Edgard Chow (Technical Manager) Improving the performance of bulk packaging of liquids through the use of modified ethylene vinyl alcohol (EVOH) Edgard Chow (Technical Manager) Robert Armstrong (TS&D Director) Kuraray America Inc. Pasadena, TX SPE Polyolefins Conference Houston TX February 2012

Agenda EVAL™ EVOH Liquid packaging formats Typical applications Properties Liquid packaging formats Bag-in-box Intermediate bulk containers Flexitants Improving the properties of EVOH Conventional EVOH Amorphous EVOH Elastomer modified EVOH

24 27 32 35 38 44 48 Ethylene and Vinyl ALcohol What is EVOH? Higher density Higher melt point Higher barrier 24 27 a semi-crystalline thermoplastic and a random copolymer of Ethylene and Vinyl ALcohol 32 35 Ethylene mol % (CH2-CH2)m (CH2-CH)n 38 EVAL is a random copolymer of ethylene and vinyl alcohol We have a broad range of grades which we nominate by their ethylene mole content The lower the ethylene, the higher the barrier The higher the ethylene, the higher the flexibility OH 44 More flexible More orientable 48

(Outside of packaging) EVOH Protects Food (Outside of packaging) Oxygen, off-odors, off-flavors, other contaminants Flavor, aroma, vitamins, modified atmosphere gases (Inside of packaging)

Versatility of EVOH Oxygen barrier Aroma barrier Vitamin protection Flavor preservation Solvent barrier Hydrocarbon barrier Oxygen EVAL é muito conhecido na industria alimentícia, cosméticos, agroquímicos, e automotiva por sua alta barreira ao oxigênio e alta resistência química. Aqui estão algumas das aplicações comerciais. Toluene Xylene Mint Vitamin C Coffee

Agenda EVAL™ EVOH Liquid packaging formats Typical applications Properties Liquid packaging formats Bag-in-box Intermediate bulk containers Flexitants Improving the properties of EVOH Conventional EVOH Amorphous EVOH Elastomer modified EVOH

The Iconic BIB Application Advantage over glass More functional Single cup dispensing convenience No headspace Can stay open up to 21 days More sustainable* 85% less packaging/landfill waste 53% less CO2 emissions Source: www.betterwinesbetterworld.com/

Adopted Wine Industry Specifications Wine BIB Requirements High barrier 0.5 ~ 0.8 cc/m2.day.atm @ 20°C, 65%RH EVAL™ L171B = 27mol% Et. EVOH High abuse resistance Transportation Abuse Potential Outcome Standard Test Method Up/down motion in land Side/side motion in sea Pinhole formation OTR deterioration ASTM F193-92 ASTM D3985 Adopted Wine Industry Specifications 0 pinholes max. after 200 gelbo flex cycles 2 pinholes max. after 400 gelbo flex cycles OTR < 1.0 cc/m2.day.atm

Oxygen transmission rate Evaluation Method ASTM F193-92 Reapproved 2004 45 CPM, full flex condition ASTM D3985 20°C, 65%RH Gelbo flex testing Oxygen transmission rate

Evaluation of Market Samples PE inner liner Barrier outer liner Inner layer : PE40 Outer layer : (in) PE30//VM-PET12//EVA40 (out) OTR : 1.0cc/m2/day/atm, 2.8cc/m2/day/atm WVTR : 5.7g/m2/day Inner layer : PE90 Outer layer : (in) PE40/Tie/EVOH6/Tie/PE60 (out) OTR : 0.8cc/m2/day/atm WVTR : 2.6g/m2/day Inner layer : PE40 Outer layer : (in) EVA15/Tie/EVOH6/Tie/EVA7 //ON10//PE30 (out) OTR : 0.6cc/m2/day/atm WVTR : 5.9g/m2/day Test conditions: OTR:20ºC/65%RH, WVTR:40ºC/90%RH

Evaluation of Market Samples Oxygen Transmission Rate After Gelbo Flex

BIB Applications (3 – 20L) Drums (200L) IBC(1000 – 1500 L) Olive Oil Coffee concentrate Cola Syrup Juice concentrate Drums (200L) IBC(1000 – 1500 L) Aran Packaging Bluesept55® Sealed Air Cryovac Entapack®

Flexitank Market Typically in the 12,000 to 36,000L range Must comply with the Code of Standards by the Container Owners Association The flexitank market size is ~500,000 units Recent 7-layer installation by Raven Industries

Flexitank Benefit 20 ft Container payload 15% higher than IBCs 44% higher than drums Source: www.unedecom.com

Flexitank Market EPT Wine-Pac™ has a third inner liner of EVOH film OTR of 0.4 cc/m2.day Applications Food & beverage: wine, oils, juice concentrates, etc. Cosmetics: detergents, bleaching solutions, cleaners, etc. Industrial chemicals: adhesives, paints, biofuels, fuel additives, etc. Source: http://eptpac.com

Trends with big bags The larger the bag, … the lower the barrier requirements Surface area to volume ratio factor but the higher the physical abuse on the bag Normal stresses induced by higher loads Use of multiple liners similar to BIB is also practiced 3 – 20L institutional BIB 3 – 5L retail BIB 200 – 1500L IBC 12000 – 36000L Flexitank

High Barrier Flexitank Challenges Limited experience base producing large, thick bags with thin EVOH layers Larger dies, longer residence time in the melt demand improved thermal stability Use of higher ethylene grades Selection of EVAL 7-series Longer time for the bubble to reach its finished geometry Higher ethylene grades have a lower recrystallization temperature Higher flex crack resistance Use of softer modified grades

Agenda EVAL™ EVOH Liquid packaging formats Typical applications Properties Liquid packaging formats Bag-in-box Intermediate bulk containers Flexitants Improving the properties of EVOH Conventional EVOH Amorphous EVOH Elastomer modified EVOH

Failure Mechanism of Pinhole Formation Fatigue Cracking From radical generation on to micro-crack generation Inhibition of crack growth is critical to improve flexible crack resistance

EVAL Technologies for Liquid Packaging Type Technology Illustration Flex crack resistance EVAL Conventional Good EVAL SP Amorphous EVOH Better EVAL FS Elastomer modified EVOH Domain-matrix Best

Film Pilot Equipment Materials Gelbo flex conditions Blown film production Brampton Engineering 7-layer, 6” pancake die Cast film production Toyo-seiki 20mm metering screw 300mm coat hanger die Materials Sclair FP120 C8-LLDPE Ultrathene UE624000 18% vinyl acetate EVA Admer NF498A LLDPE-based tie resin Dupont Byner 3861 EVA-based tie resin Various types of EVAL Gelbo flex conditions 45 CPM, full flex, room temperature

Effect of EVOH Grade and Thickness Number of gelbo cycles to create one (1) pinhole Coex blown film structure: LLDPE/Tie/EVAL/Tie/LLDPE = 36 / 5 / X / 5 / 36μm

Effect of Structure Stiffness Number of gelbo cycles to create one (1) pinhole Film structure 20μm monolayer cast film 90μm blown film: LLDPE/LL-Tie/EVAL/LL-Tie/LLDPE = 36/5/8/5/36μm 90μm blown film: LL+EVA/EVA-Tie/EVAL/EVA-Tie/LL+EVA = 36/5/8/5/36μm

Flex Crack Resistance of EVAL FS101 Number of gelbo cycles to create one (1) pinhole Structure: 90μm blown film: LLDPE/LL-Tie/EVAL/LL-Tie/LLDPE = 36/5/8/5/36

More developments underway Number of gelbo cycles to create one (1) pinhole Structure: 20μm monolayer cast film

EVAL Grades for Liquid Packaging Type Technology Flex crack resistance Grades (et.mol%) EVAL Conventional Good L171(27) F171(32) H171(38) E171(44) EVAL SP Amorphous EVOH Better SP521(27) J171(32) XEP-1035(38) EVAL FS Elastomer modified EVOH Best FS101(32) XEP-1273(32)

Summary EVOH has excellent barrier properties EVOH has great flex crack resistance when coextruded with softer polyolefin resins The use of EVOH in BIB is established but grades with improved the flex crack resistance for larger bags such as flexitanks have been developed We can sample any of the mentioned grades upon your request

Mr. Wataru Hirose (EVAL R&D Japan) Thank You! Presented by: Edgard Chow phone (281) 474-1558 edgard.chow@kuraray.com Acknowledgement Mr. Wataru Hirose (EVAL R&D Japan)