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

2012 Flex Pack Conference

Predicting Barrier Performance for a COC Enhanced As-Extruded Hand-

Sanitizer Barrier Film


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


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


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


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


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


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


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


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


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


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.


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


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.)


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

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

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