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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
0.01
0.1
1
10
100
1 000
10 000
0.01 0.1 1 10 100 1 000 10 000
Water Vapor Barrier [g·mil/100 in2·atm·d] 38C/90%
EVOH
Cellulose Acetate
TOPAS® COC
PCL
PA 6 Starch
PS
PC
CellulosePAN
PET
PVC hard
PVCplasticized
LCP
PVdC
PEN
BOPPHDPE
PP
LDPE EVA12
Oxy
gen
Bar
rier
[cm
3·m
il/10
0 in
2·at
m·d
] 2
3C/5
0%
PCTFE
MXD
Sources: Permeability Properties of Plastics and Elastomers, Massey, 2nd 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
CH2H2C +
CH2H2C
Metallocene Catalysis
+
Ethylene Cyclopentadiene Norbornene (C5H6)
( ) ( )m n
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)
70 - 180 (154 – 356)
Modulus of elasticity, N/mm2 (kpsi)
2300 – 3200 (330 – 460)
Tensile strength, N/mm2 (kpsi)
63 (9.1)
Density, g/cm3
1.02
Water uptake, %
< 0.01
WVTR, g-mil/100 in2 × 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*.
Isopropyl Alcohol Transmission RateCOC / LLDPE-Blends
23°C / saturated IPA vapor*
0.140.2
1.33
2.88
0
0.5
1
1.5
2
2.5
3
3.5
0 20 40 60 80 100
wt % Topas 8007
g.
10
0 m
icro
n /
(m
² 2
4h
)
* MOCON Test Labs
2012 Flex Pack Conference
Barrier Performance Calculation Input Data
Package dimensions – One liter (33.8 fluid oz.) volume, 0.1 m2 (156 in2)
Contents – 75% isopropyl alcohol (IPA), 24% water, 1% additives
Barrier requirements- <0.3% weight loss in 8 weeks at 23oC (73oF) = 3g
Film structure – 100µ total LLDPE/ COC / LLDPE film
COC barrier* Water – 1.08 g.25µ/m2.day (0.07 g.mil/100 in2.day)IPA – 0.56 g.25µ/m2.day (0.036 g.mil/100 in2.day)
m-LLDPE barrier* Water – 3.20 g.25µ/m2.day (0.21 g.mil/100 in2.day) IPA – 11.5 g.25µ/m2.day (0.74 g.mil/100 in2.day)
* 23oC and saturation
2012 Flex Pack Conference
X1
X2
X3
P1
P2
P3
PTotal
Permeability
XT X1 X2 X3
PT P1 P2 P3
= + +
XT
X1 X2 X3
P1 P2 P3
+ +
PT =
Permeability is modeled as a resistance in series
Permeability Modeling
2012 Flex Pack Conference
Thickness in microns Water Transmission rate IPA Transmission rate Total transmission rate Total package wt. loss***
100 micron (4-mil) Total gram/m2.day* gram/m2.day** gram/m2.day in 8 weeks
LLDPE COC LLDPE grams %50 0 50 0.43 1.32 1.75 98 9.8
43.75 12.5 43.75 0.375 0.386 0.731 41 4.1
37.5 25 37.5 0.29 0.225 0.515 28.9 2.9
31.25 37.5 31.25 0.259 0.16 0.42 23.5 2.4
24 wt % water at a molecular weight of 18 g/mole calculates to 54 mole % water75 wt % IPA at a molecular weight of 66 g/mole calculates to 46 mole % IPA
* water transmission rate times mole fraction of water, 0.54** IPA transmission rate times mole fraction of IPA, 0.46
*** one liter and 0.10 m2 surface area
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
0.001
0.01
0.1
1
10
3.61 3.559 3.509 3.46 3.413 3.378 3.333 3.289 3.247 3.215 3.175 3.13 3.09 3.06 3.02 2.98 2.95 2.91 2.88 2.85 2.82 2.78
1000 / T (kelvin)
25% RH
85% RH
38oC23oC20oC16oC12oC8oC4oC
Data generated by Pauly Permeation Laboratory
70oC
Alcohol
Effect of Test Temperature
2012 Flex Pack Conference
Other factors to be aware ofPolymer 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
SubstanceRelative Barrier
to LDPE, approx.Permeability
23oC, g 0.1mm/m2 day
Moisture Water 3-5 x 0.23Oxygen 8 x 230
Gases Carbon Dioxide 29 x 640Nitrogen 1 x 32Ethanol 35 x 0.13
Polar Isopropyl Alcohol 14 x 0.14Solvents Acetone 0.02**
Acetic Acid 20 x 0.04*Methanol 6 xLimonene 8 x
Aromas Onion 10 xSardine Oil 5 x
TOPAS 8007F-04
* 20% Acetic Acid, μg 100 μm /m2 day
** @ 40oC
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 § 177.1520 “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 http://vm.cfsan.fda.gov/~dms/opa-fcn.html)
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