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High Aroma Barrier Films For Food Packaging
1. 2005 PLACE
Conference September
27-29 Las Vegas,
Nevada
Topas® Cyclic Olefin Copolymers in Food
Packaging – High Aroma Barrier
Combined with Low Extractables
Presented by:
Randy Jester
Associate Engineer
Ticona LLC
2. COC - A New Family of Thermoplastic Materials
Olefinic Resin
Amorphous, Clear and
Colorless
High Purity
High Moisture Barrier
Good Chemical Resistance
Easy to Process
2
3. Ticona’s COC Production Plant in Oberhausen, Germany
Production plant on stream
since Oct 2000
30 000 tons / year production capacity
Backward integrated in Norbornene
Largest Cyclic Olefin Copolymer (COC)
plant in the world
Large scale production of COC enables the production of a
cost competitive product for use in packaging applications
3
4. COC - Synthesis and Structure
H2 C CH2 +
Readily available raw
Ethylene Cyclopentadiene Norbornene materials
Highly efficient catalyst
+ H2 C CH2
Low usage
Metallocene Catalyst removed as part
Catalysis
of process
( )(m
)n
High purity product
Amorphous
Crystal clear
COC
4
5. COC is amorphous
The COC molecule is a chain of small CH2-CH2 links
randomly interspersed with large bridged ring elements
It cannot fold up to make a regular structure, i.e., a
crystallite
NB NB NB NB
COC has no crystalline melting point, but only a glass
transition temperature, Tg , at which the polymer goes from
“glassy” to “rubbery” behavior
5
6. COC - Basic Properties
Glass transition temperatures in [°C]
Glass clear, Transparent
70 - 180
Modulus of elasticity in [N/mm2] High UV Transmission
2600 - 3200
Resistant to Alcohols, Acids,
Tensile strength in [N/mm2] Bases, Polar Solvents
66
High Purity, Low Extractables
Density in [g/cm3]
1.02 Low Water Transmission Rate
(WVTR)
Water uptake in [%]
< 0.01 Biocompatible
Water permeability in [g × mm/m2 × day]
0.02 - 0.04 Halogen-free
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7. COC – Regulatory Status
FDA Regulation 21 CFR 177.1520 (3.9)
COC FDA Food Contact Notification (FCN #75) became effective
August 22, 2000, covers films, sheets, and articles made therein from
and molded articles for repeated use.
COC FDA Food Contact Notification (FCN #405) became effective
May 20, 2004, expands #75 to cover all applications, including bottles.
FDA Drug Master File, DMF# 12132, established.
FDA Device Master File, MAF# 1043, established.
The monomers are listed in the EU-Directive 2002/72/EG
Norbornene has a SML = 0.05 mg/kg.
COC meets all major regulatory requirements for food
contact and medical use
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8. COC - Barrier Properties
10000
LDPE EVA/PE PCL
PS
Oxygen Permeability [cm3/m2*d*bar]
1000 HDPE
PVC
BOPP PC
PP plasticized Cellulose Acetate
100
COC PVC hard
PET
10 Starch
PEN PA 6
PAN
1
PVDC Cellulose
0,1 EVOH
Film thickness: 100 µm
LCP
0,01
0,01 0,1 1 10 100 1000 10000
Water Permeability [g/m2*d]
COC can extend the shelf life of products
due to its very high moisture barrier
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9. LLDPE 80% COC / 20% LLDPE
1
0.9
Relative Transmission Rate
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0 Oxygen* Water** d-limonene*** Onion*** Sardine***
* 23C & 50% RH
** 38C & 90% RH
*** 23C, MOCON technique, saturated vapor of “paste”
COC in LLDPE blends can reduce transmission rates by 70 to 90%
for gases/vapors at blend levels as low as 80%. This blend level
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typically achieves >90% of the barrier properties of 100% COC.
10. Scalped d-Limonene
1400.00
1195.08
1200.00 1110.76
Concentration (ng/cm2)
1000.00 Purge & Trap-Thermal
Desorption-GC-M S
Analysis Data
800.00
600.00
400.00
200.00
0.00
100% COC 100% LLDPE
Scalping of d-Limonene by COC is similar to that of LLDPE, indicating
that the solubility of d-Limonene in COC is similar to that of LLDPE
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11. Factors Affecting Permeability
Permeability (normalized transmission) is the product of
diffusivity (kinetic factor) and solubility (thermodynamic factor).
The similar levels of equilibrium scalping indicate that solubility
of d-limonene is similar in LLDPE and COC.
This information indicates that the primary factor affecting the
reduced permeability of COC is diffusivity.
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12. Glassy vs. Rubbery State
The COCs in this study have Tg’s in the 68-80oC range, well
above the measurement conditions. LLDPE on the other hand has
a Tg of –128oC and is in a rubbery state
Polymers in the rubbery state typically have a higher free volume
due to a high level of molecular mobility, which increases
diffusion rates of permeants.
Polyethylene and COC are both non-polar materials and would in
general have similar solubility parameters for most permeants.
It can be generalized that for many permeants, COC will produce
an improved barrier as compared to polyethylene since it will
typically be in the glassy state under use conditions.
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13. 10% ETOH Extractables (major components)
40
35 oligomers (etoh extract)
Concentration (ng / cm )
3
30 Total etoh extractables
25
20
15
10
5
0
100% COC (80C Tg) 100% LLDPE 100% COC (68C Tg)
Elevated temperature (60oC for 24 hours) extraction shows that
COC has significantly lower extractables than LLDPE including
about 50% lower oligomer levels which can produce off tastes in food
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14. Conclusions
COC has better aroma barrier than polyethylene and can reduce aroma/flavor
loss from food when it is utilized as a barrier layer in food packaging.
COC can also reduce the transmission of objectionable odors to surrounding
areas and should have utility in disposable food storage bags.
Low extractables in COC reduces the possibility of generating an “off-taste” in
water or susceptible foods when used as a contact layer or just under a seal layer
in packaging.
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15. I would like to thank the following people at
Ticona for their contributions to this paper:
•Adam Barton
•Robert Roschen
•Rick Vliet
•Arno Wolf
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16. Thank You
PRESENTED BY
Randy Jester
Engineer Associate
Ticona LLC
randy.jester@ticona.com
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