(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-dibromoma- lonamide 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 microor- ganisms 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 con- taining 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-dibro- momalonamide 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 micro- organisms 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 microorgan- isms, 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 micro- organisms. 55 [0011] The terms "2,2-dibromomalonamide," "dibromomalonamide," and "DBMAL" mean a compound represented by the following formula: 2 EP 2 582 238 B1 5 [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 phos- phate, 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 formu- lations 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