2012 Flex Pack Conference Predicting Barrier Performance for a COC Enhanced As-Extruded Hand- Sanitizer Barrier Film

2012 Flex Pack Conference Hand Sanitizer Refill Application Typical Application – A one liter flexible pouch containing a mixture of water and alcohol with gel and fragrance additives. Commonly utilized films – OPP or OPET films laminated with aluminum foil for barrier or metalized to meet barrier requirements Disadvantages of existing films - Multi step processes of lamination or metalization add complexity and cost - Basic film extruders cannot produce a suitable as extruded product - Opaque packages do not highlight clear gel contents. Limitations of as-extruded films - Conventional polyolefin films have insufficient water and alcohol barrier - Common high barrier polymers such as EVOH are poor barriers for polar materials - Good polar barrier polymers such as PCTFE are expensive and halogenated. - EVOH, nylons, PCTFE require a tie-layer for use with polyolefins

2012 Flex Pack Conference Cyclic Olefin Copolymer (COC) - Barrier Properties Water Vapor Barrier [g·mil/100 in 2 ·atm·d] 38C/90% EVOH Cellulose Acetate TOPAS ® COC PCL PA 6 Starch PS PC Cellulose PAN PET PVC hard PVC plasticized LCP PVdC PEN BOPP HDPE PP LDPE EVA12 Oxygen Barrier [cm 3 ·mil/100 in2·atm·d] 23C/50% PCTFE MXD Sources: Permeability Properties of Plastics and Elastomers, Massey, 2 nd Edition; various datasheets; internal data

2012 Flex Pack Conference TOPAS ® COC - Synthesis and Structure Readily available raw materials Highly efficient catalyst  Low usage  Catalyst removed as part of process  High purity product Amorphous Crystal clear CH 2 H2CH2C + H2CH2C Metallocene Catalysis + Ethylene Cyclopentadiene Norbornene (C 5 H 6 ) ( )( ) mn TOPAS COC Ethylene

2012 Flex Pack Conference COC - Basic Properties Glass Clear, Transparent Sterilizable via Steam, EtO, gamma, beta (E-beam) Resistant to Alcohols, Acids, Bases, Polar Solvents High Purity, Low Extractables Low Water Transmission Rate (WVTR) Biocompatible Halogen-free Glass transition temperatures, °C(°F) (154 – 356) Modulus of elasticity, N/mm 2 (kpsi) 2300 – 3200 (330 – 460) Tensile strength, N/mm 2 (kpsi) 63 (9.1) Density, g/cm Water uptake, % < 0.01 WVTR, g-mil/100 in 2 × day (38°C/90%RH) 0.24 – 0.40

2012 Flex Pack Conference COC/PE Blends Isopropyl Alcohol Barrier COC / LLDPE blends have significantly reduced IPA permeability as compared to pure LLDPE*. * MOCON Test Labs

2012 Flex Pack Conference Barrier Performance Calculation Input Data Package dimensions – One liter (33.8 fluid oz.) volume, 0.1 m 2 (156 in 2 ) Contents – 75% isopropyl alcohol (IPA), 24% water, 1% additives Barrier requirements - <0.3% weight loss in 8 weeks at 23 o C (73 o F) = 3g Film structure – 100µ total LLDPE/ COC / LLDPE film COC barrier* Water – 1.08 g.25µ/m 2.day (0.07 g.mil/100 in 2.day) IPA – 0.56 g.25µ/m 2.day (0.036 g.mil/100 in 2.day) m-LLDPE barrier* Water – 3.20 g.25µ/m 2.day (0.21 g.mil/100 in 2.day) IPA – 11.5 g.25µ/m 2.day (0.74 g.mil/100 in 2.day) * 23 o C and saturation

2012 Flex Pack Conference X1X1 X2X2 X3X3 P1P1 P2P2 P3P3 P Total Permeability X T X 1 X 2 X 3 P T P 1 P 2 P 3 =++ XTXT X 1 X 2 X 3 P 1 P 2 P 3 ++ PTPT = Permeability is modeled as a resistance in series Permeability Modeling

2012 Flex Pack Conference Performance criteria of <3 gram weight loss can be met with a 25 micron (1-mil) COC barrier layer in a 100 micron (4-mil) extruded film. Model Calculations

2012 Flex Pack Conference Topas COC barrier exhibits the normal linear relationship when log transmission is plotted against the reciprocal of absolute temperature (Arrhenius relationship). Transmission increases linearly as humidity increases. Barrier of TOPAS ® 8007 COC 38 o C23 o C20 o C16 o C12 o C8oC8oC4oC4oC Data generated by Pauly Permeation Laboratory 70 o C Alcohol Effect of Test Temperature

2012 Flex Pack Conference Other factors to be aware of Polymer density (crystallinity) – Within the polyethylene family barrier will increase as density increases. Polymer/ Penetrant interactions – Presence of solvents that can dissolve or swell the polymer will greatly decrease barrier. This is especially critical for amorphous polymers but semicrystalline materials are also affected such as EVOH with water. Glass Transition Temperature (Tg) – Going above the Tg (from glassy to rubbery state) of a polymer will significantly decrease barrier. Pressure/Humidity Differential – It is the differential pressure or in the case of water the humidity that is driving the transport across the polymer film.

2012 Flex Pack Conference TOPAS ® COC – Gas & Aroma Barrier

2012 Flex Pack Conference TOPAS ® COC - Organoleptic Data TOPAS ® COC… Results: TOPAS outperforms LLDPE in outgas and extractables very low oligomer outgas with TOPAS 8007F-04 Study by Rutgers University, Center for Advanced Food Technology Extractables (10%ethanol in H2O, 60°C, 24h) Outgas (80°C, 30min.)

2012 Flex Pack Conference TOPAS COC meets all major regulatory requirements for food contact and medical use TOPAS ® COC – Food & Medical Approval USA FDA regulation 21 CFR § “Olefin polymers” (3.9) FDA Food Contact Notification (FCN #75) became effective August 22, 2000, covers films, sheets and articles made there from FDA Food Contact Notification (FCN #405) became effective May 20, 2004, expands #75 to cover all applications including bottles (See ) FDA Drug Master File -- DMF #12132 FDA Device Master File -- MAF #1043 Europe The monomers are listed in EU Directive 2002/72/EG (Plastics Directive) Norbornene has a Specific Migration Limit (SML) of 0.05 mg/kg