BIOCIDAL COMPOSITIONS AND USE THEREOF

Abstract: A biocidal composition which comprises a mixture of n-alkyl dimethyl benzyl ammonium chloride and n-dodecylguanidine or water soluble salt thereof. A method for controlling the growth of slime forming microbes in an aqueous system which comprises adding to the system a growth inhibiting amount of a composition comprising a mixture of n-alkyl dimethyl benzyl ammonium chloride, and n-dodecylguanidine or water soluble salt thereof.

Description: The present invention relates to biocidal compositions and their use in controlling the growth of slime forming microbes in an aqueous system. The formation of slimes by microorganisms is a problem that is encountered in many aqueous systems. For example, the problem is not only found in natural waters such as, of example, lagoons, lakes or ponds, and confined waters (as, for example, in pools), but also in such industrial systems as, for example, cooling water systems, air washer systems and pulp and paper mill systems. Such locations all possess conditions which are conducive to the growth and reproduction of slime-forming microorganisms. In both once-through and recirculating cooling systems, for example, which employ large quantities of water as a cooling medium, the formation of slime by microorganisms is an extensive and constant problem. Airborne organisms are readily entrained in the water from cooling towers and find this warm medium an ideal environment for growth and multiplication. Aerobic and heliotropic organisms flourish on the tower proper while other organisms colonize and grow in areas such as, for example, the tower sump and the piping and passages of the cooling system. The slime formation not only aids in the deterioration of the tower structure in the case of wooden towers, but also, by its deposition on metal surfaces, promotes corrosion. In addition, slime carried through the cooling system plugs and fouls items such as, for example, lines, valves and strainers, and also deposits on heat exchange surfaces. In the latter case, the impedance of heat transfer can greatly reduce the efficiency of the cooling system. In pulp and paper mill systems, slime formed by microorganisms is commonly encountered and causes fouling, plugging, or corrosion thereof. The slime also becomes entrained in the paper produced to cause breakouts on the paper machines, with consequent work stoppages and the loss of production time, and/or is responsible for unsightly blemishes in the final production, which result in rejects and wasted output. The previously discussed problems have resulted in the extensive utilization of biocides in cooling water and pulp and paper mill systems. Materials which have enjoyed widespread use in such applications include chlorine, chlorinated phenols, organo-bromines, and various organo-sulphur compounds. All of these compounds are generally useful for this purpose but each is attended by a variety of impediments. For example, chlorination is limited both by its specific toxicity for slime-forming organisms at economic levels and by the tendency of chlorine to react, which results in the expenditure of the chlorine before its full biocidal function is achieved. Other biocides are attended by odour problems and hazards in respect to storage, use or handling which limit their utility. To date, no one compound or type of compound has achieved a clearly established predominance in respect to the applications discussed. Likewise, lagoons, ponds, lakes, and even pools, either used for pleasure purposes or used for industrial purposes for the disposal and storage of industrial wastes, become, during the warm weather, beseiged by slime due to microorganism growth and reproduction. In the case of the recreational areas the problem of infection is obvious. In the case of industrial storage or disposal of industrial materials, the microorganisms cause additional problems which must be eliminated prior to use of the material or disposal of the waste. Naturally, economy is a major consideration in respect to all of these biocides. Such economic considerations attach to both the cost of the biocide and the expense of its application. The cost performance index of any biocide is derived from the basic cost of the material, its effectiveness per unit of weight, the duration of its biocidal or biostatic effect in the system treated, and the ease and frequency of its addition to the system treated. To date, none of the commercially available biocides has exhibited a prolonged biocidal effect. Instead, their effectiveness is rapidly reduced as the result of exposure to physical conditions such as, for example, temperature, association with ingredients contained by the system toward which they exhibit an affinity of substantivity, etc., with a resultant restriction or elimination of their biocidal effectiveness, or by dilution. As a consequence, the use of such biocides involves their continuous or frequent addition to systems to be treated and their addition to a plurality of points or zones in the systems to be treated. Accordingly, the cost of the biocide and the labour cost of such means of applying it are considerable. In other instances, the difficulty of access to the zone in which slime formation is experienced precludes the effective use of a biocide. For example, if in a particular system there is no access to an area at which slime formation occurs the biocide can only be applied at a point which is upstream in the flow system. However, the physical or chemical conditions, e.g., chemical reactivity or thermal degradation, which exist between the point at which the biocide may be added to the system and the point at which its biocidal effect is desired render the effective use of a biocide impossible. Similarly, in a system experiencing relatively slow flow, such as, for example, a paper mill, if a biocide is added at the beginning of the system, its biocidal effect may be completely dissipated before it has reached all of the points at which this effect is desired or required. As a consequence, the biocide must be added at a plurality of points, and even then a diminishing biocidal effect will be experienced between one point of addition to the system and the next point downstream at which the biocides may be added. In addition to the increased cost of utilizing and maintaining plural feed points, a gross uneconomic situation with respect to the cost of the biocide is experienced. Specifically, at each point of addition, an excess of the biocide must be added to the system in order to compensate for that portion of the biocide which will be expended in reacting with other constituents present in the system or experience physical changes which impair its biocidal activity. Use of specific n-alkyl dimethyl benzyl ammonium chlorides and n-dodecylguanidine salts, singly, as a biocide is known in the art. For instance n-dodecylguanidine hydrochloride and n-dodecyl­ guanidine acetate are both listed at 21 CFR §176.170 as being F.D.A. acceptable antimicrobial agents for paper and paperboard use under certain conditions. Similarly, n-alkyl (C₁₂ - C₁₈) dimethyl benzyl ammonium chloride is listed at 21 CFR 176.300 as being a slimicide that may be safely used in the manufacture of paper and paperboard products that contact food. Use of specific n-alkyl dimethyl benzyl ammonium chlorides in various biocidal compositions is also disclosed in US-A- 3 934 025, US-A- 3 827 873, and US-A- 3 881 008. Other patent specifications which may be noted of possible interest include US-A- 3 264 172; US-A- 3 142 615; US-A- 2 906 595; and US-A- 2 409 883. It has now been surprisingly found that mixtures of n-alkyl dimethyl benzyl ammonium chlorides and n-dodecylguanidine hydrochloride or water soluble salts therefore are especially efficacious in controlling the growth of slime-forming microbes. According to the present invention there is provided a biocidal composition which comprises a mixture of n-alkyl dimethyl benzyl ammonium chloride and n-dodecylguanidine or water soluble salt thereof. The present invention also provides a method for controlling the growth of slime-forming microbes in an aqueous system which comprises adding to the system a growth inhibiting amount of a composition comprising a mixture of n-alkyl dimethyl benzyl ammonium chloride, and n-dodecylguanidine or water soluble salt thereof. The n-alkyl dimethyl benzyl ammonium chloride is sometimes hereinafter referred to as "quat" and the n-dodecylguanidine or water soluble salt thereof is sometimes hereinafter referred to as "DGH". A preferred "quat" is one comprising an alkyl distribution of (50% C₁₄, 40% C₁₂, 10% C₁₆). The weight ratio of DGH to quat is preferably from about 1:2 to about 1:8. The composition of the present invention has been found to be especially efficacious in controlling the growth of bacterial microbes, particularly the Klebsiella pneumoniae species. This particular species is a member of the capsulated, facultative class of bacteria and is generally present in air, water and soil. These bacteria continually contaminate open cooling systems and pulping and papermaking systems and are among the most common slime formers. This slime may be viewed as being a mass of agglomerated cells stuck to­ gether by the cementing action of the gelatinous polysaccharide or proteinaceous secretions around each cell. The slimy mass entraps other debris, restricts water flow and heat transfer, and may serve as a site for corrosion. The fact that the Klebsiella species used in the tests is a facultative species is important as, by definition, such bacteria may thrive under either aerobic or anaerobic conditions. According­ ly, by reason of demonstrated efficacy in the growth inhibition of this particular species, one can expect similar growth inhibition attributes when other aerobic or anaerobic bacterial species are en­ countered. The n-alkyl (50% C₁₄, 40% C₁₂, 10% C₁₆) dimethyl benzyl ammonium chloride is commercially available from various sources. For instance, it is sold under the trademark "Maquat 1412" from Mason Chemical Co., "Onyx 8358" from Onyx Chemical Co., or "Hyamine 3500" by Lonza Inc. As to the water soluble n-dodecylguanidine salt that may be used, the hydrochloride, acetate, carbonate and nitrate salts may be mentioned as being exemplary. The preferred hydrochloride salt is commercially available under the trademark "Cytox 2013" or "Cytox 2014" from American Cyanamid. In accordance with the present invention, the combined quat:DGH treatment may be added to the desired aqueous system in need of biocidal treatment, in an amount of preferably from about 0.001 to about 200 parts of the combined treatment to one million parts (by weight) of the aqueous medium. More preferably, about 5 to about 50 parts of the combined treatment per one million parts (by weight) of the aqueous medium is added. The combined treatment is added, for example, to cooling water systems, paper and pulp mill systems, pools, ponds, lagoons, or lakes, to control the formation of bacterial microorganisms, which may be contained by, or which may become entrained in, the sys­ tem to be treated. It has been found that the quat/DGH compositions and methods of utilization of the treatment are efficacious in con­ trolling the facultative bacterium, Klebsiella pneumoniae , which may populate these systems. It is thought that the combined treatment composition and method of the present invention will also be effica­ cious in inhibiting and controlling all types of aerobic and anaero­ bic bacteria. Surprisingly, it has been found that when the quat/DGH in­ gredients are mixed, in certain instances, the resulting mixtures possess a higher degree of bactericidal activity than that of the individual ingredients comprising the mixture. Accordingly, it is possible to produce a highly efficacious bactericide. Because of the enhanced activity of the mixture, the total quantity of the bacterial treatment may be reduced. In addition, the high degree of bacteri­ cidal effectiveness which is provided by each of the ingredients may be exploited without use of higher concentrations of each. The following experimental data were developed. It is to be remembered that the following examples are to be regarded solely as being illustrative, and not as restricting the scope of the inven­ tion. Quat and DGH were added in varying ratios and over a wide range of concentrations to a liquid nutrient medium which was subsequently inoculated with a standard volume of a suspension of the facultative bacterium Klebsiella pneumoniae . Growth was measured by determining the amount of radioactivity accumulated by the cells when ¹⁴C-glucose was added as the sole source of carbon in the nut­ rient medium. The effect of the biocide chemicals, alone and in com­ bination, is to reduce the rate and amount of ¹⁴C incorporation into the cells during incubation, as compared to controls not treated with the chemicals. Additions of the biocides, alone and in varying com­ binations and concentrations, were made according to the accepted "checkerboard" technique described by M. T. Kelley and J.M. Matsen, Antimicrobial Agents and Chemotherapy . 9: 440, (1976). Following a four hour incubation, the amount of radioactivity incorporated in the cells was determined by counting (¹⁴C liquid scintillation proced­ ures) for all treated and untreated samples. The percent reduction of each treated sample was calculated from the relationship: Plotting the % reduction of ¹⁴C level against the concen­ tration of each biocide acting alone results in a dose-response curve, from which the biocide dose necessary to achieve any given % reduction can be interpolated. Synergism was determined by the method of calculation de­ scribed by F. C. Kull, P. C. Eisman, H. D. Sylwestrowicz and R. L. Mayer, Applied Microbiology 9, 538, (1961) using the relationship: where: Q a = quantity of compound A, acting alone, producing an end point Q b = quantity of compound B, acting alone, producing an end point Q A = quantity of compound A in mixture, producing an end point Q B = quantity of compound B in mixture, producing an end point The end point used in the calculations is the % reduction caused by each mixture of A and B. Q A and Q B are the individual con­ centrations in the A/B mixture causing a given % reduction. Q a and Q b are determined by interpolation from the respective dose-response curves of A and B as those concentrations of A and B acting alone which produce the same % reduction as each specific mixture produced. Dose-response curves for each active acting alone were de­ termined by linear regression analysis of the dose-response data. Data were fitted to a curve represented by the equation shown with each data set. After linearizing the data, the contributions of each biocide component in the biocide mixtures to the inhibition of radio­ isotope uptake were determined by interpolation with the dose re­ sponse curve of the respective biocide. If, for example, quantities of Q A plus Q B are sufficient to give a 50% reduction in ¹⁴C content, Q a and Q b are those quantities of A or B acting alone, respectively, found to give 50% reduction in ¹⁴C content. A synergism index (SI) is calculated for each combination of A and B. Where the SI is <1, synergism exists. Where the SI = 1, additivity exists. Where SI>1, antagonism exists. The data in the following Tables come from treating Kleb­ siella pneumoniae , a common nuisance bacterial type found in indus­ trial cooling waters and in pulping and paper making systems, with varying ratios and concentrations of quat and DGH. Shown for each combination is the % reduction of ¹⁴C content, the calculated SI, and the weight ratio of quat to DGH. In accordance with Tables I-III supra., unexpected results occurred more frequently within the product ratios of DGH product: Quat product of from about 1:1 to 1:8. Since the tested DGH product was about 35% active and the Quat product about 80% active, this range translates to a range of DGH:Quat (100% actives basis) of from about 1:2 to about 1:8. At present, it is preferred that the commer­ cial product embodying the invention comprise a weight ratio of about 1:2 DGH:Quat.

Claims: 1. A biocidal composition which comprises a mixture of n-alkyl dimethyl benzyl ammonium chloride and n-dodecylguanidine or water soluble salt thereof. 2. A composition according to claim 1, wherein the n-alkyl dimethyl benzyl ammonium chloride comprises an alkyl distribution of (50% C₁₄, 40% C₁₂, 10% C₁₆). 3. A composition according to claim 1 or 2, wherein the weight ratio of the n-dodecylguanidine or water soluble salt thereof to the n-alkyl dimethyl benzyl ammonium chloride is from about 1:2 to about 1:8. 4. A method for controlling the growth of slime forming microbes in an aqueous system which comprises adding to the system a growth inhibiting amount of a composition comprising a mixture of n-alkyl dimethyl benzyl ammonium chloride, and n-dodecylguanidine or water soluble salt thereof. 5. A method according to claim 4, wherein the n-alkyl dimethyl benzyl ammonium chloride comprises an alkyl distribution of (50% C₁₄, 40% C₁₂, 10% C₁₆). 6. A method according to claim 4 or 5, wherein the weight ratio of the n-dodecylguanidine or water soluble salt thereof to the n-alkyl dimethyl benzyl ammonium chloride is from about 1:2 to about 1:8. 7. A method according to any of claims 4 to 6, wherein the composition is added to the aqueous system in an amount of from about 0.1 to about 200 parts per weight of the composition per million parts by weight of the aqueous system. 8. A method according to claim 7, wherein the composition is added to the system in an amount of from about 5 to about 50 parts per million of the aqueous system. 9. A method according to any of claims 4 to 8, wherein the microbes comprise bacteria. 10. A method according to any of claims 4 to 8, wherein the microbes comprise Klebsiella pneumoniae bacteria. 11. A method according to any of claims 4 to 10, wherein the aqueous system comprises a cooling water system. 12. A method according to any of claims 4 to 10, wherein the aqueous system comprises a pulping and papermaking system.

Inventors: DONOFRIO, DEBORAH KALMAN, SWERED, PAUL
Applicants: BETZ EUROPE, INC.
Application year: 1987
Main classification: A01N47
IPC codes: A01N47, C02F1