USOO923431 OB2 (12) United States Patent (10) Patent No.: US 9.234,310 B2 Kramer et al. (45) Date of Patent: Jan. 12, 2016 (54) FABRIC HAVING ULTRAVOLET (2013.01): D06M 2101/06 (2013.01): D06M RADIATION PROTECTION, ENHANCED 2200/25 (2013.01): D06M 2400/01 (2013.01); RESISTANCE TO DEGRADATION, AND Y10T 442/259 (2015.04) ENHANCED RESISTANCETO FIRE (58) Field of Classification Search None (71) Applicants: Robert B Kramer, St. Louis, MO (US); See application file for complete search history. Ronald Kramer, St. Louis, MO (US); Nicholas Marshall, Charleston, SC (56) References Cited (US); Jason Rosenberg, Shorewood, WI (US); Ram B. Gupta, Richmond, VA U.S. PATENT DOCUMENTS (US) 6,034,003 A 3/2000 Lee 6,607,994 B2 8, 2003 Soane et al. (72) Inventors: Robert B Kramer, St. Louis, MO (US); 7,262,160 B2 8, 2007 Black Ronald Kramer, St. Louis, MO (US); 7,754,625 B2 7/2010 Hendriks et al. Nicholas Marshall, Charleston, SC 2004f0074.012 A1 4/2004 Heidenfelder et al. (US); Jason Rosenberg, Shorewood, WI 2005/0175530 A1 8/2005 Baglioni et al. (US); Ram B. Gupta, Richmond, VA 2006/0235178 A1* 10/2006 Wang et al. ..................... 528.21 2009/0233507 A1 9, 2009 Gross et al. (US) 2010/0092761 A1* 4/2010 Koch et al. .................... 428,328 (73) Assignee: The Sweet Living Group, LLC, St. 2012/0196.134 A1* 8, 2012 Weinelt et al. ................ 428.447 Louis, MO (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WO 2010/O18075 2, 2010 patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS Copending U.S. Appl. No. 14/549,776 to Kramer et al.* (21) Appl. No.: 14/522,844 Vigneshwaran et al. "Functional finishing of cotton fabrics using Zinc oxide-soluble starch nanocomposites”, published Sep. 22, 2006 by (22) Filed: Oct. 24, 2014 the Institute of Physics Publishing in Nanotechnology 17 (2006), pp. Prior Publication Data 5087-5095. (65) Farouk et al. "ZnO Nanoparticles-Chitosan Composite as Antibacte US 2015/O1 O7029 A1 Apr. 23, 2015 rial Finish for Textiles', published in the International Journal of Carbohydrate Chemistry, research article accepted on Nov. 6, 2012, Related U.S. Application Data Hindawi Publishing Corporation, vol. 2012, Article ID 693629, pp. 1-8.* (63) Continuation-in-part of application No. 14/245,152, Clark (“A Double Beam UV-Visible Absorption Spectrometer'. filed on Apr. 4, 2014, and a continuation-in-part of copyright 2006, pp. 1-7. available online at http://www.chemguide. application No. 13/632,223, filed on Oct. 1, 2012, now co.uk/analysis/uvvisible/spectrometer.html).* Pat. No. 8,690,964, and a continuation-in-part of Vikram P Dhende et al., One-Step Photochemical Synthesis of Per application No. 13/317,152, filed on Oct. 11, 2011, manent, Nonleaching. Ultrathin Antimicrobial Coatings for Textiles now Pat. No. 8,277,518. and Plastics, ACS Applied Materials and. Blanchard and Graves, Phosphorylation of Cellulose with Some Int. C. Phosphonic Acid Derivatives, Textile Research Journal, 2003, 73. (51) 22-26. D06M II/44 (2006.01) Fangli et al., Preparation and properties of Zinc oxide nanoparticles D06M 23/02 (2006.01) coated with zinc aluminate, Journal of Materials Chemistry, 2003, 13, D06M 23/10 (2006.01) 634-637. D06M 3/53 (2006.01) CID 3/12 (2006.01) (Continued) CID 3/37 (2006.01) CID 7/00 (2006.01) Primary Examiner — Harold Pyon D06M II/50 (2006.01) Assistant Examiner — Katie L. Hammer D06M II/68 (2006.01) (74) Attorney, Agent, or Firm — David H. Chervitz D06M 3/288 (2006.01) D06M 3/432 (2006.01) (57) ABSTRACT D06M 23/08 (2006.01) A method for treating a fabric for ultraviolet radiation pro DO6M IOI/06 (2006.01) tection, enhanced resistance to degradation, and enhanced (52) U.S. C. resistance to fire is disclosed which comprises the steps of CPC ............. D06M II/44 (2013.01): CI ID 3/1213 adding Zinc oxide nanoparticles to a solution of 3-glycidy (2013.01); CIID 3/37 (2013.01): CIID loxypropyl-trimethoxysilane, placing a fabric in the mixture 17/0039 (2013.01): D06M II/50 (2013.01); of Zinc oxide particles and 3-glycidyloxypropyl-trimethox D06M II/68 (2013.01): D06M 13/288 ysilane, curing the fabric, and washing the fabric. Other meth (2013.01): D06M 13/432 (2013.01): D06M ods of treating a fabric are disclosed. 13/513 (2013.01): D06M 23/02 (2013.01); D06M 23/08 (2013.01): D06M 23/10 17 Claims, No Drawings US 9.234,310 B2 Page 2 (56) References Cited on Carboyxlic Acid-Terminated SAMs, Chemistry of Materials, 2005, 26(6), 4514-4522. OTHER PUBLICATIONS Zhang et al., Surface Functionalization of Zinc Oxide by Carboxyalkylphosphonic Acid Self-Assembled Monolayers, Gelest, Inc., 'Silane coupling agents: connecting across boundaries.” Langmuir, 2010, 26(6), 4514-4522. http://www.gelest.com/pdf/couplingagents.pdf, 60 pages, undated Vikram P Dhende et al., One-Step Photochemical Synthesis of Per but prior to Oct. 11, 2011. manent, Nonleaching. Ultrathin Antimicrobial Coatings for Textiles Hau et al., Effect of Chemical Modification of Fullerene-Based Self and Plastics, ACS Applied Materials and Interfaces Forum Article, Assembled Monolayers on the Performance of Inverted Polymer American Chemical Society, Jun. 21, 2011, 2830-2837. Solar Cells, Applied Materials and Interfaces, 2010(7), 1892-1902. Nina Griep-Raming et al... Using BenZophenone-Functionalized Lu and Ng, Efficient, One-Step Mechanochemical Process for the Phosphonic Acid to Attache Thin Polymer Films to Titanium Sur Synthesis of ZnO Nanoparticles, Industrial Engineering Chemical faces, Langmuir, 2004. 11811-1 1814. Reasearch, 2008, 47, 1095-1101. A. Yadav et al., Functional finishing in cotton fabrics using Zinc oxide Law et al., ZnO-Al2O3 and ZnO TiO2 Core—Shell Nanowire nanoparticles, Bullentin of Material Sciences, vol. 29, No. 6, Nov. Dye-Sensitized Solar Cells, Journal of Physical Chemistry B, 2006, 2006, 641-645. 110(45), 22652-22663. Y.L. Lam et al., Effect of zinc oxide on flame retardant finishing of Perez et al., TEMPO-Mediated Oxidation of Cellulose III, plasma pre-treated cotton fabric, Cellulose (2011) 18:151-165. Biomacromolecules, 2005, 17(20), 5048-5056. Turgeman et al., Crystallization of Highly Oriented ZnO Microrods * cited by examiner US 9,234,310 B2 1. 2 FABRIC HAVING ULTRAVOLET ment less protective. A challenge for a clothing manufacturer RADIATION PROTECTION, ENHANCED is to provide clothing having both protection from the Sun and RESISTANCE TO DEGRADATION, AND being comfortable to wear. ENHANCED RESISTANCETO FIRE Ultraviolet light exposure causes degradation in natural and synthetic fabrics, mainly due to the breakage of the poly CROSS REFERENCE TO RELATED mer chains. The Smaller polymer chains have a lower APPLICATIONS mechanical strength which in turn significantly reduces the overall strength of the fibers or the fabric. In addition, the UV This application is a continuation-in-part of U.S. patent light can cleave or oxidize the dye molecules which results in 10 the loss of color over time. Once fabric or clothing degrades application Ser. No. 14/245,152 filed on Apr. 4, 2014, which over time, the fabric or clothing may have to be discarded due was a continuation of U.S. patent application Ser. No. 13/632, to the appearance of the fabric or clothing. Due to degradation 223 filed on Oct. 1, 2012, which is now U.S. Pat. No. 8,690, of the fabric or clothing, the fabric or clothing may not have 964, which was a continuation-in-part of U.S. patent appli been worn for an acceptable period of time. If the clothing cation Ser. No. 13/317,152 filed on Oct. 11, 2011, which is 15 was expensive, being only able to wear the clothing for a short now U.S. Pat. No. 8,277,518. period of time will not be acceptable to the wearer or pur chaser of the clothing. The wearer or purchaser may not BACKGROUND purchase the same brand in the future due to the problem encountered with the previous purchase. It is also known that This disclosure relates to a fabric having ultraviolet radia ultraviolet light exposure causes color degradation in natural tion protection, and more specifically, to a fabric having ultra and synthetic fabrics. Once the color or colors in fabric or violet (UV) radiation protection incorporated into the fabric. clothing degrades, the fabric or clothing may have to be Further, this disclosure relates to a fabric having enhanced discarded due to the unacceptable appearance of the fabric or ability to resist degradation of the fabric. The disclosure also clothing. provides methods to provide enhanced resistance to color 25 Additives to fabric, such as TiO, can absorb UV light to degradation of a fabric and enhanced resistance to fiber lower the photo-degradation of the polymer and dyes. How strength degradation of a fabric. This disclosure provides ever, upon absorption of the UV light, the surface of TiO, methods to provide enhanced resistance to fire of a fabric. particles become catalytically active due to production of an Ecological friendly fabrics or Eco-friendly fabrics are electron-vacancy pair. The produced electrons and radicals gaining in popularity and use in clothing. An Eco-friendly 30 attack the polymer around the particle Surface and cause it to fabric may be a natural fiber Such as cotton, hemp, or bamboo cleave, which can propagate crack in the fiber. In fact, the which has been grown in soil that has not been treated with surface photo-reactive property of TiO is successfully used pesticides for a number of years. Some examples of other to destroy pollutant molecules in the residential air purifiers.