HK1168250B - Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and metal compounds - Google Patents

Description

Composition of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and metal compound

The present application is a divisional application of an invention patent application having an application date of 2007, 31.1.2007, application number of 200780001144.7(PCT/EP2007/050927), entitled "composition of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and metal compound".

The present invention relates to a combination of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, or a salt thereof, and a copper or zinc compound, which provides an enhanced protective effect against fouling organisms (fouling organisms). In particular, the present invention relates to a composition comprising 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, or a salt thereof, and one or more than one compound selected from Cu₂O、Cu(OH)₂、CuSO₄2-mercaptopyridine copper oxide, CuSCN, CuCO₃、ZnO、ZnCl₂、ZnSO₄A combination of zineb (zineb), and a copper or zinc compound of 2-mercaptopyridine zinc oxide; the above components are in respective proportions to provide a synergistic effect against fouling organisms and the use of these compositions for protecting materials against fouling organisms.

It has now been found that 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (hereinafter referred to as component I) and a compound selected from Cu₂O、Cu(OH)₂、CuSO₄2-mercaptopyridine copper oxide, CuSCN, CuCO₃、ZnO、ZnCl₂、ZnSO₄The combination of zineb, and a copper or zinc compound of 2-mercaptopyridine zinc oxide (hereinafter referred to as component II) has a synergistic effect on the control of fouling organisms. As used herein, "controlling" is defined to include inhibiting fouling organisms from adhering to or residing on the surface of an object, removing fouling organisms that adhere to the surface of an object, and controlling the growth of fouling organisms.

4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile is disclosed in EP-0,312,723 for use in controlling molluscs (molusss). The compound may be represented by the formula:

EP-0,746,979 describes the use of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile in antifouling compositions which are applied to waterThe lower surface to prevent fouling organisms from adhering to the underwater surface. WO-03/039256 discloses 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and bezoar for protecting materials against fouling organismsA combination of oxazine (betaxazin), DCOIT, tolyfluoronide (tolylfluoranid), and dichlorofluoronide (dichlofluoranid).

The copper and zinc compound, also referred to as component (II), is the following:

component (II-a): cu₂O or copper (I) oxide;

component (II-b): cu (OH)₂Or copper (II) hydroxide;

component (II-c): CuSO₄Or copper (II) sulfate;

component (II-d): the copper 2-mercaptopyridine oxide is one or two molecules of 2-mercaptopyridine oxide (pyrithione) with a copper ligand, particularly Cu⁺Or Cu²⁺To form (1-hydroxy-2 (1H) pyridinethiosulfuric acid (thionato) -O, S) copper (CAS 154592-20-8) or bis (1-hydroxy-2 (1H) -pyridinethiosulfuric acid-O, S) copper (CAS 14915-37-8);

component (II-e): CuSCN or copper thiocyanate;

component (II-f): CuCO₃Or copper carbonate;

component (II-g): oxides of ZnO or Zn (II);

component (II-h): ZnCl₂Or chloride of Zn (II);

component (II-i): ZnSO₄Or a sulfate of Zn (II);

component (II-j): zineb or zinc ethylenebis- (dithiocarbamate); and

component (II-k): 2-mercaptopyridine zinc oxide or (bis (1-hydroxy-2 (1H) -pyridinethiosulfuric acid-O, S) -T-4) zinc.

Throughout the present specification, whenever the term "4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile" or component (I) is used, it is intended to include the compound in base form or in salt form, the salt form being obtained by reaction of the base form with a suitable acid. Suitable acids include, for example, inorganic acids such as hydrohalic acids, i.e., hydrofluoric, hydrochloric, hydrobromic and hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, and the like; or organic acids such as acetic acid, propionic acid, glycolic acid, 2-hydroxypropionic acid, 2-oxopropionic acid, oxalic acid, malonic acid, succinic acid, (Z) -2-butenedioic acid, (E) -2-butenedioic acid, 2-hydroxysuccinic acid, 2, 3-dihydroxybutanedioic acid, 2-hydroxy-1, 2, 3-propanetricarboxylic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, 4-methyl-benzenesulfonic acid, cyclohexanesulfamic acid, 2-hydroxybenzoic acid, 4-amino-2-hydroxybenzoic acid and the like. The component (I) may also be present in the form of solvates, such as hydrates.

The copper and zinc compounds as component (II) can also be used in the form of hydrates. For example, CuSO₄Can be obtained in the form of anhydrous powders, but can also be present in hydrated form, for example CuSO₄·5H₂O。ZnSO₄Commercially available in both the monohydrate and heptahydrate forms. CuCl₂Are commercially available in the form of anhydrous powders and dihydrate. The hydrated form of component (II) is intended to be encompassed by the term component (II) as used throughout this specification.

Surfaces or objects exposed to moist or aqueous environments are easily infested with aquatic organisms such as algae (algae), fungi (fungi), bacteria, microorganisms, and aquatic animals such as tunicates (tunicates), hydroids (hydroids), bivalves (bivalves), bryozoans (bryozoans), polychaetes (chaetes works), sponges (sponges), barnacles (barnacles), and mollusks. When these organisms reside or adhere to the surface, the value of the exposed object is diminished. The attachment or retention of this organism is also known as the structural "foul smell". The exterior, but possibly also the interior, of the object can deteriorate, change in surface, for example from smooth, clean and streamlined to rough, dirty and messy, the weight of the object can increase due to the deposition of organisms and their residues, and the vicinity of the object can be obscured or hindered. The function of the object and the system involved is reduced and the quality of the water-containing environment is deteriorated. A common method of controlling the adhesion of fouling organisms is to treat the structure to be protected with a coating comprising an anti-fouling agent.

The combinations claimed in the present invention are particularly suitable for protecting surfaces or objects which are in constant or frequent contact with water against fouling or algal adhesion or retention, comprising applying to the surface or object a composition comprising one of component (I) and component (II) in respective proportions to provide a synergistic effect against fouling organisms.

Examples of such surfaces or objects are for example: hulls, harbour installations, piers and stakes, dry docks, water locks, lock (locks), mooring towers, pontoons, off-shore oil supply equipment, drilling platforms, bridges, pipelines, fishing nets, cables, ballast tanks, tanks for holding water for boats drawing water from water consortia (infested bodies of water), recreational equipment such as surfboards, jet boats (jetski) and surfboards, and any other object that is in constant or frequent contact with water.

The invention also provides a method for protecting materials, especially surfaces or objects which are in constant or frequent contact with water, against fouling organisms, which comprises applying to the object a composition comprising an effective fouling-resistant amount of a combination of component (I) and one of the components (II), wherein the amounts of component (I) and component (II) are in respective proportions, thereby providing a synergistic effect against fouling organisms.

The present invention also provides a method of protecting a surface comprising applying to the surface a composition comprising an effective antifouling amount of a combination of component (I) and one of component (II), wherein the amounts of component (I) and component (II) are in respective proportions, thereby providing a synergistic effect against antifouling organisms. A particularly important use of the method of the invention comprises a method of inhibiting fouling of a ship's hull which comprises applying to the hull an antifouling composition according to the invention. For example, foul odors on the hull of a boat increase frictional resistance while relatively reducing speed and maneuverability and increasing fuel consumption and increasing maintenance costs associated with removing foul odors.

Compositions comprising a combination of component (I) and one of the components (II), in which the amounts of component (I) and component (II) are in respective proportions, so as to provide a synergistic effect against fouling organisms, useful for protecting constructions such as: swimming pools, baths, cooling water circulation lines and industrial baths in various installations, such as manufacturing plants or in air-conditioning installations, the function of which can be impaired by the presence and/or proliferation of fouling organisms. Further examples are buildings and parts of buildings such as floors, outer and inner walls or ceilings, places subject to moisture such as cellars, bathrooms, kitchens, washrooms and the like, and they are foul-smelling hotbeds. Not only is foul smelling a problem from a hygienic and aesthetic point of view, but it also causes economic losses because the building and/or decorating materials deteriorate more rapidly than expected.

Another application of the combination of the invention is the treatment or disinfection of ballast water (ballst water) to reduce or eliminate the presence of aquatic organisms such as phytoplankton (dinoflagellates and diatoms), crustaceans (crabs, shrimps, copepods, cephalopods), rotifers, polychaetes, mollusks, fish, echinoderms, ctenophores, and coelenterates.

The synergistic antifouling compositions of the invention can also be used in various applications:

industrial aqueous process liquors, such as cooling water, process waters and suspensions of pulp and paper mills, secondary oil recovery systems, spinning fluids, metal working fluids and the like.

-protecting an aqueous functional liquid in a tank or tank, for example: polymer emulsions, aqueous paints and adhesives, glues, starch slurries, thickening solutions, gelatins, wax emulsions, inks, polishes, pigment and mineral slurries, latexes, coagulating additives (cement additives), drilling muds, toiletries (toiletries), aqueous cosmetic preparations, pharmaceutical preparations, and the like.

The term "fouling organisms" is intended to encompass organisms that adhere to, reside, grow on or are close to various surfaces, especially in humid or aqueous environments such as sea water, fresh water, brackish water, rain water, but also cooling water, drainage water, waste water and sewage. The fouling organisms are Algae (Algae), for example: microalgae (Microalgae), for example: supercilia maxima (Amphora), chaetoceros sp (Achnanthes), Navicula (Navicula), chaetoceros pterocarpa (aphiprora), straight-chain algae (Melosira), oval algae (coconeis), Chlamydomonas (Chlamydomonas), Chlorella (Chlorella), filaria (Ulothrix), neckercella (Anabaena), Phaeodactylum (Phaeodactylum), Porphyridium (Porphyridium); kelp (Macroalgae), for example: enteromorpha (Enteromorpha), Cladophora (Cladophora), exophyta (Ectocarpus), Acrocchaetium (Acrocchaetium), Ceramium (Ceramium), Rhodophyta (Polyphosnia), and Streptomyces sp; fungi (fungi); microorganisms (microbes); tunicates (tunicates), including members of the Ascidiacea class (Ascidiacea), such as Ciona intestinalis, Listeria monocytogenes (Diplosoma listeria) and Podochium sp (Botryllus schlossiei); members of the Hydra class, including the Lepidioides (Clava squamata), the Bei Obelia (Hydractinia echinata), the Obelia longissima (Obelia genita), and the Hydra tuba (Tubularia rynx); bivalves including purple clams (Mytilus edulis), Crassostrea virginica (Crassostrea virginica), Ostrea Ostrea (Ostrea edulis), Crassostrea gigas (Ostrea chilia), Zebra mussels (Dressena polymorpha) and Rusaera rudis (Lasaea rubra); bryozoans (bryozoans) including: electrora pilosa, Bugula neritina and Bowerbankia gracilis; polychete worms (polychaete worms), including the hydoides norvegica; sponge (sponge); and members of the Crustacea (crutacea), including Artemia (Artemia) and sprawl (cirriparia) (barnacles), such as striated barnacles (Balanus amphorita), mingrel (Lepas anatifora), barnacles (Balanus), halloysters (Balanus), incised barnacles (Balanus), compact barnacles (Balanus), canula glaucatus (Balanus), and ivy (Balanus bararus); and acorn barnacle (Elminius modestus) and Nepeter flower cage (Verruca).

In a composition comprising a combination of component (I) and one of the components (II), the respective proportions of component (I) and one of the components (II) are such that a synergistic effect on the fouling organisms is obtained when compared with a composition comprising component (I) alone or component (II) alone as active ingredient. As will be appreciated by those skilled in the art, this synergistic effect can be obtained in a range of ratios of component (I) to component (II) in the composition, depending on the type of fouling organism for which the effect measurement is to be made and the substrate to be treated. The determination of the synergistic effect of such a combination can be performed according to the method of "toxicity Plate Assay" described in experiment 1, in accordance with the teachings of the present application. In general, however, it can be stated that for most fouling organisms, the appropriate weight ratio of the amounts of component (I) to component (II) in the combination should be in the range from 10:1 to 1: 10. In particular, this range is from 8: 2 to 2: 8, more particularly from 3:1 to 1:3 or 2:1 to 1: 2. Another specific ratio of component (I) to component (II) in the compositions of the invention is a ratio of 1:1 between component (I) and one of the components (II).

The amount of each active ingredient in the composition comprising the combination of component (I) and one of the components (II) will be such that a synergistic effect is obtained. It is especially contemplated that the ready to use composition of the present invention comprises ingredient (I) in an amount of at least 1% by weight of the total weight of the composition. More particularly such ready-to-use compositions comprise component (I) in an amount of from 1% to 40% by weight, based on the total weight of the composition. The amount of component (II) in the ready-to-use composition will be such that a synergistic anti-fouling effect is obtained. Especially the amount of component (II) may be from 1 to 20 wt%, more especially from 2 to 10 wt%, based on the total weight of the dry matter of the composition. The antifouling compositions to be used directly in many instances can be obtained from concentrates, for example emulsifiable concentrates, suspension concentrates, or soluble concentrates, after dilution with aqueous or organic medium, such concentrates being intended to be covered by the term composition used in the definition of the invention. Concentrates for use in the form of paint compositions can be diluted to a ready-to-use mixture in a spray container shortly before use.

Compositions comprising a combination of component (I) and one of component (II) in corresponding proportions providing a synergistic effect on antifouling organisms are therefore suitable for use with carriers and additives, the latter including wetting agents, dispersing agents, sticking agents, adhesives, emulsifying agents and the like such as those commonly used by the person skilled in the art in the preparation of antifouling compositions. The anti-fouling compositions of the invention may further comprise suitable substances known in the art of formulation, such as natural or regenerated minerals, solvents, dispersants, surfactants, wetting agents, adhesives, thickeners, binders, anti-freeze agents, repellents, colour additives, corrosion inhibitors, water repellents, siccatives, UV stabilisers and other active ingredients. Suitable surfactants are nonionic, cationic and/or anionic surfactants having excellent emulsifying, dispersing and wetting properties. The term "surfactant" will also be understood to include mixtures of surfactants.

Antifouling compositions comprising a combination of component (I) and one of the components (II) in the respective proportions providing a synergistic effect on antifouling organisms can be prepared in any known manner, for example by homogeneously mixing, coating and/or grinding the combination of active ingredients, i.e. the active ingredient (I) and one of the active ingredients (II), with the selected carrier material and, where appropriate, further additives such as surfactants, dispersants, thickeners, binders, colour additives, corrosion inhibitors and the like, in one or more steps.

Suitable carriers for solid formulations, such as dusts, dispersible or flowable powders, are any dispersants which do not adversely affect the active ingredient, for example clays (e.g. kaolin, bentonite, acid clay and the like), talc (e.g. talc, agalmatolite (agalmatolite) powder and the like), silicas (e.g. diatomaceous earth, silicic anhydride, mica powder and the like), aluminas, sulfur powders, activated carbon and the like. These solid carriers may be used alone or in combination of two or more species.

Suitable carriers for liquid formulations are any liquids which do not adversely affect the active ingredient, for example: water, alcohols (e.g., methanol, ethanol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), ethers (e.g., dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (e.g., hexane, kerosene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, etc.), amides (e.g., dimethylformamide, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, fatty acid glycerides, etc.), and nitriles (e.g., acetonitrile, etc.). These solvents may be used alone or in combination of two or more species.

Emulsifiable concentrates of the antifouling compositions according to the invention can also be obtained by diluting the combination of component (I) and component (II) with at least one suitable organic solvent, i.e. a liquid carrier, followed by the addition of at least one solvent-soluble emulsifier. Solvents suitable for such formulations are generally water-immiscible and belong to the classes of hydrocarbons, chlorinated hydrocarbons, ketones, ethers, alcohols and amides, and can be chosen correctly by the person skilled in the art depending on the solubility of component (I) and component (II), respectively. Emulsifiable concentrates usually contain, in addition to the organic solvent, from about 10 to 50% by weight of the combination of active ingredients, from about 2 to 20% by weight of emulsifiers and up to 20% of other additives such as stabilizers, corrosion inhibitors and the like. The combination of components (I) and (II) may also be formulated as a concentrate of suspension, which is a stable suspension of the active ingredient in a (preferably organic) liquid intended to be diluted with water before use. In order to obtain such a non-settling flowable product, it is generally necessary to incorporate therein up to about 10% by weight of at least one suspending agent selected from known protective colloids and rheotropic agents (thixotropic agents). Other liquid formulations like aqueous dispersions and emulsions, e.g. from the dilution of wettable powders or concentrates with water (as previously described), and which may be of the water-in-oil or oil-in-water type, are also within the scope of the present invention.

The present invention also provides a protective antifouling composition, for example in the form of a paint, coating or varnish, comprising said combination of components (I) and (II) and one or more than one additive suitable for its formulation. The total amount of the combination of components (I) and (II) in such protective compositions may range from 2 to 10% (weight/volume). Suitable additives for use in the protective composition are quite conventional in the art and include, for example, at least one organic binder (preferably in aqueous form) such as an emulsion of acrylic or vinyl type or a rosin (rosin) compound; inorganic carriers such as calcium carbonate; surfactants, as previously explained; a viscosity modifier; a corrosion inhibitor; pigments such as titanium dioxide; stabilizers such as sodium benzoate, sodium hexametaphosphate and sodium nitrite; inorganic or organic colorants and the like. Methods of formulating such additives with component (I) and one or more than one component (II) of the present invention are also within the knowledge of those skilled in the art. Such protective compositions are useful not only for the disposal (cure) and/or to limit the destructive action of fouling organisms, but also to prevent deterioration in materials that may be subjected to harmful environmental and fouling organisms.

The antifouling compositions according to the invention can be applied by a variety of conventional methods, such as hydraulic spraying, air blast spraying, air spraying, micronisation, dusting, or spreading or pouring. The most suitable method will be selected by the person skilled in the art according to the desired goal and prevailing conditions, i.e. the kind of fouling organisms to be controlled and the type of devices available and the type of material to be protected.

As previously indicated, the combination of ingredients (I) and (II) is preferably applied in the form of a composition in which the two said ingredients are intimately mixed to ensure simultaneous application to the material to be protected. The application or application of the two components (I) and (II) can also be a "sequential-combined" application or application, i.e. the components (I) and (II) are applied or applied alternately (alternativelly) or sequentially (sequentially) at the same place, so that they are necessarily mixed together at the site to be treated. This can be achieved if the continuous application or application takes place within a short time, for example less than 24 hours, preferably less than 12 hours. Such an alternating method can be carried out, for example, by using a suitable single pack comprising at least one container filled with a formulation containing the active ingredient (I) and at least one container filled with a formulation containing the active ingredient (II). The invention therefore also encompasses a product comprising the following (a) and (b):

- (a) a composition comprising 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, or a salt thereof, as component (I), and

- (b) containing elements selected from Cu₂O、Cu(OH)₂、CuSO₄2-mercaptopyridine copper oxide, CuSCN, CuCO₃、ZnO、ZnCl₂、ZnSO₄A combination of zineb and 2-mercaptopyridine zinc oxide as component (II),

in combination, for simultaneous or sequential use,

wherein said (a) and (b) are in respective proportions to provide a synergistic effect against fouling organisms.

Experiment: flat disc test for toxicity

Experiment 1: flat disc test for toxicity

Name of the main compound: 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile as component (I)

Name of the combination partner: -Cu₂O as component (II-a);

-Cu(OH)₂as component (II-b);

-CuSO₄·5H₂o as component (II-c);

-copper 2-mercaptopyridineoxide, i.e. copper bis (1-hydroxy-2 (1H) -pyridinethiosulphate-O, S), as component (II-d);

-CuSCN as component (II-e);

-CuCO₃as component (II-f);

-ZnO as component (II-g);

-ZnCl₂as component (II-h);

-ZnSO₄·7H₂o as component (II-i);

-zineb as component (II-j);

-2-mercaptopyridine zinc oxide as component (II-k).

Storing the solution: 8000 and 80.000ppm, in DMSO

And (3) test combination: % product A +% product B

100+0

80+20

66+33

50+50

33+66

20+80

0+100

Concentration of all single active ingredients in toxicity test:

a series of concentrations was increased in 1/3 steps: 0.03-0.04-0.05-0.06-0.08-0.11-0.15-0.20-0.27-0.35-0.47-0.63-0.84-1.13-1.50-2.00-2.67-3.56-4.75-6.33-8.44-11.25-15.00-20.00-26.70-35.60-47.46-63.28-84.38-112.50-150.00-200.00 ppm.

Concentration of all active ingredients in the combination test:

a series of concentrations was increased in 1/3 steps: 0.08-0.11-0.15-0.20-0.27-0.35-0.47-0.63-0.84-1.13-1.50-2.00-2.67-3.56-4.75-6.33-8.44-11.25-15.00-20.00 ppm.

For having CuSO₄And ZnSO₄In the case of the combination of (a), (b),

a different series of 1/3 steps was used:

0.03-0.05-0.06-0.08-0.11-0.14-0.19-0.25-0.34-0.45-0.60-0.80-1.07-1.42-1.90-2.53-3.38-4.50-6.00-8.00ppm。

culture medium: algae: BG11 liquid inorganic Medium

Artemia (Artemia salina): artificial sea water

Experimental equipment: 24-hole plate

Algae species:

(1): chlorococcum (Chlorella vulgaris) CCAP211/12

(2): colletoceros orbicularis (Anabaena cylindrica) CCAP 1403/2A

(3): infusorium (Chlamydomonas sphagnophila) CCAP 11/36E inoculum:

algae: 1990 microliters of two week old culture Artemia (Artemia) diluted 1/10-fold in BG 11: 1990 microliter of Artificial seawater with 20-40 artemia larvae (incubated for 24 hours)

The culture conditions are as follows: 21 ℃, 65% relative humidity, 1000lux, 16 hours light period

Evaluation of algae: after 3 hours of exposure

Artemia: after 24 hours of exposure

The synergistic effect between component (I) and one of the components (II) is determined by means of a customary and accepted method using the Synergy Index (Synergy Index) as described by Kull F.C. et al in Applied Microbiology, 9, pages 538-541 (1961), calculated as follows for both compounds A and B:

wherein:

●Q_Acompound a concentration, expressed in ppm, acting alone, gives an endpoint (e.g. MIC),

●Q_athe concentration of compound a, expressed in ppm, in the mixture, which gives an endpoint (e.g. MIC),

●Q_Bcompound B concentration, expressed in ppm, acting alone, gives an endpoint (e.g. MIC),

●Q_bthe concentration of compound B, expressed in ppm, in the mixture, gives an endpoint (e.g. MIC).

The MIC is the minimum inhibitory concentration, i.e., the lowest concentration of each test compound or mixture of test compounds that is sufficient to inhibit visible growth.

Antagonism is indicated when the Synergy Index (SI) is greater than 1.0. When SI equals 1.0, additivity (addivity) is indicated. When the SI is less than 1.0, a synergistic effect is exhibited.

Antagonism is indicated when the Synergy Index (SI) is greater than 1.0. When SI equals 1.0, additivity is indicated. When the SI is less than 1.0, a synergistic effect is exhibited.

Table 1: MIC values (minimum inhibitory concentration in ppm) and synergy indices of various active ingredients and combinations thereof against Artemia (Artemia salina)

Table 2: MIC values (minimum inhibitory concentration in ppm) and synergy indices for various algae-resistant active ingredients and combinations thereof

Algae species:

(1): chlorococcum (Chlorella Vulgaris)

(2): necklace algae (Anabaena cylindrica)

(3): chlamydomonas sp (Chlamydomonas sphagnophila)

Claims (8)

1. A composition comprising 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile or a salt thereof as component (I), and CuSO as component (II)₄The composition of (a); wherein the weight ratio of component (I) to component (II) is from 10:1 to 1:10, thereby providing a synergistic effect against fouling organisms.

2. The composition of claim 1 wherein the weight ratio of component (I) to component (II) is from 3:1 to 1: 3.

3. A composition according to any one of claims 1-2 wherein the weight ratio of component (I) to component (II) is from 2:1 to 1: 2.

4. The composition of any of claims 1-2, wherein component (I) is present in an amount ranging from 1% to 40% by weight relative to the total weight of the composition.

5. Use of a composition according to any one of claims 1 to 4 for controlling fouling organisms.

6. A method of protecting a material against fouling organisms, wherein the method comprises applying or applying an antifouling effective amount of a composition according to any one of claims 1 to 4.

7. A method of disinfecting ballast water by adding an anti-fouling effective amount of the composition of any of claims 1-4.

8. A product, comprising:

(a) a composition comprising 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile or a salt thereof as component (I), and

(b) comprising CuSO₄The composition of the component (II) of (1),

in combination, for simultaneous or sequential use,

wherein the weight ratio of (I) to (II) is from 10:1 to 1:10, thereby providing a synergistic effect against fouling organisms.