USOO620729OB1 (12) United States Patent (10) Patent No.: US 6,207,290 B1 Blum et al. (45) Date of Patent: Mar. 27, 2001 (54) ANTIFOULANT COMPOSITIONS AND 5,397,385 3/1995 Watts. METHODS OF TREATING WOOD 5,466.299 11/1995 Jan. 5,603,775 2/1997 Sioberg. Inventors: Melvin Blum, Wantagh, NY (US); 5,628,271 5/1997 McGuire. (75) 5,629,045 5/1997 Veech. Michael Roitberg, Highland Park, NJ 5,635,192 6/1997 Terry et al.. (US) 5,639,464 6/1997 Terry et al.. (73) Assignee: Burlington Bio-Medical & Scientific FOREIGN PATENT DOCUMENTS Corp., Farmingdale, NY (US) 0 745 325 12/1996 (EP). (*) Notice: Subject to any disclaimer, the term of this 53-28632 * 3/1978 (JP) ................................. CO9D/3/58 patent is extended or adjusted under 35 2-18468 1/1990 (JP). U.S.C. 154(b) by 0 days. 3-90005 4/1991 (JP). OTHER PUBLICATIONS (21) Appl. No.: 09/055,785 Chemical Abstract vol. 72:80438y (1970). Chemical Abstracts vol. 81:65344g (1974). (22) Filed: Apr. 7, 1998 Chemical Abstract vol. 67:22923p (1967). (51) Int. Cl." .............................. B05D3/00; B32B 7/00 Chemical Abstracts vol. 82:32508f (1975). (52) U.S. Cl. .......................... 428/540; 428/195; 428/541; Chemical Abstracts vol. 85:889b (1976). 428/543; 106/18.32; 106/18.28 Chemical Abstracts vol. 85:890v (1976). (58) Field of Search ..................................... 428/540, 541, * cited by examiner 428/195,543; 106/18.32, 18.28 Primary Examiner William Krynski (56) References Cited ASSistant Examiner-Dawn L. Garrett (74) Attorney, Agent, or Firm-Oliff & Berridge, PLC U.S. PATENT DOCUMENTS (57) ABSTRACT 3.896,753 7/1975 Shepherd et al.. 3,981.252 9/1976 Ticker. Anti foulant compositions include 10, 10'- 3.990,381 11/1976 Shepherd et al.. oxybisphenoxarsine and/or phenarsazine oxide with a qua 4,168,562 9/1979 Maasberg. ternary ammonium Salt. The antifoulant compositions may 4,624,679 11/1986 McEntee. also include adjuvants Such as fungicides, ultraViolet 4,761,247 8/1988 Rei et al.. 4,842,932 6/1989 Burton. absorbers, and antioxidants. The antifoulant compositions 4,891,391 1/1990 McEntee. can be used in fresh or Sea water paints. In addition, the 4,995,914 2/1991 Teter. antifoulant composition may be used to Stain or impregnate 5,118,346 6/1992 Wehner et al. ..................... 106/18.3 Wood, thus preserving the wood. 5,167,721 12/1992 McComas et al. 5,376,705 12/1994 Leys et al.. 26 Claims, 1 Drawing Sheet U.S. Patent Mar. 27, 2001 US 6,207,290 B1 US 6,207,290 B1 1 2 ANTIFOULANT COMPOSITIONS AND (OBPA) and/or phenarsazine oxide (PZO) with quaternary METHODS OF TREATING WOOD ammonium Salts. In embodiments, the antifoulant composi BACKGROUND OF THE INVENTION tions may further comprise fungicides, ultraViolet absorbers, and antioxidants. The compositions can be used, for 1. Field of Invention example, in fresh or Sea water antifoulant paints. In addition, The present invention is directed to antifoulant composi tions and methods of treating wood with Such compositions. the compositions can be used, as Solutions or Stains, to More specifically, the present invention is directed towards impregnate wood, for example, bulkheads, piers, docks, fresh and Sea water antifoulant compositions comprising foundations, rail ties, posts, pilings, groins, construction 10,10'-oxybisphenoxarsine (OBPA) and/or phenarsazine timber, and the like. oxide (PZO) with a quaternary ammonium salt. The compositions according to the present invention 2. Description of Related Art exhibit Superior and unexpected results with respect to Antifoulant compositions containing OBPA or PZO are biocidal lifetime as compared to traditional compositions. In generally known. addition, the organic arsenic compounds of the present U.S. Pat. Nos. 3,990,381 and 3,896,753 to Shepherd et al. invention are much leSS toxic to the environment than disclose hydrophilic polymers having encapsulated therein 15 traditional copper, chromium, and arsenic (CCA) based antifouling agents that are applied as a coating to underwater preservatives since they do not leech out. Further, OBPA and portions of a marine Structure. The inorganic and organic PZO are not affected by electrolytic degradation such as the antifoulants include cuprous oxide and 10,10'- copper, tin and Zinc Salts in conventional antifoulants. oxybisphenoxarsine. Moreover, the composition according to the present inven JP 02-18468 A1 discloses a coating containing 10,10'- tion are much lighter than conventional antifoulant compo oxybisphenoxarsine to prevent acquatic organisms and algae Sitions containing toxic or heavy metal compounds or their from Sticking to materials. Such as fishing nets. Salts and oxides. USSR 248,121 (CAS 72:80438y) discloses antifoulant DETAILED DESCRIPTION OF PREFERRED paints consisting of an arsenic compound Such as bis (phenoxarsin-10-yl)ether. USSR 248,121 (CAS 81:65344g) 25 EMBODIMENTS discloses antifoulant paints prepared by mixing pigments According to the present invention, an antifoulant com and phenoxarsine derivatives Such as bis(10-phenoxarSyl) position comprises OBPA and/or PZO and a quaternary oxide. ammonium Salt. In embodiments, other organo arsenicals Chemical Abstract vol. 67:22923p discloses an organo can be used in place of, or in combination with, OBPA toxic antifouling paint containing phenarSazine derivatives and/or PZO, including, but not limited to, arsanilic acid, Such as phenarSazine oxide. roXarSone, methyl arSonic acid, mono methyl arsinic acid, U.S. Pat. No. 5,397,385 to Watts discloses an antifouling mono sodium methyl arsonate (MSMA), and cacodylic acid. coating composition that uses capsaicin as an antifouling The antifoulant compositions contain any effective amount agent. The antifouling composition can be used in combi 35 of OBPA and/or PZO. In embodiments the antifoulant nation with conventional antifouling coatings, paints and compositions contain about 0.5-50 wt. % of an organo binders and applied to wood, metal and plastic Surfaces. The arsenical, preferably about 2-25 wt.%, and more preferably antifouling composition may also be added to other mate about 3–7 wt.% of the composition. rials in molding processes to form various articles of manu According to the present invention, a quaternary ammo facture and molded products, Such as boat hulls and water 40 nium Salt may be added to the antifoulant compositions as a pipes, to resist fouling by organisms common in fresh water Stabilizer and Synergizer. The quaternary ammonium Salts and Sea water. include, but are not limited to, denatonium Saccharide, U.S. Pat. No. 5,629,045 to Veech discloses coatings denatonium chloride, denatonium benzoate, denatonium containing lipid Soluble, non-toxic biodegradable Substances oleate, palmitate, lidocaine, lidocaine HCl, benzylalkonium that prevent fouling of marine Structures Such as boats by 45 Salts and combinations thereof. In embodiments, the qua shell bearing Sea animals, Such as barnacles. A preferred ternary ammonium Salts are added in an amount of about inhibitor is pepper containing capsaicin. The inhibitor is 0.05-10 wt.%, more preferably about 1–3 wit. % of the incorporated into Standard marine paints, impregnants, Var composition. nishes and the like. In embodiments, the composition may optionally contain JP 03 90005 discloses making a rubber composition 50 about 0.2 to about 20 wt.% capsaicinates, preferably about containing OBPA into a sheet to prevent shellfish from 0.5 to about 5 wt.% denatonium capsaicinate. Other com adhering to Ships. positions are exemplified by U.S. Patent Application Serial U.S. Pat. Nos. 5,639,464 and 5,635,192 to Terry et al. No. 08/929,621, incorporated by reference herein in its disclose biocidal protective coatings for heat eXchanger coils entirety. formed by applying a polymeric composition containing an 55 The antifoulant compositions according to the present organic water resistant polymer that has associated with it an invention work exceptionally well as antifoulant additives effective amount of a biocidal compound to inhibit for fresh and sea water antifoulant paints. Further, if OBPA corrosion, fouling, and biocidal buildup on the coils. The and/or PZO Solutions are Soaked or impregnated into Wood, biocidal compounds may be 10,10-OXybisphenarsine. the resultant treated wood is as good as conventional CCA U.S. Pat. No. 5,367,705 to Leys et al. discloses a water 60 (Copper, Chromium and Arsenic) pressure treated wood that proof coating that is virtually ingestion proof by marine life is conventionally used for protecting bulk heads, piers, and that may contain denatonium Saccharide, Synthetic docks, ties, posts, piling, construction timber, and the like. capsaicin and an ultraViolet absorber. Solvents used to treat or impregnate wood with the compo Sitions of the present invention include, but are not limited SUMMARY OF THE INVENTION 65 to, isodecyl alcohol (IDA), benzyl alcohol, methanol, dim The present invention is directed to marine antifoulant ethyl Sulfoxide, hexane diol, chloroform, phentyl alcohol, compositions comprising 10,10'-oxybisphenoxarsine propylene glycol, 3-phenyl 1-propanol, methylene chloride, US 6,207,290 B1 3 4 nonyl phenol, benzene, triphenyl phosphate, toluene, antimicrobial, biocidal, insecticidal, and termiticidal com benzaldehyde, dimethyl formamide, isopropyl alcohol, ethyl positions demonstrate a lifetime of about 60 months or cellusolve, methyl cellusolve, dioctyl phthalate. CCA nor greater. Wood treated with the antifoulant, antifungal paints mally comprises 25 wt.% arsenic acid, 25 wt.% chromic or Stains according to