WO2008047097A1

WO2008047097A1 - Antifungal coating composition

Info

Publication number: WO2008047097A1
Application number: PCT/GB2007/003932
Authority: WO
Inventors: Alexander Cornish; Anja Greiner
Original assignee: Syngenta Participations Ag
Priority date: 2006-10-20
Filing date: 2007-10-16
Publication date: 2008-04-24
Also published as: GB0620930D0

Abstract

The present invention relates to, inter alia, an antifungal coating composition, in particular paint, capable of controlling fungi on an Industrial Material said composition comprising: (A) an isothiazolone; (B) thiabendazole and (C) propiconazole. In a particular embodiment said (A), (B) and (C) are present in said composition in amounts which produce a synergistic fungicidal effect. The composition is particularly suitable for the treatment of Industrial Materials.

Description

ANTIFUNGAL COATING COMPOSITION

The present invention relates to antifungal coating compositions, in particular paints and their use in the protection of Industrial Materials. More specifically the compositions contain fungicidally effective amounts of an isothiazolone, thiabendazole and propiconazole.

The present invention is directed, inter alia, towards the provision of a coating composition having the following characteristics: (a) good efficacy against fungi which are capable of colonising and thus adversely affecting the technical integrity and/or cosmetic appearance of Industrial Materials; (b) exhibit good compatibility with the environment in which the Industrial Material is used; (c) can be formulated and manufactured in a cost effective way; and (d) are stable during use and storage for a reasonable period of time.

In addition to the above, in the light of environmental and governmental regulatory pressures, there is an increasing desire to reduce or eliminate certain compounds which are no longer acceptable for use in the treatment of materials. One example of such a compound is carbendazim which has been used previously as a biocide in a number of materials including paints. The present invention therefore seeks to provide an improved composition which does not contain any of the drawbacks of the compositions in the prior art.

According to the present invention there is provided a coating composition comprising as fungicidally active ingredient a mixture of: (A) an isothiazolone; (B) thiabendazole; and (C) propiconazole.

The present invention further provides a composition as described above wherein said isothiazolone, said thiabendazole and said propiconazole are present in said composition in amounts which produce a synergistic fungicidal effect.

Surprisingly, we have discovered that isothiazolones such as N-octylisothiazolin- 3-one (OIT) act synergistically when mixed with the triazole fungicides thiabendazole and propiconazole. Moreover, this synergistic effect is retained when the composition is a coating composition, for example paint. This composition therefore represents a major step forward in the protection of materials via the use of these fungicidal compounds in amounts which produce the said surprising synergistic effect. Such synergy not only brings about the enhancement of the spectrum of action with respect to the fungi to be controlled but achieves an effect which extends the range of action of component (A), component (B) and component (C) in two ways. Firstly, the rates of application of component (A), component (B) and component (C) are lowered whilst the action remains equally good. Secondly, the active ingredient mixture still achieves a high degree of fungal control even where the individual components have become totally ineffective in such a low application rate range. This allows, on the one hand, a substantial broadening of the spectrum of fungi that can be controlled and, on the other hand, increased safety in use. However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties which can also be described, in a wider sense, as synergistic activity. Examples of such advantageous properties that may be mentioned are: activity towards resistant strains and improved characteristics of the materials to which the compositions are added. Throughout this specification the expression "composition" embraces the various mixtures or combinations of components according to the invention. For example, the composition may comprise a single "already mixed" form of (A), (B) and (C) and this composition may be applied to the material. Alternatively the composition may be formed via a mixture of separate formulations of the single active ingredient components which are applied to the material in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components is not in itself essential for working the present invention.

The present invention still further provides a composition as described above wherein said isothiazolone is an isothiazolin-3-one. In a particular embodiment said isothiazolone is N-octylisothiazolin-3-one (OIT). Isothiazolones are described in GB 1224662. Examples such as N-octylisothiazolin-3-one (OIT) are well known and available in the art.

Thiabendazole and Propiconazole are both mentioned in "The Pesticide Manual" (The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council). Thiabendazole (2-(thiazol-4- yl)benzimidazole; 2-(l,3-thiazol-4-yl)benzimidazole) is described therein under entry number (790) and propiconazole (l-[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2- ylmethyl]-lH-l,2,4-triazole) under (675).

The present invention still further provides a composition as described above selected from the group consisting of: paint; varnish, stain, lacquer and plaster. Ih a further embodiment said coating is a lacquer. In a further embodiment said composition is paint. Paint can comprise, for example, a film former and a carrier (which carrier can be water and/or an organic solvent) and optionally a pigment, hi a still further embodiment of the invention there is provided a method of manufacturing a paint comprising an antifungal agent which method comprises generating a paint which comprises a film former, a carrier and optionally a pigment and adding a composition of the fungicides as described herein. Methods for the incorporation of the compositions of the invention into materials such as paints are well known to the person skilled in the art.

In a still further embodiment said coating composition can be one of the following: primers, semi gloss coatings, gloss coatings, flat coatings, topcoats, stain- blocking coatings, penetrating sealers (for porous substrates, concrete, and marble), elastomeric coatings, mastics, caulks, and sealants, board and panelling coatings, transportation coatings, furniture coatings, and coil coatings, bridge and tank coatings and surface marking paints, leather coatings and treatments, floor care coatings, paper coatings, personal care coatings such as for hair, skin, nails, woven and nonwoven fabric coatings and pigment printing pastes, and adhesive coatings such as, for example, pressure sensitive adhesives and wet- and dry- laminating adhesives and plaster.

The present invention still further provides a composition as described above wherein the weight ratio of said (A) isothiazolone and said (B) thiabendazole in said composition is 1 :20 to 20:1. In a particular embodiment the weight ratio of said (A) isothiazolone and said (B) thiabendazole in said composition is 1:10 to 10:1. In a further embodiment the weight ratio of said (A) and said (B) in said composition is 1:20 to 20:1, and wherein the weight ratio of the combination of components (A)Z(B) (isothiazolone and thiabendazole) to the weight ratio of component (C) propiconazole is from 20:1 to 1 :20. In a still further embodiment the weight ratio of said combination of components (A)/(B) (isothiazolone and thiabendazole) to the weight ratio of component (C) propiconazole is from 10:1 to 1:10. In a further embodiment of the invention the weight ratio of said (A) isothiazolone and said (B) thiabendazole in said composition is 1 : 8. In a still further embodiment of the invention the weight ratio of said (A) isothiazolone and said (B) thiabendazole in said composition is 1 :4. In a particular embodiment of the invention the amount of thiabendazole added to the composition exceeds the amount of isothiazolone added to said composition. In a particular embodiment of the invention the weight ratio of said (A) and said (B) in said composition is as described herein. In a particular embodiment of the invention the amount of thiabendazole added to the composition exceeds the amount of propiconazole which in turn exceeds the amount of isothiazolone added to said composition.

The present invention still further provides Industrial Materials comprising a composition as described above. "Industrial Material" includes those materials used in construction and the like. For example, Industrial Material may be structural timber, doors, cupboards, storage units, carpets, particularly natural fibre carpets such as wool and hessian, plastics, wood (including engineered wood) and wood plastic composite, hi addition to this, Industrial Material includes adhesives, sealants, joining materials and joints and insulation material. In a particular embodiment "Industrial Material" means structural timber. In a further embodiment "Industrial Material" means engineered wood. In a further embodiment "Industrial Material" means plastic.

Plastics includes plastic polymers and copolymers, including: acrylonitrile butadiene styrene, butyl rubber, epoxies, fluoropolymers, isoprene, nylons, polyethylene, , polyurethane, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polyvinylidene fluoride, polyacrylate, polymethyl methacrylate, polyurethane, polybutylene, polybutylene terephthalate, polyether sulfone, polyphenyllenoxide, polyphenylene ether, polyphenylene sulfide, polyphtatamide, polysulphene, polyester, silicone, styrene butadiene rubber and combinations of polymers. In a further embodiment "Industrial Material" means polyvinyl chloride (PVC). In a further embodiment "Industrial Material" means polyurethane (PU). In a further embodiment "Industrial Material" means wood plastic composite (WPC). Wood plastic composite is a material that is well known in the art. A review of WPCs can be found in the following publication - Craig Clemons - Forrest Products Journal. June 2002 VoI 52. No. 6. pp 10- 18. "Wood" is to be understood as meaning wood and wood products, for example: derived timber products, lumber, plywood, chipboard, flakeboard, laminated beams, oriented strandboard, hardboard, and particleboard, tropical wood, structural timber, wooden beams, railway sleepers, components of bridges, jetties, vehicles made of wood, boxes, pallets, containers, telegraph-poles, wooden fences, wooden lagging, windows and doors made of wood, plywood, chipboard, joinery, or wooden products which are used, quite generally, for building houses or decks, in building joinery or wood products that are generally used in house-building including engineered wood, construction and carpentry. "Industrial Material" also includes cooling lubricants and cooling and heating systems, ventilation and air conditioning systems and parts of production plants, for example cooling-water circuits. "Industrial Material" also includes wallboards such as gypsum based wallboards.

The present invention still further provides a composition capable of controlling fungi on an Industrial Material said composition comprising as fungicidally active ingredient a mixture of: (A) an isothiazolone; (B) thiabendazole; and (C) propiconazole. The present invention further provides a composition as described in the preceding sentence wherein said isothiazolone, said thiabendazole and said propiconazole are present in said composition in amounts which produce a synergistic fungicidal effect. Such compositions may also be added to the Industrial Materials referred to above. Thus the Industrial Material may comprise the composition as described above and/or be coated with a coating composition as described above. Examples of ways in which the fungus or Industrial Material can be treated with a composition according to the invention are: by including said composition in the Industrial material itself, absorbing, impregnating, treating (in closed pressure or vacuum systems) said material with said composition, dipping or soaking the building material, or coating the building material for example by curtain coating, roller, brush, spray, atomisation, dusting, scattering or pouring application.

The fungi to which the composition of the present invention is applicable are those fungi which are capable of colonising Industrial Materials. The effects of colonisation of materials by these fungi include discoloration of the material often accompanied by unpleasant smells. The growth of the fungi also usually contributes to the physical destruction of the materials. Various health problems have been attributed to such fungi with most common being allergic reactions and in some cases, human infection. Certain fungi which are capable of growing on Industrial materials are also thought to be carcinogenic. Examples of fungi to which, the compositions of the present invention are applicable include: Alternaria alternata, Aspergillus flavus, Aspergillus terreus, Aspergillus fumigatus, Aspergillus repens, Aspergillus versicolor, Candida albicans, Chaetomium globosum, Cladosporium cladosporioides, Cladosporium herbarum, Cladosporium sphaerospermum, Coniophora puteana, Curvularia genticulata, Diplodia natalensis, Epidermophytonfloccosum, Fusarium oxysporum, Gliocladium virens, Gloeophyllum trabeum, Humicola grisea, Lecythophora mutabilis, Lentinus cyaihiformis, Lentinus lepidus, Memnionella echinata, Mucor indicus, Mucor racemosus, Oligoporus placenta, Paecilomyces variotii, Penicillium citrinum, Penicillium funiculosum, Penicillium ochrochloron, Penicillium purpurogenum, Penicillium pinophilum, Penicillium variabile, Petriella setifera, Phanerochaete chrysosporium, Phoma violacea, Poria placenta, Rhodotorula rubra, Schizophyllum commune, Sclerophoma phytiophila Scopulariopsis brevicaulis, Serpula laaymans, Sporobolomyces roseus, Stemphyliwn dendriticum, Trichophyton mentagrophytes, Trichurus spiralis, Trichophyton rubruni, Ulocladium atrum and Ulocladium chartarum. Of particular concern are: Alternaria alternata, Alternaria tenuissima, Aspergillus niger, Aspergillus versicolor, Aureobasidium pullulans, Chaetomium globosum, Cladosporium cladosporioides, Coniophora puteana, Gloeophyllum trabeum, Memnionella echinata, Mucor indicus, Oligoporus placenta, Penicillium citrinum, Penicillium chrysogenum, Penicillium funiculosum, Penicillium pinophilum, Sclerophoma phytiophila, Stachybotrys atra, Stachybotrys chartarum, and Ulocladium chartarum.

The present invention still further provides a surface treated with a coating composition as described above. In a particular embodiment the surface is treated with the paint as described above. In a particular embodiment the surface is a gypsum based wallboard. In a further embodiment said surface is a wall and the like. In a still further embodiment said surface comprises a building. In a still further embodiment said surface comprises wood.

The present invention still further provides a method for the prevention and/or treatment of growth and/or infestation of a fungus on an Industrial Material comprising adding a fungicidally effective amount of a composition as described above to said Material.

The present invention still further provides the use of a composition as described above in a method of controlling fungal growth on an Industrial Material. The present invention still further provides a ldt comprising comprising (A) an isothiazolone; (B) thiabendazole; and (C) propiconazole. In a particular embodiment said isothiazolone, said thiabendazole and said propiconazole are present in said kit in amounts such that when mixed they are capable of producing a synergistic fungicidal effect. In a still further embodiment said kit comprises an Industrial material and a means for applying the said isothiazolone, said thiabendazole and said propiconazole to said material. In a still further embodiment said isothiazolone is an isothiazolin-3-one, more preferably N-octylisothiazolin-3-one (OIT).

The compositions according to the invention may comprise additional active ingredients in addition to the synergistic combinations mentioned above. For example, the composition may additionally comprise a further fungicide selected from the group consisting of: AC 382042 (N-(I -cyano-l,2-dimethylpropyl)-2-(2,4-dichlorophenoxy) propionamide), acibenzolar-S-methyl, alanycarb, aldimorph, anilazine, azaconazole, azafenidin, azoxystrobin and other strobilurin fungicides, benalaxyl, benomyl, benthiavalicarb, biloxazol, bitertanol, blasticidin S, boscalid (new name for nicobifen), bromuconazole, Bronopol, bupirimate, captafol, captan, carboxin, carpropamid, carvone, CGA 41396, CGA 41397, chinomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, cyamidazosulfamid, cyazofamid (IKF-916), cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-ρyridyl disulphide 1,1 -dioxide, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, diiodomethyl-p-tolylsufone (Amical, from Dow) O,O-di-rso-propyl-jS'-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, Dithiocarbamates, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethyl (Z)-N-benzyl-iV([methyl(methyl-thioethylideneaminooxy- carbonyl)amino]thio)-β-alaninate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil (AC 382042), fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fiuoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, itninoctadine, iniinoctadine triacetate, 3-iodo-2-propynyl butylcarbamate (IBPC), ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY 248908, mancozeb, maneb, MBT mefenoxam, mepanipyrim, mepronil, metalaxyl, metalaxyl M, metconazole, metiram, metiram-zinc, metominostrobin, metrafenone, MON65500 (N-allyl-4,5-dimethyl-2-trimethylsilylthioρhene-3-carboxamide)₅ myc- lobutanil, ΝTΝ0301, neoasozin, nickel dimethyldithiocarbamate, nitrothale-isopropyl, nuarimol, 2-0-octyl-4~isothiazohn -3 -one (Skane M 8 Rohm& Hass), ofurace, organomercury compounds, orysastrobin, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propineb, propionic acid, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, Sodium and Zinc Pyrithione (Omadine chemistry from Arch Chem.), pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, silthiofam (MON 65500), S-imazalil, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thifluzamide, 2-(thiocyano- methylthio)benzothiazole, thiophanate-methyl, thiram, tiadinil, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb, ziram, zoxamide and compounds of the formulae:

Alternatively or additionally, the composition may comprise an algaecide or herbicide, for example terbutryn, irgarol and prometryn. In a particular embodiment of the invention there is provided a coating composition as described above which additionally comprises terbutryn. In a still further embodiment there is provided a method as described above wherein the composition as described above additionally comprises terbutryn. In a still further embodiment there is provided the use as described above wherein the composition as described above additionally comprises terbutryn.

In a still further aspect of the invention there is provided a coating composition comprising: (A) propiconazole and (B) thiabendazole, wherein preferably said propiconazole and said thiabendazole are present in said composition in amounts which produce a synergistic fungicidal effect.

In a still further aspect of the invention there is provided a coating composition comprising as fungicidally active ingredient a mixture of: (A) propiconazole; (B) thiabendazole; and (C) 3-iodo-2-propynyl butylcarbamate (PBC) wherein preferably said propiconazole, said thiabendazole and said IPBC are present in said composition in amounts which produce a synergistic fungicidal effect. IPBC is well known to the person skilled in the art and commercially available.

In a still further aspect of the invention there is provided a coating composition comprising: (A) difenoconazole and (B) thiabendazole, wherein preferably said difenoconazole and said thiabendazole are present in said composition in amounts which produce a synergistic fungicidal effect.

In a still further aspect of the invention there is provided a coating composition comprising: (A) azoxystrobin and (B) thiabendazole, wherein preferably said azoxystrobin and said thiabendazole are present in said composition in amounts which produce a synergistic fungicidal effect.

The present invention still further provides a composition as described above selected from the group consisting of: paint; varnish, stain, lacquer and plaster. In a further embodiment said coating is a lacquer. In a further embodiment said composition is paint. Azoxystrobin and difenoconazole are both mentioned in "The Pesticide Manual"

(The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop Protection Council). Azoxystrobin (methyl (#)-2-{2-[6-(2- cyanophenoxy)pyrimidm-4-yloxy]phenyl}-3-niethoxyacrylate) is described under entry number 47 and difenoconazole (cis,frans-3-clήoτoA-[4-meXb.yl-2-(lH-l,2,4-tήazol-l- ylmethyl)-l,3-dioxolan-2-yl]phenyl 4-chlorophenyl ether) is described under entry number 247. The invention will now be described with reference to the following non-limiting examples:

The following compounds and formulations were used:

Test organisms and media used:

For the different tests 021-2006, 022-2006, 023-2006 different paint was used as matrix.

Propagation of the different fungi:

Altemaria alternata (DSM 326.65), Penicilliumfunicolosum (DSM 1944), and Aspergillus niger (DSM 1957) were separately cultivated on PDA or V8 media to suppress sporulation. Spore suspensions were produced for each fungus. Spore concentrations of approx. 1,000,000 spores/ml were used.

Test method used: The test used commercially available water based exterior paints. The test was conducted according to VdL-RL 06 (Resistance of coatings to fungi). For the test the paint was mixed with the compounds in the rates mentioned above. The paint was then painted onto filter paper (S&S LS 14) as carrier material. After painting the samples were dried for 5 days at 24°C, 60% relative humidity. Then the paint samples were placed in petri dishes containing PDA media and inoculated with the fungi, using spore suspensions with a concentration of 1,000,000 spores/ml.

The plates were then sealed and incubated at 28°C for 3 weeks.

In addition also non inoculated paint samples and non treated samples were prepared as a reference. The evaluation was performed by assessing the growth of the fungi related to the check growth. The results are expressed as % growth relative to the check (values of 0-100% growth). Afterwards the results were converted in % growth inhibition.

Analysis:

For the mixtures of different fungicides the synergism was calculated based on the Colby equation, which is described below:

A synergistic effect exists whenever the action of the active ingredient combination of the compound of formula I and one or more compounds of formula II and lit is greater than the sum of the actions of the active ingredients applied individually.

The fungicidal action to be expected, We, for a given combination of three fungicides can be calculated as follows (see COLBY, S. R. "Calculating synergistic and antagonistic response of herbicide combinations". Weeds 15, pages 20-22; 1967):

We _^ (A + B + C) - (A * B + A * C + B * C) IlOO + A * B * C /10000 wherein:

A = % activity in the case of treatment with the compound of formula I at rate x, in comparison with untreated control (= 0%).

B = % activity in the case of treatment with a compound of formula II at rate y, in comparison with untreated control.

C = % activity in the case of treatment with a compound of formula III at rate z, in comparison with untreated control. We - expected activity (% activity in comparison with untreated control) after treatment with the compound of formula I and compounds of formula II and III at a rate of x + y+z kg of active ingredient.

If the activity actually observed is greater than the expected value We (factor observed activity/expected activity >1.2), there is a synergistic effect. The synergistic effect of the combinations of the active ingredient of AZO with the active ingredients described above is demonstrated in the following results.

Results AU rates below are expressed as mg ai/1 (i.e. ppm)

Mixtures of TBZ&OIT

Mixtures of TBZ&PPZ

Mixtures of TBZ&PPZ&OIT

Mixtures of TBZ&PPZ&EPBC

Mixture of TBZ&DFZ

Mixture of TBZ&AZO

Claims

1. A coating composition comprising as fungicidally active ingredient a mixture of: (A) an isothiazolone; (B) thiabendazole; and (C) propiconazole.

2. A composition according to claim 1 wherein said isothiazolone, said thiabendazole and said propiconazole are present in said composition in amounts which produce a synergistic fungicidal effect.

3. A composition according to claim 1 or 2 wherein said isothiazolone is an isothiazolin-3-one.

4. A composition according to any one of claims 1 to 3 wherein said isothiazolone is N-octylisothiazolin-3-one (OIT).

5. A composition according to any one of claims 1 to 4 selected from the group consisting of: paint; varnish, stain, lacquer and plaster.

6. A composition according to claim 5 which is paint.

7. A composition according to any one of claims 1 to 6 wherein the weight ratio of said (A) isothiazolone and said (B) thiabendazole in said composition is 1:20 to 20:1.

8. A composition according to claim 7 wherein the weight ratio of said (A) isothiazolone and said (B) thiabendazole in said composition is 1:10 to 10:1.

9. A composition according to any one of claims 1 to 8 wherein the weight ratio of said (A) and said (B) in said composition is 1:20 to 20:1, and wherein the weight ratio of the combination of components (A)/(B) (isothiazolone and thiabendazole) to the weight ratio of component (C) propiconazole is from 20:1 to 1:20.

10. A composition according to claim 9 wherein the weight ratio of said combination of components (A)/(B) (isothiazolone and thiabendazole) to the weight ratio of component (C) propiconazole is from 10:1 to 1:10.

11. Industrial Materials comprising a composition according to any one of claims 1 to 10.

12. A surface treated with the paint according to claim 6.

13. A method for the prevention and/or treatment of growth and/or infestation of a fungus on an Industrial Material comprising adding a fungicidally effective amount of a composition according to any one of claims 1 to 10 to said Material.

14. Use of a composition according to any one of claims 1 to 10 in a method of controlling fungal growth on an Industrial Material.

15. A kit comprising comprising (A) an isothiazolone; (B) thiabendazole; and (C) propiconazole.

16. A kit according to claim 15 wherein said isothiazolone, said thiabendazole and said propiconazole are present in said kit in amounts such that when mixed they are capable of producing a synergistic fungicidal effect.

17. A kit according to claim 15 or claim 16 which further comprises an Industrial material and a means for applying the said isothiazolone, said thiabendazole and said propiconazole to said material.

18. A kit according to any one of claims 15 to 17 wherein said isothiazolone is an isothiazolin-3-one, more preferably N-octylisothiazolin-3-one (OIT).