USOO8546502B2 (12) United States Patent (10) Patent No.: US 8,546,502 B2 Shimanaka et al. (45) Date of Patent: Oct. 1, 2013 (54) METHOD FOR PRODUCING DYE POLYMER, JP 2000-500516 A 1, 2000 DYE POLYMER AND USE OF THE SAME JP 2000-514479. A 10, 2000 JP 2000-515181 A 11, 2000 JP 2005-345512 A 12/2005 (75) Inventors: Hiroyuki Shimanaka, Chuo-ku (JP); JP 2005-352053 A 12/2005 Toshiyuki Hitotsuyanagi, Chuo-ku (JP); JP 2006-16488 * 1, 2006 Yoshikazu Murakami, Chuo-ku (JP); JP 2006-016488 A 1, 2006 JP 2006-167674 * 6, 2006 Atsushi Goto, Uji (JP); Yoshinobu JP 2006-0167674. A 6, 2006 Tsujii, Uji (JP); Takeshi Fukuda, Uji JP 2007-277533 A 10/2007 (JP) WO WO97, 18247 A1 5, 1997 WO WO98/O1478 A1 1, 1998 (73) Assignees: Dainichiseika Color & Chemicals Mfg. WO WO 98.01480 A1 1, 1998 Co., Ltd., Chuo-ku, Tokyo (JP); Kyoto WO WO99,05099 A1 2, 1999 University, Kyoto-shi, Kyoto (JP) OTHER PUBLICATIONS (*) Notice: Subject to any disclaimer, the term of this Shimizu Itaru, JP2006016488 (Jan. 2006), English Translation.* patent is extended or adjusted under 35 Shimizu Itaru et al., JP2006 167674 (Jun. 2006), English Transla U.S.C. 154(b) by 0 days. tion. Hawker, C., et al., New Polymer Synthesis by Nitroxide Mediated (21) Appl. No.: 12/737,239 Living Radical Polymerizations, Chemical Review, vol. 101, No. 12, 2001, pp. 3661-3688. (22) PCT Filed: Jun. 26, 2009 Kamigaito, M., et al., Metal-Catalyzed Living Radical Polymeriza tion, Chemical Review, vol. 101, No. 12, 2001, pp. 3689-3745. Yamago, S., et al., Organotellurium Compounds as Novel Initiators (86). PCT No.: PCT/UP2009/061705 for Controlled/Living Radical Polymerizations, Journal of the S371 (c)(1), American Chemical Society, vol. 124, No. 12, 2002, pp. 2874-2875. Dec. 20, 2010 Yamago, S., et al., Tailored Synthesis of Structurally Defined Poly (2), (4) Date: mers by Organotellurium-Mediated Living Radical Polymerization (87) PCT Pub. No.: WO2009/157536 (TERP), Journal of the American Chemical Society, vol. 124, No. 46, 2002, pp. 13666-13667. PCT Pub. Date: Dec. 30, 2009 Goto, A., et al., Mechanism-Based Invention of High-Speed Living Radical Polymerization Using Organotellurium Compounds and (65) Prior Publication Data Azo-Initiators, Journal of the American Chemical Society, vol. 125, No. 29, 2003, pp. 8720-8721. US 2011/0112242 A1 May 12, 2011 (30) Foreign Application Priority Data * cited by examiner Primary Examiner — William Cheung Jun. 27, 2008 (JP) ................................. 2008-168361 (74) Attorney, Agent, or Firm — Chapman and Cutler LLP (51) Int. Cl. (57) ABSTRACT CSF2/00 (2006.01) CSF 4/00 (2006.01) Disclosed are a production process of a dye polymer having a COSL 33/06 (2006.01) dye content of from 1 to 50 wt %, and the dye polymer and its (52) U.S. Cl. use. The production process includes Subjecting an addition USPC ........... 526/193; 526/204; 526/208; 526/210; polymerizable monomer to living radical polymerization by 524/560 using, as a polymerization initiator, a dye having a polymer (58) Field of Classification Search ization initiating group enabling the living radical polymer USPC .................. 524/560; 526/193,204, 208, 210 ization. The dye polymer and a composition of the dye poly See application file for complete search history. mer and a pigment are useful as good coloring agents for various products or articles. The colored products or articles (56) References Cited are high in transparency, and are provided with high added value. The dye polymer can also be used as a dispersant for FOREIGN PATENT DOCUMENTS pigments, thereby making it possible to afford pigment dis JP 1963-013530 B T 1963 persions excellent in dispersion properties and dispersion JP 1964-003980 B 4, 1964 stability. JP 1974-010690 B 3, 1974 JP 1985-027697 B 7, 1985 10 Claims, No Drawings US 8,546,502 B2 1. 2 METHOD FOR PRODUCING DYE POLYMER, ization to afford a block copolymer although such block DYE POLYMER AND USE OF THE SAME copolymerization can be hardly conducted by the conven tional radical polymerization. This living radical polymeriza This application is a 35 U.S.C. 371 National Stage appli tion process also features that the selection of appropriate cation of International Application Number PCT/JP2009/ initiating groups makes it possible to produce polymers of 061705 filed on Jun. 26, 2009, which claimed priority of various higher structures, such as graft copolymers and Star Japan Patent Application Number 2008-168361 filed on Jun. polymers. 27, 2008. The contents of the aforementioned applications are Developed as specific examples of the above-described hereby incorporated by reference. living radical polymerization process include the nitroxide 10 mediated polymerization (NMP) process that makes use of TECHNICAL FIELD dissociation and bonding of amine oxide radicals (Non-patent Document 1), the atom transfer radical polymerization This invention relates to a production process of a dye (ATRP) process that polymerizes a monomer in the presence polymer, the dye polymer and its use. According to the of a halogen compound as a polymerization initiator by using present invention, the dye polymer which is formed of a dye 15 and a polymer bonded together via a covalent bonds can be a heavy metal Such as copper, ruthenium, nickel or iron and a easily produced with a high polymerization yield at low price, ligand capable of forming a complex with Such a metal and moreover, the dye polymer can be obtained by a novel (Patent Document 6, Patent Document 7, and Non-patent polymerization process that uses materials, which do not Document 2), the reversible addition-fragmentation transfer place much load on the environment, without needing any (RAFT) process that subjects an addition-polymerizable special compound or compounds. The dye polymer is useful, monomer to radial polymerization by using a dithiocarboxy either singly or as a composition with a pigment, as a coloring late ester, a Xanthate compound or the like as a polymerization agent for various applications. initiator (Patent Document 8), the macromolecular design via interchange of xanthate (MADIX) process (Patent Document BACKGROUND ART 25 9), the degenerative transfer (DT) process that makes use of a heavy metal Such as an organotellurium compound, organo Dye polymers, each of which is formed of a polymer of an bismuth compound, organoantimony compound, antimony addition-polymerizable monomer and a dye bonded together, halide, organogermanium compound or germanium halide are conventionally known, and by various production pro (Patent Document 10 and Non-patent Document 3), and so cesses, typically by radical polymerization processes, these 30 on. Extensive research and development work is underway on dye polymers can be obtained from various compounds. the living radical polymerization process. Examples of these production processes include a process The use of the above-described process is considered pos that copolymerizes a dye monomer, which is formed of a dye sible to obtain a dye polymer by introducing an initiating and an addition-polymerizable, unsaturated bond introduced group, which can induce living radical polymerization, into a therein, with another radically-polymerizable monomer 35 dye and conducting living radical polymerization by using the (Patent Document 1 and Patent Document 2), and a process initiating group. For example, a dye polymer formed of a that reduces a dye, which contains a nitro group, to form an pigment and a polymer bonded thereto has been obtained by amino group, diazotizes the amino group into a radical gen the atom transfer radical polymerization (ATRP) process, in erating group, and by using the resultant compound as a which a Sulfonated chloride group or brominated alkyl group radical polymerization initiator, Subjects an addition-poly 40 is introduced into an organic pigment and an addition-poly merizable monomer to radical polymerization (Patent Docu merizable monomer is polymerized by using, as a polymer ment 3 to Patent Document 5). ization initiator, the resulting derivative and as a catalyst, a In addition, a living radical polymerization process has copper compound and a ligand capable of forming a complex also been developed, which is a novel and precise polymer with the copper compound (Patent Document 11). In accor ization process that initiates polymerization from a specific 45 dance with the ATRP process, a polymer (pigment dispersant) initiating group. This living radical polymerization process having an aromatic ring at an end thereof has also been generally means a process that stabilizes the polymerizable obtained by using an aromatic ring compound (Patent Docu radical end with a stable group, causes the stable end group to ment 12). dissociate under the action of heat or a catalyst to form a Prior Art Documents radical at the end of the polymer, and polymerizes a monomer 50 Patent Documents at the moment of the dissociation. The existence of a com Patent Document 1: JP-A-38-13530 pound, which has a stable group, in a polymerization system Patent Document 2: JP-A-41-17063 results in immediate bonding of the stable group to the poly Patent Document 3: JP-A-39-3980 merradical so that the radical end of the polymer is stabilized. Patent Document 4: JP-B-49-10690 This process prevents a bimolecular termination reaction or 55 Patent Document 5: JP-B-60-27697 disproportionation reaction as a side reaction of radical poly Patent Document 6: JP-A-2000-500516 merization and does not deactivate the radical as a reactive Patent Document 7: JP-A-2000-514479 end, that is, a "living radical polymerization process. Patent Document 8: JP-A-2000-515181 In this living radical polymerization process, the polymer Patent Document 9: WO99/05099 ization proceeds as time goes on, and based on the amount of 60 Patent Document 10: UP-A-2007-277533 polymerization initiating groups at the initiation of the reac Patent Document 11: JP-A-2006-16488 tion, the molecular weight of a polymer is determined and Patent Document 12: JP-A-2006-167674 controlled, and the molecular weight distribution of the Non-patent Documents resulting polymer can be controlled very narrow (molecular Non-patent Document 1: Chemical Review (2001) 101, weight distribution, PDI: 1 to 1.3).