn

30 0.78 85 61 85 17 2 0 0 0 0.39 87 76 79 0 0 0 0 0 0.20 97 81 67 0 0 0 0 0 1.56 85 89 68 8 0 23 0 0 6.253.13 80 88 80 67 74 72 89 44 55 24 25 22 15 7 0 0 25.0012.50 100 67 100 100 100 100 84 84 87 94 100 100 100 100 95 100

35 18 12 19 23 74 33 92 91

40 Zn Alone Zn 78.1 39.1 19.5 156.3 625.0 312.5 2500.0 1250.0 45 9 4 0 2 29 21 100 50 100 DBMAL DBMAL Alone

55 mg/lGrowth of Inhibition % mg/lth Grow of tion Inhibi % mg/l DBMAL 2500.0 1250.0 625.0 312.5 156.2 78.1 39.0 19.5 6.25 3.13 1.56 0.78 0.39 0.20 25.00 12.50

8 EP 2 582 238 B1

Claims

1. A method for controlling microorganism growth in an aqueous or water-containing system, the method comprising treating the aqueous or water-containing system with an effective amount of a biocidal composition comprising: 2,2- 5 dibromomalonamide and a metal selected from the group consisting of silver, copper and mixtures thereof.

2. A method according to claim 1 wherein the aqueous or water-containing system is a paint, coating, aqueous emulsion, latex, adhesive, ink, pigment dispersion, household or industrial cleaner, detergent, dish detergent, mineral slurry polymer emulsion, caulk, adhesive, tape joint compound, disinfectant, sanitizer, metalworking fluid, construction 10 product, personal care product, textile fluid, spin finish, industrial process water, oilfield functional fluid, fuel, air washer, wastewater, ballast water, filtration system, swimming pool or spa water.

3. A biocidal composition comprising: 2,2-dibromomalonamide and a metal, wherein the metal comprises silver.

15 4. A composition according to claim 3 wherein the silver is provided from an inorganic or organic source selected from: silver acetate, silver acetylacetonate , silver arsenate, silver benzoate, silver bromate, silver bromide, silver carbonate, silver chlorate, silver chloride, silver chromate, silver citrate hydrate, silver cyanate, silver cyclohexanebutyrate, silver fluoride, silver heptafluorobutyrate, silver hexafluoroantimonate, silver hexafluoroarsenate, silver hexafluorophosphate, silver hydrogen fluoride, silver iodate, silver iodide, silver lactate, silver metavanadate, silver methanesul- 20 fonate, silver methenamine, silver molybdate, silver nitrate, silver nitrite, silver oxide, silver pentafluoropropionate, silver perchlorate hydrate, silver perchlorate monohydrate, silver perchlorate, silver phosphate, silver phthalocyanine, silver picolinate, silver protein, silver proteinate, silver p-toluenesulfonate, silver selenide, silver sulfadiazine, silver sulfate, silver sulfide, silver sulfite, silver telluride, silver tetrafluoroborate, silver thiocyanate, silver trifluor oa- cetate, silver trifluoromethanesulfonate, and silver tungstate. 25 5. A composition according to any one of claims 3-4 which is a paint, coating, aqueous emulsion, latex, adhesive, ink, pigment dispersion, household or industrial cleaner, detergent, dish detergent, mineral slurry polymer emulsion, caulk, adhesive, tape joint compound, disinfectant, sanitizer, metalworking fluid, construction product, personal care product, textile fluid, spin finish, industrial process water, oilfield functional fluid, fuel, air washer, wastewater, ballast 30 water, filtration systems, swimming pool or spa water.

6. A biocidal composition comprising: 2,2-dibromomalonamide and a metal, wherein the metal comprises copper and wherein the composition is a paint, coating, aqueous emulsion, latex, adhesive, ink, pigment dispersion, household or industrial cleaner, detergent, dish detergent, mineral slurry polymer emulsion, caulk, adhesive, tape joint com- 35 pound, disinfectant, sanitizer, metalworking fluid, construction product, personal care product, textile fluid, spin finish, industrial process water, oilfield functional fluid, fuel, air washer, wastewater, ballast water, filtration systems, swimming pool or spa water.

7. A composition according to claim 6 wherein the copper is provided from an inorganic or organic source selected 40 from: copper acetate; copper acetylacetonate; copper bromide; copper carbonate; copper chloride; copper chromite; copper cyanide; copper cyclohexanebutyrate; copper D-gluconate; copper fluoride; copper formate hydrate; copper hexafluoroacetylacetonate hydrate; copper hydroxide; copper iodide; copper iodide dimethyl sulfide complex; copper iodide trimethylphosphite complex; copper methoxide; copper molybdate; copper nitrate; copper oxide; copper oxychloride; copper perchlorate hexahydrate; copper pyrophosphate hydrate; copper selenide; copper selenite; 45 copper sulfate; copper sulfide; copper tartrate hydrate; copper telluride; copper thiocyanate; copper thiophene-2- carboxylate; copper thiophenolate; copper trifluoroacetylacetonate; copper 1-butanethiolate; copper 2-ethylhexanoate; copper 3-methylsalicylate; or copper trifluoromethanesulfonate.

8. A composition according to any one of claims 3-7 wherein the weight ratio of 2,2-dibromomalonamide to the metal 50 is between 1000:1 and 1:100.

9. A composition according to any one of claims 3-5 wherein the weight ratio of 2,2-dibromomalonamide to the metal is between 800:1 and 1:1.

55 10. A composition according to any one of claims 6-7 wherein the weight ratio of 2,2-dibromomalonamide to the metal is between 100:1 and 1:1.

9 EP 2 582 238 B1

Patentansprüche

1. Ein Verfahren zum Kontrollieren des Wachstums von Mikroorganismen in einem wässrigen oder wasserhaltigen System, wobei das Verfahren das Behandeln des wässrigen oder wasserhaltigen Systems mit einer wirksamen 5 Menge einer bioziden Zusammensetzung beinhaltet, beinhaltend: 2,2-Dibrommalonamid und ein Metall, ausgewählt aus der Gruppe bestehend aus Silber, Kupfer und Mischungen daraus.

2. Verfahren gemäß Anspruch 1, wobei das wässrige oder wasserhaltige System eine Farbe, eine Beschichtung, eine wässrige Emulsion, Latex, ein Haftmittel, Tinte, eine Pigmentdispersion, ein Haushalts- oder Industriereiniger, ein 10 Reinigungsmittel, ein Geschirrreinigungsmittel, eine Mineralschlamm-Polymeremulsion, unreiner Baryt, ein Haft- mittel, eine Bandfugenverbindung, ein Antiseptikum, ein Desinfektionsmittel, ein Metallverarbeitungsfluid, ein Bau- produkt, ein Körperpflegeprodukt, ein Gewebefluid, ein Spinnzusatz, ein Nutzwasser, ein funktionales Ölfeldfluid, ein Brennstoff, ein Luftwäscher, Abwasser, Ballastwasser, ein Filtrationssystem, Schwimmbadwasser oder Mine- ralwasser ist. 15 3. Eine biozide Zusammensetzung, die Folgendes beinhaltet: 2,2-Dibrommalonamid und ein Metall, wobei das Metall Silber beinhaltet.

4. Zusammensetzung gemäß Anspruch 3, wobei das Silber von einer anorganischen oder organischen Quelle bereit- 20 gestellt wird, ausgewählt aus: Silberacetat, Silberacetylacetonat, Silberarsenat, Silberbenzoat, Silberbromat, Sil- berbromid, Silbercarbonat, Silberchlorat, Silberchlorid, Silberchromat, Silbercitrathydrat, Silbercyanat, Silbercyclo- hexanbutyrat, Silberfluorid, Silberheptafluorbutyrat, Silberhexafluorantimonat, Silberhexafluorarsenat, Silberhexa- fluorphosphat, Silberfluorwasserstoff, Silberiodat, Silberiodid, Silberlactat, Silbermetavanadat, Silbermethansulfo- nat, Silbermethenamin, Silbermolybdat, Silbernitrat, Silbernitrit, Silberoxid, Silberpentafluorpropionat, Silberperchlo- 25 rathydrat, Silberperchloratmonohydrat, Silberperchlorat, Silberphosphat, Silberphthalocyanin, Silberpicolinat, Sil- berprotein, Silberproteinat, Silber-p-toluolsulfonat, Silberselenid, Silbersulfadiazin, Silbersulfat, Silbersulfid, Silber- sulfit, Silbertellurid, Silbertetrafluorborat, Silberthiocyanat, Silbertrifluoracetat, Silbertrifluormethansulfonat und Sil- berwolframat.

30 5. Zusammensetzung gemäß einem der Ansprüche 3-4, die eine Farbe, eine Beschichtung, eine wässrige Emulsion, Latex, ein Haftmittel, Tinte, eine Pigmentdispersion, ein Haushalts- oder Industriereiniger, ein Reinigungsmittel, ein Geschirrreinigungsmittel, eine Mineralschlamm-Polymeremulsion, unreiner Baryt, ein Haftmittel, eine Bandfugen- verbindung, ein Antiseptikum, ein Desinfektionsmittel, ein Metallverarbeitungsfluid, ein Bauprodukt, ein Körperpfle- geprodukt, ein Gewebefluid, ein Spinnzusatz, ein Nutzwasser, ein funktionales Ölfeldfluid, ein Brennstoff, ein Luft- 35 wäscher, Abwasser, Ballastwasser, Filtrationssysteme, Schwimmbadwasser oder Mineralwasser ist.

6. Eine biozide Zusammensetzung, die Folgendes beinhaltet: 2,2-Dibrommalonamid und ein Metall, wobei das Metall Kupfer beinhaltet und wobei die Zusammensetzung eine Farbe, eine Beschichtung, eine wässrige Emulsion, Latex, ein Haftmittel, Tinte, eine Pigmentdispersion, ein Haushalts- oder Industriereiniger, ein Reinigungsmittel, ein Ge- 40 schirrreinigungsmittel, eine Mineralschlamm-Polymeremulsion, unreiner Baryt, ein Haftmittel, eine Bandfugenver- bindung, ein Antiseptikum, ein Desinfektionsmittel, ein Metallverarbeitungsfluid, ein Bauprodukt, ein Körperpflege- produkt, ein Gewebefluid, ein Spinnzusatz, ein Nutzwasser, ein funktionales Ölfeldfluid, ein Brennstoff, ein Luftwä- scher, Abwasser, Ballastwasser, Filtrationssysteme, Schwimmbadwasser oder Mineralwasser ist.

45 7. Zusammensetzung gemäß Anspruch 6, wobei das Kupfer von einer anorganischen oder organischen Quelle be- reitgestellt wird, ausgewählt aus: Kupferacetat; Kupferacetylacetonat; Kupferbromid; Kupfercarbonat; Kupferchlorid; Kupferchromit; Kupfercyanid; Kupfercyclohexanbutyrat; Kupfer-D-gluconat; Kupferfluorid; Kupferformiathydrat; Kupferhexafluoracetylacetonathydrat; Kupferhydroxid; Kupferiodid; Kupferiodid-Dimethylsulfidkomplex; Kupferio- didtrimethylphosphitkomplex; Kupfermethoxid; Kupfermolybdat; Kupfernitrat; Kupferoxid; Kupferoxychlorid; Kupfer- 50 perchlorathexahydrat; Kupferpyrophosphathydrat; Kupferselenid; Kupferselenit; Kupfersulfat; Kupfersulfid; Kupfer- tartrathydrat; Kupfertellurid; Kupferthiocyanat; Kupferthiophen-2-carboxylat; Kupferthiophenolat; Kupfertrifluorace- tylacetonat; Kupfer-1-butanthiolat; Kupfer-2-ethylhexanoat; Kupfer-3-methylsalicylat; oder Kupfertrifluormethansul- fonat.

55 8. Zusammensetzung gemäß einem der Ansprüche 3-7, wobei das Gewichtsverhältnis von 2,2-Dibrommalonamid zu dem Metall zwischen 1000 : 1 und 1 : 100 beträgt.

9. Zusammensetzung gemäß einem der Ansprüche 3-5, wobei das Gewichtsverhältnis von 2,2-Dibrommalonamid zu

10 EP 2 582 238 B1

dem Metall zwischen 800 : 1 und 1 : 1 beträgt.

10. Zusammensetzung gemäß einem der Ansprüche 6-7, wobei das Gewichtsverhältnis von 2,2-Dibrommalonamid zu dem Metall zwischen 100 : 1 und 1 : 1 beträgt. 5

Revendications

1. Une méthode pour maîtriser la croissance de microorganismes dans un système aqueux ou contenant de l’eau, la 10 méthode comprenant le fait de traiter le système aqueux ou contenant de l’eau avec une quantité efficace d’une composition biocide comprenant : du 2,2-dibromomalonamide et un métal sélectionné dans le groupe consistant en l’argent, le cuivre et des mélanges de ceux-ci.

2. Une méthode selon la revendication 1 dans laquelle le système aqueux ou contenant de l’eau est une peinture, un 15 enduit, une émulsion aqueuse, un latex, un adhésif, une encre, une dispersion de pigment, un nettoyant ménager ou industriel, un détergent, un détergent à vaisselle, une émulsion polymère de boue minérale, un mastic, un adhésif, un composé pour joint en bande, un désinfectant, un assainisseur, un fluide de travail des métaux, un produit de construction, un produit de soins d’hygiène personnelle, un fluide de textiles, un ensimage de filature, des eaux industrielles, un fluide fonctionnel de gisement de pétrole, un carburant, un laveur d’air, des eaux usées, des eaux 20 de ballast, un système de filtration, de l’eau de piscine ou de spa.

3. Une composition biocide comprenant : du 2,2-dibromomalonamide et un métal, dans laquelle le métal comprend de l’argent.

25 4. Une composition selon la revendication 3 dans laquelle l’argent est fourni à partir d’une source inorganique ou organique sélectionnée parmi : l’acétate d’argent, l’acétylacétonate d’argent, l’arsénate d’argent, le benzoate d’argent, le bromate d’argent, le bromure d’argent, le carbonate d’argent, le chlorate d’argent, le chlorure d’argent, le chromate d’argent, l’hydrate de citrate d’argent, le cyanate d’argent, le cyclohexane butyrate d’argent, le fluorure d’argent, l’heptafluorobutyrate d’argent, l’hexafluoroantimonate d’argent, l’hexafluoroarsénate d’argent, l’hexafluo- 30 rophosphate d’argent, l’hydrogénofluorure d’argent, l’iodate d’argent, l’iodure d’argent, le lactate d’argent, le méta- vanadate d’argent, le méthane sulfonate d’argent, la méthénamine d’argent, le molybdate d’argent, le nitrate d’argent, le nitrite d’argent, l’oxyde d’argent, le pentafluoropropionate d’argent, l’hydrate de perchlorate d’argent, le monohydrate de perchlorate d’argent, le perchlorate d’argent, le phosphate d’argent, la phtalocyanine d’argent, le picolinate d’argent, la protéine d’argent, le protéinate d’argent, le p-toluène sulfonate d’argent, le séléniure d’argent, la sulfa- 35 diazine d’argent, le sulfate d’argent, le sulfure d’argent, le sulfite d’argent, le tellurure d’argent, le tétrafluoroborate d’argent, le thiocyanate d’argent, le trifluoroacétate d’argent, le trifluorométhane sulfonate d’argent, et le tungstate d’argent.

5. Une composition selon l’une quelconque des revendications 3 à 4 qui est une peinture, un enduit, une émulsion 40 aqueuse, un latex, un adhésif, une encre, une dispersion de pigment, un nettoyant ménager ou industriel, un détergent, un détergent à vaisselle, une émulsion polymère de boue minérale, un mastic, un adhésif, un composé pour joint en bande, un désinfectant, un assainisseur, un fluide de travail des métaux, un produit de construction, un produit de soins d’hygiène personnelle, un fluide de textiles, un ensimage de filature, des eaux industrielles, un fluide fonctionnel de gisement de pétrole, un carburant, un laveur d’air, des eaux usées, des eaux de ballast, des 45 systèmes de filtration, de l’eau de piscine ou de spa.

6. Une composition biocide comprenant : du 2,2-dibromomalonamide et un métal, dans laquelle le métal comprend du cuivre et dans laquelle la composition est une peinture, un enduit, une émulsion aqueuse, un latex, un adhésif, une encre, une dispersion de pigment, un nettoyant ménager ou industriel, un détergent, un détergent à vaisselle, 50 une émulsion polymère de boue minérale, un mastic, un adhésif, un composé pour joint en bande, un désinfectant, unassainisseur, unfluide detravail des métaux, un produit de construction,un produit de soins d’hygiène personnelle, un fluide de textile, un ensimage de filature, des eaux industrielles, un fluide fonctionnel de gisement de pétrole, un carburant, un laveur d’air, des eaux usées, des eaux de ballast, des systèmes de filtration, de l’eau de piscine ou de spa. 55 7. Une composition selon la revendication 6 dans laquelle le cuivre est fourni à partir d’une source inorganique ou organique sélectionnée parmi : l’acétate de cuivre ; l’acétylacétonate de cuivre ; le bromure de cuivre ; le carbonate de cuivre ; le chlorure de cuivre ; le chromite de cuivre ; le cyanure de cuivre ; le cyclohexane butyrate de cuivre ;

11 EP 2 582 238 B1

le D-gluconate de cuivre ; le fluorure de cuivre ; l’hydrate de formate de cuivre ; l’hydrate d’hexafluoroacétylacétonate de cuivre ; l’hydroxyde de cuivre ; l’iodure de cuivre ; le complexe de diméthylsulfure et d’iodure de cuivre ; le complexe de triméthylphosphite et d’iodure de cuivre ; le méthoxyde de cuivre ; le molybdate de cuivre ; le nitrate de cuivre ; l’oxyde de cuivre ; l’oxychlorure de cuivre ; l’hexahydrate de perchlorate de cuivre ; l’hydrate de pyro- 5 phosphate de cuivre ; le séléniure de cuivre ; le sélénite de cuivre ; le sulfate de cuivre ; le sulfure de cuivre ; l’hydrate de tartrate de cuivre ; le tellurure de cuivre ; le thiocyanate de cuivre ; le thiophène-2-carboxylate de cuivre ; le thiophénolate de cuivre ; le trifluoroacétylacétonate de cuivre ; le 1-butanethiolate de cuivre ; le 2-éthylhexanoate de cuivre ; le 3-méthylsalicylate de cuivre ; ou le trifluorométhane sulfonate de cuivre.

10 8. Une composition selon l’une quelconque des revendications 3 à 7 dans laquelle le rapport pondéral du 2,2-dibromomalonamide au métal est compris entre 1 000/1 et 1/100.

9. Une composition selon l’une quelconque des revendications 3 à 5 dans laquelle le rapport pondéral du 2,2-dibromomalonamide au métal est compris entre 800/1 et 1/1. 15 10. Une composition selon l’une quelconque des revendications 6 à 7 dans laquelle le rapport pondéral du 2,2-dibromomalonamide au métal est compris entre 100/1 et 1/1.