Non-Migrating Polymeric Slip Additive In LDPE Films
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Cyclic-Olefinic Copolymers as Non-Migrating Polymeric Slip Additives
in LDPE Cast Films
Author: David R. ConstantSpeaker: Randy D. Jester
TAPPI/ANTEC Exchange 2002
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Abstract
Cyclic-Olefinic Copolymers (COC) use is growing in flexible packaging films
Attributes include easy processing, stiffness, heat resistance, moisture barrier and clarity
Can be used as a non-migratory slip and antiblock additive in polyolefins, depending on:
the matrix LDPE density
type and blend level of COC
process conditions
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Overview
Blends of COC in LDPE can reduce C.O.F. to 0.2 - 0.4
Low C.O.F. can be achieved with as little as 5 -10%COC
Key factors contributing to low C.O.F. include:
Tg of the COC
“Low” process melt temperature
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BackgroundConventional slip additives are an integral part of the packaging films industry
Conventional slip additives function by “blooming” to film surfaces, occasionally causing product consistency “issues”
Non-migrating slip additives have seen limited success for many years
COC’s provide an alternative, organic,ethylene based, polymeric choice
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COCs are produced by combining ethylene, norbornene
and metallocene catalysts
C H 2C H 2
Tg range: 70 - 170CRefractive index: ~ 1.53
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ExperimentalMaterials: MI Density Tg°C
Dow 4012 LDPE 12 0.918 -127
Equistar NA 952 2 0.918 -127
Equistar NA 324 3 0.931 -127
Topas 8007 COC 1.8 1.02 80 (low)
Topas 5013 COC < 1.0 1.02 136 (high)
Extrusion:
25 mm Killion (DS), DSB I barrier type screw, 30: 1 L/D, Maddock Mixing head
T range: 160 - 260°C, Cast rolls: 35°C,film: 51 microns
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Testing Equipment:
for C.O.F. MTS 8016 Tensile testing machine, 200 g sled, 150 mm/min, 23°C, 50% r.h. (ASTM D 1894)
Static and Dynamic Measurements
Microscopy Optical (phase contrast, 625X), Scanning Electron (SEM, 2400X), and Atomic Force (AFM, 700X)
DMA TA Instruments Dynamic Mechanical Analyzer (DMA), model 2980, tension mode on MD film, 3°C/min. temperature sweeps, at 10HZ
Experimental (cont.)
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C.O.F. Baseline
Typical C.O.F. Interpretations for films:High Slip 0.10 - 0.20Medium Slip 0.21 - 0.40Low Slip 0.41 - 0.70Neglible Slip > 0.70
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Fig. 1a C.O.F vs. Tm for 10% 80 Tg and 10% 136 Tg COCs in 12 MI LDPE(1st Column = Static 2nd Column = Dynamic)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
C.O.F.
Note: C.O.F. Values ~ same @ 5% COC
160C 180C 200C 240C 250C 260C
80°C Tg136°C Tg
Process Temperature °C
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0
10
20
30
40
50
60
Fig. 1b % Haze vs. Tmelt for 10 & 5% COC in 12 MI LDPE1st Column = 10 % COC 2nd Column = 5 % COC
160C 180C 200C 240C 250C 260C
80°C Tg136°C Tg
Process Temperature °C
% HAZE
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-128.34°C-3.57°C
77.39°C
26.33°C
-21.75°C
73.20°C
25.36°C
103.62°C
0.1
Tan
Del
ta
0.1
1
10
100
1000
10000
Loss
Mod
ulus
(MP
a)
0.1
1
10
100
1000
10000
Sto
rage
Mod
ulus
(MP
a)
-130 -80 -30 20 70 120
Temperature (°C)
Sample: T0839; 90%LDPE4012+10%8007Size: 15.3730 x 10.0000 x 0.0500 mmMethod: Topas-Blend-TempSweComment: 90%LDPE Dow4012+10%Topas8007;3°C/min,1Hz,60microns
DMAFile: C:...\T0839A_DMA.001Operator: Dr. A. Romo-UribeRun Date: 18-Oct-01 11:00
Universal V2.5H TA Instruments
Fig. 2 DMA Data: LDPE, 80°C Tg COC and LDPE + 10% 80°C Tg COC( γ, β, α and α’ Transitions)
36.39°C
1.39°C
102.96°C
-20.42°C
-127.03°C
39.12°C
-127.36°C
0.1
Tan
Del
ta
0.1
1
10
100
1000
10000
Loss
Mod
ulus
(MP
a)
0.1
1
10
100
1000
10000
Sto
rage
Mod
ulus
(MP
a)
-130 -80 -30 20 70 120
Temperature (°C)
Sample: T0844-Dow4012 LDPE film, 2 milSize: 16.8980 x 10.0000 x 0.0520 mmMethod: Topas-Blend-TempSweComment: Dow 4012 LDPE (2 mil); 3°C/min, 10Hz, 50microns
DMAFile: C:...\T0844A_DMA.001Operator: Dr. A. Romo-UribeRun Date: 23-Oct-01 12:56
Universal V2.5H TA Instruments
92.39°C
26.23°C
-125.72°C
-125.72°C
26.96°C
78.03°C
0.1
1
Tan
Del
ta
1
10
100
1000
10000
Loss
Mod
ulus
(MP
a)
1
10
100
1000
10000
Sto
rage
Mod
ulus
(MP
a)
-130 -80 -30 20 70 120
Temperature (°C)
Sample: T746;Topas COC 8007 2.8mil filmSize: 21.6210 x 12.0000 x 0.1200 mmMethod: Topas-Blend-TempSweComment: Topas 8007;TSwe@3°C/min,-130 to 100°C;10 Hz
DMAFile: F:...\T0746_DMA.001Operator: Dr. A. Romo-UribeRun Date: 30-Mar-01 17:05
Universal V2.5H TA Instruments
LDPELDPE + COC
COC
92°C
77°C
Note: α transitions in tan δ curve show “some” degree of miscibility.
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Fig.3 Phase Contrast Optical Microscopy: 80% 12 MI LDPE + 20% 80°C Tg COC,
51 µm cross section, 625X
200C
160C
180C
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Fig.4 SEM, 80% 12 MI LDPE + 20% 80°C Tg COC, 51 µm, cross section, 2400X
160C 180C
200C
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Fig. 5 AFM : 80% 12 MI LDPE + 20% 80°C Tg COC, 80 µm measured surface area, ( 700X )
160C 180C
200C
High Surface Roughness = Low C.O.F.
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3.5
1.1
5.2
3.8
1.4
0.8
2.5
1.3
0.0
1.0
2.0
3.0
4.0
5.0
6.0
COF Value .
0.9310.918
Fig. 6 Effect of LDPE density on C.O.F.( 2-3 MI LDPE / 80°C COC Blends )
1st Column = Static 2nd Column = DynamicTm = 260°C
COC Blend Level ( % )
10% 20%20% 10%
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Fig. 7 Effect of 80°C Tg COC Blend level on COF in LDPE1st Column = Static 2nd Column = Dynamic
0.74
0.42
0.290.20
0.58
0.440.34
7.5 7.5
0.25
0
0.2
0.4
0.6
0.8
1
1.2
1.4
COF value
10 % 20 % 40 % 60 % 80 %
Tm = 240°CLDPE δ = 0.918LDPE MI = 2
COC Blend Level ( % )
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Conclusions and Recommendations
COC can reduce C.O.F. to commercially acceptable levels of 0.2 - 0.4 in cast LDPE filmsTg and Processing Conditions are Critical
Tm for blends with 80°C Tg COC: 160 - 180C ( ~320 - 350F)Tm for blends with 136°C Tg COC: 240C ( ~465F)
Blend Level and Density of the LDPE matrix are FactorsClarity
Haze expectation: up to 50%Contact Clarity: Good
Other Expectations:Printability, like LLDPESealing, dependent on Tg and level of the COC used
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1
AcknowledgementsI would like to thank the following people for their
contributions to this paper:Dr. Rong Chen
Dr. Angel Romo-Uribe
Darrin Behrens
Robert Roschen
Rick Vliet
Betsy Kelly
Kathy Fitzgibbon
Betty Fernekess
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Back-ups
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Fig. 8 C.O.F. of 90%LLDPE / 10% 136°C COC in Cast Film vs. Process Temperature
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
LLD/COC blend & Process Temperature
C.O.F.
static dynamic
160°C 180°C 200°C
LLDPE: 1 MI, .920
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Fig. 9 %Haze of 90%LLDPE / 10% 136°C COC in Cast Film vs. Process Temperature
0
10
20
30
40
50
60
70
80
90
LLD/COC blend & Process Temperature
% Haze
160°C 180°C 200°C
LLDPE: 1 MI, .920
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Fig. 10 136°C Tg COC
79.17°C
27.33°C
164.00°C
-127.06°C
150.08°C
0.1
1
Tan
Del
ta
0.1
1
10
100
1000
10000
Loss
Mod
ulus
(MP
a)
0.1
1
10
100
1000
10000
Sto
rage
Mod
ulus
(MP
a)
-140 -100 -60 -20 20 60 100 140 180
Temperature (°C)
Sample: 38970-03-6;Topas5013,-140-200°CSize: 16.4290 x 12.2000 x 0.5700 mmMethod: Topas5013-TempSweComment: 100% Topas 5013.50rpm;3°C/min,1Hz,10microns
DMAFile: C:...\T0831A_DMA.001Operator: Dr. A. Romo-UribeRun Date: 16-Oct-01 12:03
Universal V2.5H TA Instruments
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Fig 11 12 MI LDPE + 10% 136°C Tg COC
tan (delta)
10HzE'
E"
77.48°C
-113.77°C
-5.96°C
11.60°C
49.94°C
-14.09°C
50.00°C
0.1
1
Tan
Del
ta
0.1
1
10
100
1000
10000
Loss
Mod
ulus
(MP
a)
0.1
1
10
100
1000
10000
Sto
rage
Mod
ulus
(MP
a)
-150 -100 -50 0 50 100 150
Temperature (°C)
Sample: T0976C Topas 501-K11-2Size: 14.6500 x 13.2000 x 0.1300 mmMethod: Topas-Blend-TempSweComment: 90% LDPE + 10% Topas 5013 film
DMAFile: D:...\T0976C_DMA_Film.001Operator: T. DeStioRun Date: 18-Apr-02 15:18
Universal V2.5H TA Instruments