WO2006087356A2

WO2006087356A2 - Synergistic antifouling compositions comprising (4-isopropylpyridinio)methyldiphenylboron

Info

Publication number: WO2006087356A2
Application number: PCT/EP2006/060012
Authority: WO
Inventors: Jan Pieter Hendrik Bosselaers; Tony Mathilde Jozef Kempen; Ludo Antoinnette De Witte
Original assignee: Janssen Pharmaceutica N.V.
Priority date: 2005-02-18
Filing date: 2006-02-16
Publication date: 2006-08-24
Also published as: WO2006087356A3

Abstract

The present invention relates to antifouling compositions comprising the biocide (4-isopropylpyridinio)methyldiphenylboron together with another biocide selected from bethoxazin, 2-methylthio-4-(tert-butyl-amino)-6-(cyclopropylamino)-s-triazine, diuron, DCOIT, tolylfluanid, triphenyl(pyridine)borane, glutaric dialdehyde, tebufenpyrad, pyridaben, fenazaquin, menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite in respective proportions to provide a synergistic effect against plant and animal fouling. This invention thus relates to the field of protection of materials such as e.g. underwater objects, protection of wood, wood products, biodegradable materials and coatings which are exposed to a humid or aqueous environment.

Description

SYNERGISTIC ANTIFOULING COMPOSITIONS COMPRISING (4-ISOPROPYLPYRIDINIO)METHYLDIPHENYLBORON

[0001] The present invention relates to antifouling compositions comprising the biocide (4-isopropylpyridinio)methyldiphenylboron together with another biocide selected from bethoxazin, 2-methylthio-4-(fe/t-butyl-amino)-6-(cyclopropylamino)-s- triazine, diuron, DCOIT, tolylfluanid, triphenyl(pyridine)borane, glutaric dialdehyde, tebufenpyrad, pyridaben, fenazaquin, menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite in respective proportions to provide a synergistic effect against plant and animal fouling. This invention thus relates to the field of protection of materials such as e.g. underwater objects, protection of wood, wood products, biodegradable materials and coatings which are exposed to a humid or aqueous environment.

[0002] It has now been found that the combination of the biocide (4-isopropyl- pyridinio)methyldiphenylboron (hereinafter referred to as component I) and another biocide (hereinafter referred to as component II) selected from bethoxazin, 2-methyl- thio-4-(fe/t-butyl-amino)-6-(cyclopropylamino)-s-triazine, diuron, DCOIT, tolylfluanid, triphenyl(pyridine)borane, glutaric dialdehyde, tebufenpyrad, pyridaben, fenazaquin, menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite has a synergistic effect on the control of fouling organisms. As used herein, "control" is defined to include the inhibition of attachment or settlement of fouling organisms to the surface of an object, the removal of fouling organisms that are attached to the surface of an object, and the growth of fouling organisms.

[0003] The biocidal component (I) is (4-isopropylpyridinio)methyldiphenylboron (CAS Registry Number 159565-88-5) or abbreviated as IPMB which structure may be represented as follows :

component (I)

- -

[0004] The antifoulant properties of component (I) and its use in a method for the protection of aquatic structures against fouling by marine or freshwater fouling organisms have been disclosed in WO-97/42823.

[0005] The biocidal components (II) are :

• bethoxazin (component ll-a) is disclosed as compound (87) in WO-95/05739 as an antibacterial, anti-yeast, antifungal, algicidal, anti-crustacean, molluscicidal and general antifouling agent. It is the generic name of 3-(benzo[b]thien-2-yl)-5,6- dihydro-1 ,4,2-oxathiazine 4-oxide, which compound is represented by the formula

component (ll-a)

• 2-methylthio-4-(fe/t-butyl-amino)-6-(cyclopropylamino)-s-triazine (component ll-b) is described in US-4,242,119 as an algicide useful for combating sea-water algae. Said component (ll-b) is sometimes also referred to as "irgarol" and is represented by the formula

component (ll-b)

• diuron (component ll-c) is described in US-2, 655,445 and its use as an algicide in anti-fouling paints has been disclosed in GB-2,278,361. It is the generic name of the compound 1 ,1-dimethyl-3-(3,4-dichlorophenyl)urea, which is represented by the formula

component (ll-c)

• DCOIT (component ll-d) is described in US-4, 127,687 for use in the control of marine plant and animal life such as algae, hydroids and barnacles. It is the generic name of the compound 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone, which compound is represented by the formula - -

component (ll-d)

tolylfluanid (component ll-e) has a broad spectrum antimicrobial activity and is the generic name of the compound 1 ,1-dichloro-Λ/-[(dimethylamino)sulfonyl]-1-fluoro- Λ/-phenyl-methanesulfenamide, which compound is represented by the formula

(CH₃)₂N- ?S-N-S-C(CI₂)F component (ll-e)

• triphenyl(pyridine)borane (component ll-f) is antifoulant which may be represented by the formula

component (ll-f)

• glutaric dialdehyde (component ll-g) is used as a biocide, which compound is represented by the formula

OHC-(CH₂)₃-CHO component (ll-g)

• tebufenpyrad (component ll-h) is a mitochondrial electron transport inhibitor (METI) used an acaricide, which compound is represented by the formula

(component (ll-h)

• pyridaben (component ll-i) is a mitochondrial electron transport inhibitor (METI) used an acaricide, which compound is represented by the formula - -

component (IN)

fenazaquin (component ll-j) is a mitochondrial electron transport inhibitor (METI) used an acaricide, which compound is represented by the formula

component (ll-j)

• menadione sodium bisulfite (component ll-k) and its derivatives with the heterocyclic bases triazine and piperazine selected from menadione piperazine bisulfite (component (ll-k-1)) and menadione triaminotriazine bisulfite (component

(ll-k-2)) have been disclosed in EP-1 ,479,295 for use in biocidal compositions. Menadione sodium bisulfite is the generic name of 1 ,2,3,4-tetrahydro-2-methyl-1 ,4- dioxo-2-naphthalenesulfonic acid sodium salt, which compound is represented by the formula

component (ll-k)

[0006] Wherever the term "(4-isopropylpyridinio)methyldiphenylboron" or component (I), one of the components (II), or component (ll-a) to component (ll-k), is used, it is meant to include said compound both in base or in salt form, the latter being obtained by reaction of the base form with an appropriate acid. Appropriate acids comprise, for example, inorganic acids, such as the hydrohalic acids, i.e. hydrofluoric, hydrochloric, hydrobromic and hydroiodic, sulfuric acid, nitric acid, phosphoric acid, phosphinic acid and the like; or organic acids, such as, for example, acetic, propanoic, hydroxyacetic, 2-hydroxypropanoic, 2-oxopropanoic, ethanedioic, propanedioic, butanedioic, (Z)-2-butenedioic, (E)-2-butenedioic, 2-hydroxybutanedioic, 2,3-dihydroxybutanedioic, 2-hydroxy-1 ,2,3-propanetricarboxylic, methanesulfonic, ethanesulfonic, benzenesulfonic, 4-methyl-benzenesulfonic, cyclohexanesulfamic, 2-hydroxybenzoic, 4-amino-2-hydroxybenzoic and the like acids. Said component (I) and components (II) may also exist in the form of solvates, such as hydrates. - -

[0007] Surfaces or objects exposed to humid or aqueous environments are readily colonized by aquatic organisms such as algae, fungi, bacteria, microbes, and aquatic animals such as, e.g. tunicates, hydroids, bivalves, bryozoans, polychaete worms, sponges, barnacles, molluscs and Crustacea. As these organisms settle on or attach to said surfaces, the value of the exposed objects diminishes. The attachment or settlement of said organisms is also known as 'fouling' of a structure. The exterior, but possibly also the interior of the object may deteriorate, the surface changes, e.g. from smooth, clean and streamlined to rough, foul and turbulent, the weight of the object increases by the deposit of the organisms and their remnants, and the vicinity of the object may become obstructed or encumbered. The function of the object and system involved lowers and the quality of the aqueous environment deteriorates. The common method of controlling the attachment of fouling organisms is by treating the structure to be protected with a coating which comprises an antifouling agent.

[0008] Fouling of surfaces or objects exposed to humid or aqueous environments often starts with the attachment or settlement of slime and algae. This roughens the smooth surface thereby easing the settlement of other fouling organisms such as, e.g. tunicates, barnacles, Crustacea, molluscs and the like. Hence, the algicidal properties of antifouling compositions to protect surfaces from fouling are important.

[0009] The compositions of the present invention are especially suitable to protect surfaces or objects in constant or frequent contact with water from fouling or attachment or settlement of algae, by applying to said surfaces or objects an antifouling composition comprising component (I), and one of the components (II) in respective proportions to provide a synergistic effect against fouling organisms. Examples of said surfaces or objects are for instance, shiphulls, harbor installations, piers and pilings, drying docks, sluice-gates, locks, mooring masts, buoys, offshore oil rigging equipment, drilling platforms, bridges, pipelines, fishing nets, cables, ballast water tanks, ship reservoirs that draw water from infested bodies of water, recreational equipment, such as surfboards, jet skis, and water skis, and any other object in constant or frequent contact with water.

[0010] The invention also provides a method to protect materials, in particular surfaces or objects in frequent or constant contact with water, against fouling organisms by applying to said objects an antifouling composition comprising an effective antifouling amount of component (I) in combination with one of the - -

components (II) in respective proportions to provide a synergistic effect against fouling organisms.

[0011] The present invention further provides a method of protecting a surface which comprises applying to the surface an antifouling composition in accordance with the invention. An especially important use of the method of the invention comprises a method for inhibiting fouling of a ship's hull, which comprises applying to the hull an antifouling composition in accordance with the invention. Fouling on the hulls of ships for example increases frictional drag with a corresponding decrease in speed and maneuverability and an increase in fuel consumption and increased maintenance costs associated with removal of the fouling.

[0012] The compositions of the present invention are useful to eliminate, kill or inhibit the growth of fouling organisms that are present in marine or freshwater and can be used in a method of disinfecting ballast water by adding an antifouling effective amount of a composition according to the present invention to said ballast water.

[0013] Further, antifouling compositions in accordance with the invention can be used to protect constructions such as, e.g. swimming pools, baths, cooling water circulation circuits and industrial baths in various installations, e.g. in manufacturing plants or in air-conditioning installations, the function of which can be impaired by the presence and/or the multiplication of fouling organisms. Further examples are buildings and parts of buildings such as floors, outer and inner walls or ceilings, or places suffering from dampness such as cellars, bathrooms, kitchens, washing houses and the like, and which are hot-beds for fouling. Fouling not only is problematic from the viewpoint of hygiene and aesthetics, but also causes economic losses because said buildings and/or decorating materials deteriorate more rapidly than desired.

[0014] The antifouling compositions of the present invention can also be used in a variety of other applications :

- industrial aqueous process fluids, e.g. cooling waters, pulp and paper mill process waters and suspensions, secondary oil recovery systems, spinning fluids, metal working fluids, and the like

- in-tank/in-can protection of aqueous functional fluids, e.g. polymer emulsions, water based paints and adhesives, glues, starch slurries, thickener solutions, gelatin, wax emulsions, inks, polishes, pigment and mineral slurries, rubber latexes, concrete additives, drilling mud's, toiletries, aqueous cosmetic formulations, pharmaceutical formulations, and the like. [0015] The term "fouling organisms" is meant to comprise organisms that attach, settle, grow on or adhere to various kinds of surfaces, in particular in humid or aqueous environments such as, marine waters, fresh waters, brackish waters, rain water, and also cooling water, drainage water, waste water and sewage. Fouling organisms are Algae such as, for example, Microalgae, e.g. Amphora, Achnanthes, Navicula, Amphiprora, Melosira, Cocconeis, Chlamydomonas, Chlorella, Ulothrix, Anabaena, Phaeodactylum, Porphyridium; Macroalgae, e.g. Enteromorpha, Cladophora, Ectocarpus, Acrochaetium, Ceramium, Polysiphonia and Hormidium sp.; fungi; microbes; tunicates, including members of the class Ascidiacea such as Ciona intestinalis, Diplosoma listerianium, and Botryllus schlosseri; members of the class Hydrozoa, including Clava squamata, Hydractinia echinata, Obelia geniculata and Tubularia larynx; bivalves, including Mytilus edulis, Crassostrea virginica, Ostrea edulis, Ostrea chilensia, Dreissena polymorpha (zebra mussels) and Lasaea rubra; bryozoans, including Electra pilosa, Bugula neritina, and Bowerbankia gracilis; polychaete worms, including Hydroides norvegica; sponges; and members of the class Crustacea, including Artemia, and Cirripedia (barnacles), such as Balanus amphitrite, Lepas anatifera, Balanus balanus, Balanus balanoides, Balanus hameri, Balanus crenatus, Balanus improvisus, Balanus galeatus, and Balanus eburneus; and Elminius modestus, and Verruca.

[0016] The relative proportions of component (I) and (II) in the embodied antifouling compositions are those proportions which result in unexpected synergistic effect against fouling organisms, especially against algae, when compared to a composition including, as an active ingredient, either component (I) alone or a component (II) alone. As will readily be understood by those skilled in the art, the said synergistic effect may be obtained within various proportions of components (I) and (II) in the composition, depending on the kind of fouling organism towards which effect is measured and the substrate to be treated. Based on the teachings of the present application, determination of the synergistic effect of such combinations can be performed according to the procedures of the Poison Plate Assay as described in Experiments 1 and 2. As a general rule, however, it may be said that for most fouling organisms the suitable proportions by weight of the amount of component (I) to component (II) in the active composition should lie in the range from 10:1 to 1 :10. Particularly, this range is from 8:2 to 2:8, more particularly from 3:1 to 1 :3 or 2:1 to 1 :2. Another particular ratio for the antifouling compositions of the present invention is a 1 :1 ratio between component (I) and one of the components (II). - -

[0017] The quantity of each of the active ingredients in the antifouling compositions according to the present invention will be so that a synergistic antifouling effect is obtained. In particular it is contemplated that the ready to use compositions of the present invention comprise component (I) in an amount of at least 1 wt % based on the total weight of the composition. More particular such ready to use compositions comprise component (I) in an amount from 1 wt% to 40 wt% based on the total weight of the composition. The amount of component (II) in said ready to use compositions will be so that a synergistic antifouling effect is obtained. In particular the amount of component (II) may range from 1 wt% to 20 wt%, more particular from 2 wt% to 10 wt% based on the total weight of the dry mass of the composition. In many instances the antifouling compositions to be used directly can be obtained from concentrates, such as e.g. emulsifiable concentrates, suspension concentrates, or soluble concentrates, upon dilution with aqueous or organic media, such concentrates being intended to be covered by the term composition as used in the definitions of the present invention. Concentrates used in the form of a paint composition can be diluted to a ready to use mixture in a spray tank shortly before use.

[0018] The combination of components (I) and (II) is thus suitably used together with carriers and additives, including wetting agents, dispersing agents, stickers, adhesives, emulsifying agents and the like such as those conventionally employed by the artisan in preparing antifouling compositions. The antifouling compositions of the present invention may further comprise suitable substances known in the art of formulation, such as, for example natural or regenerated mineral substances, solvents, dispersants, surfactants, wetting agents, adhesives, thickeners, binders, anti-freeze agents, repellents, colour additives, corrosion inhibitors, water-repelling agents, siccatives, UV-stabilizers and other active ingredients. Suitable surfactants are non- ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

[0019] The antifouling compositions of the present invention may be prepared in any known manner, for instance by homogeneously mixing, coating and/or grinding the combination of active ingredients (i.e. component (I) and one of the components (II)), in a one-step or multi-steps procedure, with the selected carrier material and, where appropriate, the other additives such as surface-active agents, dispersants, thickeners, binders, colour additives, corrosion inhibitors and the like. - -

[0020] Suitable carriers for solid formulations, such as dusts, dispersable or flowable powders, are any dispersant that does not adversely affect the active ingredients, for example, clays (for example, kaolin, bentonite, acid clay, and the like), talcs (for example, talc powder, agalmatolite powder, and the like), silicas (for example, diatomaceous earth, silicic acid anhydride, mica powder, and the like), alumina, sulfur powder, activated charcoal, and the like. These solid carriers may be used either singly or in combination of two or more species

[0021] Appropriate carriers for liquid formulations are any liquid that does not adversely affect the active ingredients, for example, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, etc.), ketones (for example, acetone, methyl ethyl ketone, etc.), ethers (for example, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (for example, hexane, kerosene, etc.), aromatic hydrocarbons (for example, benzene, toluene, xylene, solvent naphtha, methyl naphthalene, etc.), halogenated hydrocarbons (for example, chloroform, carbon tetrachloride, etc.), acid amides (for example, dimethyl formadide, etc.), esters (for example, methyl acetate ester, ethyl acetate ester, butyl acetate ester, fatty acid glycerin ester, etc.), and nitriles (for example, acetonitrile, etc.). These solvents may be used either singly or in combination of two or more species.

[0022] Emulsifiable concentrates of the antifouling compositions according to the present invention can also be obtained upon dilution of the combination of components (I) and (II) with at least a suitable organic solvent (i.e. a liquid carrier) followed by the addition of at least a solvent-soluble emulsifying agent. Solvents suitable for this type of formulation are usually water-immiscible and belong to the hydrocarbon, chlorinated hydrocarbon, ketone, ester, alcohol and amide classes of solvents, and they can be properly selected by those skilled in the art based on the solubility's of components (I) and (II) respectively. Emulsifiable concentrates usually contain, in addition to the organic solvent(s), from about 10 to 50% by weight of the combination of active ingredients, from about 2 to 20% of emulsifying agent(s) and up to 20% other additives such as stabilisers, corrosion inhibitors and the like. The combination of components (I) and (II) may also be formulated as a suspension concentrate, which is a stable suspension of the active ingredients in a (preferably organic) liquid intended to be diluted with water before use. In order to obtain such a non-sedimenting flowable product, it is usually necessary to incorporate therein up to about 10% by weight of at least a suspending agent selected from known protective colloids and thixotropic - -

agents. Other liquid formulations like aqueous dispersions and emulsions, for example obtained by diluting a wettable powder or a concentrate (such as previously described) with water, and which may be of the water-in-oil or the oil-in-water type, also lie within the scope of the present invention.

[0023] The present invention also provides protective antifouling compositions, for instance in the form of paints, coatings or varnishes, comprising the said combination of components (I) and (II) together with one or more additives suitable for their formulation. The total amount of the combination of components (I) and (II) in such protective compositions may range from 2 to 10% (w/v). Suitable additives for use in said protective compositions are quite conventional in the art and include, for instance, at least an organic binder (preferably in aqueous form) such as an acrylic or vinyl- based emulsion or rosin compounds; mineral carriers such as calcium carbonate; surface-active agents such as previously described; viscosity regulators; corrosion inhibitors; pigments such as titanium dioxide; stabilisers such as sodium benzoate, sodium hexametaphosphate and sodium nitrite; mineral or organic colorants and the like. The ways of formulating such additives together with active biocidal ingredients such as those of the present invention is also well within the knowledge of those skilled in the art. Such protective compositions may be used not only to cure and/or limit the damaging effects of fouling organisms but also in order to prevent deterioration to occur on materials which may be subjected to the harmful environment and effects of fouling organisms.

[0024] The antifouling compositions according to the present invention can be applied by a number of conventional methods, such as hydraulic spray, air-blast spray, aerial spray, atomising, dusting, scattering or pouring. The most appropriate method will be chosen by those skilled in the art in accordance with the intended objectives and the prevailing circumstances, namely the kind of fouling organism to be controlled, the type of equipment available and the type of material to be protected.

[0025] As previously indicated, the combination of components (I) and (II) is preferably applied in the form of compositions wherein both said ingredients are intimately admixed in order to ensure simultaneous administration to the materials to be protected. Administration or application of both components (I) and (II) can also be a "sequential-combined" administration or application, i.e. component (I) and component (II) are administered or applied alternatively or sequentially in the same place in such a way that they will necessarily become admixed together at the site to be treated. This will be achieved namely if sequential administration or application takes place within a short period of time e.g. within less than 24 hours, preferably less than 12 hours. This alternative method can be carried out for instance by using a suitable single package comprising at least one container filled with a formulation comprising the active component (I) and at least one container filled with a formulation comprising an active component (II). Therefore the present invention also encompasses a product containing : - (a) a composition comprising (4-isopropylpyridinio)methyldiphenylboron as component (I), and - (b) a composition comprising a component (II), selected from bethoxazin,

2-methylthio-4-(fe/t-butyl-amino)-6-(cyclopropylamino)-s-triazine, diuron, DCOIT, tolylfluanid, triphenyl(pyridine)borane, glutaric dialdehyde, tebufenpyrad, pyridaben, fenazaquin, menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite as a combination for simultaneous or sequential use, wherein said (a) and (b) are in respective proportions to provide a synergistic effect against fouling organisms, in particular algae.

Experimental part Experiment 1 : Poison plate assay

1. Poison plate assay in 24 multi-well plates

[0026] Activity against algae growth was determined with the poison plate assay. A calculated amount of a stock solution (containing either 1000 ppm of (4-isopropyl- pyridinio)methyldiphenylboron, bethoxazin, 2-methylthio-4-(fe/t-butyl-amino)-6- (cyclopropylamino)-s-triazine, diuron, or DCOIT in DMSO) was pipetted into multiwell plates in order to reach a final test concentration ranging from 0.11 to 2.50 ppm and mixed with a warm culture medium. The medium was inoculated with 1190 μl of a 1/10 dilution in BG 11 liquid mineral medium of a two week old algae culture. The multi-well plates were kept at 21⁰C, a relative humidity of 65% and light-dark cycle of 16 hours a day (1000 Lux photoperiod).

[0027] The lowest concentration of each test compound or mixture of test compounds sufficient to inhibit visible growth was taken as the minimum inhibitory concentration (MIC). The MIC were taken as end points of activity. End points for the combinations of component (I) with one of the components (II) were then compared with the end points for the pure active test compound when employed individually. - -

[0028] The following algae species were used in the poison plate assay : Chlorella vulgaris, Anabaena cylindrica and Chlamydomonas sphagnophila.

[0029] Synergism between component (I) and one of the components (II) was determined by a commonly used and accepted method described by KuII F. C. et al. in Applied Microbiology, 9, 538-541 (1961) using the Synergy Index, which is calculated as follows for two compounds A and B:

Synergy Index (Sl) = -3iL + .Qk QA QB

wherein:

• Q_A is the concentration of compound A in ppm, acting alone, which produced an end point (e.g. MIC),

• Q_a is the concentration of compound A in ppm, in the mixture, which produced an end point (e.g. MIC), • Qβ is the concentration of compound B in ppm, acting alone, which produced an end point (e.g. MIC),

• Qb is the concentration of compound B in ppm, in the mixture, which produced an end point (e.g. MIC).

[0030] When the Synergy Index is greater than 1.0, antagonism is indicated. When the SI is equal to 1.0, additivity is indicated. When the SI is less than 1.0, synergism is demonstrated.

Table 1 : MIC-values (minimum inhibitory concentration in ppm) and synergy index of various active ingredients and their combination against Chlorella vulgaris for bethoxazin, 2-methylthio-4-(fe/t-butyl-amino)-6-(cyclopropyl- amino)-s-triazine and DCOIT and Anabaena cylindrica for diuron

- -

Experiment 2 : poison plate assay Name of the primary compound: (4-isopropyl-pyridinio)methyldiphenylboron as component (I)

Name of the combination partners: - bethoxazin as component (ll-a); - 2-methylthio-4-(fe/t-butyl-amino)-6-(cyclopropyl- amino)-s-triazine as component (ll-b);

- DCOIT as component (ll-d);

- tolylfluanid as component (ll-e);

- triphenyl(pyridine)borane as component (ll-f);

- glutaric dialdehyde as component (ll-g);

- tebufenpyrad as component (ll-h);

- pyridaben as component (ll-i);

- fenazaquin as component (ll-j); - -

- menadione piperazine bisulfite as component (ll-k-1);

- menadione triaminotriazine bisulfite as component (ll-k-2).

Stock solution: 8000 and 80.000 ppm in DMSO

Test combinations: % productA + % product B

100 + 0

80 + 20

66 + 33

50 + 50

33 + 66

20 + 80

0 + 100

Concentrations of total single active ingredient in the tests : a series of concentrations increasing with steps of 1/3 : 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.

Concentrations of total active ingredient in the combination tests : a series of concentrations increasing with steps of 1/3: 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.

Culture medium : algae: BG 11 liquid mineral medium Aiiemia salina: artificial seawater

Experimental set up : 24-well plates

Species of algae : (1 ) : Chlorella vulgaris CCAP 211/12

(2) : Anabaena cylindrica CCAP 1403/2A

(3) : Chlamydomonas sphagnophila CCAP 11/36 E

Inoculum : algae: 1990 μl of a 1/10 dilution in BG 11 of a two week old culture Aiiemia: 1990 μl artificial seawater with 20 - 40 Artemia larvae

(24 hours old) - -

Culture conditions : 21⁰C, 65 % relative humidity, 1000 lux, 16 hour photoperiod

Evaluation: algae: after 3 weeks of exposure Aiiemia: after 24 hours of exposure

Synergism between component (I) and one of the components (II) was determined by a commonly used and accepted method described by KuII F. C. et al. in Applied Microbiology, 9, 538-541 (1961) using the Synergy Index, which is calculated as follows for two compounds A and B:

Synergy Index (Sl) = +

wherein:

• Q_a is the concentration of compound A in ppm, in the mixture, which produced an end point (e.g. MIC),

• Q_B is the concentration of compound B in ppm, acting alone, which produced an end point (e.g. MIC), • Qb is the concentration of compound B in ppm, in the mixture, which produced an end point (e.g. MIC).

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

When the Synergy Index is greater than 1.0, antagonism is indicated. When the SI is equal to 1.0, additivity is indicated. When the SI is less than 1.0, synergism is demonstrated.

When the Synergy Index is greater than 1.0, antagonism is indicated. When the SI is equal to 1.0, additivity is indicated. When the SI is less than 1.0, synergism is demonstrated. - -

Table 2 : MIC-values (minimum inhibitory concentration in ppm) and synergy index of various active ingredients and their combination against Artemia salina

- -

Table 3 : MIC-values (minimum inhibitory concentration in ppm) and synergy index of various active ingredients and their combination agains algae

Species of algae : (1 ) : Chlorella vulgaris

(2) : Anabaena cylindrica

(3) : Chlamydomonas sphagnophila

Claims

- -Claims

1. A composition comprising a component (I), (4-isopropylpyridinio)methyldiphenyl- boron, and a component (II) selected from bethoxazin, 2-methylthio-4-(fe/t-butyl- amino)-6-(cyclopropylamino)-s-triazine, diuron, DCOIT, tolylfluanid, triphenyl-

(pyridine)borane, glutaric dialdehyde, tebufenpyrad, pyridaben, fenazaquin, or menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite, whereby component (I) and component (II) are present in respective proportions to provide a synergistic effect against fouling organisms, and a carrier.

2. A composition according to claim 1 wherein the component (II) is bethoxazin.

3. A composition according to claim 1 wherein the component (II) is 2-methylthio-4- (fe/t-butyl-amino)-6-(cyclopropylamino)-s-triazine.

4. A composition according to claim 1 wherein the component (II) is diuron.

5. A composition according to claim 1 wherein the component (II) is DCOIT.

6. A composition according to claim 1 wherein the component (II) is tolylfluanid.

7. A composition according to claim 1 wherein the component (II) is triphenyl-

(pyridine)borane.

8. A composition according to claim 1 wherein the component (II) is glutaric dialdehyde.

9. A composition according to claim 1 wherein the component (II) is tebufenpyrad, pyridaben, or fenazaquin.

10. A composition according to claim 1 wherein the component (II) is menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite.

11. A composition according to any of claims 1 to 10 wherein the ratio by weight of component (I) to one of the components (II) is 10:1 to 1 :10.

12. A composition according to any of claims 1 to 10 wherein the ratio by weight of component (I) to one of the components (II) is 3:1 to 1 :3. - -

13. A composition according to any of claims 1 to 12 wherein the amount of component (I) ranges from 1 wt% to 40 wt% based on the total weight of the composition.

14. Use of a composition according to any of claims 1 to 13 for the control of fouling organisms.

15. A method of protecting materials against fouling organisms, wherein the said method comprises administration or application of an antifouling effective amount of a composition according to any of claims 1 to 13.

16. A method according to claim 15 wherein the materials are fishing nets.

17. A method of disinfecting ballast water by adding an antifouling effective amount of a composition according to any of claims 1 to 13.

18. A product containing

(a) a composition comprising (4-isopropylpyridinio)methyldiphenylboron as component (I), and (b) a composition comprising a component (II), selected from bethoxazin,

2-methylthio-4-(fe/t-butyl-amino)-6-(cyclopropylamino)-s-triazine, diuron, DCOIT, tolylfluanid, triphenyl(pyridine)borane, glutaric dialdehyde, tebufenpyrad, pyridaben, fenazaquin, menadione sodium bisulfite and its derivatives menadione triaminotriazine bisulfite and menadione piperazine bisulfite, as a combination for simultaneous or sequential use, wherein said (a) and (b) are in respective proportions to provide a synergistic effect against fouling organisms, in particular algae.