US009 150782B2 (12) United States Patent (10) Patent No.: US 9,150,782 B2 Lee et al. (45) Date of Patent: Oct. 6, 2015 (54) FLUORESCENT TRACER FOR (56) References Cited WATER-SOLUBLE FILMS, RELATED METHODS, AND RELATED ARTICLES U.S. PATENT DOCUMENTS (71) Applicant: MONOSOL, LLC, Merrillville,- - - - IN (US) 2.477,3832,220,099 A 11/19407, 1949 GuentherLewis et al. (72) Inventors: David M. Lee, Crown Point, IN (US); (Continued) Stephen Bullock, Chicago, IL (US); Nicholas Zeese, Michigan City, IN (US) FOREIGN PATENT DOCUMENTS (73) Assignee: MONOSOL, LLC, Merrillville,- - - - IN (US) EP OO791680 197434 A2 10,8, 19971986 (*) Notice: Subject to any disclaimer, the term of this (Continued) patent is extended or adjusted under 35 OTHER PUBLICATIONS U.S.C. 154(b) by 0 days. Dye Tracing, Wikipedia Entry, downloaded from the Internet at (21) Appl. No.: 14/562,148 <http://en.wikipedia.org/wiki/Dye tracing> (page last modifed Apr. 26, 2014). (22) Filed: Dec. 5, 2014 (Continued) (65) Prior Publication Data Primary Examiner — Kiho Kim US 2015/O159082 A1 Jun. 11, 2015 (74) Attorney, Agent, or Firm — Marshall, Gerstein & Borun LLP Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 61/912,689, filed on Dec. Disclosed herein are fluorescent tracer compositions and 6, 2013. water-soluble polymer compositions containing fluorescent s compounds for tracing one or more components in the poly (51) Int. Cl. mer compositions. More particularly, the disclosure relates to GOIN 2L/64 (2006.01) fluorescent tracer compositions including a fluorophore and a C09K II/02 (2006.01) bitterant aversive component to be incorporated into a water soluble polymer composition Such as a water-soluble film. An (Continued) aversive compound Such as a bitterant is desirably incorpo (52) U.S. Cl. rated into the polypolvmer compositionp as a deterrent to ingestion9. CPC ............... C09K II/025 (2013.01); Co9K II/06 of the polymer composition (or an article made therefrom). (2013.01); CIID3/0005 (2013.01): CIID Qualitative or quantitative detection of the fluorophore in the 3/2096 (2013.01): CI ID3/3418 (2013.01); polymer composition can be correlated to a qualitative or (Continued) quantitative detection of a corresponding traced material in the polymer composition, for example the bitterant aversive (58) Field of Classification Search component. Related articles and methods for making and CPC .................... G01N 2021/6441; G01N 33/582: using the polymer compositions are also disclosed. GO1N 33/58 See application file for complete search history. 38 Claims, 3 Drawing Sheets 2O y 30 3 Z NAe co-N US 9,150,782 B2 Page 2 (51) Int. Cl. 2003, OO60390 A1 3/2003 Demeyere et al. C09K II/06 (2006.01) 2003/O126282 A1 7/2003 Sarkar et al. CID 3/42 2006.O1 2003. O1393.12 A1 7, 2003 Caswell et al. (2006.01) 2004/0204337 A1 10, 2004 Corona et al. CID 3/00 (2006.01) 2005/0101507 A1 5/2005 Jaynes CID 3/37 (2006.01) 2005/0123935 A1* 6/2005 Haugland et al. ................. 435/6 CID 3/20 (2006.01) S.O.E. A. S. V.'Wa C al. 252,67 CID 3/34 (2006.01) 2010, 0175845 A1 7, 2010 Gauto et al. (52) U.S. Cl. 2011/0023240 A1 2/2011 Fossum et al. CPC ................ CI ID3/3753 (2013.01); C1 ID 3/42 2011/O1894.13 A1 8/2011 Denome et al. (2013.01); G0IN 21/6428 (2013.01); C09K 58,886. A. 58. E. ret al. 221 1/1007 (2013.01); C09K221 1/1088 ee et al. (2013.01); G0IN 2021/6439 (2013.01) FOREIGN PATENT DOCUMENTS (56) References Cited EP 1375637 A1 1/2004 EP 2196531 A1 6, 2010 U.S. PATENT DOCUMENTS EP 2258820 A1 12/2010 GB 1 137741. A 12, 1968 3,664,961 A 5, 1972 Norris WO WO-96,08555 A1 3/1996 3,919,678 A 1 1/1975 Penfold WO WO-2014/026855 A1 2/2014 4,000,093 A 12/1976 Nicol et al. WO WO-2014/026856 A1 2/2014 4,222,905 A 9, 1980 Cockrell, Jr. 4,239,659 A 12/1980 Murphy OTHER PUBLICATIONS 4,246,612 A 1/1981 Berry et al. 4,810,410 A 3, 1989 Diakun et al. International Search Report and Written Opinion, International 5,114,611 A 5/1992 Van Kralingen et al. Application No. PCT/US2014/068848, mailed Mar. 5, 2015. 5,137,646 A 8, 1992 Schmidt et al. Suo et al., Poly (vinyl alcohol) thin film filled with CdSe ZnS 5,227,084 A 7, 1993 Martens et al. quantum dots: fabrication, characterization and optical properties, 5,783,541.5,576,281. A 1 7/19981/1996 TacketBunch et al. al. Mater.later. Chem. Phys,Phvs. 119:237-42 (2010).(2010 6,468,554 B1 10/2002 Ichino Final Report: Study of Aversive Agents, U.S. Consumer Product 6,599,871 B2 7, 2003 Smith Safety Commission (Nov. 18, 1992). 2002/0033004 A1 3f2002 Edwards et al. 2003, OO60387 A1 3, 2003 HSu et al. * cited by examiner U.S. Patent Oct. 6, 2015 Sheet 1 of 3 US 9,150,782 B2 a Emission Wavelength, 2. Figure 1A Emission Wavelength, 2. Figure 1B U.S. Patent Oct. 6, 2015 Sheet 2 of 3 US 9,150,782 B2 2O y 30- 3 at . SOE O. 400 A.O. AO 430 AO ASO Emission Wavelength, 2 (nm) Figure 3 U.S. Patent Oct. 6, 2015 Sheet 3 of 3 US 9,150,782 B2 y = 1449.1x+356.22, R2 = 0.9952 O --goxpogopos O.O O.2 O.4 O.6 O.8 1.O 1.2 1.4 Fluorophore Active Concentration in Solution (ppm) Figure 4 US 9,150,782 B2 1. 2 FLUORESCENT TRACER FOR rated into the polymer composition as a deterrent to ingestion WATER-SOLUBLE FILMS, RELATED of the polymer composition (or an article made therefrom) by METHODS, AND RELATED ARTICLES a child or animal. Qualitative or quantitative detection of the fluorophore in the polymer composition can be correlated to FIELD OF THE DISCLOSURE a qualitative or quantitative detection of a corresponding traced material in the polymer composition, for example the The present disclosure relates generally to fluorescent bitterant aversive component. tracer compositions and to water-soluble polymer composi The disclosed compositions and methods address the tions containing fluorescent compounds for tracing one or issues noted above for detection and quantitation of one or more components therein. More particularly, the disclosure 10 more components (e.g., a bitterant) in a water-soluble poly relates to fluorescent tracer compositions including a fluoro mer composition, e.g. for quality assurance purposes, for phore and a bitterant aversive component to be incorporated example when Such components are not measurable using into a water-soluble polymer composition Such as a water standard analytical tools. The disclosed compositions and soluble film. methods solve this problem by incorporating a fluorophore as 15 a tracer for the material to be detected or quantitated. The BACKGROUND fluorophore is incorporated at a level that can be detected and/or measured accurately and easily by various optical Water-soluble polymeric compositions such as films methods (e.g., visual observation by a human, or spectropho include a variety of components such as water-soluble poly tometric determination). When the fluorophore and the traced mers (e.g., polyvinyl alcohol (PVOH)), plasticizers, and vari material are incorporated at a known ratio, quantitative detec ous other additives. Such compositions are commonly used as tion and measurement of the fluorophore can be correlated to packaging materials to simplify dispersing, pouring, dissolv quantitative detection and measurement the traced material. ing and dosing of a material to be delivered. For example, Unsuccessful past attempts by the present inventors packets made from water-soluble film are commonly used to included the incorporation of various ultraviolet (UV) package household care compositions, e.g., as a pouch con 25 absorbers into a PVOH solution as a tracer for a target mate taining a laundry or dish detergent. A consumer can directly rial. It was thought that the UV absorptivity of the PVOH add the pouch to a mixing vessel. Such as a bucket, sink or solution could be measured by a UV-Vis spectrometer to washing machine. Advantageously, this provides for accurate detect the target materials. The method proved to be unsuc dosing while eliminating the need for the consumer to mea cessful, however, as the PVOH solution itself was absorptive Sure the composition. The pouch may also reduce mess that 30 to UV light, and the necessary levels of incorporation of the would be associated with dispensing a similar composition tracer UV absorber were too high to be practical. Addition from a vessel, such as pouring a liquid laundry detergent from ally, the sensitivity to changes in tracer UV absorber concen a bottle. The pouch also insulates the composition therein tration was too low, requiring concentration changes of from contact with the users hands. In Sum, Soluble polymeric greater than 10% to be measurable. This in turn led to the film packets containing pre-measured agents provide for con 35 inability of reliably measuring changes in target material Venience of consumer use in a variety of applications. concentration of less than 10%, which is not precise enough It can be difficult to qualitatively detect or quantitatively for Some applications. measure various components of water-soluble polymeric Other attempts by present inventors for the particular appli compositions, in particular after formed into a solid material cation of tracing a denatonium bitterant in a water-soluble Such as a film. Such compositions can be difficult to analyze 40 polymer composition included the use of water-soluble fluo using analytical tools such as HPLC (high-pressure liquid rophore tracers within the film formulations.