Development of new BOPP Barrier Films by Coextrusion and Simultaneous Biaxial Orientation Brueckner Maschinenbau GmbH, Siegsdorf, Germany,

Dr. M. Wolf, Dr. J. Breil, Dipl.-Ing. R. Lund: Abstract: Semiindustrial production of transparent, biaxial oriented polypropylene (BOPP) barrier films with very thin EVOH layers and excellent barrier properties was successful. Also EVOH based display shrink barrier films as well as opaque, density reduced barrier films were produced. Comparisons with commercial film types will be presented, PVDC based barrier films could be replaced. Metalized UHB BOPP films with improved OTR barrier values of about 0.2 cm/m d bar (0,01 cc/ 100in2 d bar) (23C (73,4F)/ 75% r.h.) will be discussed. Aluminium and metalized BOPET-films could be substituted. First successful application tests of the new EVOH based packaging barrier films have been performed in the framework of a funded network project, mainly as snack packages. Further cost reductions could be achieved by producing a multifunctional, biaxial oriented EVOH based barrier film in one step, saving converting steps. 1) Introduction: Biaxial stretching of thermoplastic polymer films improves mechanical, optical as well as barrier film properties. This refinement by a biaxial stretching process is applied for many thermoplastics, the worldwide capacity for biaxially oriented films amounts to about 12.5 Million t/ a in 2008. The biggest share with 65% comes from BOPP, followed by BOPET with 26%. As in recent years the profit margins for standard biaxial oriented films, e.g. BOPP coex or BOPP tape decreased mainly due to high resin prices and overcapacity, many BOPP producers are looking for added-value specialty BOPP films. Additionally, as summarized in figure 1, current market trends are demanding new packaging solutions. Main general trends in our opinion are cost reduction and convenience.

Figure 1: General market needs/ trends and derived possible film developments. 1

2) Processes for the production of biaxial oriented films: There are three different techniques to produce biaxial oriented films: The sequential tenter frame process, the simultaneous tenter frame orientation as well as the double-bubble process, which is also a simultaneous stretching method. Thereby for different film types certain processes have prevailed: For example BOPP and BOPET are mainly produced by the sequential process, whereas for BOPA all three techniques are used at about the same shares.

Figure 2: Sequential and simultaneous biaxial stretching techniques for film production. With the sequential stretching process the first step is a stretching of an extruded cast sheet in machine direction between roll pairs at very high stretching speeds. As a second step in transverse direction the film is gripped by a transfixed clip system and via a track rail stretched over the width. Due to reasons of product quality and processing stability the stretching ratios in MD as well as in TD, MD resp. TD, can be varied only between rather narrow limits, typical values for e.g. BOPP are MD=5 and TD=9. By contrast, with the simultaneous tenter frame process the MD- and TD stretching is done at moderate stretching speeds (max. 300 %/s ) but at the same time. This is possible due to a continuous extension of the distances between clips in machine direction during the simultaneous transverse track rail stretching. Due to a low flexibility in stretching ratios as well as high mechanical efforts and low line speeds the long well known simultaneous pantograph- or spindel-systems are seldom used. These disadvantages were overcome by the simultaneous tenter frame LISIM technology, an abbreviation for Linear Motor Simultaneous Stretching Technology as shown in figure 3. With this new technology all clips can be separately driven by linear motors, thus, in comparison to the sequential process, significantly increasing the utilizable range of MD- as well as TD-stretching ratios, as shown in figure 4. Even MD stretching ratios up to 10 are possible, resulting in a significant enhancement of mechanical film properties, e.g. Emodulus, in machine resp. processing direction as shown in table 1: The higher the MD stretching ratio the higher the mechanical value.

Figure 3: Principle - Linearmotor Simultaneous Stretching Technology

Figure 4: Comparison of simultaneous and sequential stretching process regarding utilizable range of stretching ratios in MD- and TD direction. Additional selected advantages of the simultaneous linear motor process are a broad accessible range of shrinkage film properties, processability of high barrier EVOH grades as well as contact free stretching of very low SIT materials as shown in figure 31-5).

Table 1: Comparison of simultaneous and sequential stretching process regarding mechanical film properties in MD- and TD direction.

The double-bubble-process results in balanced film properties by simultaneous stretching of a cooled and reheated bubble. Disadvantageous regarding film product quality and reproducibility is in contrast to tenter frame processes - the difficult control of temperatures and other process parameters of this open double-bubble process. Additionally film output is rather low, typically 300 kg/h.

3) Simultaneous biaxial orientation of different EVOH grades Among the transparent high barrier films the fastest growing barrier film materials are EVOH and glass coated film structures as shown in table 26). Despite the efforts to make EVOH more useful in oriented films to our knowledge only about 5% of the total EVOH film consumption are used in oriented film applications, including also monoaxially oriented films. Table 2 : Amount of high-barrier materials worldwide.

For our experiments we used EVOH grades with varying ethylene contents of the company Kuraray, the chemical formula is given in figure 5. The ethylene contents have significant influences on several processing parameters as well as endfilm properties. For example a higher ethylene content gives better orientability and a better moisture barrier, but on the other hand results in lower barrier properties. Orientation of EVOH should result in higher barrier and mechanical properties. At the starting point of our investigations we found, that the crystallisation of EVOH types with a certain ethylene content causes a deterioration of the stretchability, resulting in net structures and therefore bad optical film properties, as shown in figure 6 on the left side. This means, that obviously the crystallisation temperature of a certain EVOH type, especially with lower ethylene contents, e.g. 24%, overlaps the optimum orientation temperature range of polypropylene, the base material of our barrier films. Especially the sequential orientation process of EVOH is difficult due to MD orientation crystallisation and formation of microfibril structures, which result upon transverse stretching in voids and other optical defects.

Figure 5: Influence of the ethylene content of different EVOH grades on their processability and film properties

Figure 6: Comparison of optical film properties under polarized light for sequential (left) and simultaneous (right) tenter film samples. By using the simultaneous tenter frame stretching technology we found a way to overcome this problem: A simultaneous orientation at low stretching temperatures and high stretching 5

speeds subdues crystallization and enables the defect free stretching of EVOH coex layers, resulting in films as shown in figure 6 on the right side. Starting point of the high barrier evaluations were laboratory scale experiments on a discontinuous laboratory stretching frame, developing the principles for the production of optical defect free 7-layer barrier films with thin EVOH layers. The upscaling experiments on a continuous simultaneous linear motor pilot line could be performed successfully. It was first time possible to produce biaxially oriented barrier film rolls with thin EVOH layers (1,3 - 1,8 m) and total thicknesses between 20 and 30 m and EVOH grades containing 24% and 27% of ethylene without optical defects. A typical layer distribution is shown in figure 7. OTR values of about 1 cm/m d bar (23C (73,4F)/ 75% r.h.) could challenge PVDC coated BOPP films as summarized in table 3.

Figure 7: Structure of a 7-layer transparent BOPP/ EVOH barrier film and key characteristics Table 3: Comparison between novel biaxial oriented 7-layer barrier films and commercial products

By using suitable polypropylene based copolymers in the thick intermediate layers it was also possible to produce display shrink barrier films with shrinkage values depending on applied temperature up to 50% in MD- and TD-direction, as shown in figure 8.

Figure 8: Shrinkage data of a 7-layer transparent display BOPP/ EVOH barrier film . Besides transparent and shrink barrier films also density reduced white opaque films could be produced successfully. By adding inorganic fillers into the intermediate PP-layer the formation of vacuoles occurred upon biaxial stretching. The resulting white opaque barrier films with an total density of 0,78 g/ cm3 (Solid PP: 0.91 g/ cm3 yield increase for 30m: 16%) display excellent UV protection of the filling goods. OTR- and WVTR-values are only slightly higher than for transparent barrier films, typical values are OTR=3,5 cm/m d bar (0,23 cc/ 100in2 d bar) (23C (73,4F)/ 75% r.h.) and WVTR=1.4 g/ m2 d (0,09 g/ 100in2 d) (23C (73,4F), 85% r.h.). It is known, that barrier properties of EVOH containing barrier films deteriorate with increasing humidity7). Figure 9 summarizes for different EVOH types at an EVOH layer thickness of about 1,5 m the dependence of the OTR values from the applied relative humidity.

Figure 9: Influence of relative humidity on OTR values of BOPP based EVOH barrier films at EVOH thickness of 1,5 m 7

Figure 9 also clearly shows, that - compared to PVDV coated films and even SiOx coated BOPP films - the biaxial stretched EVOH barrier films show improved OTR values over a very broad range of relative humidity, at least up to 85%-90% r.h.. In our opinion even for wet packaging goods, due to the layer of PP between good and EVOH, relative humidities between 80 and 85% are realistic conditions and in this range the biaxial oriented barrier films show only minor barrier deviations. The EVOH stretching trials can be summarized as follows: Sequential stretching is possible for EVOH grades with ethylene content of 44% and higher, but simultaneous stretching by contrast is possible with all available types, even down to a content of 24% ethylene high stretching speeds and/ or low stretching temperatures suppress crystallization and thus net structures, enabeling the production of films without optical defects and good OTR values. Due to the choice of base material and machine settings theres a high flexibility in end film properties, examples are shrink barrier and density reduced opaque white films. Barrier measurements have shown, that chain orientation effects due to the biaxial stretching process improve the barrier properties of EVOH by an factor of about 2.38)

4) Ultra-High Barrier Metalized and SiOx coated BOPP UHB Film Besides EVOH based, predominantly transparent barrier films also metalized, simultaneously biaxial oriented ultra-high-barrier-films, abbreviated as UHB-films, with exceptional OTR values have been developed. Also transparent UHB films with SiOx coating could be produced. Their OTR values of 0.2 cm/ m d bar (0,013 cc/ 100in2 d bar (23C (73,4F)/ 75% r.h.) approach those of aluminium foil and are about 250 times lower than that of standard BOPP metalized films, which are in the range of 40-70 cm/ m d bar. Aluminium foil is essentially impenetrable by moisture and oxygen. However, when packages made with foil are subjected to the repeated manipulation and handling that are common with manufacturing, cartoning, shelf stocking and consumer handling in the retail environment, they can develop pinholes and become permeable10). But an even more important reason to replace thin aluminium foil with metalized BOPP ultra high barrier films are permanently increasing aluminium prices and the fact, that thin foils have a thickness of 7 m, whereas the aluminium coatings on BOPP films are in a thickness range of 40-60 nm.

Figure 10: Structure of a metalized 5-layer UHB-barrier film and main characteristics 8

Figure 10 summarizes the detailed structure and main characteristics of the UHB-film: A very thin 0.5-0.8 m surface layer of a so called high surface energy polymer results in a very strong bonding of the evaporated aluminium to this film surface, among others due to a very high surface energy in the range 52-56 dyn. No surface treatment by e.g. corona or flame is necessary to reach these surface energy values. By using standard optical densities of about 2.3 exceptional OTR values down to 0,15 cm3/ m2 d bar (0,01 cc/ 100in2 d bar) have been obtained, a typical WVTR value is 0.3 g/ m2 d (0,02 g/ 100in2 d). As the high surface energy polymer layer can be applied in thicknesses clearly below 1 m a cost-efficient production is possible. Alternatively a transparent SiOx coated UHB film with similar barrier values has been manufactured. At the moment a UHB film with the given polymer layer composition can be obtained without optical defects only by the simultaneous biaxial tenter frame process.

5) Joint Project along the Added Value Chain: Thin Films In the framework of a funded network project called Thin Films8,9,11-13) the above discussed EVOH based biaxial stretched barrier films as well as the UHB film have been included into thin packaging film laminates for commercial nut snack filling goods to possibly substitute current snack packagings. In the course of this project different packaging film systems have been analyzed along the entire value-added chain, starting from products of film producers like Kopafilm or in this case Brueckner, followed by metalization and lamination steps, e.g. on Applied Films and Wipak equipment, up to food packaging trials with Bosch VFFS-machines at food companies like Kraft and Lorenz. Main packaging goods were nut and chips snacks. The project partners are summarized in figure 11. The overall project coordination was with the Fraunhofer IVV (Institute for Process Engineering and Packaging) in Freising, Germany. Financial fundings were granted by the German BMBF (German Federal Ministry for Education and Research).

Figure 11: Joint Project Along the Added Value Chain: Thin Films The target of this project was to demonstrate with selected film systems along the entire added value chain up to the final application, that a 50% reduction in material is possible without significant limitations of the technical functionality. Interesting questions among 9

others were the minimum thickness values to obtain the required film properties, e.g. sufficient dimension stability to prevent damaging of coating layers by elongation of the base film or sufficient E-modulus to produce packages without wrinkles. Main motivations for material reductions are of course cost savings, but also the European packaging law, which makes avoidance and material reduction a priority. The demonstration of conformity with the European packaging directive is possible according to DIN EN 13 427 ff, reduction of material input at retained functionality is in this norm an explicitly termed criteria 8,9,10-12). One reference packaging system we investigated is a three layer packaging for peanut snacks, meaning it is a triplex compound with two required laminating steps. One of the layers, the middle one is metalized, either 15m BOPP or 12 m BOPET, inner layer is a 50m PE blown film, outer layer usually is a reverse printed BOPET film. The detailed structure is given In figure 12 on the left side. During first trials we successfully reduced the thickness values of single layers and switched from triplex to duplex laminates, using e.g. 7m strong BOPET films against 30-40m strong BOPE/ PP sealing layers, the latter biaxial oriented to compensate for losses in mechanical stability. Additionally for the example of peanut snacks we substituted the commercial film laminate for a duplex laminate of a transparent EVOH based barrier film and a 30 m biaxial oriented sealing layer. For UV protection also the white opaque EVOH based barrier film has been tested. This approach also resulted in an overall thinner laminate structure as well as possible cost savings regarding material and production costs up to 25%, as illustrated in figure 12. In the following selected results from the network project thin films will be presented and discussed. Figure 13 gives an overview of OTR and WVTR values for commercial and experimental high barrier laminates. For PET based film systems the thinner 7 m films show after metalization and lamination comparable, partly even slightly improved barrier values in comparison to thicker film systems. Also the investigated EVOH based barrier film laminates with biaxial oriented sealing film layer for peanut snack packaging display OTR values of about 0,3 m3/ m2 day bar (0,02cc/ 100in2 d bar) and WVTR values below 0.8 g/ m2 d (0,051 g/ 100in2 d), thus challenging metalized systems BOPETmet/ PE. The same is true for the barrier values of the UHB film based barrier laminate.

Figure 12: Cost comparison between commercial triplex packagings for peanut snacks against experimental novel biaxial oriented EVOH based duplex laminates 10

Figure 13: Comparison of OTR and WVTR values for commercial and experimental packaging film laminates As summarized in figure 14 for BOPP/ BOPP-systems the thin films are comparable to the thicker reference films also regarding aroma permeation. The required breakthrough time for excellent aroma barrier is t 30 days (720 h)11). In the case of BOPET- and EVOH-based barrier film laminates no breakthrough times could be determined as the measuring values were clearly below the detection limit.

Figure 14: Aroma breakthrough data for selected packaging barrier film laminates. Additionally we investigated, how possible elongation processes during the further processing chain, e.g. during lamination, influence the barrier values of different film laminates, 11

especially coated ones8,9). The most delicate laminates were those based on very thin BOPET/ PE films. In contrast for EVOH based systems a slight elongation initially resulted in a reproducible barrier value improvement. Assuming that a 2% film elongation has no negative impact on barrier values, figure 15 shows, that the arising forces during the lamination step are clearly smaller than those necessary for a 2% elongation of the film systems, therefore no deteriorated barrier values have to be expected.

Figure 15: Overview of forces for a 2% elongation of different film systems in comparison to arising forces during a lamination step. Comparable results have been obtained during the packaging process for VFFS packaging machines at the film form shoulder and at the film propulsion unit, but only when continuous working VFFS machines are used. Packaging trials with selected barrier laminates and different snack filling goods with following sensory tests have been successfully performed. For the system biaxial oriented BOPP EVOH// BOPP7 BOPE a shelf life of 6 month has been granted. Several trials with thin films with 100% tight packages have been performed11). The findings of the funded network project thin films can be summarized as follows: With biaxial orientation the thickness of film laminates based on vacuum coated film structures can be reduced down to 50% compared to standard film laminates. Resulting barrier properties are comparable or even better than for standard film laminates. Barrier properties of thin film laminates are not impaired by following converting processes, as the resulting elongations are clearly below critical values, when using an continuous working, vertical packaging machine. Intact sealed seams down to o 27m for BOPP/ BOPP and o 37m for BOPET/ BOPP-PE Handling and acceptance by end users has to be evaluated.

For more information please visit www.duenne-folien.de 8,9,11-13) 12

6) Path forward (Integrated Production Process) and Conclusion A next possible future step for further cost reductions could be the total elimination of lamination steps. Nowadays the production of a barrier film laminate based on vacuum coating technology (e.g. aluminium, SiOx, AlOx) usually takes four processing steps: Extrusion of the carrier film, e.g. BOPP, BOPET, BOPA Extrusion of the sealing film, e.g. c-PP, c-PE Barrier coating of the carrier film Lamination of sealing layer to carrier layer

As the main driving factor in the film supply chain are costs, it would be advantageous not only to save material by reduced thicknesses, but to produce a barrier film with all required functionalities, including barrier as well as e.g. sealing properties by a one-step extrusion process and a following biaxial orientation with the simultaneous tenter frame process. In terms of an integrated production process all necessary functionalities depending on the requirements of the packaged good should be implemented in one processing step. By developing, testing also in long-term storage trials with packaged goods - and producing one-step high barrier films with barrier values challenging laminated structures based on e.g. PET-Al or PET-SiOx, the replacement of these now existing, clearly more expensive barrier laminates is our long-term target. Figure 16 proposes cost savings of up to 45% for replacing a triple laminate BOPET/ BOPETmet/ PE for peanut snack packagings by a biaxially oriented 7-layer EVOH containing one-step BOPP barrier film structure with reduced sealing layer thickness (estimated costs). The technical feasibility regarding required barrier and sealing properties has been proven in the funded project Thin Films.

Figure 16: Assumed cost savings of about 45% for replacing a triple laminate for peanut snack packs by a biaxially oriented 7-layer EVOH-containing one-step BOPP barrier film (estimated costs). Besides the narrow application range of the funded network project there are much more applications for the discussed barrier/ high barrier films like lidding films in MAP-, CAP- and vacuum packages as well as inner bag applications with barrier protection, in the last case partly substituting paper laminates. A typical film laminate for lidding film applications as shown in figure 17 consists of a 45 m blown film sealing layer with barrier function and a biaxial oriented film for mechanical strength, e.g. a 20 m BOPP film14). 13

Figure 17: Typical film laminate for barrier lidding film applications. For inner bag applications also PVDC coated systems are in use as shown in figure 19 on the left side. Regarding barrier and mechanical properties these laminated barrier film structures could be replaced with a 50 m simultaneous biaxial oriented, frontal printed one-step film, the mechanical properties in machine and therefore processing direction of the latter due to the linearmotor stretching process even being higher, compensating for a loss in bending stiffness. Figures 18 and 19 propose cost savings of up to 40 % resp. 32%.

Figure 18: Proposed cost reduction range by one-step 7-layer barrier films for lidding film applications. 14

Figure 19: Proposed cost reduction range by one-step 7-layer barrier films for inner bag film applications. Next steps for us should be sample production for converting and packaging trials as well as discussions with film converters and end users. Additionally we will try to further optimize the properties of our films, e.g. sealing properties, hot-tack, shrink, UV protection of transparent film systems, mechanical properties and test alternative raw materials e. g. UV-Stabilizer, humidity absorbers or O2-scavengers. We think that in the future it could be possible in selected cases to substitute PVDV coated films, shrink barrier films or certain film laminates with our barrier films, additionally we hope, at least in some cases, also to penetrate into the domain of metalized films!

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Literature: [1] J. Breil - Added value speciality films produced with sequential and simultaneous stretching lines, Speciality Plastic Films 2002, 18th Annual Maack World Congress, Oct. 29-30, 2002, Swissotel Zrich, Switzerland. Breil J.: S-BOPP Film enhancement by LISIM-Technology. SP 1998 Annual world Congress, Dsseldorf, Oktober 1998. Breil J., Oedl G., Sieber B.: Synchronous Linear Drives for many Secondaries with Open Loop, 2nd International Symposium LDIA 1998, Tokyo, Japan, 6th-8th of April, 1998. Breil J.: LISIM - Linear Motor Simultaneous Stretching Technology, CMM Intern. Conference, Chicago, USA, 16th April 1997. M.A. Scarati, Polyolefin films benefit from simultaneous orientation, Modern Plastics Intern. July 1999, Vol. 29, No. 7, p. 103. Allied Development Corporation, Lakeville, MN 55044: Brueckner PVDC and EVOH Market Study, Oct., 2005. Gas barrier properties of resins, Technical Bulletin No.110, EVAL Americas, www.evalca.com. H.-C. Langowski, C. Schnweitz Dichtereduzierte Folienmaterialien Einsparpotentiale und Verarbeitungseigenschaften, Tagung Verarbeitungsmaschinen und Verpackungstechnik VVD 2006 am 23.& 24.03.2006, Dresden, Germany. H.-C. Langowski: Barrier mechanisms of vacuum coated polymers: Where are the limits for downgauging of substrates and for barrier properties of coated films? Technical Conference at the International Converting Exhibition ICE 2005, November 22nd, 2005, Munich. S. Sargeant, K. Chang Product Protection, Paper, Film & Foil Converter, March 2007, S.61-65. Fraunhofer Institute for engineering technology and packaging IVV - Final Report: Funded Research Project (BMBF): Environmental benefits in production and use of laminated packaging materials by 50% reduction in material input, March 2003 May 2006, public version, Freising, 2006. J. Breil, R. Lund, M. Wolf - Biaxially oriented BOPP barrier films with thin EVOH layers, European Metallizers Association, Spring Meeting, March 09-10, 2006, London. M. Wolf, J. Breil, R. Lund Neuartige Materialkombinationen in Barrierefolien durch Coextrusion und simultane biaxiale Orientierung, VDI-Fachtagung Extrusion 2007, 13. & 14.Juni 2007, Neu-Ulm, Germany. M. Wolf, J. Breil, R. Lund Neuartige Barrierefolien durch Coextrusion und biaxiale Orientierung, Innoform Coaching - PE und PP-Folien fr flexible Verpackungen 27.+28. November 2007, Germany.

[2] [3]

[4]

[5] [6] [7] [8]

[9]

[10] [11]

[12]

[13]

[14]

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