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TOPAS®         COC
High Barrier for Antiseptic Packaging




                                        Topas Advanced Polymers
                                        A member of Daicel/Polyplastics Group
Cyclic Olefin Copolymer (COC)
A New Family of Thermoplastic Materials


                                 Olefinic Resin

                                 Amorphous, Clear and Colorless

                                 High Purity

                                 High Moisture Barrier

                                 Good Chemical Resistance

                                 Easy to Process
TOPAS® COC - Production Plant


                          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 enables TOPAS Advanced Polymers
               to offer a product at competitive pricing
COC - Synthesis and Structure



H2 C        CH2 +
                                                     Readily available raw
 Ethylene         Cyclopentadiene       Norbornene
                                                     materials
                                                     Highly efficient catalyst
                          + H2 C        CH2
                                                        Low usage
            Metallocene
            Catalysis
                                                        Catalyst removed as part
                                                        of process
              (           )(
                          m
                                    )
                                    n
                                                        High purity product
                                                     Amorphous
                                                     Crystal clear
                    COC
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
TOPAS® COC – Regulatory Status

      FDA Regulation 21 CFR 177.1520 (3.9)
      TOPAS® 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.
      TOPAS® 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.

       TOPAS® COC meets all major regulatory requirements
               for food contact and medical use
COC - Enhancement in Value

Customized Performance

  Barrier
     WVTR – extended shelf life
     Special barrier (e.g. acetic acid, alcohol, aroma barrier,
     Iodine, moderate gas-barrier)
  Mechanical Properties
     Added stiffness – down-gauging
     Improved thermoforming
     Higher temperature resistance
     Controlled tear
     Better puncture resistance
  Seal Properties
     Low Tg COC can improve seal strength and hot tack
Typical Film Structures (mono/coex)

 COC Discrete Layer - Films

   COC monolayer-film       laminated with PP, PVC, PAN (Barex®),
   PVDC,                    PCTFE, PE/EVOH for blister packaging

   COC multilayer-film
       co-extrusion         PP / COC / PP          blister packaging
                            COC / PE-LLD / COC sleeves, twist wrap
        extrusion coating   cardboard / (LDPE) / COC / LDPE
       _________

        adhesion in co-extrusion
         • directly to PE-HD, PE-LLD, Plastomer, EVA, (PE-LD)
         • tie-layer needed for PP, PET, PA, EVOH, HDPE, (PE-LD)
            => individual cases to be checked
Typical Film Structures (blends)

  COC / Polyethylene Blend - Films

    PE-LD, PE-LLD, Plastomer, EVA
      Semi-compatible blends
      Increasing compatibility
      HDPE - LDPE - LLDPE - Plastomer

    Depending on...
      crystalline (density, refractive index)
      side chains, viscosity

    Typical blend mixes
      5 - 30% PE in COC
      5 - 30% COC in PE
COC – Market Segments
                                                Flexible Packaging
                           Emerging Markets
                                                Films for shrink, twist-wrap, sealant,
                           Non-wovens, foams,
                                                lidding, easy tear applications        Rigid Film
                           compounds
Toner Binder                                                                           Blister packaging for
Full-color printers                                                                    pharmaceutical, personal
and copiers                                                                            care, consumer
                                                                                       applications




                           Medical               Optics
                           Syringes, vials &     Precision lenses, light guides &
                           diagnostic devices    optical films




                      COC can substitute traditional products in
                             different growth markets
COC - Chemical Resistance

pH < 7 (acidic / aqueous)               pH = 7 (neutral / aqueous)                   pH > 7 (basic / aqueous)

hydrochloric acid 36 %                  Water
                                +                                            +       sodium hydroxide 50 %                +
sulfuric acid 40 %                      Aqueous solution                             ammonia (aq. Sol.) 35 %
nitric acid 65 %
                                +       of soap                              +                                            +
acetic acid > 94 %              +       saline solution
                                +                                            +

Polar organic solvents                  Aromatic solvents                            Non-polar organic solvents

ethanol, methanol,                      Benzaldehyde                                 Pentane, hexane,
                                                                                                                          -
butanol, isopropanol,           +
                                        Toluene                              -       heptane etc. (alkanes)
(short chain alcohols)                  Benzene                              -       Gasoline (petrol ether)              -
Acetone, butanone                       Chlorinated Solvents                         Norbornene
                                                                             -                                            -
(short chain ketones)           +
                                        Other
                                          Oleic Acid
                                                                             -

         +   resistant, increase of weight < 3% or loss of weight < 0,5%, elongation at break not substantially altered
         -   limited resistance, increase of weight 3-8% or loss of weight 0,5-5%, elongation at break reduced by < 50%
             not resistant, increase of weight > 8% or loss of weight > 5%, elongation at break reduced by > 50%


                             COC is resistant to acids, alcohols,
                                 bases and polar solvents
COC - Barrier Properties
                                     10000
                                                             LDPE         EVA/PE                  PCL
                                                                                      PS
                                      1000            HDPE
Oxygen Permeability [cm3/m2*d*bar]




                                                                          PVC
                                                     BOPP                                  PC
                                                                   PP     plasticized                   Cellulose Acetate
                                       100
                                                    COC                   PVC hard
                                                                          PET
                                        10
                                                                                                                      Starch
                                                              PEN                          PA 6
                                                                           PAN
                                         1
                                                                                                        Cellulose
                                                            PVDC
                                       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
Barrier Properties in PE/COC Blends*

                                 7

                                 6         Plastomer
           [g 100 µm / m² 24h]
           Water Permeation




                                 5
                                                   38°C & 90% r.F.

                                 4

                                 3       LLDPE                  TOPAS® 8007

                                 2

                                 1

                                 0
                                     0        20        40           60      80   100
                                                   [Weight %] COC of Blend




*Materials: LLDPE Dow 2035, Plastomer ExxonMobil 3125, TOPAS® 8007F-04
Moisture Barrier of COC

                                                      WVTR Response to Temperature and Humidity
                [g 100 µm / m² 24h]
                     g.100 microns / day     1
                Water Permeation
                                   2.
                                     m




                                            0.1




                                                                                                                 25% RH

                                                                                                                 85% RH


                                           0.01
                                               3.61    3.559   3.509   3.46     3.413   3.378   3.333   3.289   3.247   3.215   3.175


                                                                              1000 / T (kelvin)
                                                  COC barrier exhibits the normal linear relationship when log
                                             transmission is plotted against the reciprocal of absolute temperature.
                                                    Transmission increases linearly as humidity increases.



Data generated by Pauly Permeation Laboratory, 8007F-04
Ethanol Barrier

                                                               23°C / saturated Etoh vapor*

                                                5                                                  4.44
                                              4.5
                    [gg. 100 micron / (m² 2
                    Ethanol Permeation


                                                4
                       100 µm / m² 24h]


                                              3.5
                                                3
                                              2.5
                                                2
                                              1.5                              1.01
                                                1
                                              0.5         0.124
                                                0
                                                       TOPAS 8007        Exxon Mobil          Dow 2045 LLDPE
                                                                         HDZ 222 HDPE



                                                    COC has significantly reduced ethanol permeability as
                                                              compared to other polyolefins*.




* MOCON Test Labs
COC/PE Blends Isopropyl Alcohol Barrier


                                                                                   COC / LLDPE-Blends
                                                                                   23°C / saturated IPA vapor*
                                                                3.5
                                     g. 100 micron / (m² 24h)
                                      [g 100 µm / m² 24h]
                                                                 3        2.88
                                                                2.5
                    IPA Permeation




                                                                 2
                                                                1.5
                                                                                      1.33
                                                                 1
                                                                0.5
                                                                                                                      0.2     0.14
                                                                 0
                                                                      0          20          40          60      80         100
                                                                                       Wt %wt % Topas 8007
                                                                                            TOPAS 8007

                                                                          COC / LLDPE blends have significantly reduced IPA
                                                                             permeability as compared to pure LLDPE**.




* MOCON Test Labs
** Dow 2045
Isopropyl Alcohol Barrier

                                                        Response to Temperature

                                   10oC                                  23oC                             40oC
          [g 100 µm / m² 24h]



                                  10                                                                          9.2
         IPA Permeation




                                   1                                        1.94
                                                                                                              0.52
                                        0.48
                                                                             0.14
                                  0.1


                                 0.01
                                        0.00675
                                                                                         TOPAS 8007F-04
                                                                                         Dow 2045 LLDPE
                                0.001
                                    3.53                                 3.378                            3.13


                                                                 1000 / T (kelvin)



                                               COC barrier exhibits the normal linear relationship when log
                                               transmission is plotted against the reciprocal of absolute
                                               temperature. IPA transmission at room temperature through
                                               COC is 14 times less than for LLDPE at 23oC.




Data generated by MOCON, saturated vapor
COC/PE Blends Iodine Barrier

                                                                                        COC / LLDPE-Blends**
                                                                              40°C / 7% Tincture of Iodine, water accumulation
                                                                    6
                                                                            5.5
                                        mg. 100 micron / (m² 24h)


                                                                    5
                                         [g 100 µm / m² 24h]
                    Iodine Permeation




                                                                    4

                                                                    3

                                                                    2

                                                                    1
                                                                                               0.45
                                                                    0                                                 0.05
                                                                        0              20         40         60           80      100
                                                                                                wt % Topas 8007

                                                                                  COC / LLDPE blends have significantly reduced Iodine
                                                                                       permeability as compared to pure LLDPE*.



• MOCON Test Labs
** 1018CA LLDPE
Conclusions

 •   COC functions well as a discrete layer combined with polyethylene or in
     blends.
 •   COC functions as an effective barrier for common antiseptic solutions. At
     room temperature:
      – COC has ~5 times the water barrier of LLDPE
      – COC has ~36 times better ethyl alcohol barrier than LLDPE
      – COC has ~21 times better isopropyl alcohol barrier than LLDPE
      – COC has ~110 times better Iodine barrier than LLDPE

 •   COC is in the FDA Drug master-file system
Disclaimer
NOTICE TO USERS: To the best of our knowledge, the information contained in this publication is accurate, however we do not assume
any liability whatsoever for the accuracy and completeness of such information. The information contained in this publication should not be
construed as a promise or guarantee of specific properties of our products. All technical information and services of Topas are intended for
use by persons having skill and experience in the use of such information or service, at their own risk.

Further, the analysis techniques included in this publication are often simplifications and, therefore, approximate in nature. More vigorous
analysis techniques and prototype testing are strongly recommended to verify satisfactory part performance. Anyone intending to rely on
any recommendation or to use any equipment, processing technique or material mentioned in this publication should satisfy themselves
that they can meet all applicable safety and health standards.

It is the sole responsibility of the users to investigate whether any existing patents are infringed by the use of the materials mentioned in
this publication.

Properties molded parts, sheets and films can be influenced by a wide variety of factors including, but not limited to, material selection,
additives, part design, processing conditions and environmental exposure. Any determination of the suitability of a particular material and
part design for any use contemplated by the user is the sole responsibility of the user. The user must verify that the material, as
subsequently processed, meets the requirements of the particular product or use. The user is encouraged to test prototypes or samples of
the product under the harshest conditions to be encountered to determine the suitability of the materials.

Material data and values included in this publication are either based on testing of laboratory test specimens and represent data that fall
within the normal range of properties for natural material or were extracted from various published sources. All are believed to be
representative. These values alone do not represent a sufficient basis for any part design and are not intended for use in establishing
maximum, minimum, or ranges of values for specification purposes. Colorants or other additives may cause significant variations in data
values.

We strongly recommend that users seek and adhere to the manufacturer’s current instructions for handling each material they use, and to
entrust the handling of such material to adequately trained personnel only. Please call Topas-hotline +49(0)180-5186727 or visit
www.topas.com for additional technical information and for the appropriate Safety Data Sheets before attempting to process our products.
Moreover, there is a need to reduce human exposure to many materials to the lowest practical limits in view of possible adverse effects.
To the extent that any hazards may have been mentioned in this publication, we neither suggest nor guarantee that such hazards are the
only ones that exist.

The products mentioned herein are not intended for use in medical or dental implants.

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High Alcohol Barrier Films In Antiseptic Packaging

  • 1. TOPAS® COC High Barrier for Antiseptic Packaging Topas Advanced Polymers A member of Daicel/Polyplastics Group
  • 2. Cyclic Olefin Copolymer (COC) A New Family of Thermoplastic Materials Olefinic Resin Amorphous, Clear and Colorless High Purity High Moisture Barrier Good Chemical Resistance Easy to Process
  • 3. TOPAS® COC - Production Plant 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 enables TOPAS Advanced Polymers to offer a product at competitive pricing
  • 4. COC - Synthesis and Structure H2 C CH2 + Readily available raw Ethylene Cyclopentadiene Norbornene materials Highly efficient catalyst + H2 C CH2 Low usage Metallocene Catalysis Catalyst removed as part of process ( )( m ) n High purity product Amorphous Crystal clear COC
  • 5. 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
  • 6. TOPAS® COC – Regulatory Status FDA Regulation 21 CFR 177.1520 (3.9) TOPAS® 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. TOPAS® 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. TOPAS® COC meets all major regulatory requirements for food contact and medical use
  • 7. COC - Enhancement in Value Customized Performance Barrier WVTR – extended shelf life Special barrier (e.g. acetic acid, alcohol, aroma barrier, Iodine, moderate gas-barrier) Mechanical Properties Added stiffness – down-gauging Improved thermoforming Higher temperature resistance Controlled tear Better puncture resistance Seal Properties Low Tg COC can improve seal strength and hot tack
  • 8. Typical Film Structures (mono/coex) COC Discrete Layer - Films COC monolayer-film laminated with PP, PVC, PAN (Barex®), PVDC, PCTFE, PE/EVOH for blister packaging COC multilayer-film co-extrusion PP / COC / PP blister packaging COC / PE-LLD / COC sleeves, twist wrap extrusion coating cardboard / (LDPE) / COC / LDPE _________ adhesion in co-extrusion • directly to PE-HD, PE-LLD, Plastomer, EVA, (PE-LD) • tie-layer needed for PP, PET, PA, EVOH, HDPE, (PE-LD) => individual cases to be checked
  • 9. Typical Film Structures (blends) COC / Polyethylene Blend - Films PE-LD, PE-LLD, Plastomer, EVA Semi-compatible blends Increasing compatibility HDPE - LDPE - LLDPE - Plastomer Depending on... crystalline (density, refractive index) side chains, viscosity Typical blend mixes 5 - 30% PE in COC 5 - 30% COC in PE
  • 10. COC – Market Segments Flexible Packaging Emerging Markets Films for shrink, twist-wrap, sealant, Non-wovens, foams, lidding, easy tear applications Rigid Film compounds Toner Binder Blister packaging for Full-color printers pharmaceutical, personal and copiers care, consumer applications Medical Optics Syringes, vials & Precision lenses, light guides & diagnostic devices optical films COC can substitute traditional products in different growth markets
  • 11. COC - Chemical Resistance pH < 7 (acidic / aqueous) pH = 7 (neutral / aqueous) pH > 7 (basic / aqueous) hydrochloric acid 36 % Water + + sodium hydroxide 50 % + sulfuric acid 40 % Aqueous solution ammonia (aq. Sol.) 35 % nitric acid 65 % + of soap + + acetic acid > 94 % + saline solution + + Polar organic solvents Aromatic solvents Non-polar organic solvents ethanol, methanol, Benzaldehyde Pentane, hexane, - butanol, isopropanol, + Toluene - heptane etc. (alkanes) (short chain alcohols) Benzene - Gasoline (petrol ether) - Acetone, butanone Chlorinated Solvents Norbornene - - (short chain ketones) + Other Oleic Acid - + resistant, increase of weight < 3% or loss of weight < 0,5%, elongation at break not substantially altered - limited resistance, increase of weight 3-8% or loss of weight 0,5-5%, elongation at break reduced by < 50% not resistant, increase of weight > 8% or loss of weight > 5%, elongation at break reduced by > 50% COC is resistant to acids, alcohols, bases and polar solvents
  • 12. COC - Barrier Properties 10000 LDPE EVA/PE PCL PS 1000 HDPE Oxygen Permeability [cm3/m2*d*bar] PVC BOPP PC PP plasticized Cellulose Acetate 100 COC PVC hard PET 10 Starch PEN PA 6 PAN 1 Cellulose PVDC 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
  • 13. Barrier Properties in PE/COC Blends* 7 6 Plastomer [g 100 µm / m² 24h] Water Permeation 5 38°C & 90% r.F. 4 3 LLDPE TOPAS® 8007 2 1 0 0 20 40 60 80 100 [Weight %] COC of Blend *Materials: LLDPE Dow 2035, Plastomer ExxonMobil 3125, TOPAS® 8007F-04
  • 14. Moisture Barrier of COC WVTR Response to Temperature and Humidity [g 100 µm / m² 24h] g.100 microns / day 1 Water Permeation 2. m 0.1 25% RH 85% RH 0.01 3.61 3.559 3.509 3.46 3.413 3.378 3.333 3.289 3.247 3.215 3.175 1000 / T (kelvin) COC barrier exhibits the normal linear relationship when log transmission is plotted against the reciprocal of absolute temperature. Transmission increases linearly as humidity increases. Data generated by Pauly Permeation Laboratory, 8007F-04
  • 15. Ethanol Barrier 23°C / saturated Etoh vapor* 5 4.44 4.5 [gg. 100 micron / (m² 2 Ethanol Permeation 4 100 µm / m² 24h] 3.5 3 2.5 2 1.5 1.01 1 0.5 0.124 0 TOPAS 8007 Exxon Mobil Dow 2045 LLDPE HDZ 222 HDPE COC has significantly reduced ethanol permeability as compared to other polyolefins*. * MOCON Test Labs
  • 16. COC/PE Blends Isopropyl Alcohol Barrier COC / LLDPE-Blends 23°C / saturated IPA vapor* 3.5 g. 100 micron / (m² 24h) [g 100 µm / m² 24h] 3 2.88 2.5 IPA Permeation 2 1.5 1.33 1 0.5 0.2 0.14 0 0 20 40 60 80 100 Wt %wt % Topas 8007 TOPAS 8007 COC / LLDPE blends have significantly reduced IPA permeability as compared to pure LLDPE**. * MOCON Test Labs ** Dow 2045
  • 17. Isopropyl Alcohol Barrier Response to Temperature 10oC 23oC 40oC [g 100 µm / m² 24h] 10 9.2 IPA Permeation 1 1.94 0.52 0.48 0.14 0.1 0.01 0.00675 TOPAS 8007F-04 Dow 2045 LLDPE 0.001 3.53 3.378 3.13 1000 / T (kelvin) COC barrier exhibits the normal linear relationship when log transmission is plotted against the reciprocal of absolute temperature. IPA transmission at room temperature through COC is 14 times less than for LLDPE at 23oC. Data generated by MOCON, saturated vapor
  • 18. COC/PE Blends Iodine Barrier COC / LLDPE-Blends** 40°C / 7% Tincture of Iodine, water accumulation 6 5.5 mg. 100 micron / (m² 24h) 5 [g 100 µm / m² 24h] Iodine Permeation 4 3 2 1 0.45 0 0.05 0 20 40 60 80 100 wt % Topas 8007 COC / LLDPE blends have significantly reduced Iodine permeability as compared to pure LLDPE*. • MOCON Test Labs ** 1018CA LLDPE
  • 19. Conclusions • COC functions well as a discrete layer combined with polyethylene or in blends. • COC functions as an effective barrier for common antiseptic solutions. At room temperature: – COC has ~5 times the water barrier of LLDPE – COC has ~36 times better ethyl alcohol barrier than LLDPE – COC has ~21 times better isopropyl alcohol barrier than LLDPE – COC has ~110 times better Iodine barrier than LLDPE • COC is in the FDA Drug master-file system
  • 20. Disclaimer NOTICE TO USERS: To the best of our knowledge, the information contained in this publication is accurate, however we do not assume any liability whatsoever for the accuracy and completeness of such information. The information contained in this publication should not be construed as a promise or guarantee of specific properties of our products. All technical information and services of Topas are intended for use by persons having skill and experience in the use of such information or service, at their own risk. Further, the analysis techniques included in this publication are often simplifications and, therefore, approximate in nature. More vigorous analysis techniques and prototype testing are strongly recommended to verify satisfactory part performance. Anyone intending to rely on any recommendation or to use any equipment, processing technique or material mentioned in this publication should satisfy themselves that they can meet all applicable safety and health standards. It is the sole responsibility of the users to investigate whether any existing patents are infringed by the use of the materials mentioned in this publication. Properties molded parts, sheets and films can be influenced by a wide variety of factors including, but not limited to, material selection, additives, part design, processing conditions and environmental exposure. Any determination of the suitability of a particular material and part design for any use contemplated by the user is the sole responsibility of the user. The user must verify that the material, as subsequently processed, meets the requirements of the particular product or use. The user is encouraged to test prototypes or samples of the product under the harshest conditions to be encountered to determine the suitability of the materials. Material data and values included in this publication are either based on testing of laboratory test specimens and represent data that fall within the normal range of properties for natural material or were extracted from various published sources. All are believed to be representative. These values alone do not represent a sufficient basis for any part design and are not intended for use in establishing maximum, minimum, or ranges of values for specification purposes. Colorants or other additives may cause significant variations in data values. We strongly recommend that users seek and adhere to the manufacturer’s current instructions for handling each material they use, and to entrust the handling of such material to adequately trained personnel only. Please call Topas-hotline +49(0)180-5186727 or visit www.topas.com for additional technical information and for the appropriate Safety Data Sheets before attempting to process our products. Moreover, there is a need to reduce human exposure to many materials to the lowest practical limits in view of possible adverse effects. To the extent that any hazards may have been mentioned in this publication, we neither suggest nor guarantee that such hazards are the only ones that exist. The products mentioned herein are not intended for use in medical or dental implants.