USOO711 8616B2 (12) United States Patent (10) Patent No.: US 7,118,616 B2 Gillard et al. (45) Date of Patent: Oct. 10, 2006 (54) PAINT COMPOSITIONS COMPRISING 5,382.281 A 1, 1995 Kuo ESTERS OF ROSIN AND PROCESS OF 5,436,284 A 7/1995 Honda et al. PRODUCTION THEREOF 5,545,823. A 8, 1996 Kuo et al. 5,712.275 A 1/1998 Van Gestel (75) Inventors: Michel Gillard, Louvain-la-Neuve 5,767,171 A 6/1998 MatSubara et al. (BE); M Vos, Nivelles (BE) 5,795,374. A * 8/1998 Itoh et al. ..................... 106/16 ; Varcel Vos, IN1Velles 6,069,189 A 5/2000 Kramer et al. 6,110,990 A 8/2000 Nakamura et al. (73) Assignee: Sigma Coatings B.V., Uithoorn (NL) 6,248,806 B1 6/2001 Codolar et al. 6,303,701 B1 10/2001 Isozaki et al. (*) Notice: Subject to any disclaimer, the term of this 6,559,202 B1 5/2003 t al patent is extended or adjusted under 35 6,710, 117 B1 3/2004 Gillard et al. U.S.C. 154(b) by 0 days. 6,828,030 B1* 12/2004 Arimura et al. ............ 428.447 2003,0162924 A1 8, 2003 Vos et al. (21) Appl. No.: 10/492,766 2005/008O159 A1 4/2005 Omoto et al. ............... 523,122 (22) PCT Filed: Oct.e 25,a? a 9 2002 FOREIGN PATENT DOCUMENTS EP OOO1711 * 5, 1979 (86). PCT No.: PCT/EPO2/11957 EP O 131 621 9, 1987 EP O 297 505 1, 1989 S 371 (c)(1), EP O 526 441 2, 1993 (2), (4) Date: Feb. 10, 2005 EP O 530 205 12/1994 GB 2 152 947 8, 1985 (87) PCT Pub. No.: WO03/037999 WO WO 84,02915 8, 1984 PCT Pub. Date: May 8, 2003 OTHER PUBLICATIONS The Condensed Chemical Dictionary, Hawley et al., 1974, p. 653.* (65) Prior Publication Data J.D. Nicholson. The Analyst, 103, 1224, 193-222 (1978). M. Lalonde et al., Synthesis, 817-845 (1985). US 2005/O131099 A1 Jun. 16, 2005 Duane F. Zinek et al. J. Gas Chromatography 6(3), 158-160 (1968). O O CAS Registry No. 514-10-3 record in STN Registry file. (30) Foreign Application Priority Data CAS Registry No. 214-14-50-6 record in STN Registry file. Oct. 30, 2001 (EP) O1204141 International Preliminary Examination Report for PCT/EP02/11957 • - ws 1- a w u wu Zu f · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · no data provided. (51) Int. Cl. * cited by examiner C09D 5/16 (2006.01) C09D 93/04 (2006.01) Primary Examiner David M. Brunsman (52) U.S. Cl. ......................... 106/16, 106/218: 106,236 (74) Attorney, Agent, or Firm-Goodwin Procter LLP (58) Field of Classification Search ............. 106/15.05, 106/218, 236, 16 (57) ABSTRACT See application file for complete search history. A paint composition comprising silylesters of rosin. Sily (56) References Cited lesters of rosin are used in self-polishingp 9. antifoulingg ppaints alone or in combination with other binder components. A U.S. PATENT DOCUMENTS process is also defined for the addition of silylesters to paint 4,918, 147 A 4, 1990 Yamamori et al. compositions. 4,962,135 A 10, 1990 Braeken et al. 5, 112,397 A 5/1992 Farmer, Jr. et al. 13 Claims, No Drawings US 7,118,616 B2 1. 2 PAINT COMPOSITIONS COMPRISING EP 289481 and EP 526441 (Sigma Coatings), WO ESTERS OF ROSIN AND PROCESS OF 9744401 (Hempel's) disclose systems based on rosin in PRODUCTION THEREOF combination with a film forming binder. However, the coatings produced in accordance with these specifica This is a national phase filing of International Application tions suffer from the technical problem that their coat No. PCT/EP02/11957, which was filed on Oct. 25, 2002, and ings are nowadays classified as "ablative' since the published in English on May 8, 2003 and is entitled to erosion is not based on a real chemical hydrolysis but priority of European Patent Application No. 01204141.4 rather on a complex process which weakens the Surface filed Oct. 30, 2001. layer by a combination of dissolving and leaching The present invention relates to paint compositions, more 10 followed by frictional abrasives forces leading to particularly, it relates to the use of silylesters as binder in higher Surface roughness (at micron scale ablative self-polishing antifouling paints. pattern) and an irregular erosion rate of the coating. Many existing antifouling paints used for ships to prevent Systems based on copper (or Zinc) acrylates are described barnacles and other marine life from attaching to the ships in EP 342276 (Nippon Paint), GB 2311 070 (Kansa hulls work by slowly leaching metallic compounds into the 15 iPaint), U.S. Pat. No. 5,545,823 and U.S. Pat. No. sea. But studies have shown that these compounds persist in 5,382.281 (Yung Chi Paint). Based on cheap raw mate the water, killing sea life, harming the environment and rials these tin-free systems suffer from several draw possibly entering the food chain. One of the most effective backs. Indeed, their production requires a dedicated types of antifouling paint, developed in the 1960s, contains equipment and their composition is very difficult to the organotin tributyltin (TBT), which has been proven to assess by chemical analysis. Further, the use of copper cause deformations in oysters and sex changes in whelks. in antifouling systems will certainly be restricted in the The International Maritime Organization (IMO), a unit of forthcoming years. An example of that trend is the the United Nations, adopted on 5 Oct. 2001 an International Dutch ban on the application of copper-containing Convention on the Control of Harmful Antifouling Systems antifouling paints on yachts Smaller than 25 meters. at the end of a five-day Diplomatic Conference held in 25 Systems based on silyl acrylates were disclosed by M&T London. (WO 8402915, EP 00131621), and further developed The proposed antifouling convention comes in response by Chugoku (EP 775733), Nippon Oils & Fats (EP to Assembly resolution A.895 (21) Antifouling systems used 297505, EP 646630, EP 714957, EP 802243) and on ships, adopted by IMO in November 1999, which called Sigma Coatings (WO 0162811 and WO 0162858) on IMO's Marine Environment Protection Committee ( 30 It is known in the art that rosin or rosin derivatives may MEPC) to develop an instrument, legally binding through be used in combination with hydrolysable acrylates in order out the world, to address the harmful effects of antifouling to improve Some of their properties. systems used on ships). EP 530205 (Courtaulds) discloses the use of rosin amine The resolution calls for a global prohibition on the appli D in combination with copper acrylates. cation of organotin compounds which act as biocides in 35 WO 0043460 (Akzo Nobel) discloses some advantages of antifouling systems on ships by 1 Jan. 2003, and a complete using blends of rosin (and its derivatives) with Zinc?copper prohibition on the presence of organotin compounds which acrylates. act as biocides in antifouling systems on ships by 1 Jan. EP 1016681 (Chugoku) discloses that the blending of 2008. rosin (and its derivatives) with trialkylsilyl(meth)acrylate The harmful environmental effects of organotin com 40 co-polymers improve the ability to erode at Static conditions pounds were recognized by IMO in 1990, when the MEPC (e.g. during the outfitting period in the building of new adopted a resolution which recommended that Governments ships) and by this having a Superior antifouling perfor adopt measures to eliminate the use of antifouling paint mance. The recoatability and the resistance to cracking and containing TBT on non-aluminium hulled vessels of less detachment were also claimed to be improved by this than 25 meters in length and eliminate the use of antifouling 45 blending paints with a leaching rate of more than 4 micrograms of EP 802243 (Nippon Oils & Fats) discloses blends of at TBT per day. Some countries, such as Japan, have already least one compound selected from rosin, rosin derivatives banned TBT in antifouling paint for most ships. and rosin metal salts with certain polymers containing There is therefore a need in the art for improved erodable organosilyl ester groups as binder in self-polishing antifoul antifouling paint compositions containing no organotin 50 ing paints, leading to improved properties after long-term compound, while retaining the good antifouling and self immersion. Nowadays, the ship owners continue to request polishing properties of the tin-containing antifouling paints an excellent performance over increasingly longer periods of of the prior art. time, in order to reduce the frequency of dry-docking the Tin-free systems are well known in the art: 55 ships to apply a fresh coating on their hulls. There is thus a Antifouling paints containing rosin and similarly soluble continuous need in the art for alternative and improved salts thereof have existed for many years. Rosin is self-polishing antifouling paint compositions. slightly soluble in seawater (8.6x10 mol/L at The inventor has surprisingly found that the “ablative' pH-8.1). Due to its low molecular weight, rosin is effect of the paints, particularly antifouling paints, based on blended with another binder to provide an appropriate 60 rosin or rosin metal salts could be largely overcome by using film-forming performance. silylesters of rosin (alternatively called silylated resinates or Paints based on a combination of wood rosin with copper silyl abietates). or zinc-pyrithione have been found to thicken or gel Thus the present invention provides paint compositions unacceptably within a few days. U.S. Pat. No. 5,112, comprising silylesters of rosin in the binder system.