USOO7666504B2 (12) United States Patent (10) Patent No.: US 7,666,504 B2 Ochi et al. (45) Date of Patent: Feb. 23, 2010 (54) NANOPOROUS FIBER WITH 3,516,239 A * 6/1970 Fukuda et al. .............. 442/193 UNCONNECTED PORES FOR IMPROVED 3,716,614 A 2, 1973 Okamoto et al. .............. 264/49 ADSORPTIVITY 3,957,936 A * 5, 1976 Lauchenauer ................ 264/53 4,468.434 A 8, 1984 Sekimoto et al. ............ 428,372 (75) Inventors: Takashi Ochi, Mishima (JP); Akira 4,515,859 A * 5/1985 De Maria et al. ............ 428,398 Kishiro, Mishima (JP); Shuichi Nonaka, Otsu (JP); Takaaki Mihara, (Continued) Mishima (JP); Norio Suzuki, Shizuoka (JP) FOREIGN PATENT DOCUMENTS (73) Assignee: TORAY Industries, Inc., Tokyo (JP) JP S60-155770 * 5, 1985 .............. 428,315.5 (*)c Notice: SubjectSub to any disclaimer,disclai theh term off thisthi JP H03-052610S60-167969 A * 8,3, 19851991 ...................... ... 264/45.6 55/524 patent is extended or adjusted under 35 JP HO8-158251 * 6/1996 U.S.C. 154(b) by 170 days. JP HO8-296.123 * 11, 1996 (21) Appl. No.: 11/489,606 JP HO9-157943 A * 6, 1997 JP 10-183425 A 7, 1998 (22) Filed: Jul. 20, 2006 JP 2000-154463. A 6, 2000 (65) Prior Publication Data US 2006/0257656A1 Nov. 16, 2006 OTHER PUBLICATIONS Related U.S. Application Data Harris, Robert L. (2000). Patty's Industrial Hygiene (5th Edition) - - - vols. 1-4. (pp. 1489-1550 (renumbered 1-28)). John Wiley & Sons. (62) Division of application No. 10/523,416, filed as appli- Online version available at: http://www.knovel.com/knovel2. Toc. cation No. PCT/JP03/09532 on Jul. 28, 2003, now Pat. jsp?bookID=709&VerticalID=0.* No. 7,097,904. O O Primary Examiner Jill Gray (30) Foreign Application Priority Data (74) Attorney, Agent, or Firm Kubovcik & Kubovcik Aug. 5, 2002 (JP) ............................. 2002-227619 Mar. 10, 2003 (JP) ............................... 2003-62910 (57) ABSTRACT (51)51) InInt. Cl. The present invention provides a nanoporous fiber being Sub (52) U.S.D02G Cl. 3/34 ....................... (2006.01) 428/398.428,370. 428373. Slantiallytantially freefree Iron coarspores andd havinghhaving nomogeneously 1 428/374; 428/397; 428/394 dispersed nanopores, unlike conventional porous fibers. A 58) Field of Classification Search 557524 porous fiber has pores each having a diameter of 100 O ( f528: 82.211.344.45. less, in which the area ratio of pores each having a diameter of 4 2.5 st 1. s "...", 200 nm or more to the total cross section of the fiber is 1.5% 428/372 398. 315.5. 373. 374 395. 397. or less, and the pores are unconnected pores, or a porous fiber s 442,394 35 401 408 43 59 has pores each having a diameter of 100 nm or less, in which S lication file f 1 s - als h hi s - s the area ratio of pores each having a diameter of 200 nm or ee application file for complete search history. more to the total cross section of the fiber is 1.5% or less, the (56) References Cited pores are connected pores, and the fiber has a strength of 1.0 cN/dtex or more. U.S. PATENT DOCUMENTS 3,513,110 A * 5, 1970 Noether ...................... 521, 182 16 Claims, 34 Drawing Sheets TITANIUM. OXDE y-> SAMPLE BREAKAGE b : ENLARGED WIEW a OVERVIEW OF MONOFILAMENT US 7,666,504 B2 Page 2 U.S. PATENT DOCUMENTS 6,989, 193 B2 1/2006 Haile et al. ................. 428,364 2004/0067711 A1* 4/2004 Bliton et al. ................ 442,394 4,686,074 A 8, 1987 Okamoto .... ... 264,171 5,022,990 A 6, 1991 Doi et al. ............... 210,50042 * cited by examiner U.S. Patent Sheet 1 of 34 US 7,666,504 B2 AA@TIACIHONHVTINA:q AOVXVIÐIRGIÆVNVS<–, uztrz JLNGHWVTIHONOWNHOAAFHANHGIAO:e U.S. Patent Feb. 23, 2010 Sheet 2 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 3 of 34 US 7,666,504 B2 AAHIACIE?ONHVTINGH:C| JLNGHWNVTI.HONOWNHOAA@HIAR{{AO U.S. Patent Feb. 23, 2010 Sheet 4 of 34 US 7,666,504 B2 anti-th', 'yearantern sieghiatristickritressits. lar - . irri, U.S. Patent Feb. 23, 2010 Sheet 5 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 6 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 7 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 8 of 34 US 7,666,504 B2 U.S. Patent Feb. 23 9 2010 Sheet 9 of 34 US 7,666 9 504 B2 VEIS HONOIOETRI -NI-SCINVTISI T?n?5ñš?s ONOIOETH Y[H8IIHOJLTWNDRICHELNI U.S. Patent Feb. 23, 2010 Sheet 10 of 34 US 7,666,504 B2 . , s 1 - sha ... s . arterists arts r an . .. bri rt is i; y U.S. Patent Feb. 23, 2010 Sheet 11 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 12 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 13 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 14 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 15 of 34 US 7,666,504 B2 I'''''', '' U.S. Patent Feb. 23, 2010 Sheet 16 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 17 of 34 US 7,666,504 B2 , . - 'it-x.org.irisha'sR is a . U.S. Patent Feb. 23, 2010 Sheet 18 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 19 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 20 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 21 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 22 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 23 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 24 of 34 US 7,666,504 B2 : U.S. Patent Feb. 23, 2010 Sheet 25 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 26 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 27 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 28 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 29 of 34 US 7,666,504 B2 S r N U.S. Patent Feb. 23, 2010 Sheet 30 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 31 of 34 US 7,666,504 B2 2 U.S. Patent Feb. 23, 2010 Sheet 32 of 34 US 7,666,504 B2 FIG. 32 U.S. Patent Feb. 23, 2010 Sheet 33 of 34 US 7,666,504 B2 U.S. Patent Feb. 23, 2010 Sheet 34 of 34 US 7,666,504 B2 FIG. 34 US 7,666,504 B2 1. 2 NANOPOROUS FIBER WITH Among them, polymer blending has been actively investi UNCONNECTED PORES FOR IMPROVED gated, since this technique does not require new designing of ADSORPTIVITY polymers and Such a polymer blend can be produced by using a mono-component spinning machine. This application is a divisional of U.S. patent application 5 Separately, hollow fibers and porous fibers have been Ser. No. 10/523,416 filed on Mar. 21, 2005, now U.S. Pat. No. investigated in order to reduce the weight offibers or to impart 7,097,904 which is a 371 of international application PCT/ water-adsorptivity thereto. JP2003/009532 filed Jul. 28, 2003, which claims priority Attempts have been made to provide hollow fibers having based on Japanese Patent Application Nos. 2002-227619 and high hollowness, but such hollow portions may be crushed, 2003-62910 filed Aug. 5, 2002, and Mar. 10, 2003, respec 10 for example, as a result of false twisting. To avoid this, multi tively, which are incorporated herein by reference. islands hollow fibers, wherein a multitude of islands parts constitutes a hollow portion, using a conjugated fiber with a TECHNICAL FIELD water-soluble polymer have been developed. In such fibers, the hollow portion generally has a diameter of 1 um or more, The present invention relates to a porous fiber which has a 15 the interface between the polymer and the air in the hollow multitude of fine and even-sized nanopores and is Substan portion significantly reflects visible radiation, and the result tially free from coarse pores that reflect visible radiation. It ing fiber cannot satisfactorily develop a color. also relates to a polymer alloy fiber serving as a precursor of Porous fibers each having a multitude of pores on the order the porous fiber in the production thereof, and to a method for of Sub-micrometers have been investigated. Such porous producing the polymer alloy fiber. fibers have generally been produced not by multi-component In the following descriptions relating to the present inven fiber spinning but by polymer blend spinning. tion, the term "nanopores' means fine pores each having a Japanese Unexamined Patent Publication (Kokai) No. diameter of 100 nm or less. 2-175965, for example, describes a technique of blending a The term “nanoporous fiber' used in the present invention nylon with a PET copolymerized with a hydrophilic group, refers to a fiber containing one or more pores having a diam 25 forming a fiber from the blend, and dissolving off the copo eter of 100 nm or less per square micrometer at cross section lymerized PET from the fiberto thereby obtain a porous nylon of a fiber perpendicular to the axial direction thereof.