1. Improved Properties and Cost Efficiencies of
Cyclic Olefin Copolymer Enhanced
Forming Films
Paul D. Tatarka
SPE Annual Technical Conference
May 7, 2007
TOPAS Advanced Polymers
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2. What Are Cyclic Olefin Copolymers (COC)?
The cyclic olefin copolymer (COC) molecule is a
linear 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
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3. What Are COC Properties & Attributes?
Glass transition temperatures, °C(°F) Glass Clear, Transparent
70 - 180 (154 – 356)
Sterilizable via Steam, EtO,
Modulus of elasticity, N/mm2 (kpsi) gamma, beta (E-beam)
2600 – 3200 (380 – 460)
Resistant to Alcohols,
Tensile strength, N/mm2 (kpsi) Acids, Bases, Polar
66 (10) Solvents
Density, g/cm3
High Purity, Low
1.02 Extractables
Water uptake, %
Low Water Transmission
< 0.01 Rate
(WVTR)
WVTR, g × mm/m2 (mil/100 in2) × day
0.02 - 0.04 (0.05 – 0.10) Biocompatible
Halogen-free
TOPAS Advanced Polymers
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4. Outline
Why Use COC in Forming Films?
Thermoforming Properties:
Gauge Distribution
Crush Resistance
Volume Retention (“Snapback”)
Corner Puncture
Comparative (Spider Charts)
Nylon
Polyolefin
Ionomer
Benefits & Conclusions
TOPAS Advanced Polymers
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5. Why Use COC in Thermoforming?
Improve many physical properties
Impart new functionality, such as barrier & heat
resistance; and capability, such as deep draw
Improve thermoformability
Improve package performance & durability
Enable downgauging to satisfy source reduction
initiatives
Reduce cost of forming film
TOPAS Advanced Polymers
A member of Daicel/Polyplastics Group

6. Thermoforming Properties:
Gauge Distribution
TOPAS Advanced Polymers
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7. Thermoforming Methodology
Macron Thermoformer
Modified Blister Packaging Machine
Pressure, Not Vacuum Forming
Heated Plug Assist (60oC; Slow Speed ~1.0 sec)
Forming Tool
Dimension: 2.5 x 4.0 Inches
1-Inch Depth of Draw
Areal Draw Ratio (Ra): 1.87:1
0.5-inch Corner Radii
Thermoforming Experimental Design Matrix (Forming Window)
Temperature: Low, Medium & High
Cycle Time: 10, 14 & 18 cycles per minute
Forming Pressure: 10, 20 & 30 psi
13 Conditions Evaluated Per Film Structure
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8. Macron Thermoforming Machine
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9. Forming Temperature
Optimal
Forming Forming
TOPAS® Temperature Temperature Gauge
Film Description COC (%) Range (oC) (oC) (mil)
o-LLDPE + 15% 8007F-100 (1,C) 15 90, 95, 100 95 6.0
h-m-LLDPE + LDPE + 12% 9506 + 3% 6013 (1,C) 15 95, 100, 105 100 4.7
o-LLDPE + 20% 8007F-100 (1,C) 20 100, 105, 110 105 6.0
m-h-LLDPE + LDPE + 9506 Discrete (7,B) 24 85, 90, 95, 100 90 4.7
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 90, 95, 100, 105 95 6.0
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 90, 95, 100 90 4.0
o-LLDPE + 30% 8007F-100 (1,C) 30 100, 105, 110 105 6.0
b-LLDPE/ 8007F-100 /EVA/8007F-100/b-LLDPE (5,C) 30 85, 95, 100, 105 105 6.0
b-LLDPE + 30% 8007F-100 (1,C) 30 95, 100, 105 100 6.0
LDPE/Ionomer/LDPE (3,C) 0 80, 85, 90, 95 90 6.0
LDPE/Ionomer/LDPE (3,C) 0 80, 85, 90, 100 85 12.0
rPP/LLDPE+LDPE/rPP (5,C) 0 90, 100, 110 110 6.0
PE/tie/PA/tie/PE (5,B) 0 85, 90, 95, 100 90 5.9
Forming Temperatures Are Similar For COC & Non-COC Films
Forming Temperatures Depend On Tg Of COC, Gauge & Other Polymers
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10. Thermoforming: Gauge Distribution
Measure Formed Cavity Gauge with Magna-Mike
6 Points (4 Wall & 2 Bottom) Machine Direction
6 Points (4 Wall & 2 Bottom) Transverse Direction
5 Cavities Per Forming Condition
60 Measured Points
Coefficient of Variation (CV)
Statistic Used to Quantify Gauge Distribution
Ratio of Standard Deviation & Mean
Describes Percentage of Gauge Variation in the Part
“Optimal” CV
Identified by the Forming Conditions Yielding Lowest CV
Design Matrix or Forming Window CV
Average CV from ALL Forming Conditions
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11. Measurement Locations in MD and TD
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12. Gauge Variation: Film Structure & Cost
Optimal Forming CV Material
TOPAS® Forming Matrix CV Difference Cost Gauge
Film Description COC (%) CV (%) (%) (%) ($/MSI) (mil)
o-LLDPE + 15% 8007F-100 (1,C) 15 19.5 22.1 2.6 $0.206 6.0
h-m-LLDPE + LDPE + 12% 9506 + 3% 6013 (1,C) 15 13.5 16.2 2.7 $0.170 4.7
o-LLDPE + 20% 8007F-100 (1,C) 20 17.7 21.5 3.8 $0.217 6.0
m-h-LLDPE + LDPE + 9506 Discrete (7,B) 24 20.5 23.2 2.7 $0.190 4.7
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 26.1 28.5 2.4 $0.245 6.0
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 24.6 26.4 1.8 $0.163 4.0
o-LLDPE + 30% 8007F-100 (1,C) 30 15.8 16.8 1.0 $0.238 6.0
b-LLDPE/ 8007F-100 /EVA/8007F-100/b-LLDPE (5,C) 30 16.9 17.2 0.3 $0.215 6.0
b-LLDPE + 30% 8007F-100 (1,C) 30 13.4 15.6 2.2 $0.218 6.0
LDPE/Ionomer/LDPE (3,C) 0 8.3 13.7 5.4 $0.232 6.0
LDPE/Ionomer/LDPE (3,C) 0 10.2 13.9 3.7 $0.464 12.0
rPP/LLDPE+LDPE/rPP (5,C) 0 36.9 45.0 8.1 $0.172 6.0
PE/tie/PA/tie/PE (5,B) 0 17.8 22.7 4.9 $0.243 5.9
Gauge Variation Narrows Considerably Between The Best And All Other Forming
Conditions For Most COC Films, Suggesting COC Provides Robust Forming Window
Both COC And Ionomer Forming Films Have Low Gauge Variation
Excellent Forming Is Maintained After Downgauging
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13. Thermoforming Properties:
Volume Retention (“Snapback”)
TOPAS Advanced Polymers
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14. Cavity Support Tool: Volume Retention
Adjustable Bottom Support Can Accommodate Multiple Cavity Depths
Fill the Secured Cavity with Water and Measure Its Volume
TOPAS Advanced Polymers
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15. Volume Retention of Formed Cavities
Octene LLDPE + 8007F-04 Octene LLDPE + 8007F-100
Butene LLDPE + 8007F-100 LDPE/Ionomer/LDPE Reference
102
Volume Retention (%)
100
98
96
94
.
92
90
88
86
0 10 15 20 30 Reference
Weight Percent COC
Addition of 15% or More COC Significantly Improves
Dimensional Stability And Almost Eliminates Cavity Shrinkage
TOPAS Advanced Polymers
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16. Formed Cavities: COC & Octene LLDPE
0 10 15 20 30 % COC
Incremental Addition of COC Clearly Shows the Progressive
Improvement in Cavity Appearance
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17. Retained Volume: Film Structure & Cost
Retained Material
TOPAS® Volume Cost Gauge
Film Description COC (%) (%) ($/MSI) (mil)
o-LLDPE + 15% 8007F-100 (1,C) 15 96.7 $0.206 6.0
h-m-LLDPE + LDPE + 12% 9506 + 3% 6013 (1,C) 15 91.8 $0.170 4.7
o-LLDPE + 20% 8007F-100 (1,C) 20 100.0 $0.217 6.0
m-h-LLDPE + LDPE + 9506 Discrete (7,B) 24 89.4 $0.190 4.7
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 86.8 $0.245 6.0
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 89.9 $0.163 4.0
o-LLDPE + 30% 8007F-100 (1,C) 30 98.2 $0.238 6.0
b-LLDPE/ 8007F-100 /EVA/8007F-100/b-LLDPE (5,C) 30 94.8 $0.215 6.0
b-LLDPE + 30% 8007F-100 (1,C) 30 98.0 $0.218 6.0
LDPE/Ionomer/LDPE (3,C) 0 93.9 $0.232 6.0
LDPE/Ionomer/LDPE (3,C) 0 88.7 $0.464 12.0
rPP/LLDPE+LDPE/rPP (5,C) 0 91.5 $0.172 6.0
PE/tie/PA/tie/PE (5,B) 0 91.3 $0.243 5.9
COC-LLDPE Films Exhibit Almost No Shrinkage Or Snap-Back
Downgauging Does Not Compromise Retained Volume
Retained Volume May Be Reduced By LDPE
TOPAS Advanced Polymers
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18. Thermoforming Properties:
Crush Resistance
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19. Crush Resistance Testing Method
Formed cavities are crushed in between two parallel plates
TOPAS Advanced Polymers
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20. Crush Resistance of Formed Cavities:
Displacement (mm) at 1.9 lbf
Octene LLDPE + 8007F-04 Octene LLDPE + 8007F-100
Butene LLDPE + 8007F-100 LDPE/Ionomer/LDPE Reference
30.00
.
25.00
Displacement (mm)
20.00
15.00
10.00
5.00
0.00
0 10 15 20 30 Reference
Weight Percent COC
COC Addition Increases Crush Resistance By Reducing The Amount
Of Cavity Deflection Required to Reach 1.9 lbf Load
TOPAS Advanced Polymers
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21. Crush Resistance: Film Structure & Cost
Crush
Resistance Material
®
TOPAS (Deflection) @ Cost Gauge
Film Description COC (%) 1.9 lbf mm ($/MSI) (mil)
o-LLDPE + 15% 8007F-100 (1,C) 15 23.2 $0.206 6.0
h-m-LLDPE + LDPE + 12% 9506 + 3% 6013 (1,C) 15 26.8 $0.170 4.7
o-LLDPE + 20% 8007F-100 (1,C) 20 19.5 $0.217 6.0
m-h-LLDPE + LDPE + 9506 Discrete (7,B) 24 24.7 $0.190 4.7
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 13.8 $0.245 6.0
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 27.5 $0.163 4.0
o-LLDPE + 30% 8007F-100 (1,C) 30 15.6 $0.238 6.0
b-LLDPE/ 8007F-100 /EVA/8007F-100/b-LLDPE (5,C) 30 21.6 $0.215 6.0
b-LLDPE + 30% 8007F-100 (1,C) 30 11.8 $0.218 6.0
LDPE/Ionomer/LDPE (3,C) 0 24.6 $0.232 6.0
LDPE/Ionomer/LDPE (3,C) 0 11.8 $0.464 12.0
rPP/LLDPE+LDPE/rPP (5,C) 0 24.3 $0.172 6.0
PE/tie/PA/tie/PE (5,B) 0 21.7 $0.243 5.9
COC Improves Crush Resistance of Formed Trays
Downgauged COC Films Match Peformance of Non-COC Films
Downgauged COC Films Offers Similar Protection, But At Less Cost
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22. Thermoforming Properties:
Corner Puncture Resistance
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23. Cavity Puncture Tool: Bottom & Corner
Flexible Tool Configuration Enables Accurate
Measurement of Puncture Resistance of Formed Cavities
TOPAS Advanced Polymers
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24. Corner Puncture: Film Structure & Cost
Formed Corner Formed
Corner Puncture Material Corner
TOPAS® Puncture Retention Cost Gauge Gauge
Film Description COC (%) (lb) (%) ($/MSI) (mil) (mil)
o-LLDPE + 15% 8007F-100 (1,C) 15 5.7 82.9 $0.206 2.0 6.0
h-m-LLDPE + LDPE + 12% 9506 + 3% 6013 (1,C) 15 6.2 69.7 $0.170 1.1 4.7
o-LLDPE + 20% 8007F-100 (1,C) 20 6.2 79.0 $0.217 2.0 6.0
m-h-LLDPE + LDPE + 9506 Discrete (7,B) 24 6.1 77.1 $0.190 1.4 4.7
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 8.2 78.8 $0.245 3.1 6.0
m-h-LLDPE + LDPE + 9506/5013 Discrete (7,B) 25 6.7 94.4 $0.163 2.3 4.0
o-LLDPE + 30% 8007F-100 (1,C) 30 8.5 96.4 $0.238 2.0 6.0
b-LLDPE/ 8007F-100 /EVA/8007F-100/b-LLDPE (5,C) 30 5.9 64.0 $0.215 1.6 6.0
b-LLDPE + 30% 8007F-100 (1,C) 30 8.3 95.3 $0.218 1.8 6.0
LDPE/Ionomer/LDPE (3,C) 0 8.3 81.6 $0.232 1.8 6.0
LDPE/Ionomer/LDPE (3,C) 0 10.2 57.5 $0.464 4.0 12.0
rPP/LLDPE+LDPE/rPP (5,C) 0 5.0 56.0 $0.172 1.2 6.0
PE/tie/PA/tie/PE (5,B) 0 10.2 81.0 $0.243 1.5 5.9
Corner Puncture And Retention Improve With Addition Of COC
Films With 25 to 30 Percent COC Are As Puncture Resistant As Ionomeric Film
COC Films Can Be Downgauged Without Sacrificing Puncture Resistance
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25. Comparatives & Conclusions
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26. Monolayer COC vs. 5-Layer Nylon
5.9-mil PE/Tie/PA/Tie/PE 6-mil o-LLDPE w/30% 8007F-100
(=) Cost ($/MSI)
120
(-) Formed Corner Puncture (lb) (=) Gauge (mil)
100
80
(-) Formed Cavity Puncture (lb) 60 (=) Haze (%)
40
20
(+) Formed Cavity Gauge Variation (%) 0 (-) Gloss (60 Degree)
(-) Retained Volume (%) (-) MD Modulus (ksi)
(-) TD Tensile Strength (ksi) (-) TD Modulus (ksi)
(-) MD Tensile Strength (ksi)
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27. Monolayer COC vs. 5-Layer Polyolefin
6-mil PP/LLDPE+LDPE/PP 4.7 mil h-LLDPE w/15% 9506 & 6013
(=) Cost ($/MSI)
160
(+) Formed Corner Puncture (lb) 140 (+) Gauge (mil)
120
100
(=) Formed Cavity Puncture (lb) 80 (+) Haze (%)
60
40
20
(+) Formed Cavity Gauge Variation (%) 0 (+) Gloss (60 Degree)
(=) Retained Volume (%) (+) MD Modulus (ksi)
(+) TD Tensile Strength (ksi) (+) TD Modulus (ksi)
(-) MD Tensile Strength (ksi)
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28. 5-Layer COC vs 3-Layer Ionomer
12-mil LDPE/Ionomer/LDPE 6-mil b-LLDPE/COC/EVA/COC/b-LLDPE
(+) Cost ($/MSI)
350
(-) Formed Corner Puncture (lb) (+) Gauge (mil)
300
250
200
(-) Formed Cavity Puncture (lb) (+) Haze (%)
150
100
50
(-) Formed Cavity Gauge Variation (%) 0 (+) Gloss (60 Degree)
(-) Retained Volume (%) (+) MD Modulus (ksi)
(=) TD Tensile Strength (ksi) (+) TD Modulus (ksi)
(=) MD Tensile Strength (ksi)
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29. COC Benefits For Forming Films
Improve Thermoformability & Enhance Package
Integrity with Less Gauge Variation & Good
Dimensional Stability
Enable Downgauging to Reduce Material Cost
Improve Most Physical Properties, Including Stiffness,
Strength, Impact Resistance & Optics
Design Recommendations:
LLDPE – No Restrictions
LDPE – Minimize in LLDPE-COC Blends
Any questions?
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30. Acknowledgments
Thermoforming Team:
Adam Barton, Wolfram Goerlitz, Randy Jester,
Tim Kneale, Bernd Sparenberg
U. of Cincinnati Co-Op Students:
John Guzowski, Elizabeth Jeffries, Shery Kern,
Angela Martin, Amy Riesenberg
TOPAS® Cyclic Olefin Copolymer (COC)
Your Clear Advantage questions?
Any in Thermoforming.
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