MXPA00002301A - Synergistic antimicrobial compositions containing dodecylmorpholine or a salt thereof and dodecylamine or a salt thereof - Google Patents

Abstract

Compositions for controlling the growth of microorganisms in or on a product, material, or medium comprising synergistically effective amounts of (a) dodecylmorpholine or a salt thereof and (b) dodecylamine or a salt thereof are disclosed. 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

SYNERGISTIC ANTIMICROBIAL COMPOSITIONS CONTAINING DODECILMORFOLINE OR A SALT OF THE SAME AND DODECILAMINE OR A SALT OF THE SAME DESCRIPTION OF THE INVENTION The present invention relates to certain compositions and processes useful to control the growth of one or more microorganisms and to prevent the decomposition caused by one or more microorganisms in various products, materials or medium, particularly, in industrial products, materials or media. These products, materials or means include, but are not limited to, wood pulp, wood chips, logs, adhesives, coatings, animal skins, paper mill liquors, processed waters, pharmaceutical formulations, cosmetic and toilet formulations, geological drilling lubricants, petrochemicals, agrochemical compositions, paints, leathers, wood, metalworking fluids, water cooling (for example, cooling tower water), tanning liquors, starch, proteinaceous materials, latex paint emulsions acrylic, textiles, affluent water, recreational water, wastewater, pasteurizers, retort cookers, and lithographic fountain solutions. The novel compositions and processes incorporating the compositions of the present invention are processes or mixtures that unexpectedly show synergistic activity against microorganisms, including bacteria, fungi, algae, or mixtures thereof. Specifically, the present invention is directed to the use of compositions containing a mixture of a) dodecylmorpholine or salts thereof, and b) dodecylamine or salts thereof. Many of the products, materials, or means referred to above when wetted or subjected to water treatment are susceptible to deterioration or degradation including degradation by bacteria, fungi, algae or mixtures thereof, unless the steps are taken. to inhibit such degradation or deterioration. To control the deterioration or degradation caused by microorganisms, many types of industrial microbicides are used, but some of these biocides are of questionable utility because they have unpleasant odors, are high in cost, show low grade of effectiveness, or create dangers with respect to storage, use or handling. For example, the use of such popular industrial microbicides as organomercury compounds, organotin compounds, and phenolics have returned under great regulatory pressure in recent times due to their high toxicity and in relation to their adverse effects on the environment. Consequently, workers in the trade have continued to look for improved biocides that have low toxicity and are capable of exhibiting a prolonged biocides effect at normal us levels. Accordingly, the present invention is directed to microbicidal compositions and processes 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, algae or mixtures thereof, preferably for extended periods of time. Preferably, the compositions are also safe and economical for use. The present invention is also directed to growth control methods or processes 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, algae or mixtures thereof, preferably for extended periods of time. It is an additional object to provide such compositions that are economical for use. The methods for 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 mixture (a) dodecylmorpholine or a salt thereof and (b) dodecylamine or a salt thereof where the components are present in a synergistically effective combined amount to control the growth of at least one microorganism. The composition preferably provides superior microbicidal activity at low concentrations against a wide range of microorganisms. This composition can also be considered a surface active agent having the ability to control the growth of at least one microorganism. The present invention also provides a method for controlling the growth of at least one microorganism in, or in a material or medium susceptible to attack by the microorganism comprising the step of contacting the microorganism with the composition of the present invention or by including the composition of the present invention in a product susceptible to microbial attack, wherein the components of the composition are present in synergistically effective amount, for controlling the growth of the microorganism. The synergistically effective amount that varies according to the product, material, or means to be treated and can, by a particular application, be determined routinely without undue experimentation, by one skilled in the art in view of this description. The present invention also incorporates the separate addition of a mixture of (a) dodecylmorpholine or a salt thereof and (b) dodecylamine or a salt thereof. According to this embodiment, the components are indivlly added to the system so that the final amount of the mixture of (a) dodecylmorpholine or a salt thereof and (b) dodecylamine or a salt thereof present in the system at the time of Use is that amount synergistically effective to control the growth of at least one microorganism. The compositions of the present invention may be useful in preserving various types of industrial products, media, or materials susceptible to attack by microorganisms. Such products, media or materials include, but are not limited to, inks, pastes, wood, skins, textiles, pulp, wood chips, tanning liquors, paper mill liquors, polymer emulsions, paints, paper and other coating and gumming agents, petrochemicals, metalworking fluids, geological drilling lubricants, water cooling systems, pharmaceutical formulations and cosmetic and toilet formulations.

The compositions 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 understood by the practice of the present invention. The advantages of the present invention can be realized and obtained by means of elements and combinations particularly pointed out in the claims. It will be understood that both the above 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 microorganisms includes reducing and / or preventing such growth. It will further be understood that "controlling" the growth of at least one microorganism may include inhibiting the growth of a microorganism (i.e., there is no growth or essentially no microorganism grows). "Controlling" the growth of at least one microorganism may also include maintaining the microorganism population at a desired level and / or reducing the population to a desired level (even at undetectable limits, e.g., zero population). Thus, the products, material or means susceptible to attack by these types of microorganism can be conserved from this attack and the resulting decomposition and other detrimental effects caused by the microorganism can be minimized or avoided. In addition, it will also be understood that "controlling" the growth of at least one microorganism may also include biostatically reducing and / or maintaining a low level microorganism such that attack by a microorganism and any resulting decomposition or other deleterious effects are mitigated, example, the ratio of microorganism growth or microorganism attack ratio is slowly decreased or eliminated. When two chemical microbicides are combined or mixed in 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 antagonist 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 will produce a negative impact. Only a synergistic effect, which is less similar than either an additive or antagonistic effect, will produce a positive effect and therefore is of economic advantage. It is well known in the microbicidal literature that there is no theoretical method to provide the probability of knowledge, before actually testing, whether the additive, antagonistic or synergistic effects will be obtained when two biocides are mixed to produce a formulation. The microbicidal compositions of the invention prevention are mixtures of a) dodecylmorpholine or a salt thereof and b) dodecylamine or a salt thereof and demonstrate an unexpected synergistic effect compared to the respective unique components, and so achieved the superior, is say, greater than the additive, microbicidal activity preferably at low concentrations, against a wide variety of microorganisms. Dodecylmorpholine has the formula: The dodecylalkyl group is preferably linear in the dodecylmorpholine and the dodecylamine. A preferred salt of docecylmorpholine is O CH2 CH, N CH, CH, C12H2 < CH3COO- or CH3CH2COO-, wherein dodecylmorpholine acetate is the most preferred salt. Other preferred examples of salts include a salt of dodecylmorpholine lauric acid and a neodecanoic salt of dodecylmorpholine. Similarly, preferred salts of dodecylamine are N + H2 (C? 2H25) (CH3COO) ~ or N + H2 (C? 2H25) (CH3CH2COO) ~, with dodecylamine acetate, the dodecylamine salt being more preferred. Other preferred examples of salts include a salt of lauric acid of dodecylamine and a neodecanoic salt of dodecylamine. More than one type of dodecylmorpholine or salts thereof and / or more than one type of dodecylamine or salts thereof may be used to form the mixtures or compositions of the present invention. Examples of microorganisms controlled by the compositions of the present invention include fungi, bacteria, algae, and mixtures thereof, such as Pseudomonas aeruginosa, Enterobacter aerogenes, Chlorella Sp. , Aspergill us niger. These organisms are some of the most common organisms associated with decomposition of products, materials, or media. Since these organisms may be some of the organisms most resistant to control, the compositions of the present invention are intended to be effective against more bacteria, fungi, algae or mixtures thereof. Preferably, the compositions of the present invention have a low toxicity. The compositions of the present invention can also be considered surface active agents which can suspend microorganisms in such a state that reproduction is substantially avoided. The components of the compositions of the present invention are commercially available and can be easily synthesized from commercially available raw material. Also, the preparation of dodecylmorpholine and salts thereof are described in U.S. Patent No. 5,250,194, which is incorporated herein by reference. The components of the compositions of the present invention may be chosen based on the compatibility of these components with the products, materials, or media. The compatibility can be determined by criteria such as solubility in the fluid system and / or loss of reactivity with the fluid, material, or media in question. The compatibility is easily determined by one of ordinary skill in the art by adding the compositions of the present invention to the product, material or media to be used. When used in a fluid system, it is preferable that the composition be freely soluble in the particular fluid resulting in a uniform solution or dispersion. In the following discussion of the preferred embodiments, component (a) is dodecylmorpholine or a salt thereof and component (b) is dodecylamine or a salt thereof. As described above, components (a) and (b) are used in synergistically effective amounts. The weight ratios of (a) to (b) vary depending on the type of microorganisms, products, materials or media to which the composition is applied. A person skilled in the art can easily determine, without undue experimentation, the appropriate weight ratios for a specific application. The ratio of component (a) to component (b) preferably ranges from about 1:99 to about 99: 1, 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 response of fungicide, bactericide, and algicide can be obtained when the synergistic combination is employed in concentrations ranging from about 0.01 to about 5000 ppm of dodecylmorpholine or a salt thereof, preferably from about 0.1 to about 2000 ppm and more preferably from about 0.1 to about 1000 ppm; and from about 0.01 to about 5000 ppm of dodecylamine or a salt thereof, preferably from about 0.1 to about 2000 ppm, and more preferably from about 0.1 to about 1000 ppm. In accordance with the present invention, the composition of the present invention 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 in a product, material, or medium susceptible to attack by the microorganism comprising the step of adding 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 of preventing the decomposition of a product, material or medium caused by a microorganism, comprising the step of applying to the product, material or medium, a composition of the present invention wherein the components of a composition they 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 may vary. For example, the composition can be applied by a spraying device or by brushing on the material or product. The material or product in question can 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 can be produced. If used as a liquid preservative, for example the composition can be prepared as an aqueous emulsion. If necessary or desirable, a surfactant can be added to the composition.

Based on this 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 the composition 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 may be used include, but are not limited to, pyrethrins, nicotine, chlordane, and parathion. 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 limiting the present invention. Microbiological Evaluation A. Fungal Evaluation The mineral salt-glucose medium was used. To prepare the medium, the following ingredients were added to 1 liter of deionized water: 0.7 g of KH2P04, 0.7 g of MgSO4.7H20, 1.0 g of NH4N03, 0.005 g of NaCl, 0.002 g of FeS04.7H20, 0.002 g of ZnS04 .7H20, 0.001 g of MnS04.7H20, and 10 g of glucose. The pH of the medium was adjusted to 6 with INOH NaOH. The medium was distributed in quantities of 5 ml in test tubes and autoclaved at 121 ° C for 20 minutes. The mushroom, Aspergillus niger, was developed in a beveled tube of potato dextrose agar for 7 to 10 days and a spore suspension prepared by washing the spores of the bevelled tube in a sterile saline solution. After the addition of the biocides in the desired concentrations to the sterile mineral salt-glucose medium, the fungal spore suspension was added. The final spore concentration was approximately 106 cfu / ml. The inoculated medium was incubated at 28 ° C for 14 days. B. Bacterial Evaluation The nutrient broth (2.5 g / liter of deionized water) was prepared. This was distributed in quantities of 5 ml of test tubes and autoclaved for 20 minutes at 121 ° C. After addition to the biocides at the desired concentrations in the nutrient broth, 100 microliters of a suspension of Pseudomonas aeruginosa or Enterobacter aerogenes cells of approximately 9.3 x 10 8 cfc / ml were added and incubated at 37 ° C for 24 or 48 hours. C. Algae Test A seaweed broth was prepared by dissolving the following ingredients in 1 liter of deionized water: 1.0 g of NaN03, 50 mg of NH4C1, 58 mg of CaCl2, 0.513 g of MgSO4, 0.25 g of K2HP04, and 3.0 mg of FeCl3.6H20. The medium was distributed in quantities of 50 ml in flasks and autoclaved at 121 ° C for 20 minutes. After the autoclave, the biocides were added to the broth in the desired concentrations. Then one milliliter of a two-week culture of Chlorella sp was added and incubated at a temperature of 25-28 ° C and illuminated with a 180-foot intensity lamp (12 hours of light).; 12 hours of darkness) for 14 days. In Examples 1 to 3, the synergism was demonstrated in separate experiments by testing dodecylmorpholine or dodecylmorpholine acetate designated as component A and dodecylamine or dodecylamine acetate as component B in a series of tests varying the relationships and a range of concentrations against the Aspergillus fungus niger, the bacterium Pseudomonas aeruginosa or Enterobacter aerogenes and the alga Chlorella sp, using the methods described above. The lowest concentration of each compound mixture that completely prevents the growth of the bacteria for 24 hours or 48 hours, fungi or algae for two weeks was taken as the end points for synergism calculations. The endpoints for the various mixtures were then compared with the endpoints for the pure active ingredients unique in preparing concomitantly flasks or test tubes.

The synergism was demonstrated by the method described by Kull, E.C., Eisman, P.C. Syl estwicz, HD, and Mayer, RL, 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, acting alone, which produces a final point. QA = Concentration of compound a in parts per million, in the mixture that 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, it is also 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 a widely used and acceptable process. 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 therefore part of this application. Based on the above criteria, a synergistic activity against bacteria, fungi, and algae is observed when dodecylmorpholine or dodecylmorpholine acetate is combined with dodecylamine or dodecylamine acetate. The examples show synergistic results that can be found in Examples 1-4. It will be apparent to those skilled in the art that the required synergistically effective amounts (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 substantially small amounts of (a) the dodecylmorpholine or a salt thereof or (b) dodecylamine or a salt thereof to achieve a given effect, then it may be necessary for each parasite if it is used alone or later it could be necessary if a mere additive effect of these two biocides were obtained. 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 with the proviso that they are within the scope of the appended claims and their equivalents.

Example 1 Component A = Dodecylmorpholine Component B = Dodecylamine Example 2 Component A = Dodecylmorpholine Component B = Dodecylamine Example 3 Component A = Dodecylmorpholine Component B = Dodecylamine Example 4 Component A = Dodecylmorpholine Component B = Dodecylamine Note: The combinations of dodecylmorpholine acetate and dodecylamine acetate are not synergistic against Aspergillus niger. Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention described herein. It is intended that the specification and examples be considered as exemplary only, with true scope and spirit. of the invention being indicated by the following claims.

Claims (15)

1. CLAIMS 1. A composition for controlling the growth of at least one microorganism comprising effective amounts of synergistic microbicides of (a) dodecylmorpholine or a salt thereof and (b) dodecylamine or a salt thereof.
2. 2. The composition according to claim 1, characterized in that a dodecylmorpholine salt is dodecylmorpholine acetate, dodecylmorpholine propionate, a dodecylmorpholine lauric salt or a dodecylmorpholine neodecanoic acid salt and wherein a dodecylamine salt is dodecylamine acetate. , dodecylamine propionate, dodecylamine lauric salt or a dodecylamine neodecanoic salt.
3. 3. The composition according to claim 1, characterized in that the microorganism is selected from bacteria, fungi, algae or mixtures thereof.
4. 4. The composition according to claim 3, characterized in that the microorganism is Pseudomonas aeruginosa, Enterobacter aerogenes, Aspergillus niger or Chlorella sp.
5. The composition according to claim 1, characterized in that the weight ratio of (a) to (b) is from about 1:30 to about 30: 1.
6. 6. The composition according to claim 1, characterized in that the weight ratio of (a) to (b) is from about 1: 5 to about 5: 1.
7. The composition according to claim 1, characterized in that the ratio by weight of the concentrations are from about 0.01 to about 5000 ppm of dodecylmorpholine or a salt thereof and from about 0.01 to about 5000 ppm of dodecylamine or a salt of the same.
8. The composition according to claim 1, characterized in that the ratio by weight of the concentrations are from about 0.1 to about 1000 ppm of dodecylmorpholine or a salt thereof and from about 0.1 to about 1000 ppm of dodecylamine or a salt of the same.
9. 9. An active surface agent characterized in that it comprises a mixture of (a) dodecylmorpholine or a salt thereof and (b) dodecylamine or a salt thereof, wherein (a) and (b) are present in combined synergistic amounts to control the growth of at least one microorganism.
10. A method for controlling the growth of at least one microorganism in, or in a product, material or medium susceptible to attack such micro-magnetism, characterized in that it comprises the step of adding to the product, material or medium a composition in accordance with any of claims 1-8.
11. 11. The method according to the claim 10, characterized in that the product, material or medium is wood pulp, wood chips, logs, an adhesive, a coating, an animal skin, a paper sheet liquor, a pharmaceutical formulation, a cosmetic, a toilet formulation , a geological drilling lubricant, a petrochemical, paint, leather, wood or metal working fluid, cooling tower water, a tanning liquor, starch, a proteinaceous material, an acrylic latex paint emulsion, a textile, affluent water, recreational water, wastewater, a pasteurizer, a retort sewer, a lithographic source solution, or agricultural crops or seeds.
12. The method according to claim 10, characterized in that the composition is in the form of a solid, dispersion, emulsion or solution.
13. The method according to claim 10, characterized in that the components (a) and (b) are added separately to the product, material, or medium or where the components (a) and (b) are first combined and then added to the product, material or medium.
14. 14. A method for preventing decomposition of a product, material or medium, caused by bacteria, fungi, algae or mixtures thereof, comprising the step of applying to the product, material or medium a composition according to any of claims 1-8. wherein the composition is added in synergistically effective amounts to avoid such decomposition.
15. 15. The method according to claim 14, characterized in that the product, material or medium is a seed or crops.