USOO8841381 B2 (12) United States Patent (10) Patent No.: US 8,841,381 B2 Yamada et al. (45) Date of Patent: Sep. 23, 2014 (54) AQUEOUS POLYURETHANE RESIN 2004/OO77779 A1 4/2004 Schafheutle et al. DISPERSION AND PROCESS FOR 2004/O25997O A1 12/2004 Lockhart et al. PREPARING THE SAME 2005.0003102 A1 1/2005 Lockhart et al. 2006/0240264 A1 10/2006 Gertzmann et al. 2007, 0083002 A1 4/2007 Schafheutle et al. (75) Inventors: Takeshi Yamada, Ube (JP); Masahiro 2007/O155933 A1 7/2007 Watanabe et al. Naiki, Ube (JP) 2008.OOO4395 A1* 1/2008 Covelli et al. ................. 524,591 2008. O103282 A1 5/2008 Nagamatsu et al. (73) Assignee: Ube Industries Ltd., Ube-Shi (JP) 2008. O146767 A1 6/2008 Wamprecht et al. 2008. O1886.25 A1 8, 2008 Uchida et al. (*) Notice: Subject to any disclaimer, the term of this 2008/O194775 A1 8, 2008 Blum et al. patent is extended or adjusted under 35 2009 OO12201 A1 1/2009 Kim et al. 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Date: Feb. 24, 2011 JP 1-104612 A 4f1989 JP 2-2896.16 A 11, 1990 (65) Prior Publication Data JP 2-306427 A 12/1990 JP 3-1289.12 A 5, 1991 US 2012/0149841 A1 Jun. 14, 2012 JP 3-140318 A 6, 1991 (30) Foreign Application Priority Data (Continued) Aug. 20, 2009 (JP) ................................. 2009-190743 OTHER PUBLICATIONS Jul. 13, 2010 (JP) ................................. 2010-158493 Matsunaga, “Latest Polyurethane Material and Applied Technique— (51) Int. Cl. Road to Polyurethane Production'. The Comprehensive Materials C09D 175/04 (2006.01) and Technology for a Novel Polyurethane Production, CMC Publish C09D 175/08 (2006.01) ing Co., Ltd., Chapter 2, pp. 43, Sep. 30, 2005. (52) U.S. Cl. Odian, “Principles of Polymerization”, John Wiley & Sons, Inc., CPC ............ C09D 175/04 (2013.01); C09D 175/08 Third Edition, 7 pages, 1991. (2013.01) USPC ........................................... 524/839; 524/591 (58) Field of Classification Search Primary Examiner — Kelechi Egwim CPC ............................ C09D 175/04; C09D 175/08 (74) Attorney, Agent, or Firm — Birch, Stewart, Kolasch & USPC .................................................. 524/839,591 Birch, LLP See application file for complete search history. (56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS An object of this invention is to obtain an aqueous polyure 4,024,113 A 5, 1977 Ammons thane resin dispersion having excellent drying property, 4,103,070 A 7, 1978 Ammons which can provide a coating film having high hardness. The 4,895,894 A 1/1990 Ruetman et al. aqueous polyurethane resin dispersion comprises a polyure 4.956,438 A 9, 1990 Ruetman et al. thane resin obtained by reacting (a) a polyol compound, (b) a 5,043,381 A 8/1991 Coogan et al. 5,124,424 A 6, 1992 Endo et al. polyisocyanate compound, (c) an acidic group-containing 5,141,987 A 8/1992 Nachtkamp et al. polyol compound and (d) a chain-elongating agent, which is 5,143,997 A 9, 1992 Endo et al. being dispersed in an aqueous medium, wherein the above 5,169,895 A 12/1992 Coogan et al. 5,693,703 A 12, 1997 Hart mentioned (a) polyol compound contains at least (a1) a poly 5,738,912 A 4, 1998 Konig et al. carbonate polyol having an alicyclic structure at the main 5,859,122 A 1/1999 Umeya chain and (a2) a polymer polyol having a number average 6,096,805 A 8/2000 Lange et al. molecular weight of 500 to 5000 and having no alicyclic 6,433,072 B1 8, 2002 Gobel et al. 7,511,082 B2 3/2009 Nakamura et al. Structure. 7,538,154 B2* 5/2009 Pohl et al. ..................... 524,591 7,728,076 B2 6/2010 Wamprecht et al. 2002/0156145 A1 10/2002 Van Den Berg et al. 9 Claims, No Drawings US 8,841,381 B2 Page 2 (56) References Cited JP 2005-22O255 A 8, 2005 JP 2005-232447 A 9, 2005 JP 2005-281544. A 10, 2005 FOREIGN PATENT DOCUMENTS JP 2006-206774 A 8, 2006 JP 2006-307215. A 11, 2006 JP 3-174429 A 7, 1991 JP 2006-335951 A 12/2006 JP 3-220233. A 9, 1991 JP 2007-39673. A 2, 2007 JP 4-41517. A 2, 1992 JP 2007-119749. A 5/2007 JP 4-503226 A 6, 1992 JP 2007-245.369 A 9, 2007 JP 5-9434 A 1, 1993 JP 2008-37987 A 2, 2008 JP 5-39340 A 2, 1993 JP 2008-56760 A 3, 2008 JP 6-2001.49 A T 1994 JP 2008-150590 A T 2008 JP 6-248046 A 9, 1994 JP 2008-534710 A 8, 2008 JP 7-41539 A 2, 1995 JP 2008-248014. A 10, 2008 JP 8-193181 A T 1996 JP 10-72520 A 3, 1998 JP 2008-303284. A 12/2008 JP 10-120757 A 5, 1998 JP 2008-303285 A 12/2008 JP 10-130354 A 5, 1998 JP 2009-523188 A 6,f 2009 JP 10-273514. A 10, 1998 JP 2010-215885. A 9, 2010 JP 11-152321 A 6, 1999 JP 2010-222554. A 10, 2010 JP 2000-212240 A 8, 2000 WO WO 2006/093355 A1 9, 2006 JP 2001-334615. A 12/2001 WO WO 2006/101433 A1 9, 2006 JP 2002-128.851 A 5, 2002 WO WO 2007/0058O8 A2 1/2007 JP 2002-179787 A 6, 2002 WO WO 2008/O78754 A1 T 2008 JP 2002-179758 A 8, 2002 WO WO 2009, 145242 A1 12/2009 JP 2003-342335 A 12/2003 WO WO 2010.004951 A1 1/2010 JP 2005-8888 A 1, 2005 WO WO 2010/0983.16 A1 9, 2010 JP 2005-80643 A 3, 2005 JP 2005-113318 A 4/2005 * cited by examiner US 8,841,381 B2 1. 2 AQUEOUS POLYURETHANE RESIN Means to Solve the Problems DISPERSION AND PROCESS FOR PREPARING THE SAME The present inventors have intensively studied to solve the above-mentioned problems, and as a result, they have found TECHNICAL FIELD that an aqueous polyurethane resin dispersion excellent in drying property and providing a harder coating film can be The present invention relates to an aqueous polyurethane obtained by using a polycarbonate polyol having an alicyclic resin dispersion, more specifically to an aqueous polyure structure and a polymer polyol having a specific molecular thane resin dispersion which provides a hard coating film. weight and having no alicyclic structure as polyols in combi 10 nation, rather than using a polycarbonate polyol having an BACKGROUND ART alicyclic structure alone, whereby the present invention has accomplished. An aqueous polyurethane resin dispersion has been widely That is, the present invention has the following constitu utilized as a starting material for a paint or a coating agent, for tion. example, a starting material of a paint or a coating agent for 15 (1) An aqueous polyurethane resin dispersion which com coating an outside and inside of an aircraft, automobile, etc., prises a polyurethane resin obtained by reacting (a) a polyol an external wall Surface and a floor material of a house, and compound, (b) a polyisocyanate compound, (c) an acidic the like. The above-mentioned coating films not only play group-containing polyol compound, and (d) a chain-elongat beauty of appearances, but also take a role of protecting the ing agent, being dispersed in an aqueous medium, wherein Substrate materials, so that hardness, strength and durability the above-mentioned (a)polyol compound contains at least are required. For this purpose, an aqueous polyurethane resin (a1) a polycarbonate polyol having an alicyclic structure at dispersion which provides a harder coating film has been the main chain and (a2) a polymer polyol having number strongly desired. average molecular weight of 500 to 5000 and having no In order to satisfy the above-mentioned properties, aque 25 alicyclic structure. ous polyurethane resin dispersions using various kinds of (2) The aqueous polyurethane resin dispersion described in polyols have been developed. A polyol is a useful compound the above-mentioned (1), wherein a number average molecu as a starting material for preparing a polyurethane resin by the lar weight of (a1) the polycarbonate polyol having an alicy reaction with an isocyanate compound. For example, as a clic structure at the main chain is Smaller than a number polymer polyol, a polyester polyol, polyether polyol, poly 30 average molecular weight of (a2) the polymer polyol having carbonate polyol, etc., have been used for the preparation of no alicyclic structure. an aqueous polyurethane resin dispersion. Among the above (3) The aqueous polyurethane resin dispersion described in mentioned polymer polyols, the polycarbonate polyol has the above-mentioned (1) or (2), wherein (a2) the polymer characteristics that it provides tough coating film as com polyol having number average molecular weight of 500 to pared with those of the polyester polyol and polyether polyol. 35 5000 and having no alicyclic structure is a polyether polyol.