MXPA06007124A - Microbicidal compositions - Google Patents

Abstract

Microbicidal compositions for the protection of industrial products and use in industrial or technical systems, comprising at least two different biocides selected from the group of active substances known as fungicides, insecticides, acaricides, or herbicides in the field of crop protection. Industrial materials comprising said mixture of biocides.

Description

MICROBICIDE COMPOSITIONS Field of the Invention This invention relates to microbicidal compositions for the protection of industrial products and their use in industrial or technical systems, comprising at least two different biocides selected from the group of active substances known as fungicides, insecticides, acaricides, nematicides. or herbicides in the field of crop protection. The invention also relates to industrial materials comprising said biocide mixture. BACKGROUND OF THE INVENTION The term "microbicide" or more simply "biocide" is generally used to describe all the agents that kill microbial life. In a more specific meaning the term is used for compounds or compositions used to prevent microbial growth in industrial products and in industrial or technical systems, for example paints, coatings, plastics, water cooling systems, papermaking, wood protection , cosmetics, materials for washing and cleaning, sealing compounds, window mastic or hydraulic fluids. Microbicidal compositions for combating microorganisms in industrial products are known in the art. The details are described for example in "Microbicides", Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2000 Electronic Relay. It has been suggested to use specific compounds which are known as active substances in the field of crop protection, such as agricultural fungicides, insecticides, nematicides or herbicides, as well as biocides for industrial products and processes. As an example, one can mention the fungicide 1-dodecylguanidinium hydrochloride or -acetate, also known as "dodin", which has been suggested for use in polymeric emulsions (EP-A 1 188 377) or inhibition in industrial fluids ( WO 01/11954) and many other applications Similarly, the herbicide 2,4-dichlorophenoxyacetic acid has been suggested as a biocide for the production of paper (SU 1542912) as an additive for bitumen (DD 98102), or in anti-fouling coating compositions (EP-A 286 243). The fungicide cis-4- [3- [4- (1,1-dimethylethyl) phenyl] -2-methylpropyl] -2,6-dimethylmorpholine (fenpropimorph), has been suggested by EP-A 370 371 as a preservative for wood.

WO 96/36739 describes the fungicides (1RS, 5RS, 1RS, 5RS) -5- (4-chlorobenzyl) -2, 2-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol , (Metconazole) or cis-3- (2-Chlorophenyl) -2- (4-fluorophenyl) -2- (triazol-1-ylmethyl) -oxiran (Epoxiconazole) in combination with at least one phenolic compound as biocide for the production of the leather However, in addition to microbicidal efficiency, biocides for technical systems have to meet many additional requirements, which are by no means important for use in the field of plant protection. For example, long-term stability, stability at high temperatures or increased pressures, or stability at very high or very low pH values can be mentioned with matrices of industrial or consumer products such as cosmetic products, metalworking fluids. and paint formulations. In addition, it is desirable that they exhibit a broad spectrum of efficacy against bacteria, viruses, algae, fungi, and yeasts. Many active substances known in the field of plant protection do not give satisfactory results as biocides in industrial materials and processes. An important field of use for biocides is the so-called conservation in cans, for example, the preservation of paints, lacquers, polymeric emulsions, adhesives, PUR systems and the like packed in cans or similar containers. In such systems, the biocide has a double function. In the first place, its objective is to protect the material (water-based) while it is in the can. Secondly, its objective is also to protect the dry film obtained by using, for example, paint or lacquer. For this purpose, it is important that the biocide maintains its activity also in the dry film and also that it remains in the film in the long term and that it does not leach too quickly when the film is in contact with the water. The dodin mentioned above shows a broad spectrum of activity which is sufficient for many cases however its solubility in water is relatively high for long-term stability and therefore, films containing dodin tend to leach too quickly when they enter contact with water. Therefore, the problem to be solved by the invention was to provide microbicidal compositions especially suitable for the preservation in cans and for the preservation of films of paints, lacquers and the like based on active substances known in the field of plant protection, such such as agricultural fungicides, insecticides, acaricides, nematicides, or herbicides. DESCRIPTION OF THE INVENTION Accordingly, according to one aspect, the invention provides the use of a microbicidal composition comprising at least two different biocides, wherein said biocides are selected from the group of active substances known as fungicides, insecticides, acaricides, nematicides. , or herbicides in the field of crop protection, each comprising at least one structural element of the formula selected from the group of wherein R1 is selected from the group of F, Cl, and alkyl with Cx-C4, to kill fungi, yeasts, algae, and bacteria, in industrial materials and / or industrial processes, and wherein at least one of the biocides comprises the groups (I) and / or (II) is hydrophobic in nature. In a preferred embodiment of the invention, the composition is used in particular for the preservation in cans of coating compositions and coatings obtained by the use of such compositions. In a second aspect, the invention provides an industrial material comprising said composition of at least two said biocides. With respect to the invention, the following can be specifically established: The abbreviations used in the present application for the active substances are the ISO approved names in accordance with ISO 1750 nPesticides and other agrochemicals -Common yams. "The invention relates to the use of certain biocidal active agents in technical applications or technical products. therapeutic or medical in or on the human or animal body, and applications in the protection of crops, are not covered by the present invention. "Industrial materials" will be understood as non-living materials, when they are attacked by microbes in processes Technical-industrial materials Industrial materials which can be protected from microbial damage or destruction by formulations, which includes the invention are, for example, finishes, drilling oils, dispersions, emulsions, dyes, adhesives, lime, lacquers, pigment preparations , materials for paper processing, fabrics, materials for cloth processing s, leather, materials for processing leather, wood, coating materials, coatings and anti-fouling dyes, plastic articles, plastic substrates such as polyethylene, polypropylene, polyamide, polyurethane and the like, cosmetics, washing and cleaning materials , lubricants, coolers, hydraulic fluids, compounds for joint sealers, window mastic, thickener solutions,. fleeces as well as "layers for carpet or tapestry and other materials which can be attacked or destroyed by microorganisms." Industrial processes "will be understood as facilities, especially chemical facilities, facilities or machinery for manufacturing, in which" industrial materials "are used as auxiliaries or reaction media Examples include reaction reaction vessels, storage vessels, heating vessels (radiators), heat exchanger circuits or air conditioning units.The term "coating compositions" is well known to the skilled in the art and comprises all types of industrial materials which can be used to coat other materials where the technique used to coat is not relevant.The typical coating compositions usually comprise a binder system, a solvent or a solvent composition and Additional additives. or examples can be mentioned paints, dispersions, or lacquers for coating. According to the invention, the microbicidal composition used comprises at least two different biocides, selected from the group of active substances known as fungicides, insecticides, acaricides, nematicides, or herbicides in the field of crop protection. In a preferred embodiment of the invention, the biocides used are selected from different members of said group, that is, one is selected from the group of herbicides and another is selected from the group of fungicides. In a more preferred embodiment, the composition comprises at least one fungicide in combination with at least one compound selected from the group of insecticides, acaricides, nematicides, or herbicides. At least one of the biocides used must be hydrophobic in nature. The term "hydrophobic character" will mean in general, that the solubility in water at room temperature should not exceed about 500 ppm (mg / kg), preferably 200 ppm, more preferably 100 ppm, even more preferably 50 ppm, and more preferably 10 ppm. ppm.

Also the other biocidal (s) used should have at least a limited solubility in water at room temperature. The term "limited solubility" will mean that in general, the solubility in water at room temperature should not exceed about 1000 ppm, preferably 750 ppm, and more preferably 650 ppm. Preferably, all biocides used should be hydrophobic in nature.

At least two biocides are used each comprising at least one structural element of the general formulas (I) or (II). The structural element according to formula (I) is an aromatic ring, substituted, wherein R1 is selected from the group of F, Cl, and alkyl with Ci-C4, in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl. Optionally the aromatic ring can be substituted by one or more additional substituents R2 selected from the group of F, Cl, alkyl with C? -C4, -0-CH3 or -COOH, wherein R3 is an alkyl group with C? -C8, preferably an alkyl group with C? -C4. COOH groups should only be present as long as the hydrophobic nature or limited solubility of the biocide in water is not affected by the existence of the COOH group. In general no more than one group -COOH should be present in the biocides used for the present invention. Preferably, no -COOH group should be present. The aromatic group (I) is connected to the rest of the molecule of the active substance. As connecting groups, ether groups -O-, hydrocarbon groups, such as -CH2-, N-acyl groups -N-CO- or carbonyl groups -CO- can be used. The group (I) can also be directly connected to the heterocyclic groups or other groups. The formulas of the active compounds are known to those skilled in the art and are collected in databases such as "Compendium of Pesticide Common Yams" or "T-fae Pesticide Manual" which is also available through the internet, for example http: //www.hclrss .demon. co.uk/. Examples of suitable activated substances comprising the aromatic group (I) as a unit, comprise: Fenpropimorph Chlorfenapyr 4-Brom-2- (p-chlorphenyl) -1 - (ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile CAS: 122453-73-0 Picol nafen Dic lorprop 2,4-D Metconazole (1RS, 5RS, 1 RS, 5SR) -5- (4-chlorobenzyl) -2,2-dimethyl-1- (1H-1, 2,4-triazoi-1-ylmethyl) -cyclopentanol CAS: 125116-23-6 Epoxiconazole Chiral The structural element according to formula (II) is a divalent aromatic group which is 1,2-connected to the rest of the molecule.

The group can act as a bridging or linking group, however, in general (II) is part of a molecule comprising fused rings, that is, the two substituents R4 and R5 are linked together to form a closed ring which in itself can be connected with additional rings and / or substituents.

The group (II) can also be substituted in the 3 to 6 position by one or more substituents R1 and / or R2 as defined above. An example of a suitable active substance comprising the aromatic (II) divalent group as a unit is: Dithianon The solubilities in water at room temperature are summarized in the following table: The active substances comprising the aromatic group (I) as a unit, comprise fenpropimorph, chlorfenapyr, metconazole, epoxiconazole, 2-4-D, Dichlorprop P, and dithianon.

Examples of preferred biocides of hydrophobic character as defined, comprise fenpropimorph, chlorfenapyr, Picolinafen or Dithianon. A combination of Fenpropimorph and Dichlorprop is more preferred. Another preferred combination comprises Fenpropimorph and Epoxiconazole, Fenpropimorph and Picolinafen. The number of biocides in the composition selected from the group of active substances known as • fungicides, insecticides, nematicides, acaricides, or herbicides, can be selected by the person skilled in the art according to the desired use of the microbicidal composition. Nevertheless, in general the number should not exceed 10, preferably 5, and more preferably the number is from 2 to 4. More preferably, it is a combination of two different biocides. The weight ratio of the biocides used can be selected by the person skilled in the art according to the desired use of the microbicidal composition. For the case of two biocides the ratio in general is from about 1:10 - 10: 1, preferably 1: 5 - 5: 1, more preferably 1.2 - 2: 1, and more preferably 1.5: 1 1: 1, 5. In the case of more than two biocides, it is preferred that each of the biocides used be present in an amount of at least 10% in relation to the total amount of all the biocides used. The microbicidal composition comprising at least two different biocides in accordance with the above definition, is used to kill fungi, yeasts, algae, and bacteria in industrial materials and / or industrial processes. Examples of such organisms include fungi such as Aspergillus niger and Chaetomium globosum, yeasts such as Saccharomyces cerevisiae, Candida albicans and Malassezia fúrfur, and certain organisms such as Pseudomonas fluorescens, Pseudomonas aeruginosa, Alcaligenes faecalis, Staphylococcus aureus, Staphylococcus epidermis, Corynebacterium xerosis, Propionibacterium acnes, Pityrosporum ovale, Aspergillus niger, Alternarla alternata, Aspergillus versicolor, Aureobasidium pullulans, Cladosporium cladosporioides, Penicillium purpurogenum, Penicillium funiculosum, Phoma violaceous, Rhodotorula rubra, Sporobolomyces roseus, Stachybotrys chartarum, Ulocladium atrum, Chlorella sp, Pleurococcus sp, Nostoc muscorum , Oscillatoria tenuis, Stichococcus bacillaris, and Golden Trentepohlia. The composition can be used as such, ie only a mixture of the active components is thoroughly mixed with or distributed in the industrial product. However, the active components can be formulated in for example pastes, emulsions or solutions or suspension or placed in solid carriers. Preferably, a suitable microbicidal composition comprising the active compounds, a suitable solvent or solvent composition and optionally additional components is used. Particularly suitable are aliphatic, organic solvents, such as alcohols, ie ethanol, n-propanol or i-propanol, or aromatic solvents used in the preparation of plastics, coatings, etc. such as phenoxyalcohols, or solvents and / or emulsifiers and other known formulating agents of agrochemical formulations. However, it is also possible to formulate them as a suspension or dispersion using water or a mixture of aqueous solvents and in addition suitable emulsifiers or other formulating agents, for example, those known from agrochemical formulations. As additional components of the composition to be used there may be mentioned additives to adjust the pH, surface agents, emulsifiers, chelants, salts, corrosion inhibitors, dyes, fragrances, anti-foaming or dispersing agents, either alone or in combination. The compositions may also optionally contain additional components which are effective as biocides. In practice, the active components as defined above are preferably used to provide a final concentration of 0.001 to 10%, more preferably 0.01 to 5%, especially 0.02 to 0.5% by weight of the liquid medium (including any liquid environment to be treated ). In some anti-fouling coatings, the preferred concentrations of the active ingredient are preferably not below 0.5% and can be as high as 20%. In these formulations however, the most preferred level of active ingredient is above 1% and below 15%. The concentrates may contain between 5 and 60%, more preferably between 10 and 45%, still more preferably between 20 to 40%, especially 20 to 30%, by weight of the total concentrate of the active components. In particular, the pH of the microbicidal composition can vary from 2-12, as can that of the medium to be treated. It is preferred that the concentrate and more especially the treated product have a pH of at least 4, more preferably at least 7, still more preferably at least 8, especially 8 to 12. For use in accordance with the present invention the industrial material is it comes into contact with the microbicidal composition or the composition is used in the industrial process. The composition can be mixed cone to distribute in the industrial product or the product treated with the composition. As a general rule it can be established that in general the degree of protection is the best, the distribution is the most homogeneous of the composition in the industrial product.

In a preferred embodiment of the invention, the microbicidal composition is used for canned preservation of various compositions such as paints, lacquers, coating compositions, technical fluids and the like. In a more preferred embodiment the composition is a coating composition comprising, by way of example, calcium carbonate and / or titanium dioxide, binder, coalescer, solvent and water.

In a further preferred embodiment of the invention, the microbicidal composition is used for the protection of coatings. Such coatings, preferably thin films, can be obtained by coating a suitable substrate such as wood and masonry with the coating composition comprising the microbicidal composition as described. The invention is not limited to a specific coating technique. Suitable coating techniques can be exemplarily mentioned as spraying, painting, rapid immersion or stamping. The industrial material according to the second embodiment of the invention which comprises as biocide at least two different biocides, as defined above, usually contains the active components in a concentration of 0.05% to 2.5% by weight, preferably 0.1% to 1.0% , and more preferably 0.2% to 0.5%. Dried films of industrial materials have a high resistance against the leaching of biocides and hence are affordable for long-term protection. Through the combination, a broad spectrum activity is obtained that inhibits the growth of non-combated microorganisms by a particular biocide. The combination also offers protection due to the fact that in drying, one component will migrate to the coated surface faster than the other and hence be affordable to exterminate or inhibit the most prevalent microorganisms in the environment, while the other compound will offer general protection that also moves to the surface. The embodiments of the invention will now be described in more detail with reference to the following examples. Surface Coating A test was conducted in accordance with the BS3900 G6 and BBA MOAT 33 methods for evaluation versus fungi and algae, respectively. The methods involve painting a panel of the substrate with the coating and leaching under running water for 72 hours. The substrates are incubated for 56 days after being inoculated with fungi or algae. The performance is judged by comparing with the control samples ie without biocide, a positive control, and for fungi with substrate panels that have been leached. Performance evaluation on painted test substrates (Score of 0, 1 and 2 is considered an approval). 0 = no growth 1 = growth trace 2 = growth in 1-10% of the test surface 3 = growth in 10-30% of the test surface 4 = growth in 30-70% of the test surface 5 = growth in 70-100% of the test surface.

Table 1 - Efficacy Against Algae Growth on a Gypsum Surface, Painted Epoxiconazole, Picolinafen, Fenpropimorph, Chlorfenapyr and Dithianon exhibited an improvement against the growth of algae on the gypsum surface. Table 2 - Efficacy Against Fungal Growth on a Painted Gypsum Surface Applied Tal Cual - Without leaching with leached water - Constant running water for 72 hours Epoxiconazole and Fenpropimorph exhibited an improvement against the growth of fungi on the gypsum surface either "applied as is" or after leachate. Chlorfenapyr, Dithianon and Picolinafen were similar for unpreserved paint. Table 3 - Efficacy Against Mushroom Growth on a Painted Wood Surface Applied Tal Cual - Without leaching with leached water - Constant running water for 72 hours Chlorfenapyr and Dithianon exhibited an improvement against the growth of fungi on the wood surface. The Epoxiconazole, Picolinafen and Fenpropimorph only showed a marginal improvement. Apart from the algae data, not all active substances were effective. The combination of various attributes of individual chemistries will provide additional benefits of wide range protection. Combination of active substances Chemicals were tested for their activity against a range of organisms through the microtiter plate method. The test organisms were: ML - Micrococcus luteus SA - Staphylococcus aureus EC - Escherichia coli PA - Pseudomonas aeruginosa CF - Citrobacter freundii PM - Proteus mirabilis CA - Candida albicans SC - Saccharomyces cerevisiae AN - Aspergillus niger PF - Penicillium funiculosum AA - Alternaria alternata Using the following evaluation scale: 0 = no activity 1 = minimal inhibition 2 = inhibition 3 = clear inhibition 4 = biostatic of clear inhibition, can be biocidal activity 5 = biostatic, can be biocidal activity. The readings of 4 and possibly 3 were considered valid for biocide applications. Table 4 shows that certain molecules give broad spectrum activity against bacteria and fungi when used in combination with each other. Table 4 - Intrinsic Activity Against Bacteria and Fungi Average score Performance against organisms / non-organisms Evaluation of the score: 0 a < 3 - Poor performance > 3 - Inhibition of organisms > 4 - Biostasis, Biocide activity Dichlorprop and Dodine showed good activity against the test bacteria and fungi. Higher concentrations of 2,4-D gave a similar effect. Epoxiconazole, Fenpropimorph, Dithianon and Metconazole only exhibited anti-fungal activity at both concentrations. Hence, as an example, combining Dichlorprop at 500 ppm with Fenpropimorph also at 500 ppm provides broad spectrum microbicidal activity. Likewise other combinations can be applied together using combinations of the above chemistries such as Fenpropimorph and Dodine, etc., to provide broad spectrum performance versus microbes while using the hydrophobic and limited solubility aspects of the two chemistries individual The following examples illustrate effective combinations of active substances that provide broad spectrum protection. The first figure indicates the required level of the active substance in the first column, the second figure indicates the level of the active substance required in the first row of the table (values in ppm).

Claims (15)

1. CLAIMS 1.- The use, to exterminate fungi, yeasts, algae, and bacteria in industrial materials and / or industrial processes, of a microbicidal composition, comprising at least two different biocides, characterized in that said biocides are selected from the group of active substances known as fungicides, insecticides, nematicides, acaricides, or herbicides in the field of crop protection, each one comprises at least one structural element of the formula selected from the group of wherein R1 is selected from the group of F, Cl, and alkyl with C -C4, and wherein at least one of the biocides used is hydrophobic in nature.
2. 2. The use according to claim 1, characterized in that the aromatic ring (I) comprises one or more additional substituents R2 is independently selected from the group of F, Cl, alkyl with C1-C4, -0-CH3 or -COOH.
3. 3. The use according to claim 1 or 2, characterized in that the active substances are selected from the group of 4- [2-Methyl-3- (p-tert.-butylphenyl) -propyl] -2,6-cis-dimethylmorpholine ( Fenpropimorph), 4-Brom-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile, (Chlorfenapyr), 6- (3-trifluoromethyl-phenoxy) -amide pyridin-2- (N-4-fluorophenyl) -carboxylic acid (Picolinafen), 2,4-dichlorophenoxypropionic acid (Dichlorprop), 2,4-dichlorphenoxy-acetic acid 2,3-Dithiane-l, 4-dithia-anthraquinone (Dithianon ), (1RS, 5RS, 1RS, 5RS) -5- (4-chlorobenzyl) -2, 2-dimethyl-1- (1H-1, 2,4-triazol-1-ylmethyl) cyclopentanol, (Metconazole), and cis -3- (2-Chlorophenyl) -2- (4-fluorophenyl) -2- (triazol-1-ylmethyl) -oxiran (Epoxiconazole).
4. 4. The use according to claim 1 or 2, characterized in that the composition comprises at least one fungicide in combination with at least one compound selected from the group of insecticides, acaricides, nematicides, or herbicides.
5. 5. The use according to claim 1 or 2, characterized in that the composition comprises at least a mixture of 4- [2-Methyl-3- (p-tert.-butylphenyl) -propyl] -2,6-cis- dimethylmorpholine (Fenpropimorph) and cis-3- (2-Chlorophenyl) -2- (4-fluorophenyl) -2- (triazol-1-ylmethyl) -oxiran (Epoxiconazole).
6. 6. - The use according to claim 1 or 5, characterized in that the mixture is used for the preservation in cans of compositions.
7. 7. The use according to claim 6, characterized in that the composition is a coating composition.
8. 8. The use according to claim 1 or 5, characterized in that the mixture is used for the protection of coatings.
9. 9. - The industrial material comprising at least two different biocides for protection, characterized in that said biocides from the group of active substances known as fungicides, insecticides, acaricides, nematicides, or herbicides in the field of crop protection, each one comprising less a structural element of the formula selects from the group of wherein R1 is selected from the group of F, Cl, and alkyl with Ci-C4, and wherein at least one of the biocides used is of hydrophobic character, or
10. 10. - The industrial material according to claim 9, characterized in that the aromatic ring (I) comprises one or more additional substituents R2 is independently selected from the group of F, Cl, alkyl with Ci-C4, -0-CH3 or -COOH.
11. 11. The industrial material according to claim 9 or 10, characterized in that the active substances are selected from the group of 4- [2-Methyl-3- (p-ter-butylphenyl) -propyl] -2, 6- cis-dimethylmorpholine, Fenpropimorph), 4-Brom-2- (p-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile, (Chlorfenapyr), 6- (3-trifluoromethyl) amide -phenoxy) -pyridin-2- (N-4-fluorophenyl) -carboxylic acid (Picolinafen), 2,4-dichloro-phenoxypropionic acid (Diclorprop), 2,4-dicyclophenoxy-acetic acid (2,4-D) 2, 3-Diciano-l, 4-dithia-anthraquinone (Dithianon), (1RS, 5RS; 1RS, 5RS) -5- (4-chlorobenzyl) -2, 2-dimethyl-1- (1H-1, 2, 4- triazol-1-ylmethyl) cyclopentanol, Metconazole), and cis-3- (2-Chlorophenyl) -2- (4-fluorophenyl) -2- (triazol-1-ylmethyl) -oxiran (Epoxiconazole).
12. 12. - The industrial material according to claim 9 or 10, characterized in that the composition comprises at least one fungicide in combination with at least one compound selected from the group of insecticides, acaricides, or herbicides.
13. 13. - The industrial material according to claim 9 or 10, characterized in that the composition comprises at least a mixture of 4- [2-Methyl-3- (p-tert.-butylphenyl) -propyl] -2,6-cis-dimethylmorpholine (Fenpropimorph) and cis-3- (2-Chlorophenyl) -2- (4-fluorophenyl) -2- (triazol-1-ylmethyl) -oxiran (Epoxiconazole).
14. 14. - The industrial material according to any of claims 9 to 13, characterized in that the industrial material is a coating composition.
15. 15. - The industrial material according to any of claims 9 to 13, characterized in that the industrial material is a dry film obtained using a coating composition.