Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-07-25
2004-07-27
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S279000, C526S328500, C526S329700
Reexamination Certificate
active
06767978
ABSTRACT:
BACKGROUND OF THE INVENTION
Marine organisms such as algae and barnacles attach to the surfaces of structures placed in oceans and lakes. This marine growth has little effect on the integrity of the structure such as ships, boats, pilings, water intake and outfall (coatings) pipes. (Worms and bores do attack woods and plastics.) However, their presence can seriously hamper the operation of these systems, resulting in loss of cooling and fuel efficiency. It has been common practice to coat the substrate surfaces of wood, plastic and metal with coating compositions which inhibit attachment and/or growth of marine organisms. Such coating compositions are usually referred to as antifoulant coatings or antifoulant paints and consist of a polymeric binder material, a toxicant, a pigment, solvents, and adjuvants to aid in adhesion, flow, color, viscosity, stability, etc. The range of compositions for marine antifoulant application is enormous and has evolved from changing needs. For example, 1-2 years protection was adequate for most ships which were dry-docked every 1 or 2 years for routine maintenance and were stripped and repainted with new antifoulants while in dry dock. With the advent of the super tanker, greatly extended intervals between dry docking were required—typically 3 to 5 years. Thus, the need for longer life antifoulant coatings was created. This need was in great measure met by the extended performance made possible by polymerizable antifoulants, such as organotin methacrylates, which became part of the coating polymeric binder. Improvements were also made by creating coatings which controlled erosion and toxicant leach rates to approach the 5 year life requirement.
In addition to extended life requirements for marine antifoulant coatings, concern for the possible effects of antifoulant toxicants on the environment has encouraged the development and use of systems which attempt to control fouling through surface modification; for example, prevention of attachment through the use of silicon or fluorine containing polymers having non-stick or release properties.
The development and current state of the art of marine antifoulant coatings can be found in articles such as:
1. Clean Hulls Without Poisons: Devising and testing non-toxic marine coatings. Robert F. Brady Jr., Coatings Technology, Vol. 72#900, January 2000.
2. A New Approach in the Development and Testing of Antifouling Paints Without Organotin Derivatives. K. Vullei Rehel, B. Mariette, P. Hoarau, P. Guerin, V. Longlois, J-Y. Longlois, Journal of Coatings Technology, Vol. 70, #880, May 1998.
3. Marine Biofouling And It's Prevention on Underwater Surfaces. J. A. Lewis, Material Forum (1998), 22, 41-61.
Marine Antifoulants, Silcon/Fluorine
“Marine Biofouling and it's Prevention on Underwater Surfaces”, by Lewis, J. A., Materials Forum, (1998) 22, 41-61, is a recent comprehensive review of marine antifoulant agents. An extensive bibliography and references are included. This paper makes reference to binders studied such as acrylic copolymers with pendant hydrolysable functions and a variable hydrophobic/hydrophilic balance. Reference #45 from which this description is taken is a thesis in French, by Fadel, A.—Thesis Universite de Rennes I, “Synthesis et Application de Resines Erodable pour Peintures Antisalissures de Nouvelle Generation”, 1994. This reference does not disclose the compositions of the present invention.
WO, 0014166A1, Judith Stein, General Electric Co., 2000, 03,16 describes curable silicone foul free release coatings and articles. No fluoro compounds are present.
“Silicone Containing Fluropolymer Coatings Composition for Controlled Release of Organic Leachants”. James Griffith, Stephen Snyder, U.S. patent application Ser. No. 921054A0. This patent application discloses the use of fluoro-epoxy compounds and silicone amine curing agents rather than fluoro(meth)acrylates and silyl(meth)acrylate monomers to produce marine antifoulant binders. The resultant copolymers of Griffith are highly crosslinked.
JP 53113014, 19781003. Tachida, Toshij, “Material for the Prevention of Adhesion of Organisms in Water”. Release coating as antifoulants are prepared from fluorinated polymers, above, e.g. polytetrafluorethylene. No silicon is present.
Additional antifoulant release coatings are described in the following patents and patent applications, none of which describes the compositions of the instant invention: U.S. Ser. No. 251419A0—application, U.S. Ser. No. 92847401—application, DE 2752773, EP 874032A2, EP 885938A2, JP 0319073A2, JP 319074A2, JP 04217902A2, JP 04227770A, JP 04264168A2, JP 04264169A2, JP 04264170A2, JP 070033191A, JP 07138504A2, JP 11061002A2, JP 61097374A2.
Further information on antifouling release coatings may be found in the following articles: “The Antifouling Potential of Silicone Elastomer Polymers”, Clarkson, Nancy. Recent Advance Marine Biotechnol (1999) 3, 87-108; “Synthesis of Perfluorinated Acrylate and Methacrylate Fouling Release Polymers”, Arios, E M, Putnam, M. et al. Book of Abstracts 213
th
ACS National Meeting, San Francisco, Apr. 13-17, 1997; and “Fluoropolymers and Silicone Fouling Release Coatings”, Bultman, J. D., Griffith, James R., Recent Developments in Biofouling—Control, 1994, 383-9.
Self Polishing antifoulant paints are described in several patent and patent applications such as: EP 51930A2—Marine Paint, International Paint Co., Ltd. Sghlbontz, C M. Which describes self-polishing marine paints comprising a copolymer methacrylate, methylmethacrylate and a organotin monomer.
Hydrophobic/hydrophilic polymers for use in marine antifoulant paints have been described in the prior art.
“Graft Copolymers for Erodible Resins, from Alpha-Hydroxyacid Oligomer Macromonomers and Acrylic Monomers”, Vallae, Rehel, et al—J. Environmental Polymer Degradation (1999) 71 (1) 27-34. This article discusses the compositions with defined hydrophobic/hydrophilic balance, but differs from the present invention in the use of alpha-methacryloryloxy-alpha-hydrox acid macromonomers.
Konstandt, Felix. FR 2165881, discloses a solution of polyethylenimine or its hydrophilic derivatives with a hydrophilic acrylic polymer for coating boats below the water line. This compositions differs from the instant invention in that it lacks any fluoro-containing compounds.
EP 0801117A2—Haradaa, A., Contains hydrophobic and hydrophilic groups but does not contain the monomers of the instant invention.
JP 5214274A—Komazaki Shigeru et al.—Contains hydrophilic and hydrophobic groups but based on N-acrylic imidazole modifications.
U.S. Pat. No. 4,883,852, Shigeru, Masuoka, Hiroshi Dor, Nippon Oil and Fats Co., 1989, describes and claims marine antifouling paints which contain a polysiloxane polymer and a copolymer which may be methacrylate ester/polysiloxane polymer.
U.S. Pat. No. 5,767,171, Matrubara, Yoskisa et al. NOF Comp., 1995 Contains silylacrylates. Describes and claims marine antifoulant coatings containing copolymers of monomers which contain an acryloyloxy or methacryloyloxy group and triorganosilyl group. A third vinyl monomer may be present. Does not disclose a fluoro-containing moiety.
U.S. Pat. No. 4,593,055, Melvin Gitlitz et al, M&T Chemicals (1986). Describes erodible ship bottom paints for controlling marine fouling which are characterized by including a hydrolysable organosilylacrylic copolymer. No fluoro-monomer is disclosed.
Surface Coatings International (1999), 82 (12) Bready R F for et al. describes waterborne fluoropolymer coatings for marine fouling resistance.
JP 05186715A2—Kido, Koichiro et al, 1993, describes marine antifoulant coatings which may contain acrylates and methacrylates as well as 2,2,2-trifluoro ethylacrylates, but it does not describe the presence of hydrolysable silylacrylate groups.
JP 61097374A2, Fuyuki, Toro et al, 1986. Paint additives for marine structures are prepared by copolymerizing fluoroethyl monomers and (meth)acrylates. No silylacrylates are listed.
“Fluorinated Polymer, Synthesis Properties and Application”, Ameduri, Bruno et al.
Aubart Mark Anthony
Guittard Elisabeth Patricia
Silverman Gary Stephen
Tseng Kenneth Kuo-shu
ATOFINA Chemicals, Inc.
DeBenedictis Nicholas J.
Lipman Bernard
Roland Thomas F.
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