WO2015142757A1

WO2015142757A1 - Nuisance marine biota abatement agents for paints and enamels

Info

Publication number: WO2015142757A1
Application number: PCT/US2015/020811
Authority: WO
Inventors: Richard S. Shankman
Original assignee: Peerless Worldwide, Llc
Priority date: 2014-03-19
Filing date: 2015-03-16
Publication date: 2015-09-24

Abstract

Biologically-based and synthetic environmentally non-toxic marine anti-fouling paints and enamels and methods of producing them are disclosed. Additionally, and more specifically, the use of naturally-occurring and pharmaceutical nuisance marine biota irritating agents, enzymatic agents (to dissolve marine arthropod cements) and anti-androgen agents (to disrupt "settlement cues") are disclosed as additives in marine anti-fouling paints and enamels.

Description

NUISANCE MARINE BIOTA ABATEMENT AGENTS FOR PAINTS AND ENAMELS

[0001] FIELD OF THE INVENTION

[0002] The invention pertains to the field of marine hull, underwater pipe/structure, marina and dock/bulkhead anti-fouling technology. Theoretical and tested embodiments of novel (non-toxic) anti-fouling marine paints and enamels are disclosed.

[0003] BACKGROUND OF THE INVENTION

[0004] Ever since man took to the water, the battle has raged between man and sea creature. One of the most expensive and troubling man/sea-creature battles has always been so-called "fouling" of vessel hulls. Once they get on, barnacles hold on tight; as they biochemically cement themselves to the surface of what they choose to grow on (See Wahl, K.J. and Barlow, D.E., "Marine Biofouling: Grasping Barnacle Cement Curing from the Inside Out," NRL Review, 2010, pp. 89- 96).

[0005] Today, nuisance marine creature/biota fouling is not limited to ship hulls, but also poses a widespread problem for floating navigational buoys, seawater pipe inlets, seawalls and marina piers, etc. (See Ghanti, S.S., Battle With Barnacles, Popular Science & Technology Series, © 1987,

Defense Scientific Information and Document Centre (DESIDOC), Delhi, India). According to the National Institute of Oceanography (Dona Paula, Goa, India), biofouling of vessel hulls by nuisance marine arthropods (i.e., barnacles, of the subphylum Crustacea), costs the U.S. Navy in excess of $1 Billion per annum (see Khandeparker, L. and Chandrashekar Anil, A. "Underwater

Adhesion: the barnacle way," Int. J. of Adhesion and Adhesives, Vol. 27, Issue 2, March 2007, pp.

165-172). Likewise, the Woods Hole Oceanographic Institute of the U.S. Naval Institute

(Annapolis, Maryland, U.S.), long ago estimated that the unwanted growth of marine fauna (i.e., algae, bacterial slime, etc.) and arthropods on the underside of large U.S. Navy vessels accounted for as much as a 3% increase in their fuel consumption per month while at sea (See Marine Fouling and its Prevention, © 1952, United States Naval Institute, Annapolis, Maryland, U.S. by George Banta Publishing Co., Menasha, Wisconsin, U.S.). In the case of smaller, faster, more modern- day "destroyer-class" vessels, fuel consumption increases due to significant marine fouling can now reach as high as 50% (See, Ghanti, S.S., Battle With Barnacles, supra.). Obviously, the fouling of marine vessel hulls represents an enormous financial burden to commercial, private and military nautical fleets on a global basis.

[0006] The battle against nuisance marine biota has taken several interesting forms in the present art. Induced ultrasonic fields (in the 25 KHz to 60 KHz range) have been studied in the laboratory and later employed as a method to control/abate nuisance mollusk and algae growth on vessel hulls and underwater instruments (See U.S. Patent Number 5,735,266 to McNeal et al.; U.S. Patent Application Serial Number 2004/0005679 by Ryan, et al.; see also Leya, T. et al., "Electromagnetic Antifouling Shield (EMAS) - A Promising Novel Antifouling Technique for Optical Systems," 10^th Int. Cong, on Marine Corrosion and Fouling, February 1999, Univ. of Melbourne, Australia, Additional Paper). These efforts have met with varying degrees of limited success.

[0007] On land, successful terrestrial radio-frequency (RF) jamming of insect magnetic senses has been reported as an abatement method (see Puzova, V. M. and Kvlcalova, M., "Radio frequency magnetic fields disrupt magnetoreception in American cockroaches," J. Exp. Biol, Vol. 212, 2009, pp. 3473-3477). Also reported is the use of ultrasonic acoustic weaponry to repel human intruders near military vessel hulls and ports (See Non-Lethal Swimmer Neutralization Study, Technical Document 3138, May 2002, U.S. Navy SPAWAR Systems Center (SSC), San Diego, California U.S.). Again, these methods have proven better against humans than nuisance biota. [0008] Much of the current ship hull anti-fouling technologies as used in the current art to combat nuisance marine biota center around the application of toxic heavy-metal-based biocide-containing "bottom paints" and specially formulated (slippery and sloughing) silicon-containing ablative hull coatings/paints to the underside and hulls of vessels. This has been the longstanding approach to combating vessel hull fouling (See U.S. Patent Number 3,426,473 to Cardarelli et al.; U.S. Patent Number 4,835,050 to Clayton). Ablative paints also routinely contain biocides and pesticides. The intent of these approaches being that bio-toxic agents contained in the paint formulations continuously and rapidly leach out of the paint/enamel, creating a locally marine-toxic environment surrounding the surface to be protected. However, little can be done to prevent such toxic agents from entering the aquatic system as a whole.

[0009] As marine anti-fouling paints are generally seen to require effective biotoxic agents, those commonly employed in the art frequently take the form of highly toxic heavy-metals such as cupric/cuprous oxide, zinc pyridine, or (the now illegal in the U.S.) tin-containing Tibutylin (TBT). Other less toxic agents, such as Tralopyril and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOI) are also routinely used (See Alaska Anti-Fouling Paint Applicator Manual, December, 2012, Alaska Department of Environmental Conservation (ADEC), Juneau, Alaska, U.S.). In one notable exception, freshwater zebra mussels were reportedly successfully killed with a natural preparation of freeze-dried Phytolaca (preferably Phytolacca dodecandra) plant berries extract (See U.S. Patent Number 5,252,330 to Lee et al.).

[0010] On land, garden pests like common (nuisance gastropod) snails (Helix aspersa) and (nuisance gastropod mollusc) slugs, have long been the subject of extensive eradication efforts. As terrestrial molluscs themselves, it is theorized that the successful anti-snail/slug agents used on land can be modified for use against their similar water-borne mollusc "cousins" in marine anti- fouling applications. Despite the seeming simplicity in this approach, such adaptation and use of numerous successful (garden - terrestrial) chemical anti-snail/slug technologies for marine-based anti-nuisance molluscs paints and enamels remains unreported and is believed novel; save the limited attempt of U.S. 5,252,330 to Lee et al., to employ an ancient African terrestrial anti-snail method to combat freshwater zebra mussel infestations in the U.S. Great Lakes by use of liquid Endod berry preparations, conversely released/flushed directly into the water surrounding affected pipes and inlets.

[0011 ] There has been some study into the chemical composition of the mollusc biological cement, used to affix them to host surfaces. These barnacle cements are universally non-toxic biological (polyphenolic) protein complexes; mollusc secretions that have been studied as potential low- immunogenicity agents for use in human tissue repair. Some of these agents have in fact found their way into use in human dental applications. In the sea, barnacle cement is the strongest bonding agent known and is apparently full of potential as a future commercial glue {see Khandeparker, L. and Chandrashekar Anil, A. "Underwater Adhesion: the barnacle way," supra; Stewart, R. J., "Protein-based underwater adhesives and the prospects for their biotechnical production," Appl. Microbiol. Biotechnol., Vol. 89, 2011, pp. 27-33). In combating barnacle cement (a natural polyphenol protein complex), in an effective and "green" way, it is suggested in the science of the present invention that a greater understanding of the naturally occurring polyphenol oxidases (PPOs - enzymes) is necessary (such as those PPOs commonly found in plants), that they may be adapted or employed directly in the science of the invention as anti- fouling agents that will dissolve barnacle cement. The PPOs of plants and fungi have been studied and characterized {See Mayer, A.M., "Polyphenol oxidases in plants and fungi: Going Places? A review," Phytochemistry, Vol 67, (2006), pp. 2318-2331). [0012] Research by Duke University (Durham, North Carolina, U.S.) has suggested that barnacle cement cures (polymerizes) in much the same fashion as, and in a biochemically similar method to, clotting blood. It has therefore been suggested that eventual elucidation of the primary proteins involved in polymerization of the cement may lead to the development of agents to combat barnacle bio-fouling (See Dickinson, G.H., et al, "Barnacle Glue Cures Like Blood Clots," Inside JEB, 2009). To date, no such enzymatic anti-fouling technology is currently in use or available for sale. According to the science of the invention, natural and pharmaceutical anti-clotting compounds may be employed as active agents in anti-fouling paints to prevent polymerization of barnacle cement; this, akin to preventing/inhibiting the clotting of blood with natural anticoagulants.

[0013] The use of toxic agents in marine anti-fouling paints has been the subject of considerable worldwide debate and has been the target of numerous environmental protection agencies. It is envisioned that at some future date, use of these common classes of bio-toxic agents in marine anti-fouling paint applications will be successfully outlawed; this necessitating an entirely new (non-toxic/natural) approach to marine anti-fouling paint technology. Methods of the present invention are intended to address the need for an entirely new "green" approach to marine anti- fouling technology, by use of relatively safe agents to perturb nuisance marine biota from permanent attachment to vessels and other underwater structures.

[0014] SUMMARY OF THE INVENTION

[0015] Novel marine anti-fouling paint formulations using environmentally- friendly nuisance biota irritating, yet generally non-toxic, agents are disclosed. Some of these novel anti-fouling paint and enamel formulations contain irritating agents and biocides designed Other of these novel anti-fouling paint and enamel formulations contain enzymatic agents designed to dissolve barnacle cements. Other approaches seek to pharmacologically disrupt hormonal "settlement cues" for nuisance arthropod larvae.

[0016] BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Fig. 1 is a previously submerged test metal sample coated with non-toxic, non-biocide marine paint and having added sodium bicarbonate.

[0018] Fig. 2 is a previously submerged test metal sample coated with non-toxic, non-biocide marine paint with a liquid caffeine-containing preparation added.

[0019] Fig. 3 is a previously submerged test metal sample coated with non-toxic, non-biocide marine paint with powdered caffeine added.

[0020] Fig. 4 is a previously submerged test metal sample coated with non-toxic, non-biocide marine paint with powdered caffeine added.

[0021] Fig. 5 is a previously submerged test metal sample coated with non-toxic, non-biocide marine paint with powdered caffeine added.

[0022] Fig. 6 is a previously submerged test metal sample coated with non-toxic, non-biocide marine paint with powdered caffeine added.

[0023] DETAILED DESCRIPTION OF THE INVENTION

[0024] The U.S. Federal Insecticide, Fungicide and Rodenticide Act (FIFRA - 7 U.S.C. § 136 et seq.), exists to regulate the toxicity of agents used against nuisance biota. It is envisioned that the use of many of the theoretical embodiments of the present invention will not run afoul of U.S. Environmental Protection Agency (EPA) regulations, as many of the anti-fouling agents disclosed herein are extracts of edible extracts of natural plants.

[0025] EXPERIMENT 1 - NON-TOXIC BOTTOM PAINT

[0026] To evaluate the efficacy of non-toxic marine "bottom paint" active agent embodiments of the invention, a preparation of a one-part (1 quart) linear polyurethane "topside" (non-toxic, non- antifouling) enamel paint (Interlux® Brightside - Premium Single Part Enamel, No. 4359 - White, International Paint LLC, Union, New Jersey, U.S.) was combined with 57 ml. of a conveniently available retail concentrated liquid caffeine source (5 Hour Energy ® - Berry Flavor, Living Essentials, LLC, Farmington Hills, Michigan, U.S.) to produce an experimental non-toxic (caffeine-containing) test paint. The 5 Hour Energy ^® edible preparation contains (among other things), the following:

• Caffeine (a xanthine alkaloid) · Taurine (2-aminoethanesulfonic acid)

• Phenylalanine (an a-amino acid) · Citicoline (CDP-Choline)

• Glucuronolactone (a detoxicant) · Tyrosine (4-hydroxyphenylalanine)

• Malic Acid (a dicarboxylic acid) · Niacin (Vitamin B₃)

[0027] The caffeine-containing test paint was applied to a clean (sandblasted) piece of iron, allowed sufficient time to cure, and then was immersed in sea water along with another test preparation, containing the same non-toxic base paint, combined with a small quantity of sodium bicarbonate but not containing caffeine. Both samples were submerged in the seawater of a channel directly adjacent to the U.S. Intracoastal Waterway (ICW) in North Palm Beach, Florida for several weeks. Upon examination after removal from the seawater, the sodium bicarbonate- containing paint metal bar was completely covered in nuisance marine vegetation, yet devoid of barnacles or their larvae (see Fig. 1). The caffeine-containing paint metal bar was devoid of any vegetation or barnacles (or larvae); save several tiny areas of vegetation attachment where the paint had failed to adhere to the metal bar and bare iron was exposed (see Fig. 2). The test of the caffeine-containing paint was therefore determined to be successful against the growth of both nuisance arthropods and nuisance vegetation; whereas the sodium bicarbonate test preparation was only effective against growth of nuisance arthropods, under identical conditions.

[0028] EXPERIMENT 2 - NON-TOXIC BOTTOM PAINT

[0029] To evaluate the efficacy of non-toxic marine "bottom paint" active agent embodiments of the present invention, a preparation of a one -part (1 quart) linear polyurethane "topside" (nontoxic, non-antifouling) enamel paint (Interlux® Brightside - Premium Single Part Enamel, No. 4359 - White, International Paint LLC, Union, New Jersey, U.S.) was combined with 36 grams of pulverized commercially-available caffeine tablets (CVS Maximum Strength Caffeine Caplets, CVS Pharmacy, Inc., Woonsocket, Rhode Island, U.S.) The CVS Maximum Strength Caffeine Caplets contain (among other things), the following:

200 mg caffeine hypromellose

corn starch magnesium stearate

dextrose micro crystalline cellulose

dicalcium phosphate polyethylene glycol

artificial flavor steric acid

0030] This caffeine-containing test paint was applied to a clean fiberglass marine tabletop, allowed sufficient time to cure, and then was immersed in the seawater of a channel directly adjacent to the U.S. Intracoastal Waterway (ICW) in North Palm Beach, Florida for several weeks. Upon examination after removal from the seawater, the caffeine-containing test paint was completely covered in nuisance marine vegetation, immature and maturing barnacles and their larvae. All of the barnacles on the fiberglass were attached from beneath the surface (see Fig. 3), having matured from their larval stage attempting to use their shell as a shield to protect them from the caffeine-containing test paint. Numerous barnacle shells were empty, having been abandoned by the host arthropod (see Fig. 6). The remaining shells and nuisance vegetation were easily removed with a bare hand from the surface, revealing below a perfectly clean surface (see Figs 4 and 5).

[0031] Although the invention above has been described in the context of caffeine as an active ingredient, the scope of the invention is not to be deemed so limited.

[0032] In one embodiment, certain plant-based anti-androgens and other agents can be employed in marine anti-fouling paint formulations to inhibit or disrupt ciprid pheromone settlement cues in barnacle larvae, such as spearmint (Mentha spicata), lingzhi mushroom (Ganoderma, a/k/a "red reishi"), licorice (Glycyrrhiza glabra), Chinese peony (Paeonia lactiflora), black cohosh (Actaea racemosa), green tea extracts (Camellia sinensis) and saw palmetto (Serenoa repens) extract (See Grant, P. and Ramasamy, S., "An Update on Plant-Derived Anti- Androgens," Int. J. of Endocrin. & MetaboL, Vol. 10, Issue 2, Apr. 2012, pp. 497-502). In one embodiment, anti-bacterial biofilms on the surface of the anti-fouling paints and enamels can be employed to block nuisance ciprids and algae from choosing to colonize such protected surfaces.

[0033] In one embodiment, one or more polymorphs of ferric phosphate (Iron III phosphate) can be employed in marine anti-fouling paints and enamels to block nuisance ciprids and algae from choosing to colonize such protected surfaces. Iron phosphate is a known terrestrial molluscide (See Speiser, B and Kistler, C, "Field tests with a molluscicide containing iron phosphate," Crop Protection, Vol. 21, 2002, pp. 389-394; see also WIPO Patent Application WO/2009/048345 by Swietoslawski, Janusz).

[0034] The foregoing embodiments have been presented for the purpose of illustration and description only and are not to be construed as limiting the scope of the invention in any way.

Claims

CLAIMS What is claimed is:

1. A marine anti-fouling composition, comprising:

a base formulation; and

one or more abatement agent, the abatement agent comprising one or more of a nuisance marine biota irritating agent, a biocide, an enzymatic agent that dissolves marine arthropod cements, an anti-androgen agent that disrupts marine arthropod settlement cues and combinations thereof.

2. The marine anti-fouling composition of claim 1, wherein the nuisance marine biota irritating agent comprises a naturally-occurring composition.

3. The marine anti-fouling composition of claim 1, wherein the nuisance marine biota irritating agent comprises a pharmaceutical composition.

4. The marine anti-fouling composition of claim 1, wherein the abatement agent comprises one or more of:

(a) caffeine comprising liquid caffeine preparations, coffee grinds- based pigments and combinations thereof;

(b) bicarbonate comprising potassium bicarbonate, sodium bicarbonate and combinations thereof;

(c) cinnamic acid comprising hydroxycinnamic acid, a-cyano-4- hydroxycinnamic acid, caffeic acid, cichoric acid, chlorogenic acid, coumaric acid, coumarin, ferulic acid (3-methoxy-4-hydroxycinnamic acid), sinapinic acid (3,5-dimethoxy-4-hydroxycinnamic acid) and combinations thereof;

(d) hydroxycinnamoyltartaric acid comprising caftaric acid, coutaric acid, fertaric acid and combinations thereof;

(e) sulphate comprising sodium dodecyl sulphate (SDS); (f) mercaptan comprising 2-mercaptoethanol (2 -ME);

(g) guanidine thiocyanate;

(h) protease comprising serine-protease;

(i) an enzyme comprising catechol oxidase, polyphenol oxidase (PPO), tyrosinase and combinations thereof;

(j) garlic comprising garlic oils, garlic powders, oils comprising garlic and pepper, powders comprising garlic and oil and combinations thereof;

(k) saponin comprising a lemmatoxin, Phytolacca plant (Endod) extract, P. acinosa, P. americana, P. brachystachys, P. dioica, P. esculenta, P. lioida, P. octandra, P. rivinoides, P. rugose and combinations thereof;

(1) plant-derived anti-androgen comprising extracts of spearmint (Mentha spicata), lingzhi mushroom (Ganoderma, a/k/a "red reishi"), licorice (Glycyrrhiza glabra), Chinese peony (Paeonia lactiflora), black cohosh (Actaea racemosa), green tea (Camellia sinensis), saw palmetto (Serenoa repens) and combinations thereof; and

(m) Ferric phosphate (FeP04), comprising any of its known polymorphs or combinations thereof.

The composition of claim 4 wherein the base formulation comprises a paint. The composition of claim 5 wherein the paint comprises an enamel paint. The composition of claim 6 wherein the paint comprises polyurethane enamel paint.

The composition of claim 1 wherein the base formulation comprises an enamel.