TITLE OF THE INVENTION

POLYMER COATINGS CONTAINING PHYTOCHEMICAL AGENTS AND METHODS FOR MAKING AND USING SAME INCORPORATION BY REFERENCE

This application claims priority to U.S. Provisional Patent Application No. 60/697,818 filed My 8, 2005.

The foregoing applications, and all documents cited therein or during their prosecution and all documents cited or referenced in the application cited documents, and all documents cited or referenced herein ("herein cited documents"), and all documents cited or referenced in herein cited documents, together with any manufacturer's instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention. FIELD OF THE INVENTION

This invention relates to polymer coatings; UHMW polyethylene, VHMW polyethylene, latex compounds and latex compounds incorporating biocidal phytochemical agents. BACKGROUND OF THE INVENTION Historically, toxic chemicals including heavy metals and the salts thereof, have been add to marine paints to control the build up of marine organisms on marine vessel hulls bottoms and structures. This marine growth is known as fouling and can seriously diminish the performance of a ship's hull through the water, as well as causing structural damage. Both marine and freshwater vessels are susceptible to bottom fouling that can result in significant economic penalties.

Two chemicals, Tributyltin (TBT) and cuprous oxide (copper), have been in commercial use for decades as toxic antifouling agents in marine paints. However, tributytin is now banned worldwide due to its high toxicity to free-floating marine organisms when leached into the surrounding water. Cuprous oxide is also of concern because of the build-up of high concentrations of copper ions in harbor sediment, again after leaching from the anti-fouling coatings. Both chemicals, therefore, have a detrimental impact on the marine environment worldwide and replacements are eagerly sought. However, attempts to replace the current toxic chemicals with alternatives that are non-toxic when released into the surrounding water, or mechanical alternatives that could dislodge attaching marine growths, have met with limited success.

Antifouling coatings typically comprise combinations of binders, pigments, additives and solvents. The binders determine the characteristics of the antifouling, including leaching of biocidal components. Pigments include the antifouling toxic agent(s) and various fillers. The solvents provide the application properties, while the additives are stabilizers for extended shelf life and to prolong the efficacy of the paint once applied to the ship surface.

The three classes of antifouling paints currently in use are leaching (hard and soft), ablative coatings and self-polishing coatings (polymers). Leaching (hard and soft) is the process whereby the toxicant comes out of the paint at a controlled and sustained rate. Ablative coatings comprise a soluble matrix in the coating (film) that is made up of the natural product resin and hydrocarbons that act as a binder in the soluble matrix. Self- polishing antifoulings are of two types, those containing tin (TBT) and those that are tin- free.

Non-toxic and self polishing polymer coatings such as silicones, teflons and epoxy are coatings that offer possible alternatives to marine paints containing toxic antifouling agents, Because of the slick surface marine microorganisms have a difficult time attaching. However, these non-toxic coatings are not considered economically viable because of their cost and if a hull vessel is damaged containing one of these coatings it can't be patched. The entire hull coating has to be replaced. Besides the immersed hulls of ships and boats that are constantly exposed to an environment that allows the colonization and proliferation of attached marine plant and animal life, other non-marine structural surfaces often are subject to undesirable contamination. For example, in buildings high humidity and temperature can encourage mildew and other fungal or bacterial growth that frequently release airborne allergens thereby causing asthma and other ailments. Medical facility surfaces often demand a substantially reduced level of contaminating level of microbial colonization, usually achieved by disinfection, to avoid nosocomial infections. If persons or animals are to come into direct contact with architectural or other surfaces, it is desirable that active biocidal compounds that may be incorporated in the protective coatings be both long lasting and present minimal environmental hazards, but are effective in reducing or eliminating the harmful microbial colonizations of the surface.

Phytochemicals are known which have broad activity, preventing or inhibiting the growth of a broad spectrum of microbes, as well as exhibiting efficacy against a range of potentially marine fouling organisms such as barnacles and algae. For example, biocidal

phytochemicals have been incorporated into polymeric films useful for wrapping and protecting foodstuffs during storage as illustrated in U.S. Patent Number 5,906,825. Capsicum, at high pungency levels, has been added to marine paints to prevent the fouling of ships bottoms (see, e.g., U.S. Patent Number 5,397,385). Phytochemicals that leach out of paint dilute and disperse extremely well into water and their biodegradability ensures they do not accumulate to unacceptable levels in the environment. Their antifouling effect particularly resides in a surface effect that takes place only in the immediate environment of the painted or coated surface. This characteristic makes the compositions of the present invention comprising phytochemicals compatible with UHMW polyethylene and VHMW polyethylene, silicones and latex compounds.

A need still exists, however, for a safe, environmentally friendly alternative to toxic additives in marine paints and architectural coatings, which does not comprise a highly pungent level of capsicum that may be harmful to the applicant of the paint and to individuals who may come into direct contact with a treated surface. Citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention. SUMMARY OF THE INVENTION

The present invention provides polyethylene compositions, latex compounds and latex compounds that may comprise at least one environmentally benign phytochemicals suitable for use in preventing the colonization of a treated surface by a variety of biological species. One aspect, therefore, of the invention is antifouling marine coatings for materials used in the aqua culture industry using UHMV & VHMV polyethylene and other types of compression molding and latex compounds. UHMV (Ultra High Molecular Weight) polyethylene polymer is a linear polyethylene with a molecular weight in the range of 3,000,000 to 10,000,000. This value represents the "average molecular weight". Therefore, UHMW polymers have a molecular weight average 10 times that of conventional high density polyethylene resins. The higher molecular weight is what gives UHMW polymers a unique combination of characteristics making it more suitable for many applications where lower molecular weight grades fail. VHMW polyethylene (Very High Molecular Weight polyethylene) polymer is a linear polyethylene with a molecular weight in the range of

500,000 to 3,000,000. UHMV & VHMV polyethylene offers the following characteristics, making it a superior polymer carrier for marine antifouling phytochemicals. It is the highest abrasion resistance of any thermoplastic polymer, outstanding impact strength even at very low temperatures, an excellent sliding material due to the low coefficient of friction, self-

lubricating (non-caking and sticking), good chemical and stress cracking resistance and FDA and USDA approved. These compositions are low maintenance.

The compositions of the invention may further comprise control release agents such as, for example, micro-encapsulation of the phytochemicals to maintain sustained and prolonged release of the biocidal agents at the treated surface.

It is noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as "comprises", "comprised", "comprising" and the like can have the meaning attributed to it in U.S. Patent law; e.g., they can mean "includes", "included", "including", and the like; and that terms such as "consisting essentially of and "consists essentially of have the meaning ascribed to them in U.S. Patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention.

These and other embodiments are disclosed or are obvious from and encompassed by, the following Detailed Description. DETAILED DESCRIPTION

The present invention provides coating compositions comprising environmentally benign phytochemicals suitable for use in preventing the colonization of a treated surface by various biological species on materials used in the aqua culture industry. Aqua culture is the business of the regulation and cultivation of water plants and animals for human use or consumption. There is a tremendous build up of marine fouling on the materials used in aqua culture, such as, ropes, nets, buoys, cages, traps, etc., which is costing the industry billions of dollars annually through labor intense maintenance to clean these materials. There is a need for a nontoxic antifouling coating and for the aqua culture industry to reduce the labor intense problem of cleaning fouling from aqua culture equipment. The polyethylene-based compositions of the invention are also useful for the construction of such structures as cages for the culturing offish and other marine organisms wherein the growth on the surface of the cages of fouling algae and sedentary organisms is undesirable. The bars of the cages, ropes and other items in contact with the marine environment, for example, may be of the polyethylene compositions comprising biocidal phytochemicals that prevent the fouling growth from forming or surviving.

Polyethylene(or other polymers such as porous nylon, cellulose, nitrocellulose and the like) biocidal compositions containing phytochemicals according to the present invention may also be formed as porous sheets for use as filters such as reverse osmosis

filters which may be clogged by growth thereon of such as bacteria, algae or fungi during use.

One aspect, therefore, of the invention is antifouling marine coatings using UHMV & VHMW polyethylene and other types of compression molding. UHMV, Ultra High Molecular Weight polyethylene Polymer is a linear polyethylene with a molecular weight in the range of 3,000,000 to 10,000,000. Very High Molecular Weight polyethylene Polymer is a linear polyethylene with a molecular weight in the range of 500,000 to 3,000,000 as shown, for example, in Table 1 below

Table 1

UHMW MECHANICAL PROPERTIES

(1) Izod Impact Strength: Samples have two(15o +/- l/2o) notches on opposite sides to a depth of 5mm.

These Polyetheyenes have to be applied using rubber, silicone or acrylic adhesives that have the following properties and characteristics.

One aspect, therefore, of the invention is antifouling marine coatings using latex. As an example; Isoprene Isobutylene Rubber (HR) latex processed by prevulcanized BL- 100 (IIR) latex compound with the following chemical formula: 10% PVA low viscosity, 60% zinc oxide oleporsion, 68% sulfur dispersion, 50% butyl zimate slurry, 65% zetax dispersion and hodag PX 139. Inert fillers may be used to improve the overall strength of the latex such as clays, tales or silicates, which may offer a better transport route for the phytochemicals and reduce costs.

The following is a list, as examples, of phytochemicals: Helichysum italicum (flavonoids); Corydalis pallida (protoberberine alkloids); Shiraia bambusicola (perylenequinones); Fraxinum omus (hydroxycoumarins); Podocarpus nagi (totarol and nortiterpene dilactones); Heterotheca inuloides (sesquiterpenoids); Pelargonium spp. (essential oils); Piper sarmentosum (phenylpropanoids); Allium spp. (extract); Juniperus procera (diterpenes); Achillea conferta (flavonoids, flavones, sesquiterpenoid lactones); Magnolia virginiana (lignans, neolignans); Eucalyptus euglobal (euglobal); Armillaria mellea (armillaric acid); Dracena mannii (spirostanol saponin); Piper aduncum fchromenes, prenylated benzoic acid); Rhamnaceae spp. (cyclopeptide alkaloids); Buddleja globosa (Verbascoside); Cephalocereus senilis (phytoalexin aurone); Salvia albocaerulea

(diterpene); Gomphrena martiana and Gomphrena boliviana (extracts); Paepalanthus spp. (vioxanthin); Helichrysum stoechas and Helichrysum crispum (extracts); Achillea ptarmica (trans-pinocarveyl hydroperoxides); Dehaasia incrassata (alkaloids); Asteraceae spp. (extracts); Arctotis auriculate (extracts); Eriocephalus africanus (extracts): Felicia erigeroides (extracts); Hemerocallis fulva (phytosterols, fatty acid esters); Psoralea juncea (plicatin B); Pluchea symphytifolia (caffeic acid esters); Tovomitopsis psychotrifolia (Vitamin E derivative); Celosia argentea (triterpenoid saponins and flavonoids); Azadirachta indica (tetranortriterpenoid, mahmoodin, protolimonoids, naheedin); Moraceae spp. (coumarins); Hypericum erectum (phloroglucinol derivatives); Podospora appendiculate (Appenolides A, B, & C, furanones); Artemisia princeps var. orientalis, Artemisia capillaris, Artemisia mexicana and Artemisia scoparia (extract); Paddy malt (mash extract); Kigelia pinnata (extract); Acalypha wilkesiana (extract); seaweeds, seagrass and lemongrass (essential oils); Borrieria latifolia, Borreria setidens, Hedyotis diffusa), Hedyotis nudicaulis, Morinda elliptica, Morinda umbellata, Sida rhombifolia, and Vitex ovata (extracts); Tabebuia impetiginosa, Achyrocline spp., Larrea divaricata, Rosa borboniana, Punica granatum, Psidium guineense, Lithrea ternifolia (extracts); Lepechinia caulescens, Lepidium virginicum and Tanacetum parthenium (extracts); Talaromyces flavus (extracts); Daucus carota (extract); Flabellia petiolata, Caulerpa prolifera, Halimeda tuna, Corallina elongata, Lithophyllum lichenoides, Phyllophora crispa, Cystoseira spp., Halopteris spp., Codium spp., Valonia utricularis, Posidonia oceanica, Zostera noltii and Cymodocea nodosa (extracts); Centauraea orientalis, Diospyros khaki, Sida hermaphrodita, Forsythia intermedia, Scutellaria polydon, Eugenia malaccensis and Eugenia jambolana (extracts); Fritillaria L. spp. (ebeinone, steroidal alkaloids); Kigelia pinnata, Peperomia pellucida, Populus nigra, Populus balsamifera and Populus deltoides

(extracts); Melaleuca alternifolia (essential oil); Elfvingia applanata (naringenin); Ficus sycomorus, grapefruit seed, Garlic, Allicin, Peat, Strophantus hispidus, Secamone afzeli, Mitracarpus scaberi, Entada abyssinjca, Terminalia spinosa, Harrisonia abyssinica, Ximinea caffra, Azadirachta indica, Spilanthes mauritiana, Terminalia spinosa (extracts); Cyanobacteria (ambigols A and B, tjipanazole); coffee (extract); Sporochnus pedunculatus, Dalbergia melanozylon, Celastrus scandens, Juglans nigra, Kalmia latifolia, Pelargonium xhortorum, Rhus glabra and Lindera benzoin (extracts); Striga densiflora, Striga orobanchioides, Striga lutea, Pistacia lentiscus L., Mitracarpus villosus, Bixa orellana, Bridelia ferruginea, Alpinia katsumadai, Alpinia officinarum, Artemisia capillaris, Casia obtusifolia, Dendrobium moniliforme, Epimedium grandiflorum, Glycyrrhiza glabra, Lithosperum erythrorhizon, Magnolia obovata, Morus bonbycis, Natopterygii incisium, Polygonum multiflorum, Primus mume, Rheum palmatum, Ricinus communis, Sophora flavescens, Swertia japonica, black pepper, rosemary, red pepper, Isopyrum thalictroides, Calotropis procera, Chrysanthemum spp., Holarrhena antidysenterica, Lunularia crusiata, Dumertiera hirsuta, Exormotheca tuberifera, and liverwort (extracts); Filipendula ulmaria, Salix glauca, Usnea filipendula, Clkadina arbuscula (salicylic compounds); Tanacetum parthenium, Thymus capitatus, and Elfingia applanata (extracts); Fraxinus qrnus fhydroxycoumarins, esculin, esculetin, fraxin, and fraxetin); Zizyphus nummularia, LONGO VITAL, Pelargonium spp., Scaevola sericea, Psychotria hawaiiensis, Pipturus albidis, Aleurites moluccana, Solanum niger, Piper methysticum, Barringtonia asiatica, Adansonia digitata, Harungana madagascariensis, Jacaranda mimosaefolia, Erythroxylum catauba, Bidens pilosa, Lemna minor, Potamogeton spp., Nasturtium officinale, Apium nodiflorum, Agaricus subrutilescens, Amanita virosa, Amanita pantherina, Lycoperdon perlatum, Psidium guajava, Averrhoa carambola, musa sapientum, Carica papaya, Passiflora edulis, Lansium domesticum and Baccaurea motleyana (extracts); horse radish, celandine grass, bur marigold and yarrow grass (extracts); Abuta grandifola, Cyperus articulatus, Gnaphalium spicatum, Pothomorphe peltata, Ficus sycomorus, Ficus Benjamina, Ficus bengalensis, Ficus religiosa, Alchornea cordifolia, Bridelia feruginea, Eucalyptus citriodora, Hymenocardia acida, Maprounea africana, Monachora arbuscula, Tedania ignis, Arenosclera spp., Amphimedon viridis, Polymastia janeirensis, Aplysina fulva,

Pseudaxinella lunaecharta, Nelumbium speciosum and Mycale arenosa (extracts); cloves (eugenol acetate and iso-eugenol); Chrysthanemum boreale fsesquiterpenoid lactones); Eucalyptus globulus, Punica granatum, Bocconia arborea, Syzygium brazzavillense, Syzygium guineense, Carthamus tinctorius), Ginkgo biloba, Mosla chinensis, Salvia

officinalis, and Cinnamomum cassia (extracts); Cryptolepis sanguinolenta (alkaloids, cryptolepine); Chelidonium majus (alkaloids, berberine, coptisine); Vitex agnus-castus (extract); Cladonia substellata (usnic acid); Ellagic acid, Fuligo septica, Tubifera microsperma (extract); Mundulea monantha, Tephrosia linearis ffiavonoids); Lpomoea fistulosa (extract); Pimento, dioica (essential oils); Ratϊbida latipalearis, Teloxys graveolens, Dodonaea viscosa, Hypericum calycinum, Hyptis albida, Hyptis pectinata, Hyptis suaveolens and Hyptis verticillata (extracts); Asteriscus graveolones (bisabolone hydroperoxides); Derris scandens, Alnus rubra, Araliaceae family (extracts); Vinca rosea, Australian tea tree oil, peppermint oil, sage oil, thymol, eugenol and Thuja orientalis (extracts); Anacardium occidentale (phenolic lipids); Oidiodendron tenuissimum (extract); Acacia nilotica and Acacia farnesiana (polyphenol, tannin); Teminalia alata and Mallotus phillipinensis (extracts); Piectranthus grandidentatus (abientane diterpenoids); Pumica granatum and Datura metel (extracts); tea, Agave lecheguilla, Chamaesyce hirta, Baccharis glutinosa and Larrea tridentata (extracts); Camelia sinensis and Euphorbia hirta (theaflavin, polyphenon 60); Tabernaemontana pandacaqui, Yucca shidigera, Hemistepa lyrata, Yougia japonica, Prunella vulgaris, Lamium amplexicaule, Juniperus chinensis, Ixeris dentata, Gnaphalium affine, Chelidonium majus, Spirea prunifolia, Erythronium japonicum, Taxus wallichiana, Ganoderma lucidum Drava nemorosa, Youngia capillaris, Equisetum arvense, Australiam Lavender, Black Seed, Catuaba casca, Cineole, Damiana, Dicranum scoparium, Eucalptus oil, Ginger, and Grape seed (extracts); Neem seed, bark, and leaf extract; Neem oil; New Zealand Manuka extract; Nicotiana tabacum extract; olive leaf extract; a-pinene and b-pinene extracts; Rhubarb root extract; Syringa vulgaris extract; Tea tree oil (Terpinen-4-ol, a-terpinene, y-terpinene, a-terpineol, Terpinolene); Thyme (extract) and Vitamin E (extract). Microorganisms which may be inhibited by biocidal phytochemicals useful in the present invention include, but are not limited to: Fungi, such as Aspergillus flavus, A. fumigalus, A, niger, Blastomyces dermatitidis, Candida spp., Coccidioides immitis, Cryptococcus neoformans, Fusarium culmorum, Geotrichum spp., Histoplasma capsulatum, Malassezia furfur, Microsporum spp., Mucor racemosus, Nocardia spp., Paracoccidioides brasiliensis, Penicillium spp., Rhizopus higricans, Saccharomyces cerevisiae, Sporothrix schneckii, Torulopsis spp., Trichophyton spp, Bacteria, such as Aerobacter aerongenes, Aeromonas hydrophila, Bacillus cereus, Bacillus subtilis, Bordetella pertussis, Borrelia burgdorferi, Campylobacter fetus, C. jejuni, Corynebacterium diphtheriae, C. bovis, Desulfovibrio desulfurica, Escherichia coli 0157:H7, Enteropathogenic E. coli,

Enterotoxin-producing E. coli, Helicobacter pylori, Klebsiella pneumoniae, Legionella pneumophila, Leptospira interrogans, Mycobacterium tuberculosis, M. bovis, Neisseria gonorrhoeae, N. meningitidis, Proteus mirabilis, P. vulgaris, Pseudomonas aeruginosa, Rhodococcus equi, Salmonella choleraesuis, S. enteridis, S. typhimurlum, S, typhosa, Shigella sonnei, S. dysenteriae, Staphylococcus aureus, S. epidermidis, Streptococcus anginosus, S, mutans, Vibrio cholerae, Yersinia pestis, Y. pseudotuberculosis, Actinomycetes, Stretomyces reubrireticuli, Streptoverticillium reticulum, Thermoactinomyces vulgaris, Viruses, such as Adenoviruses, Coronaviruses, Cytomegalovirus, Enteroviruses, Epstein-Barr virus, Herpes simplex virus, Hepatitis viruses, Human Immunodeficiency virus, Human Parvoviruses, Influenza viruses,

Morbillivirus, Mumps virus, Norwalk viruses, Papillomaviruses, Paramyxovirus, Poxvirus, Rabies virus, Reoviruses, Rotaviruses, Rubella virus, Respiratory Synctial virus, Rhinoviruses, Varicella zoster virus, Parasites such as Ancyclostoma braziliense, Anisakis, Babesia microti, Balantidum coli, Blastocystis hominis, Chilomastix mesnili, Cryptosporidium parvum, Cyclospora, Dientamoeba fragilis, Diphyllobothrium latum, Echinococcus granulosus, Entamoeba coli, E. histolytica, Enterocytozoon, Fasciola hepatica, Giardia lamblia, Iodamoeba butschlii, Isospora belli, Leishmania brasiliensis, L. donovani, L. tropica, Paragonimus westermani, Plasmodium vivax, Pnemocystis carinii, Sarcocytis hominis, Strongyloides stercoralis, Taenia solium, Toxoplasma gondii, Trichomonas vaginalis, Trichinella spiralis, Trypanosoma cruzi.

It is further intended that the compositions of the present invention will be effective against marine and/or freshwater organisms capable of attaching to and colonizing the submerged hull surfaces of ships and boats, including parazoans, coelenterates such as polychaete and oligochaete worms, molluscs, arthropods including crustaceans such as, but not limited to, acorn and goose barnacles and to be effective in inhibiting the attachment and or development of the adult or larval forms of the targeted organisms. The compositions of the present invention can also be effective against marine and freshwater plants including algae and higher plants that can attach to a ship hull and submerged aquaculture systems. Exemplary phytochemicals that exhibit activity against multiple organisms useful in the present invention are illustrated in Table 2 below. Each phytochemical is classified as to general activity (anti-bacterial; anti-viral; anti-fungal; anti-crustacean; larvicidal; insecticidal; molluscicidal; or anti-nematodal) and specific examples of organisms against which the phytochemical is active are provided. However, it is to be recognized by one of

ordinary skill in the art that the phytochemicals included in the table are provided for illustrative purposes only and are not meant to an exhaustive listing and with the recognition that certain phytochemicals may be active against more than one class of organism:

Table 2

*H<* strong activity for phytochemical

One aspect of the present invention provides coating compositions, especially a marine coating for the antifouling treatment of the submerged portion of the hull of a ship or boat, and most especially for inhibiting the fouling of submerged aquaculture apparatus, including, but not limited to, nets, cages, ropes and the like commonly used in the industry, comprising an environmentally friendly antifouling additive in the form of at least one phytochemical. In general terms, the present invention is directed to polymers containing phytochemicals and methods of making and using the same such as; UHMW polyethylene and VHMW polyethylene coatings and other compression polymers. These polyetheylenes have to be applied using rubber, silicone or acrylic adhesives. Phytochemicals especially useful in the present invention include, but are not limited to, grapefruit seed extract, capsicum, capsaicin, polymers containing phytochemicals and methods of making and using the same pomegranate extract of rind, pulp & seed, menthol, camphor, camphor oil, zosteric acid, Zostera noltil, partheniol, lemon grass oil, tea tree oil, clove oil, garlic, citric acid, vitamin E, and other phytochemicals exhibiting biocidal activity to be used in any combination. Grapefruit Seed Extract is an effective phytochemical biocide with activity against bacteria, fungi, and some parasites, an example of which is available commercially as P-50 from Chemie Research, Castleberry, Florida. Partheniol, a compound taken from the guayule plant, prevents fouling on wood and metal surfaces. The rate of migration or the release of the phytochemical composition contained within the marine paints, coatings and polymers may be modified by further including in the compositions a release agent such as Vitamin E, a chemical releaser such as citric acid, or an anti-oxidant such as Vitamin E. The chemical releaser may be the same as the phytochemical agent. Vitamin E further possesses antimicrobial properties, and thus may itself function as a biocidal phytochemical, which may work in conjunction with or separately from marine paint binders.

Phyto chemicals suitable for use in the compositions of the present invention and which are known to function as anti-oxidants, as well as to possess antimicrobial properties include, but are not limited to, Panax ginseng; Panax quinquefolius; Bixa orellana; Humulus lupulus; Spinacia oleracea; Arctium lappa; Cichorium intybus; Cynara scolymus; Helianthus annum; Inula helenium; Armoracia rusticana; Momordica charantia; Vaccϊnium corymbosum; Vaccinium myrtillus; Avena sativa; Oryza sativa; Lavandula latifolia; Marrubium vulgare; Melissa officinalis; Mentha pulegium; Mentha spicata; Nepeta cataria; Ocimum basilicum; Origanum onites; Perilla frutescens; Prunella vulgaris; Rosmarinus officinalis; Salvia officinalis; Salvia sclarea; Satureja hortensis; Thymus vulgaris; Laurus nobilis; Arachis hypogaea; Glycine max; Glycyrrhiza glabra;

Glycyrrhiza uralensis; Lens culinaris; Phaseolus coccineus; Phaseolus lunatus; Phaseolus vulgaris; Phaseolus vulgaris; Pisum sativum; Psophocarpus tetragonolobus; Pueraria lobata; Tamarindus indica; Tamarindus indica;* Viciafaba; Vigna angularis; Vigna mungo; Vigna radiata; Allium ampeloprasum; Allium cepa; Allium sativum; Asparagus officinalis; Linum usitatissimum; Morus alba; Eucalyptus globulus; Pimenta dioica;

Syzygium aromaticum; Olea europaea; Oenothera biennis; Sesamum indicum; Plantago asiatica; Fagopyrum esculentum; Prunus cerasus; Prunus spinosa; Rosa canina; Rubus fruticosus; Rubus idaeus; Coffea arabica; Citrus aurantium; Citrus par adisi; Ribes nigrum; Ribes rubrum; Capsicum frutescens; Solanum tuberosum; Solanum tuberosum; * Theobroma cacao; Camellia sinensis; Coriandrum sativum; Cuminum cyminum; Daucus carota; Trachyspermum ammi; Vitis vinifera; Curcuma longa; Zingiber officinale. Other antioxidants that are useful in the present invention include, but are not limited to, lysine, butylatedhydroxytoulene (BHT), butylatedhydroxyanisole (BHA), grape seed extract, Pine Bark extract (Proanthocyanidins), beta carotene, bilberry extract, ascorbic acid, Ginkgo biloba extract, green tea extract, tumeric, zinc picolinate, zinc oxide, iron oxide, calcium carbonate and selenium. Selected antioxidant(s) maybe used alone or in combination when combined with the phytochemical(s) in the coating formulas of the present invention.

For applications using leaching paints (coatings), ablative paints (coatings) or self- polishing coatings (polymers) wherein the phytochemical component of the paint compositions comprises the capsicum , synthetic capsaicin, tannin, tannic acid, camphor, camphor oil, Zostera noltil, and/or menthol for their antimicrobial activity, with or without a migration release agent, the components of the leaching paints (coatings), ablative paints (coatings) and self-polishing polymers (coatings) may contain any combination of the primers, resins, pigments, solvents, paint binders and anti-settling agents known to those of

skill in the art that provide effective application properties to, for example, the submerged region of a ship's hull and aquaculture systems.

The amounts of the biocidal agents added to the composition are also dependent upon the particular application. Factors to consider are the conditions under which the composition is to be used, the microorganisms to be inhibited, the duration of the use, whether the object to be protected is a submerged, and the active concentration of the antimicrobial agents that is desired. For example, capsicum can be added in an amount from about 1 ppm to about 2,000,000 ppm, depending upon the desired application.

It should be understood that the present invention is broadly drafted, in one embodiment, towards incorporating phytochemicals as biocidal agents into polymeric materials suiable for the coating of submerged surfaces. In several preferred embodiments of the present invention, capsicum, citric acid extract, and grapefruit seed extract maybe used as biocidal agents. The present invention, however, encompasses the use of many other biocidal agents. In the various embodiments of the invention, a preferred phytochemical is capsicum /synthetic capsaicin alone or in combination with other phytochemicals is used as a fouling preventive agent in marine paints (coatings). Capsicum is a food or food seasoning commonly known as "hot pepper." The active heat ingredient in capsicum is capsaicin which is a mixture of two unsaturated and three saturated homologs. This mixture is also referred to as capsaicinoids, and includes dihydrocapsaicin and nordihydro capsaicin. The pungency of capsaicin (capsiacinoids) is measured in Scoville heat units and typically range from 60,000 to 1,500,000 heat units. The compositions of the present invention comprise capsicum having Scoville heat units derived from natural capsicum or synthetic capsacin from 60,000 to 1,500,00 scoville heat units. The pungency (the heat ingredients) of the capsicum may be removed of, either partially or totally, for use as an antifouling additive in marine coatings, even though the heat unit index.

Chemical ingredients in capsicum are known to have antimicrobial activity, such as; 1,8-cineole, acetic acid, alpha-terpineol, benzaldehyde, beta-ionone, caffeic acid, caryophyllene, chlorogenenic acid, cinnamic acid, delta-3-carene, ferulic-acid, limonene, myrcene, p-coumaric-acid, pulegone, querectin, rutin, scopoletin, terpinen-4-ol and thujone. Also useful in the present invention as a fouling preventive additive in marine paints

(coatings) is the phytochemical tannic acid. Tannins are classified into two broad groups: the hydrolysable and the condensed or non-hydrolysable tannins. The hydrolysable tannins are usually compounds containing a central core of glucose or other polyhydric alcohol esterified with gallic acid (gallotannins) or hexahydroxydiphenic acid (ellagitannins). The

condensed ones are mostly flavolans or polymers of flavan-3-ols (catechins) and/or flavan 3:4-idols (leucoanthocyanidins). They are more resistant to breakdown. Frequently, tannins isolated from a plant bear the characteristics of both groups. Tannins may occur in almost any part of a plant-root, stem, trunk bark, leaves and fruit. The compositions of the invention further comprise a menthol such as, but not limited to, mentholpropylreneglycolcarbonate. A particularly useful synthetic menthol preparation for inclusion in the compositions of the present invention is FRESCALIN™ (Symrise GmbH & Co, Holzminden, Germany) and comprising at least 50% by weight of isopulegol, between 25% and 49.99% by weight of 5-methyl-2-(l-methylethyl)- cyclohexanol and between 25% and 49.99% by weight of mentholpropylreneglycolcarbonate. This synthetic menthol preparation is especially effective in combination with capsicum at inhibiting marine growth when included in anti- fouling paints and coatings.

The compositions of the invention may further comprise extracts from Renilla reniformis including the antifoulant diterpenes Renillafoulin A, Renillafoulin B, Renillafoulin C and the like and combinations thereof.

The compositions of the invention further comprise pomegranate, Punica granatum, L.(punicaceae) using in whole or in part as fractions the following active chemicals found in pomegranate 1 ,2,3,4,6-PENTA-O-GALLOYL-BETA-D-GLUCOSE ; 1,2,4,6-TETRA-O- GALLOYL-BETA-D-GLUCOSE ; ASCORBIC- ACID ; ASIATIC-ACID ; BETA- SITOSTEROL ; BETULINIC-ACID ; BORIC- ACID ; CALCIUM-OXALATE ; CASUARININ ; CHLOROGENIC-ACID ; CITRIC-ACID ; CORILAGIN ; DELPHINIDIN-3-GLUCOSIDE ; ELAIDIC-ACID ; ELLAGIC-ACID ; ELLAGITANNIN ; ESTRADIOL ; ESTRONE ; FRIEDELIN ; GALLIC-ACID ; GRANATIN-A ; GRANATINS ; ISOPELLETIERINE ; LINOLEIC-ACID ; MALIC-ACID ; MALVIDIN ; MALVIDIN-PENTOSE-GLYCOSIDE ; MASLINIC- ACID ; NEO-CHLOROGENIC- ACID ; NIACIN ; PALMITIC-ACID ; PANTOTHENIC-ACID ; PELLETIERINE ; PHOSPHATIDYL-CHOLINE ; POLYPHENOLS ; PROTOCATECHUIC-ACID ; PUNICAFOLIN ; PUNICALAGIN ; PUNICALIN ; RIBOFLAVIN ; SORBITOL ; STEARIC-ACID ; STRICTININ ; SULFUR ; TANNIN ; THIAMIN ; URSOLIC-ACID ; Pomegranate extract and certain prepared fractions is especially effective in combination with Grapefruit Seed Extract at inhibiting marine growth when included in anti-fouling paints and coatings.

The compositions of the present invention may further include a chemical releaser, which is used to facilitate the controlled release of the phytochemical from the polymer matrix. The chemical releaser facilitates the release of the phytochemical composition from the polymer or paint. The releaser may be, for example, citric acid, a phytochemical that also exhibits antibacterial activity. Zinc oxide, iron oxide or citric acid extract can be added to the polymer or paint (coatings) alone or in combination with other phytochemicals, with or without anti-oxidants like Vitamin E. The release agents used in the phytochemicals and the release agents used in the and polymer coatings can have a synergistic effect, depending on the desired release containing phytochemicals to prevent marine organism fouling. The amounts (by volume) and combinations (number) of the phytochemical agents added to the coatings may be adjusted according to the particular application, relevant factors including the conditions under which the phytochemical composition is to be used, thickness of the polymer coating, the rate of release of the phytochemical, polishing rate, the types of marine organisms that need controlling may vary, the duration of the use of the phytochemicals in these coatings, and the active concentration of the phytochemical desired. In some cases there may be a need for additional substances such as wetting or emulsifying agents, pH buffering agents, adjuvants, gelling or viscosity enhancing additives, preservatives, colors, and the like, depending upon the use. The present invention also provides biocidal polymer coatings formulated for application in non-marine environments such as architectural polymer coatings. In such cases, the biocidal agents released into the environment will not be as great as when immersed in marine or freshwater conditions.

When making any of the compositions of the present invention, the phytochemicals, antioxidants, and chemical releasers may be added either together or sequentially to the polymer coatings. The mixture is then mixed until the phytochemicals are evenly dispersed within the polymer coatings before processing of the polymer coating. The applications of the finished product may be compression molded, form molded, sprayed, brushed or extruded.

In various embodiments of the polymer coatings of the present invention, biocidal phytochemicals of the present invention may be added in any combination for fouling- release coatings at levels of at least 0.001% to about 60% by weight.

In one embodiment of the present invention, the phytochemicals can be active in the inhibition or control of hard marine fouling (e.g. barnacles) and soft fouling (for example by algae) or a phytochemical may only be active against one type of fouling, and therefore a combination of phytochemicals is required to achieve efficacy.

In various embodiments of the invention, the phytochemical capsicum, having a degree of pungency of between 50,000 to 1,500,000 Scoville heat units, is combined with one or more other biocidal phytochemicals and added to a marine paint or coating to control marine fouling. In other embodiments of the invention, the phytochemical capsicum, having a degree of pungency of between 50,000 to 1,500,000 Scoville heat units, is combined with one or more other biocidal phytochemicals and added to an architectural paint or coating to control marine fouling.

In one embodiment, the phytochemical, capsicum may be combined with other phytochemicals and added to marine paint to control marine fouling, wherein the capsicum is substantially free of the heat causing ingredient capsaicin.

The phytochemical grapefruit seed extract may be added to polymer coatings to control marine fouling. In one embodiment of the invention, the phytochemical grapefruit seed extract may be processed into a concentrated state and the glycol substantially removed from the extract before adding to the polymer coating. In another embodiment, the phytochemical may be selected from extracts of cloves, garlic and/or clove oil.

In preferred embodiments of the invention, the paint may comprise a paint base, grapefruit seed extract, a menthol such as FRESCALIN™ and capsicum.

In another embodiment, the phytochemical may include grapefruit seed extract, which exhibits anti-bacterial, anti-parasitic, and anti-fungal activity. Grapefruit seed extract is available commercially as P-50 from Chemie Reasearch, Castleberry, Florida. The grapefruit seed extract can be added to architectural and marine polymer coatings alone or in combination with other phytochemical. hi another embodiment, the phytochemical may include Pomegranate Extract alone, or in combination with Grapefruit Seed Extract. The extract Pomegranate rind, seed and pulp has shown to have algicide properties. Pomegranate Extract in combination with Grapefruit Seed Extract in combination has shown to have a synergist antimicrobial effect.

In an alternative embodiment, the phytochemical camphor is used in combination with other phytochemicals as a marine organism-fouling preventive. Camphor is a crystalline ketone derived from the wood of the camphor tree Cinnamomum camphora.

In another alternative embodiment, the paint phytochemical additive for fouling prevention maybe lemon grass oil which is a natural by-product of lemon grass and is extracted by steam and other nontoxic extraction methods. Lemon grass oil exhibits antifungal and anti-bacterial activity and may be added to marine paints in combination with

other phytochemicals. Antioxidants, such as Vitamin E, or releasers, such as citric acid may also be added with the phytochemical composition to the polymer coatings.

In yet another alternative embodiment, the polymer coating-fouling preventive may be Tea Tree Oil. Tea Tree Oil is a natural by-product of the tea tree, {Melaleuca species). Tea Tree Oil is extracted through natural non-toxic processes such as steam. Tea Tree Oil exhibits anti-fungal and anti-bacterial activity. Tea Tree Oil may be added to polymer coatings in combination with other phytochemicals, releasers like citric acid, or antioxidants like Vitamin E.

In other embodiments of the compositions of the present invention, the phytochemical component may be selected from tannic acid (tannins), menthol or derivatives thereof, camphor oil, clove and/or clove oil and garlic.

In one embodiment of the compositions of the present invention, the phytochemical combination comprises capsicum having between 50,000 and 1,500,000 Scoville units, tannic acid and menthol or a derivative thereof. In another embodiment the phytochemical combination comprises capsicum having between 50,000 and 1,500,000 Scoville units, tannic acid, clove oil, garlic and menthol, hi yet another embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units), tannic acid, garlic and clove oil.

In one embodiment of the paints and coatings of the present invention, the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units and clove oil and optionally garlic. In another embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units, clove oil, garlic and Zostera noltil, with or without vitamin E. In one embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units), tannic acid, menthol and Zostera noltil. hi still another embodiment the phytochemical combination comprises capsicum having between 50,000 to 1,500,000 Scoville heat units), tannic acid, camphor, pomegranate, menthol and Zostera noltil.

In embodiments of the polymer coatings of the present invention, biocidal phytochemicals of the present invention may be added in any combination to polymer coatings, at levels from about 0.1% to about 60% by volume or 0.1% to about 60% lbs/100 lbs of polymer.

In other embodiments of the polymer coatings of the present invention, phytochemicals of the present invention may be added in any combination to levels from about 0.001% to about 40% by volume, or 0.001% to about 40% lbs/100 lbs of polymer

In embodiments of the polymer coatings of the present invention, phytochemicals of the present invention may be added in polymer coatings at levels from about 10% to about 60% by volume or 0.1% to about 60% lbs/100 lbs of polymer.

One aspect of the invention, therefore, is a composition comprising a polymer base and a biocidal composition comprising a grapefruit seed extract, a pomegranate extract, a capsicum preparation, and a menthol. One embodiment of this aspect of the invention is a composition wherein the polymer base is selected from a UHMW polyethylene, VHMW polyethylene and a latex- based compound.

In the embodiments of this aspect of the invention, the biocidal composition may comprise one or more biocidal phytochemical agents isolated from a grapefruit seed extract or a pomegranate extract.

This aspect of the invention further encompasses compositions further comprising one or more biocidal phytochemical agents, wherein the biocidal phytochemical agent is an anti-bacterial; an anti-viral; an anti-fungal; an anti-crustacean; a larvicidal; an insecticidal; a molluscicidal or an anti-nematodal biocidal phytochemical. In he embodiments of the invention, the anti-bacterial biocidal phytochemical may be isolated from Annona muricata {Annonaceae), A.squamosa, Panax ginseng {Araliaceae), Capparis spinosa (Cappaήdaceae), Calendula officinalis (Compositae), Cynara scolymus {Compositae), Cucurbita pepo (Cucurbitaceae), Cymbopogon citratus (Gramineae), Mentha spicata (Labiatae), Ocimum basilicum (Labiatae), Rosmarinus officinalis {Labiatae), Glycyrrhiza glabra {Leguminosae), Allium sativum (Liliaceae), Aloe vera {Liliaceae), Citrus reticulata {Rutaceae), Oenothera biennis {Onagraceae), Plantago major {Plantaginaceae), Punica granatum {Punicaceae), Ribes nigrum {Saxifragaceae), Camellia sinensis {Theaceae), Curcuma longa {Zingiber aceae), Zingiber officinale {Zingiberaceae) or an alga, the anti-fungal biocidal phytochemical may be isolated from Annona muricata {Annonaceae), Panax ginseng {Araliaceae), Capparis spinosa

(Capparidaceae), Calendula officinalis (Compositae), Cucurbita pepo (Cucurbitaceae), Cymbopogon citratus (Granimeae), Mentha spicata (Labiatae), Ocimum basilicum (Labiatae), Rosmarinus officinalis (Labiatae), Glycyrrhiza glabra (Leguminoseae), Allium sativum (Liliaceae), Aloe vera (Liliaceae), Sesamum indicum {Pedaliaceae), Punica

granatum (Punicaceae), Citrus aurantium (Rutaceae), Citrus reticulata (Rutaceae), Ribes nigrum (Saxifragaceae), Camellia sinensis (Theaceae), Curcuma longa (Zingiberaceae) or Zingiber officinale {Zingiberaceae) or an alga, the anti-crustacean biocidal phytochemical may be isolated from Annona muricata (Annonaceae) or Zingiber officinale {Zingiberaceae), the larvicidal biocidal phytochemical is isolated from Annona squamosa, Mammea americana {Guttiferae), Ocimurn Basilicum (Labiateae), Allium sativum {Liliaceae) or Curcuma longa {Zingiberaceae), the insecticidal biocidal phytochemical may be isolated from Annona muricata (Annonaceae), Annona reticulata {Annonaceae), Annona squamosa (Annonaceae), Cucurbita pepo (Cucurbitaceae), Mammea americana {Guttiferae), Mentha spicata (Labiatae), Ocimum basilicum (Labiateae), Rosmarinus officinalis (Labiatae), Citrus reticulata {Rutaceae) or Curcuma longa {Zingiberaceae), the molluscicidal biocidal phytochemical may be isolated from Annona squamosa (Annonaceae), Ocimum Basilicum (Labiateae) or Camellia sinensis {Theaceae) and the anti-nematodal biocidal phytochemical may be isolated from Glycyrrhiza glabra (Leguminoseae) or Phaseolus vulgaris {Leguminosae).

Another aspect of the invention is a coating composition comprising a polymer base selected from UHMW polyethylene, VHMW polyethylene, a latex compound or a vinyl acrylic, and an environmentally friendly antifouling biocidal composition comprising a grapefruit seed extract, a pomegranate extract, a capsicum preparation and a menthol, and optionally an additive in the form of one or more biocidal phytochemical agents.

In various embodiments of this aspect of the invention, the coating composition is a marine coating for suitable for application to a submerged surface or the submerged portion of an aquaculture system.

In one embodiment of the invention, the composition comprises a marine coating further comprising a rubber, silicone or acrylic adhesive.

In other embodiments according to the invention, the composition further optionally comprises one or more biocidal phytochemical agents is selected from a camphor, a camphor oil, zosteric acid, Zostera noltil, partheniol, a lemon grass oil, a tea tree oil, a tannic acid, a tannin, a clove oil and a garlic, or a isolated component thereof,. Other embodiments of the compositions according to the present invention further comprise at least one additive selected from the group consisting of a leaching paint, a ablative paints or a self-polishing coating, wherein the components of the additive comprise one or more of a primer, a resin, a pigment, a solvent, a paint binder and an anti-settling agent.

Still other embodiments of the invention further comprise a chemical releaser, wherein the chemical releaser facilitates a controlled release of a biocidal phytochemical from the polymer.

In one embodiment of the invention, the chemical releaser is selected from citric acid, zinc oxide, iron oxide, vitamin E.

Yet other embodiments of the compositions of the invention may further comprise one or more additives selected from the group consisting of a wetting or emulsifying agent, a pH buffering agent, a gelling or viscosity enhancing agent, a preservative and a coloring agent. In the embodiments of the invention, the capsicum preparation is about 1 ppm to about 2,000,000 ppm. and the menthol is mentholpropylreneglycolcarbonate or a synthetic derivative thereof.

In other embodiments of the invention, the compositions may further comprise an extract from Renilla reniformis, wherein the extract comprises a diterpene, Renillafoulin A, Renillafoulin B, Renillafoulin C, or any combination thereof.

Yet another aspect of the invention is a method of inhibiting the fouling of a submerged surface or the submerged portion of an aquaculture system comprising applying to a surface or an aquaculture system to be submerged an antifouling coating comprising a composition according to the present invention. In embodiments of this aspect of the invention, the antifouling coating can be attached to the submerged or submersible surface or an aquaculture system by an adhesive.

It should be understood that the present invention is not limited to the specific compositions or methods described herein and that any composition having a formula or method steps equivalent to those described falls within the scope of the present invention. Preparation routes of the composition and method steps for treating marine polymer coating surfaces are merely exemplary so as to enable one of ordinary skill in the art to make the composition and use it according to the described process and its equivalents. It will also be understood that although the form of the invention shown and described herein constitutes preferred embodiments of the invention, it is not intended to illustrate all possible forms of the invention. The words used are words of description rather than of limitation. Various changes and variations may be made to the present invention without departing from the spirit and scope of the invention.

The invention will now be further described by way of the following non-limiting example.

Example : Antifouling of marine immersed painted surfaces

A biocidal paint was used to coat the surface of a metal plate. Control plates were similarly coated with a paint not containing the biocidal agents, or with a commercially available marine antifouling paint. The plates were immersed in open ocean water and periodically examined for the extent of marine colonization.

At the end of six moths of immersion, the control metal plates were heavily encrusted with both animal and plant growth including brown and green algae, acorn barnacles and marine worms, hi contrast, however, the plates treated with the paint had very little marine growth over more than 90% of the exposed surface, and where there was growth it was significantly less than would be expected for the period of exposure used.

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Having thus described in detail preferred embodiments of the present invention, it is to be understood that the invention defined by the above paragraphs is not to be limited to particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope of the present invention.