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WO 2010/093536 Al (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 19 August 2010 (19.08.2010) WO 2010/093536 Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C08G 18/02 (2006.01) C08G 18/28 (2006.01) kind of national protection available): AE, AG, AL, AM, C08G 18/08 (2006.01) C08G 18/79 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, C08G 18/09 (2006.01) C08G 18/83 (2006.01) CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, C08G 18/10 (2006.01) DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, (21) International Application Number: KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, PCT/US20 10/022967 ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (22) International Filing Date: NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, 3 February 2010 (03.02.2010) SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (25) Filing Language: English (84) Designated States (unless otherwise indicated, for every (26) Publication Language: English kind of regional protection available): ARIPO (BW, GH, (30) Priority Data: GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, 12/370,100 12 February 2009 (12.02.2009) US ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, (71) Applicant (for all designated States except US): PPG IN¬ ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, DUSTRIES OHIO, INC. [US/US]; 3800 West 143rd MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, SM, Street, Cleveland, Ohio 441 11 (US). TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). (72) Inventors; and (75) Inventors/Applicants (for US only): CHASSER, Antho¬ Declarations under Rule 4.17: ny M. [US/US]; 1409 Fernledge Drive, Allison Park, — as to applicant's entitlement to apply for and be granted Pennsylvania 15 101 (US). FITZGERALD, Lawrence J . a patent (Rule 4.1 7(H)) [US/US]; 316 Ramsgate Drive, Gibsonia, Pennsylvania 15044 (US). KALSANI, Venkateshwarlu [IN/US]; 2745 Published: Saxony Place, Devlins Pointe, Allison Park, Pennsylvania — with international search report (Art. 21(3)) 15 101 (US). — before the expiration of the time limit for amending the (74) Agents: PALLADINO, Donald R. et al; PPG Industries, claims and to be republished in the event of receipt of Inc., One PPG Place, 39th Floor, Pittsburgh, Pennsylva amendments (Rule 48.2(h)) nia 15272 (US). (54) Title: POLYCARBODIIMIDES HAVING ONIUM SALT GROUPS (57) Abstract: Disclosed are polycarbodiimides having onium salt groups, as well as methods for their production. POLYCARBODIIMIDES HAVING ONIUM SALT GROUPS CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is related to (i) United States Patent Application Serial No. 12/370,123, entitled, "Coating Compositions That Include Oniura Salt Group Containing Polycarbodiimides", filed concurrently herewith; and (ii) United States Patent Application Serial No. 12/370,161, entitled "Antimicrobial Coating Compositions, Related Coatings and Coated Substrates", also filed concurrently herewith. FIELD OF THE INVENTION [0002] The present invention is directed to polycarbodiimides having onium salt groups. BACKGROUND OF THE INVENTION [0003] It is sometimes desirable to include agents, such as quaternary onium salts, silver ions, iodine ions, and the like, into coatings in order to provide a surface that is capable of killing harmful microorganisms. [0004] Silver ions, for example, are sometimes embedded in a porous material, such as zeolite, which is incorporated into a coating composition. In these situations, the silver ions are released gradually into the coating to impart antimicrobial properties, but the eventually depletion of the silver ions will ultimately render the coating ineffective. Moreover, a significant problem associated with such antimicrobial agents is their tendency to cause discoloration of the composition into which they are incorporated. This discoloration results from the interaction of silver ions with other compounds, ions, and the like present in the composition into which the antimicrobial agent is incorporated. As will be appreciated, such discoloration can be particularly problematic in coatings applications where decorative properties are often critical. [0005] Quaternary onium salts can be effective antimicrobial agents in coating compositions, because they are known to selectively attack bacterial cells and not mammalian cells. Unfortunately, these materials are typically unreactive with the primary film forming resin binder of the coating composition, such as resins containing carboxylic acid groups, which are often employed in thermosetting compositions. As a result, such onium salts are susceptible to leaching out of or phase separating from the binder, thereby rendering the onium salt ineffective and/or the coating composition unsuitable for use for other reasons. [0006] As a result, it would be desirable to provide antimicrobial coating compositions that include an antimicrobial agent that will not be depleted and will not phase separate in a coating composition comprising a film-forming resin binder having functional groups. The present invention has been developed in view of the foregoing desire. SUMMARY OF THE INVENTION [0007] In certain respects, the present invention is directed to polycarbodiimides comprising terminal onium salt groups, wherein the terminal onium salt groups comprise a halogen counterion. Such polycarbodiimides may, in certain embodiments, also comprise pendant onium salt groups [0008] In other respects, the present invention is directed to polycarbodiimides comprising pendant onium salt group. Such polycarbodiimides may, in certain embodiments, also comprise terminal onium salt groups. [0009] The present invention is also directed to, inter alia, methods for making such polycarbodiimides. DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION [0010] For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. [0011] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. [0012] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of " 1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. [0013] As indicated, certain embodiments of the present invention are directed to polycarbodiimides. As used herein, the term "polycarbodiimide" refers to a polymer containing two or more units having the structure: As used herein, the term "polymer" includes oligomers and both homopolymers and copolymers, and the prefix "poly" refers to two or more. As will be appreciated, polycarbodiimides can generally be prepared by condensation reacting a polyisocyanate in the presence of a suitable catalyst to form a polycarbodiimide having terminal NCO- funclionality. [0014] Suitable polyisocyanates for use in the foregoing condensation reaction, include, without limitation, aliphatic, including cycloaliphatic, heterocyclic, and/or aromatic polyisocyanates. Such polyisocyanates can contain, for example, from 2 to 4, such as 2 isocyanate groups per molecule. Examples of suitable higher polyisocyanates are 1,2,4-benzene triisocyanate and polymelhylenc polyphenyl isocyanate. Examples of suitable aromatic diisocyanates are 4,4'-diphenylniethane diisocyanate, 1,3-phenylene diisocyanate, 1 4-phenylene diisocyanate and tolylene diisocyanate. Examples of suitable aliphatic diisocyanates are straight chain aliphatic diisocyanates such as 1,4- tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate. Examples of suitable cycloaliphatic diisocyanates are 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, alpha, alpha-xylylene diisocyanate, dicyclohexylmethyldiisocyanate ("TMXDI"), and 4,4-methylene-bis(cyclohexyl isocyanate). Substituted organic polyisocyanates can also be used in which the substituents are nitro, ohloro, alkoxy and other groups
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