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Heat Seal Characteristics of
     Cyclic Olefin Copolymer /
       Polyethylene Blends

             Randy D. Jester
         TAPPI 2002 PLACE Conference
            Boston, Massachusetts


1
Topas® COC Manufacturing Plant

                     •   Oberhausen, Germany

                     •   Start-up October 2000

                     •   COC Capacity: 66 MM lbs.

                     •   Backward integrated in Norbornene

                     •   Cost efficient continuous process using
                         metallocene technology




Largest COC and Norbornene Plant in the World
What is COC?

                   catalyst
  + CH2   CH2                       CH2    CH2
                                                 n         m



Feedstocks                    Catalyst : Metallocenes

   Norbornene                    High activity, low residues

   Ethylene                      Narrow MW distribution

                                 Microstructure control



COC properties can be tailored by adjusting the
            Norbornene content
Abstract

• Cyclic Olefin Copolymers (COC) use is
  growing in flexible packaging films
• Attributes include easy processing, stiffness,
  heat resistance, moisture barrier and clarity
• Can be used to modify the heat sealing
  characteristics of polyethylenes:
   – improvements in seal strength
   – improvement of hot-tack strength
   – high temperature seal through capability with
     high Tg grades.
Experimental
• Materials:                     MI      Density Tg°C
   – Dow 2045 LLDPE              4       0.920     -127
   – Equistar NA 952 LDPE         2      0.918     -127
   – Equistar NA 204 LDPE         3      0.931     -127
   – Borealis 7230 LDPE          4.5     0.923     -127
   – Exxon Mobil 3125 Plastomer 1.2      0.91      -121
   – Dow 1140 Plastomer          1.2     0.902     -121
   – Ticona 8007 COC             1.8     1.02        80 (low)
   – Ticona 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
Experimental (cont.)
• Testing Equipment:
   – Tensiles MTS 8016 Tensile testing machine,, 23°C, 50%
     r.h. (ASTM D 882)
   – Microscopy Optical (phase contrast)
   – DMA TA Instruments Dynamic Mechanical Analyzer
     (DMA), model 2980, tension mode on MD film, 3°C/min.
     temperature sweeps, at 10HZ
   – Heat Seal Davinor Inc., J&B Hot Tack Tester
      • Seal Strength Test - Seal Pressure = 0.3034 N/mm (44psi), Seal
        Time = 1 sec., Cool Time = 30 sec., Peel speed = 200 mm/sec,
        sample size = 25.4 mm (1 inch ) wide.
      • Hot-Tack Test - Seal Pressure = 0.3034 N/mm (44psi), Seal Time =
        1 sec., Cool Time = 0.1 sec., Peel speed = 200 mm/sec, sample
        size = 25.4 mm (1 inch ) wide.
      • Seal Initiation Temperature - defined as seal temperature where a
        8.8 Newton seal strength is achieved.
COC allows downgauging of films
                       1.E+05                                                                           1.00

                                         Blend Modulus




                                                                                                               Thickness @ Constant Initial Stiffness(mils)
                                         Film Stiffness @Constant
                                         Thickness
                                         Blend Layer Thickness (mils)




 Blend Modulus (psi)

                       1.E+04




                                  Initial Construction: Plastomer - 0.6 mils
                                                        Dowlex 2032 - 0.8 mils
                                                        Plastomer - 0.6 mils

                       1.E+03                                                                           0.10
                                0.0%   2.5%   5.0%     7.5%    10.0%    12.5%   15.0%   17.5%   20.0%

Reference 2                                        Wt % 80C Tg                  COC


COC                        blends offer potential cost savings
Improved Ultimate Seal Strength with 80ºC Tg COC
                                        blended with LLDPE
                          40
                                                                                                0 % COC
                          35                                                                   15 % COC
Seal Strength (Newtons)




                                                                                               25 % COC
                          30

                          25

                          20

                          15
                                    Dwell Time = 250 ms
                          10        Seal Pressure = 63 psi


                          5                                                                      cast film

                          0
                               70          80        90      100    110    120    130    140   150     160   170
                               Reference 2                         Sealing Temperature (°C)


                                    COC blends produce a wider sealing window
Effect of Blending 80ºC Tg COC with LLDPE
                                            on Hot Tack Force
                           5

                                                                                                0 % COC
                                                                                                15 % COC
Hot Tack Force (Newtons)




                           4                                                                    25 % COC




                           3




                           2


                                     Dwell Time = 250 ms
                           1         Seal Pressure = 63 psi




                           0
                               70          80          90     100    110    120    130    140    150       160   170

                                    Reference 2                     Sealing Temperature (°C)


                                    COC blends produce a wider sealing window
Effect of COC Addition on Seal Strength

                                 60
                                                                      LDPE,            Den.=0.923, MI = 4.5
                                                                      LLDPE            Den.=0.920, MI=4
                                                                      Plastomer        Den.=0.91, MI=3
Seal Strength @ 120C (Newtons)




                                 50




                                 40




                                 30




                                 20




                                 10




                                  0
                                      0   20   40    60    80   100        0      20   40   60    80    100   0   10   15   20   40   60   80   100

                                                    LDPE                               LLDPE                           Plastomer

                                                                % 80ºC Tg COC in Blend
Effect of COC Addition on Hot-Tack
                        16
                                LDPE,            Den.=0.923, MI = 4.5
                                LLDPE            Den.=0.920, MI=4
                                Plastomer        Den.=0.91, MI=3
                        14
Hot Tack Strength @ 120 C
o




                        12



                        10



                            8



                            6



                            4



                            2



                            0
                                0   20      40   60   80   100          0   20   40   60   80   100   0   10   15   20   40   60   80   100


                                         LDPE                                    LLDPE                          Plastomer

                                                       % 80ºC Tg COC in Blend
Effect of 80º C Tg COC Addition on SIT
                                   140

                                                                        LDPE,            Den.=0.923, MI = 4.5
                                                                        LLDPE            Den.=0.920, MI=4
                                                                        Plastomer        Den.=0.91,        MI=3
                                   130
                                                                        Seal Initiation Temperature (SIT) = Temp. where 8.8 Newton seal strength
                                                                        achieved
Seal initiation Temperature (ºC)




                                   120




                                   110




                                   100




                                    90



                                             Seal < 8.8 N


                                    80
                                         0   20   40    60   80   100   0    20     40      60        80     100     0     10    15     20    40   60   80   100


                                             LDPE                                  LLDPE                                    Plastomer
                                                                                   % COC
Seal Strength at 120ºC of LDPE vs. LLDPE
                                   35



                                   30
                                                                      LLDPE to COC - no distortion of COC, LLDPE tore during pull
Ultimate Seal Strength (Newtons)




                                                                      LDPE to COC - no distortion of COC, LDPE peeled off cleanly
                                   25



                                   20



                                   15



                                   10




                                   5



                                   0
                                        LLDPE   60% LLDPE/                   LDPE   60% LDPE/                   LLDPE to   LDPE to
                                                40% COC                             40% COC                       COC       COC
                                                             60% LLDPE/40%                      60% LDPE /
                                                             COC @ 2X seal                      40%COC @ 2X
                                                             pressure                           seal pressure
Phase Contrast Optical Microscopy:
80% 12 MI LDPE + 20% 80°C Tg COC,
     51 µm cross section, 625X




   160C
                                       180C




               200C



 Reference 3
Seal Through Test Results
                                200

                                180
Seal BarTemperature (Celsius)




                                160

                                140

                                120

                                100

                                80                                           Initial Seal Bar
                                                                             Sticking
                                60                                           Seal Bar
                                                                             contamination
                                40
                                      LLDPE - density=0.920, MI=4
                                20
                                      Plastomer, density=0.902, MI=1.2
                                 0
                                      90% 130 Tg    5% 130 Tg   10% 130 Tg    15% 130 Tg    20% 130 Tg   30% 130 Tg   40% 130 Tg
                                      COC / 10%    COC / 95%    COC / 90%     COC / 85%     COC / 80%     COC / 70%   COC / 60%
                                      Plastomer      LLDPE       LLDPE         LLDPE          LLDPE       LLDPE         LLDPE




                                                 High Tg COC as an outer layer blend
                                             component can provide seal through capability
Conclusions
• COC/polyethylene blends can exhibit both improved
  modulus and heat seal performance
• COC is more compatible with LLDPE and Plastomers
  than LDPE
• COC level and matrix polymer affect heat seal
  performance
   – 80º Tg COC generally improves hot tack strength at all
     blend levels for the polyethylene systems studied.
   – 80º Tg COC reduced the seal strength of LDPE at
     concentrations of 20% and up while maintaining or
     improving the seal strength of LLDPE and Plastomer
• 130º Tg COC blended at levels above 20% can provide
  “seal through” capability to polyethylenes
Acknowledgements
    I would like to thank the following people for their
       contributions to this paper:
          • Dr. Rong Chen
          • Dr. Angel Romo-Uribe
          • David Constant
          • Robert Roschen
          • Rick Vliet
          • Betsy Kelly
          • Kathy Fitzgibbon
          • Betty Fernekess
1
References

1. ASTM, Designation: F 1921-98, Standard Test Methods for Hot Seal Strength
   (Hot Tack) of Thermoplastic Polymers and Blends Comprising the Sealing
   Surfaces of Flexible Webs, ASTM Standards 1999

2. R.R. Lamonte, “Stiffer, Thinner, Packaging Films with Improved Sealing
   Using Cyclic Olefin Copolymers”, Flexpac Conference, Amsterdam, Holland,
   November 2000

3. D.R. Constant, “Cyclic-Olefinic Copolymers as Non-Migrating Polymeric Slip
   Additives in LDPE Cast Films”, ANTEC 2002 Conference, San Franscico, CA
Backup Slides
Regulatory Status

  FDA Food Contact Notification (FCN No. 75) became effective August 22,
  2000
  Norbornene is listed by the EU as an approved monomer for use in polymers
  in contact with food.
  USP Class VI
  FDA Drug Master File, DMF# 12132 and Device Master File, MAF # 1043
  established



      COC meets all major regulatory requirements

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Heat Seal Characteristics of COC/PE Blends

  • 1. Heat Seal Characteristics of Cyclic Olefin Copolymer / Polyethylene Blends Randy D. Jester TAPPI 2002 PLACE Conference Boston, Massachusetts 1
  • 2. Topas® COC Manufacturing Plant • Oberhausen, Germany • Start-up October 2000 • COC Capacity: 66 MM lbs. • Backward integrated in Norbornene • Cost efficient continuous process using metallocene technology Largest COC and Norbornene Plant in the World
  • 3. What is COC? catalyst + CH2 CH2 CH2 CH2 n m Feedstocks Catalyst : Metallocenes Norbornene High activity, low residues Ethylene Narrow MW distribution Microstructure control COC properties can be tailored by adjusting the Norbornene content
  • 4. Abstract • Cyclic Olefin Copolymers (COC) use is growing in flexible packaging films • Attributes include easy processing, stiffness, heat resistance, moisture barrier and clarity • Can be used to modify the heat sealing characteristics of polyethylenes: – improvements in seal strength – improvement of hot-tack strength – high temperature seal through capability with high Tg grades.
  • 5. Experimental • Materials: MI Density Tg°C – Dow 2045 LLDPE 4 0.920 -127 – Equistar NA 952 LDPE 2 0.918 -127 – Equistar NA 204 LDPE 3 0.931 -127 – Borealis 7230 LDPE 4.5 0.923 -127 – Exxon Mobil 3125 Plastomer 1.2 0.91 -121 – Dow 1140 Plastomer 1.2 0.902 -121 – Ticona 8007 COC 1.8 1.02 80 (low) – Ticona 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
  • 6. Experimental (cont.) • Testing Equipment: – Tensiles MTS 8016 Tensile testing machine,, 23°C, 50% r.h. (ASTM D 882) – Microscopy Optical (phase contrast) – DMA TA Instruments Dynamic Mechanical Analyzer (DMA), model 2980, tension mode on MD film, 3°C/min. temperature sweeps, at 10HZ – Heat Seal Davinor Inc., J&B Hot Tack Tester • Seal Strength Test - Seal Pressure = 0.3034 N/mm (44psi), Seal Time = 1 sec., Cool Time = 30 sec., Peel speed = 200 mm/sec, sample size = 25.4 mm (1 inch ) wide. • Hot-Tack Test - Seal Pressure = 0.3034 N/mm (44psi), Seal Time = 1 sec., Cool Time = 0.1 sec., Peel speed = 200 mm/sec, sample size = 25.4 mm (1 inch ) wide. • Seal Initiation Temperature - defined as seal temperature where a 8.8 Newton seal strength is achieved.
  • 7. COC allows downgauging of films 1.E+05 1.00 Blend Modulus Thickness @ Constant Initial Stiffness(mils) Film Stiffness @Constant Thickness Blend Layer Thickness (mils) Blend Modulus (psi) 1.E+04 Initial Construction: Plastomer - 0.6 mils Dowlex 2032 - 0.8 mils Plastomer - 0.6 mils 1.E+03 0.10 0.0% 2.5% 5.0% 7.5% 10.0% 12.5% 15.0% 17.5% 20.0% Reference 2 Wt % 80C Tg COC COC blends offer potential cost savings
  • 8. Improved Ultimate Seal Strength with 80ºC Tg COC blended with LLDPE 40 0 % COC 35 15 % COC Seal Strength (Newtons) 25 % COC 30 25 20 15 Dwell Time = 250 ms 10 Seal Pressure = 63 psi 5 cast film 0 70 80 90 100 110 120 130 140 150 160 170 Reference 2 Sealing Temperature (°C) COC blends produce a wider sealing window
  • 9. Effect of Blending 80ºC Tg COC with LLDPE on Hot Tack Force 5 0 % COC 15 % COC Hot Tack Force (Newtons) 4 25 % COC 3 2 Dwell Time = 250 ms 1 Seal Pressure = 63 psi 0 70 80 90 100 110 120 130 140 150 160 170 Reference 2 Sealing Temperature (°C) COC blends produce a wider sealing window
  • 10. Effect of COC Addition on Seal Strength 60 LDPE, Den.=0.923, MI = 4.5 LLDPE Den.=0.920, MI=4 Plastomer Den.=0.91, MI=3 Seal Strength @ 120C (Newtons) 50 40 30 20 10 0 0 20 40 60 80 100 0 20 40 60 80 100 0 10 15 20 40 60 80 100 LDPE LLDPE Plastomer % 80ºC Tg COC in Blend
  • 11. Effect of COC Addition on Hot-Tack 16 LDPE, Den.=0.923, MI = 4.5 LLDPE Den.=0.920, MI=4 Plastomer Den.=0.91, MI=3 14 Hot Tack Strength @ 120 C o 12 10 8 6 4 2 0 0 20 40 60 80 100 0 20 40 60 80 100 0 10 15 20 40 60 80 100 LDPE LLDPE Plastomer % 80ºC Tg COC in Blend
  • 12. Effect of 80º C Tg COC Addition on SIT 140 LDPE, Den.=0.923, MI = 4.5 LLDPE Den.=0.920, MI=4 Plastomer Den.=0.91, MI=3 130 Seal Initiation Temperature (SIT) = Temp. where 8.8 Newton seal strength achieved Seal initiation Temperature (ºC) 120 110 100 90 Seal < 8.8 N 80 0 20 40 60 80 100 0 20 40 60 80 100 0 10 15 20 40 60 80 100 LDPE LLDPE Plastomer % COC
  • 13. Seal Strength at 120ºC of LDPE vs. LLDPE 35 30 LLDPE to COC - no distortion of COC, LLDPE tore during pull Ultimate Seal Strength (Newtons) LDPE to COC - no distortion of COC, LDPE peeled off cleanly 25 20 15 10 5 0 LLDPE 60% LLDPE/ LDPE 60% LDPE/ LLDPE to LDPE to 40% COC 40% COC COC COC 60% LLDPE/40% 60% LDPE / COC @ 2X seal 40%COC @ 2X pressure seal pressure
  • 14. Phase Contrast Optical Microscopy: 80% 12 MI LDPE + 20% 80°C Tg COC, 51 µm cross section, 625X 160C 180C 200C Reference 3
  • 15. Seal Through Test Results 200 180 Seal BarTemperature (Celsius) 160 140 120 100 80 Initial Seal Bar Sticking 60 Seal Bar contamination 40 LLDPE - density=0.920, MI=4 20 Plastomer, density=0.902, MI=1.2 0 90% 130 Tg 5% 130 Tg 10% 130 Tg 15% 130 Tg 20% 130 Tg 30% 130 Tg 40% 130 Tg COC / 10% COC / 95% COC / 90% COC / 85% COC / 80% COC / 70% COC / 60% Plastomer LLDPE LLDPE LLDPE LLDPE LLDPE LLDPE High Tg COC as an outer layer blend component can provide seal through capability
  • 16. Conclusions • COC/polyethylene blends can exhibit both improved modulus and heat seal performance • COC is more compatible with LLDPE and Plastomers than LDPE • COC level and matrix polymer affect heat seal performance – 80º Tg COC generally improves hot tack strength at all blend levels for the polyethylene systems studied. – 80º Tg COC reduced the seal strength of LDPE at concentrations of 20% and up while maintaining or improving the seal strength of LLDPE and Plastomer • 130º Tg COC blended at levels above 20% can provide “seal through” capability to polyethylenes
  • 17. Acknowledgements I would like to thank the following people for their contributions to this paper: • Dr. Rong Chen • Dr. Angel Romo-Uribe • David Constant • Robert Roschen • Rick Vliet • Betsy Kelly • Kathy Fitzgibbon • Betty Fernekess 1
  • 18. References 1. ASTM, Designation: F 1921-98, Standard Test Methods for Hot Seal Strength (Hot Tack) of Thermoplastic Polymers and Blends Comprising the Sealing Surfaces of Flexible Webs, ASTM Standards 1999 2. R.R. Lamonte, “Stiffer, Thinner, Packaging Films with Improved Sealing Using Cyclic Olefin Copolymers”, Flexpac Conference, Amsterdam, Holland, November 2000 3. D.R. Constant, “Cyclic-Olefinic Copolymers as Non-Migrating Polymeric Slip Additives in LDPE Cast Films”, ANTEC 2002 Conference, San Franscico, CA
  • 20. Regulatory Status FDA Food Contact Notification (FCN No. 75) became effective August 22, 2000 Norbornene is listed by the EU as an approved monomer for use in polymers in contact with food. USP Class VI FDA Drug Master File, DMF# 12132 and Device Master File, MAF # 1043 established COC meets all major regulatory requirements