MXPA00000278A - Synergistic antimicrobial compositions containing a dimethylamide of a carboxylic acid with a mixture of 2-(thiocyanomethylthio) benzothiazole and methylene-bis(thiocyanate) - Google Patents

Abstract

Compositions comprising a mixture of 2-(thiocyanomethylthio)benzothiazhole and methylene-bis(thiocyanate) with dimethylamide of a carboxylic acid are disclosed which are synergistically effective compared to the respective components alone in controlling the growth of microorganisms in or on a product, material, or medium. Methods to control the growth of microorganisms and prevent spoilage caused by microorganisms with the use of the compositions of the present invention are also disclosed.

Description

COMPOSITIONS ANTIMICROB NAS SINERGIST CAS CONTAINING A DIMETHYLAMIDE OF A CARBOXYLIC ACID WITH A MIXTURE OF 2- (TIOCYANOMETHYLENE) BENZOTIZAZOL AND METHYLENE-BIS (THYOCIANATE) DESCRIPTION OF THE INVENTION The present invention relates to certain compositions and processes useful for controlling the growth of one or more microorganisms and to avoid decomposition caused by bacteria, fungi and algae in various products, materials, or media, particularly industrial products, materials or media. These products, materials or media include wood pulp, wood chips, joists, adhesives, coatings, animal skins, paper sheet liquors, processed waters, pharmaceutical formulations, cosmetic and toilet formulations, geological drilling lubricants, petrochemicals, agrochemical compositions, paints, leathers, wood, metalworking fluids, cooling water (for example, cooling tower water), tanning liquors, starch, proteinaceous materials, acrylic latex paint emulsions, and textiles. The novel compositions and processes that incorporate the compositions of the present invention unexpectedly show synergistic activity against microorganisms, including bacteria, fungi and algae. Specifically, the present invention is directed to the use of compositions containing a) a mixture of 2 (-thiocyanomethylthio) benzothiazole and methylenebis (thiocyanate) with b) a dimethylaryl of a carboxylic acid. Many of the products, materials or media mentioned in the foregoing, when wetted or subjected to treatment in water, are susceptible to deterioration or degradation by bacteria and / or fungi unless the steps are taken to inhibit such degradation or deterioration. To control the deterioration or degradation caused by microorganisms, several industrial microbicides are used, but some of these biocides are of questionable utility because they have unpleasant odors, are high in cost, show low degree of effectiveness or create dangers with respect to storage, use or management. For example, the use of such popular microbicides as organomercury compounds, organotin compounds and chlorinated phenols have come under great regulatory pressures in recent times due to their high toxicity and concern about their adverse effect on the environment. Commercial workers have continued to exploit improved biocides that have low toxicity and are capable of exhibiting a prolonged biocidal effect at levels of normal use. Methylene bis (thiocyanate) can be used only at low concentrations as low toxicity biocides. However, at low concentrations, methylene-bis (thiocyanate) tends to have a narrow antimicrobial spectrum and failures to completely prevent the growth of microorganisms. Similarly, 2- (thiocyanomethylthio) benzothiazole (also known as TCMTB) can also be used only in low concentrations as a biocide. Like methylene-bis (thiocyanate), TCMTB at low concentrations tends to have a narrow antimicrobial spectrum and failures to completely prevent the growth of microorganisms at times. Accordingly, the present invention is directed to microbicidal compositions and processes that incorporate these compositions that substantially obviate one or more of the problems, limitations, and disadvantages described above and experienced by those skilled in the art. In particular, the compositions of the present invention are capable of controlling the growth of at least one microorganism, especially fungi, bacteria, or algae, over extended periods of time and are safe and economical to use. The present invention is also directed to methods or processes for controlling the growth of at least one microorganism. Accordingly, it is an object of the present invention to provide a microbicidal composition capable of controlling the growth of at least one microorganism, particularly fungi, bacteria, or algae, for prolonged periods of time. It is an additional object to provide compositions that are economical to use. Methods of controlling the growth of at least one microorganism are also objects of this invention. The present invention provides a composition for controlling the growth of at least one microorganism comprising a) a mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate) with b) a dimethylamide of a carboxylic acid wherein the components are presented in a combined synergistically effective amount to control the growth of at least one microorganism. The composition of the present invention preferably provides superior microbicidal activity at low concentrations against a wide range of microorganisms. The present invention also provides a method for controlling the growth of at least one microorganism in, or a material or medium susceptible to attack by the microorganism which comprises the step of adding to the material or medium a composition of the present invention, wherein the components of the composition are present in synergistically effective amounts to control the growth of the microorganism. The synergistically effective amount varies according to the material or medium to be treated and can, for a particular application, be routinely determined by one skilled in the art in view of the present invention. The present invention also incorporates the separate addition of a mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate) with a dimethylamide of a carboxylic acid to the products, materials or media described above. According to this modality, the components are individually added to the system either the final quantity of the mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate), and the dimethylamide present in the system at the time of use is that the synergistically effective amount to control the growth of at least one microorganism. The compositions of the present invention are also useful for preserving various types of industrial products, media, or materials susceptible to attack by microorganisms. Such means or materials include, but are not limited to, dyes, pulps, joists, hides, textiles, pulp, wood chips, tanning liquors, paper sheet liquors, polymer emulsions, paints, paper and other coatings and coating agents. gluing, metalworking fluids, geological drilling lubricants, petrochemicals, cooling water systems, pharmaceutical formulations, and cosmetic and toilet formulations. The compositions of the present invention may also be useful in agrochemical formulations for the purpose of protecting seeds or crops against microbial decomposition. Additional advantages of the present invention will be set forth in part in the description that follows, and in part will be apparent from the description, or may be learned by the practice of the present invention. The advantages of the present invention can be realized and obtained by means of the elements and combinations particularly pointed out in the claims. It will be understood that both of the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present invention as claimed. According to the methods of the present invention, controlling or inhibiting the growth of at least one microorganism includes reducing and / or preventing such growth. It will further be understood that by "controlling" the growth of at least one microorganism, the growth of the microorganism is inhibited and / or prevented. In other words, there is no growth or essentially no growth of the microorganism. "Control" the growth of at least one microorganism - keeps the population of the microorganism at a desired level, reduces the population to a desired level (even to undetectable limits, for example, zero population), and / or inhibits the growth of the microorganism. Thus, the products, material, or means susceptible to attack by these types of microorganisms are preserved from this attack and the decomposition and other resulting detrimental effects caused by the microorganism can be avoided. In addition, it will also be understood that "controlling" the growth of at least one microorganism may also include reducing and / or maintaining a low level of microorganism biostatically such that attack by a microorganism and any resulting decomposition or other deleterious effect are mitigated ie the ratio of microorganism growth or attack ratio to microorganisms is retarded or eliminated. When two chemical microbicides are combined or mixed into a product or aggregates separately three results are possible: 1) The chemicals in the product produce an additive (neutral) effect, 2) The chemicals in the product produce an antagonistic effect, or 3) The Chemicals in the product produce a synergistic effect. An additive effect has no economic advantage over the individual components. The antagonistic effect could have a negative impact. Only a synergistic effect, which is less likely to be an additive or antagonistic effect, produces a positive effect and therefore has economic advantages. It is well known in the microbicidal literature that there is a non-theoretical method to provide the possibility of knowing, before the actual test, whether the additive, antagonistic or synergistic effects will be obtained when two biocides are mixed to produce a formulation. As can be seen in the examples, concentrations as high as 900 ppm of the carboxylic acid dimethylamide itself were ineffective against the test organism. Thus, the dimethylamide of a carboxylic acid for all practical purposes can be viewed as a non-microbicidal material. This is one of the only characteristics of this invention as its use made of a non-microbicidal material such as dimethylamide to significantly improve the antimicrobial properties of a mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate). This is a very unexpected and synergistic feature of this invention. This result, from a combination of microbicides and a non-microbicidal material, is a very rare occurrence. Microbicidal compositions that combine a mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate) with a dimethylamide of a carboxylic acid demonstrate an unexpected, synergistic effect compared to the respective components alone. Thus, these compositions are superior, ie, greater than the additive, microbicidal activity at low concentrations against a wide variety of microorganisms. Examples of microorganisms include fungi, bacteria, algae and mixtures thereof such as Trichoderma harzianum and pseudomonas aeruginosa. These organisms are some of the most common organisms associated with decomposition of products, materials, or media. Since these representative organisms are also some of the hardened organisms to be controlled, the compositions of the present invention are created to be effective against most bacteria, fungi, algae and mixtures thereof. Preferably, the compositions of the present invention have a low toxicity. The preparation of 2- (thiocyanomethylthio) benzothiazole is described in U.S. Patent Nos. 3,520,976 and 5,073,638 and the methylene-bis (thiocyanate) preparation (MTC) is described in U.S. Patent No. 3,524,871, and these descriptions are fully incorporated for reference in the present. 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate) are commercially available and are also easily synthesized from raw materials, commercially available. MTC is also known as 2-methylene-bis (thiocyanate). The mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate) is sold in various concentrations under trade names such as Busan © 1009, MECT, etc. These commercial products are available from Buckman Laboratories International, Inc., and other distributors. Busan® 1009 is an emulsifiable concentrate of 10% by weight of 2- (thiocyanomethylthio) benzothiazole and 10% by weight of methylene-bis (thiocyanate). The amounts of the active ingredients in the mixture used as a component in this invention can preferably range from about 1% to about 80%, more preferably from about 1% to about 40%, by weight of 2- (thiocyanomethylthio) ) benzothiazole and from about 1% to about 80%, preferably 1% to about 40%, by weight of methylene-bis (thiocyanate). The most preferred amounts of these ingredients are those found in Busan® 1009. A description of carboxylic acid dimethylamides can be found in US Patent Nos. 4,425,186 and 5,388,644, both incorporated in their entirety for reference herein. Patent No. 5,388,644 also shows a method for performing these types of dimethylamides. The N, N-dimethylamides of the suitable carboxylic acids can preferably be prepared from straight chain carboxylic acids containing from 12 to 18 carbon atoms. Although any carboxylic acid containing 12 to 18 carbon atoms is suitable for purposes of the present invention, those carboxylic acids containing 18 carbon atoms are preferred, since such acids are readily available in large quantities at economic costs. These preferred acids are further characterized by having at least one carbon-double bond carbon. Specific acids classified within this preferred category include, but are not limited to: oleic, linoleic, linolenic, ricinoleic and mixtures thereof. Also suitable are the mixed acids found in resin, castor, corn, safflower, linseed, olive, peanut, rapeseed, sunflower, sesame, and soybean oils. A dimethylamide of this resin oil fatty acid (DMATO) can be used and is available as a primary ingredient in a Busperse® 47 dispersant, available from Buckman International Laboratories, Inc. A typical analysis of the fatty acid of resin oil (the which is converted to DMA) is as follows: Typical Analysis Fatty acid, pet 97.5 colophony acids, pet 1.0 Not saponifiable, pet 1.5 Linoleic acid, pet 45.1 Oleic acid, pet 49.5 Saturated acid, pet 1.6 Acid number 195.0 Saponification number 197.0 Color, Gardner 3.0 Specific gravity, 25 ° C./25 0.902 Concentration, ° C 2.0 Flash point, ° F 380.0 Flammability temperature, ° F 423.0 The N, N-dimethylamides of these fatty acids of resin oil will hereinafter be referred to as DMA. Specific examples of dimethylamides of a carboxylic acid include, but are not limited to, N, N-dimethyl-linolenamide, N, -dimethyltrinoleamide, N, N-dimethyloleamide, and N, N-dimethyl-linoleamide. In accordance with the present invention, mixtures of carboxylic acid dimethylamides can also be used in the composition of the present invention. The carboxylic acid dimethylamides useful in the present invention are commercially available or can be synthesized from commercially available raw materials. The dimethylamides of a carboxylic acid can be chosen, for example, based on the compatibility of the carboxylic acid dimethylamide with the products, materials, or media. The compatibility is easily determined by adding the dimethyl amide of the carboxylic acid to the products, materials, or means to be used. The compatibility can also be determined by criteria such as a solubility in a fluid system and / or loss of reactivity with the fluid in question. When used in the fluid system, for example, it is preferable that the dimethylamide of a carboxylic acid being freely soluble or dispersible in the particular fluid system, resulting in a uniform solution or dispersion. Examples of fluid systems are tanning liquors, paper sheet liquors, cooling tower waters, and paints. In the following discussion of the preferred embodiments, component (a) is a Busan® product 1009 which is an emulsifiable concentrate of a mixture of 10% by weight of 2- (thiocyanomethyl-thio) benzothiazole and 10% by weight of methylene- bis (thiocyanate) and component (b) is DMA. The DMA of choice is the N, N-dimethylamide of the fatty acids of resin oil.

As described above, components (a) and (b) are used in synergistically effective amounts. The weight ratios of (a) or (b) vary depending on the type of microorganisms, products, materials or media to which the composition is applied. One skilled in the art can easily determine in view of this description, and without undue experimentation, the appropriate weight ratios for a specific application. The ratio of component (a) to component (b) preferably ranges from about 99: 1 to about 1:99, more preferably from about 1:30 to about 30: 1, and more preferably from about 1: 5 to about 5: 1. In general, an effective fungal, bactericidal and / or algicidal response can be obtained when the synergistic combination is employed in concentrations (based on the media to be treated or emulsion used) ranging from about 0.01 to about 5000 ppm of the mixture of 2- (thiocyanomethylthio) benzothiazole and methylene bis (thiocyanate), preferably from about 0.1 to about 1000 ppm, and more preferably from about 0.1 to about 500 ppm; and from about 0.1 ppm to about 5000 ppm of dimethylamide of a carboxylic acid, preferably from about 0.1 to about 2000 ppm, and more preferably from about 0.1 to about 500 ppm. In accordance with the present invention, the composition may be in the form of a solid, dispersion, emulsion, or solution, depending on the particular application. In addition, the components of the composition can be applied separately or can be combined first and then applied to the product, material or medium. The present invention also provides a method for controlling the growth of at least one microorganism in, or a material or susceptible medium attacked by the microorganism which comprises the step of applying to the product, material or medium a composition of the present invention, wherein the components of the composition are present in synergistically effective amounts. In addition, the present invention provides a method for preventing decomposition of a product, material or medium caused by a bacterium, fungus and / or algae, comprising the step of applying to the product, material or medium a composition of the present invention wherein the Components of the composition are present in synergistically effective amounts. For example, the composition can be used to prevent the decomposition of seeds or crops, for example, cotton, barley, rice, corn, tobacco, etc.

Depending on the intended use, the mode as well as the application ratio of the composition of this invention could vary. For example, the composition could be applied by spraying or sweeping the material or product. The material or product in question could also be treated by immersion in a suitable formulation of the composition. In a liquid or liquid-like medium, the composition could be added to the medium by emptying or measuring with a suitable device so that a solution or a dispersion of the composition could be produced. If used as a liquid preservative, for example, the composition can be prepared as an aqueous emulsion. If necessary, a surfactant can be added to the composition. B-roasted in the specific application, the composition can be prepared in liquid form by dissolving the composition in an organic solvent. The compositions of the present invention can be prepared in an emulsion form by emulsifying in water, or if necessary, adding a surfactant. In accordance with the present invention, additional components such as insecticides and the like can be added to the above preparations without affecting the synergistic effects of the composition. Insecticides that can be used include, but are not limited to pyrethrins, nicotine, chlordane and parations.

The synergistic activity of the combinations described above has been confirmed using standard laboratory techniques as illustrated below. The following examples are intended to illustrate, without limitation, the scope of the present invention. Microbiological Evaluation The nutrient broth was prepared (2.5 g / liter of deionized water). This was distributed in 5 ml of quantities in test tubes and is autoclaved for 20 minutes at 121 ° C. -After the addition of the biocides in the desired concentrations to the nutrient broth, 100 microliters of a suspension of Pseudomonas aeruginosa cells of approximately 9.3 x 108 cfc / ml were added and incubated at 37 ° C for 2 hours. In the example which follows, the synergistic effect was demonstrated in separate experiments by testing a mixture of 2- (thiocyanomethyl-thio) benzothiazole and methylene-bis (thiocyanate) or Busan® 1009, designated as component A and Busperse dispersant © 47 ( DMA) as component B in a series of tests in varied relationships and a range of concentrations against the bacterium, Pseudomonas aeruginosa using the methods described above. For each component A and B in the mixture containing A and B and for each component A and B acting alone, the lowest concentration which completely prevents the growth of the bacteria for 24 hours was determined. These concentrations were used as endpoints for synergism calculations. The end points for the components alone or in mixtures described above were then compared with the endpoints for the pure active ingredients alone in concomitantly prepared test tubes. The synergism was demonstrated by the method described by Kull, E.C., Eisman, P.C., Sylwestwicz, H.D., and Mayer, R.L., 1961. Applied Microbiology. 9: 538-541 where QA / Qa + QB / Qb is less than 1 Qa = Concentration of Compound A in parts per million, acting alone, which produces a final point. Qb = Concentration of Compound B in parts per million, which acts alone, which produces a final point. QA = Concentration of Compound A in parts per million, in the mixture, which produces a final point. QB = Concentration of compound B in parts per million, in the mixture, which produces a final point. When the sum of QA / Qa and QB / Qb is greater than one, the antagonism is indicated and when the sum is equal to one, the additivity is indicated. When the sum of this value is less than one, there is synergism. This method for demonstrating synergism of the compositions of this invention is widely used and the process acceptable. More detailed information is provided in the article by Kull et al. Additional information concerning this procedure is contained in US Patent No. 3, 231,509, the description of which is herein, forms part of this application. In general, however, an effective fungal and bactericidal response can be obtained when the synergistic combination is employed in concentrations ranging from about 0.01 to about 5000 ppm of the mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate), preferably from about 0.1 to about 1000 ppm, and more preferably from about 0.1 ppm to about 500 ppm; and from about 0.1 to about 5000 ppm of dimethylamide of a carboxylic acid, preferably from about 0.1 to about 2000 ppm, and more preferably from about 0.1 to about 500 ppm. As already described, the synergistic activity results when the synergistic relationship of component (a) and component (b) is less than one. From the above examples, it is apparent that the composition comprises a mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate) with a dimethylamide (which is not a microbicide) in a synergistic amount possessing effective antimicrobial activity to inhibit growth of bacteria. It will be apparent to those skilled in the art that the synergistically effective amounts required (concentrations) will vary depending on the particular organisms and particular applications, and can easily be determined by routine experimentation. The use of a synergistically effective amount allows the use of a substantially small amount of TCMTB and MTC to achieve a given effect that might be necessary for each biocide if used alone or that might be necessary if a low additive effect of these two is obtained biocides Example 1 Component A = Busan 1009 (10% of TCMTB / 10% of MTC) Component B = Dimethylamide (DMA) Quantities of Test Organism that produce endpoints (ppm) Example 2 The synergistic activity of various combinations of 2- (thiocyanomethylthio) benzothiazole, methylene-bis (thiocyanate), and diethylamide was tested using the same techniques described above. The test organism used was Pseudomonas aeroginosa. The results are reported in the following Experiments. EXPERIMENT 1 A combination of Busperse® 47 (a 90% formulation of dimethylamide (DMA)) and BUSAN 1030 (a 30% formulation of 2- (thiocyanomethylthio) benzothiazole (TCMTB)) was tested in the following amounts. The growth was examined after 48 hours. A record of "0" indicates no growth, and a record of "+" indicates growth.

TABLE 1 The synergistic activity results according to the procedures of the present application (after 8 hours) are reported in the following Table. TABLE2 As shown above, synergism after 48 hours was demonstrated only at relatively high concentrations of at least 30 ppm of active TCMTB (at least 100 ppm of BUSAN 1030) and at least 90 ppm of active DMA (at least 100 ppm Busperse® 47). EXPERIMENT 2 A combination of Busperse® 47 (a 90% formulation of dimethylamide) and BUSAN 110 (a 10% methylene bis-thiocyanate formulation) was tested in the following amounts. The growth was examined after 28 and 48 hours. A record of "0" indicates no growth, and a record of "+" indicates growth. TABLE 3 The synergistic activity results in accordance with the procedures of the present application (after 24 hours) are reported in the following Table.

TABLE 4 Although the synergistic activity was demonstrated after 24 hours, there is no synergistic activity after 48 hours. EXPERIMENT 3 A combination according to the present invention of Busperse® 47 and BUSAN 1009 (a mixture of 10% 2- (thiocyanomethylthio) benzothiazole and 10% methylene-bis (thiocyanate)) was tested in the following amounts. Growth was examined for 24 and 48 hours. A record of "0" indicates no growth and a record of "+" indicates growth.

TABLE 5 The synergistic activity results in accordance with the procedures of the present application (after 24 hours) are reported in the following Table.

TABLE 6 The above results show synergistic activity after 24 and 48 hours with relatively low concentrations of TCMTB (0.5 ppm) and DMA (less than 90 ppm) compared to Experiment 1 above. As shown in Experiment 1, 'synergism was only demonstrated at concentrations of at least 30 ppm of TCMTB and at least 90 ppm of DMA. It will be apparent to those skilled in the art that various modifications and variations may be made in the compositions and methods of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided within the scope of the appended claims and their equivalents.

Claims (32)

1. CLAIMS 1. A composition for controlling the growth of at least one microorganism, characterized in that it comprises synergistically effective amounts of (a) a mixture of 2-thiocyanomethylthio (benzothiazole) and methylene-bis (thiocyanate), and (b) a dimethylamide of a carboxylic acid.
2. 2. The composition according to claim 1, characterized in that the microorganism is selected from bacteria, fungi, algae or mixtures thereof.
3. 3. The composition according to claim 1, characterized in that the carboxylic acid contains 12-18 carbon atoms.
4. 4. The composition according to claim 1, characterized in that the carboxylic acid has at least one carbon to a carbon double bond.
5. The composition according to claim 1, characterized in that the carboxylic acid is a straight chain carboxylic acid containing 18 carbon atoms and at least one carbon to a carbon double bond.
6. 6. The composition according to claim 5, characterized in that the straight chain carboxylic acid is linoleic acid or linolenic acid.
7. 7. The composition according to claim 5, characterized in that the straight chain carboxylic acid is oleic acid.
8. 8. The composition according to claim 5, characterized in that the straight chain carboxylic acid is ricinoleic acid.
9. 9. The composition according to claim 5, characterized in that the straight chain carboxylic acid is a mixture of acids derived from resin oil.
10. 10. The composition according to claim 5, characterized in that the straight chain carboxylic acid is a mixture of acids derived from linseed oil.
11. 11. The composition according to claim 5, characterized in that the straight chain carboxylic acid is a mixture of acids derived from safflower oil.
12. 12. The composition according to claim 5, characterized in that the carboxylic acid is a mixture of acids derived from corn acid.
13. The composition according to claim 5, characterized in that the straight chain carboxylic acid is a derivative of peanut oil, resin oil, castor oil, corn oil, safflower oil, linseed oil, olive oil , rapeseed oil, sunflower oil, sesame oil, soybean oil or mixtures thereof.
14. 14. The composition according to claim 1, characterized in that the dimethylamide of a carboxylic acid is N, N-dimethyloleamide.
15. 15. The composition according to claim 1, characterized in that the dimethylamide of a carboxylic acid is N, N-dimethyl-linolenamide.
16. The composition according to claim 1, characterized in that the dimethylamide of a carboxylic acid is N, N-dimethyltrinoleamide, N, N-dimethyl-linoleamide or N, N-dimethyloleamide.
17. 17. The composition according to claim 1, characterized in that the weight ratio of (a) to (b) is from about 99: 1 to about 1:99.
18. 18. The composition according to claim 17, characterized in that the weight ratio of (a) to (b) is from about 1:30 to about 30: 1.
19. 19. The composition according to claim 18, characterized in that the weight ratio of (a) to (b) is from about 1: 5 to about 5: 1.
20. The composition according to claim 1, characterized in that the weight ratio of the concentrations are from about 0.01 to about 5000 ppm of the mixture of 2-thiocyanomethylthio (benzothiazole) and methylene-bis (thiocyanate), and of about 0.1 at about 5000 ppm by weight of the dimethylamide of a carboxylic acid.
21. The composition according to claim 20, characterized in that the weight ratio of the concentrations are from about 0.1 to about 1000 ppm of the mixture of 2- (thiocyanomethylthio (benzothiazole) and methylene-bis (thiocyanate), and from about 0.1 to about 2000 ppm dimethylamide of a carboxylic acid.
22. The composition according to claim 21, characterized in that the weight ratio of the concentrations are from about 0.1 to about 500 ppm of the mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate), and of about 0.1 to about 500 ppm of the dimethylamide of a carboxylic acid.
23. 23. A method for controlling the growth of at least one microorganism in, or a product, material, or medium susceptible to attack by such microorganism, characterized in that it comprises the step of applying to the product, material or medium a composition comprising synergistically effective amounts. for controlling the growth of (a) a mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate), and (b) a dimethylamide of a carboxylic acid.
24. 24. The method of compliance with the claim 23, characterized in that the product, material, or medium is wood pulp, wood chips, joist, paints, leather, adhesives, coatings, animal skins, tanning liquors, paper sheet liquors, metal working fluids, petrochemicals, pharmaceutical formulations, cooling tower water, cosmetics, toilet formulations, textiles, geological drilling lubricants or agrochemical compositions for the protection of crops or seeds.
25. 25. The method of compliance with the claim 23, characterized in that the composition is in the form of a solid, dispersion, emulsion or solution.
26. 26. The method according to claim 23, characterized in that the components (a) and (b) are added separately to the product, material or medium.
27. 27. The method according to claim 23, characterized in that the components (a) and (b) are first combined and then added to the product, material or medium.
28. The method according to claim 23, characterized in that the weight ratio of the concentrations are from about 0.01 to about 5000 ppm of the mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate), and of about 0.1 ppm to about 5000 ppm by weight of the carboxylic acid dimethylamide.
29. The method according to claim 28, characterized in that the weight ratio of the concentrations are from about 0.1 to about 1000 ppm of the mixture of 2- (thiocyanatomethylthio) benzothiazole and methylene-bis (thiocyanate), and of about 0.1 to about 2000 ppm dimethylamide of a carboxylic acid.
30. 30. The method according to claim 28, characterized in that the weight ratio of the concentrations are from about 0.1 to about 500 ppm of the mixture of 2- (thiocyanomethylthio) benzothiazole and methylene-bis (thiocyanate), and of about 0.1 to about 500 ppm of the dimethylamide of a carboxylic acid.
31. 31. A method for preventing the decomposition of a product, material or medium, caused by bacteria, fungi, algae or a mixture thereof characterized in that it comprises the step of applying to the product, material or medium, a composition comprising synergistically effective amounts from (a) a mixture of 2-thiocyanomethylthio (benzothiazole) and methylene-bis (thiocyanate), and (b) a dimethylamide of a carboxylic acid.
32. 32. The method according to claim 28, characterized in that the material is seeds or crops.