New Developments Environment Friendly Adhesive Systems. Shilip Kumar Business Manager Rohm and Haas (India) Pvt. Ltd.

New Developments Environment Friendly Adhesive Systems Shilip Kumar Business Manager Rohm and Haas (India) Pvt. Ltd. August, 2008

Contents Drivers for Innovation in Adhesives Laminating Adhesives An overview New Developments : Solvent-Free Adhesives Fast Cure adhesives Retort / Boil in Bag adhesives ELM adhesives Water Based Dry Lamination adhesives

Drivers for Innovations in Adhesives Key Drivers Total Cost reduction Shorter order to ship cycle times Stricter regulations and increasing consumer awareness of food safety Packaging with enhanced features Environmental concerns Innovations to address these needs New generation Solvent-free adhesives: Fast Cure High Performance Retort Grade Water-based adhesives

Solvent-based Dry Lamination Solvents to be dried Typically 2 component polyurethane (PU) adhesives + Relatively easy to run + Versatile: General Purpose to High Performance - Residual solvent odour in laminate - Safety & Health risk - Environmental pollution - Risk of carcinogenic aromatic amine - Slower speeds versus solvent-free - Most expensive

Solvent-free Lamination No Solvents used 1 or 2 component Polyurethane (PU) adhesives + Most cost effective + High speeds + No residual odour/solvent - Needs skilled operators and good equipment - Handling of isocyanates, health risk - Risk of carcinogenic aromatic amines - Difficult to run rigid & polar substrates (e.g. PET/Foil)

Water-based Dry Lamination Water-based emulsion 1 or 2 component acrylic based adhesives + Cost effective + No residual odour + No risk of carcinogenic aromatic amines + Can be used on existing Dry Laminators at similar speeds to SB + Ease of use + Immediate slitting and processing + Environmentally safe - Drying capacity of machines - Ink compatibility - Needs Operator training

Adhesives Applications Liquids Retort Medium Performance -SB, SL, WB (lower end) High Performance Mainly SB, New SL Dry Products General Performance -SB, WB, SL Generally 2 layer laminates Typically 3 layer laminates 4 layer complex laminates

Laminating Adhesives : How They Stack Up Good Low High Fair Fair Low Low Easy Low High Fair Easy Economics Safety, Odor Risk Cure Time* Processing * - Slitting, heat sealing

Key Regulations : Adhesives in Food Packaging 21 CFR 175.105 To cover laminates subjected to room temp applications (49 C and below). 21 CFR 177.1390 Laminate structures for use at temp of >121 C (retortable laminates) 21 CFR 177.1395 Laminate structures for use at temp between 49-121 C as boilable, hot-fill. 90/128 EEC : PAA limit : 10 ppb BgVV : PAA limit : 2 ppb FDA : Compositional regulation/need for functional barrier

Solvent-Free Adhesives Concerns Low green bond. Minimum 24hrs cure time for slitting. Suitable only for General performance segment and some Medium performance jobs. Food Legislation - Carcinogenic Primary Aromatic Amine issues.

Solvent-Free New Developments Fast cure Retort / Boil in Bag Extremely Low Monomer (ELM)

New Fast Cure Solvent-Free adhesives Unique Fast Cure Technology RT Applied & Cured Similar pot life as current products 200 gms/25mm bond seen in 2 hrs Second pass & Slitting possible in 4 hours Ready to fill in 3 days (including liquids) Good Metal adhesion Met.PET & Foil Lower Work in Process (WIP) costs Hot fill FDA clearance (177.1395) 3 days with Mor-Free TM C-411 & 5 days with Mor-Free TM C-132-1 Products commercialized : Morfree L75-164 + C-411 (100 : 40 pbw) Morfree L75-164 + C-132-1 (100 : 63 pbw) To know more about our Mor-Free L75-164 Fast Cure Technology http://go.rohmhaas.com/morfree

Pot Life of MF 75-164/C-411 at 100:40 Mix Ratio Pot Life For Mor-Free L 75-164/C-411 16000.00 14000.00 Pot life at 38 C 30mins 12000.00 Viscosity, cp 10000.00 8000.00 6000.00 25 C 38 C 43 C 49 C 4000.00 2000.00 0.00 0:00:00 0:14:24 0:28:48 0:43:12 0:57:36 1:12:00 1:26:24 Time, Hours:minutes:seconds

Pot Life of MF 75-164/C-132-1 at 100:63 Mix Ratio Pot Life For Mor-Free L 75-164/C-132-1 14000.00 12000.00 Pot life at 38 C 43mins 10000.00 Viscosity, cp 8000.00 6000.00 25 C 38 C 43 C 49 C 4000.00 2000.00 0.00 0:00:00 0:14:24 0:28:48 0:43:12 0:57:36 1:12:00 1:26:24 Time, Hours:minutes:seconds

Comparative Bond Strength Development Bond Strength Development in PET/PE Avg.Load in gms/25mm 900 800 700 600 500 400 300 200 100 0 Bonds develop rapidly in 8hrs MF403A/C-411 MFL75-164/C-411 MFL75-164/C-132-1 4hrs 8hrs 24hrs 48hrs 26days

Conclusion - New Fast Cure / Hot Fill Cure response is fast, pot life is similar to more slowly curing products Fast bond development for further processing (500 gms/25mm in 8 hours) Good metal adhesion depending on coreactant choice (Mor-Free TM C- 411) A solvent free product that can be used for hot fill applications and has FDA 177.1395. Room temperature application and cure.

Solvent-Free for Retort Laminates Mor-Free TM 225 / C-33 is a new retort grade SL adhesive system Meets FDA 177.1390 and 177.1395 Better Economics due to lower coat weights as compared to SB adhesives. Is RT applied and can be RT cured, but hot room is generally recommended to speed up cure. Is more robust on all clear barrier structures. Not recommended for foil containing structures with aggressive fills

Physical Properties Mor-Free TM 225/C-33 Mix Ratio 100 : 100 pbw Viscosity 3500 / 2400 cps Sp. Gravity in gms/cc 1.176 / 1.170 Application temp 43 54 C Pot life 20mins at 54 C Coat weight 2.0 2.4 gsm

Bond Strength study Bonds - Peak Load (GLI) 2500 2000 1500 1000 500 0 Pre-Retort Bond Post Retort Bonds PetSiOX/Nylon/44 0CPP DupontLBT/SiOx Nylon/440CPP PETAlOx/Nylon/44 0CPP

Solvent-Free ELM Sources of Primary Aromatic Amines Adhesives Inks Laminate Construction Additive composition in Films Curing conditions of laminate Storage conditions of laminate Age of structure

Amines may be formed as follows: Isocyanates react with water R - NCO + H 2 0 intermediate stage, carbon dioxide splits off R - NH 2 corresponding amine is formed

Amines may be formed as follows: Polyurethanes can hydrolyse (especially under sterilization conditions) R`- O - CO - NH - R + H 2 O intermediate stage, carbon dioxide splits off R`- OH + R - NH 2

Historical Developments in Solvent-Free Technology 0 % Aliphatic Aromatic NCO level 0.1 % > 10 % ELM Extremely Low Monomer Hybrid different NCO s 2 comp MDI based 1 component

Solvent Free ELM Adhesives - Specific Advantages Superior Properties Universal product tailored to application needs with choice of coreactant Good adhesion to films, metallized films and aluminum foil Superior chemical and heat resistance with hot fill Extremely good sealability Total Safety Dramatically reduces the risk of Primary Aromatic Amine formation Reduces the risk of anti seal effect No hazardous substances, no transport or storage restrictions Easy to use and process Ambient cure, no post curing No preheating in hot rooms Extremely easy to use, less waste, clean-up and down-time To be applied at very high application speeds without misting at low application temperatures Very stable pan life, no moisture reactivity in the pan, no waste Excellent wettability of difficult substrates ELM Products Mor-Free TM 415+CR88-551 Mor-Free TM ELM415+CR88-554 Mor-Free TM ELM415+CR87-550

Mor-Free ELM Solvent-free Adhesives Food Contact & Migrations µg /100 m l/4 d m ² 10,00 9,00 8,00 7,00 6,00 5,00 4,00 3,00 2,00 1,00 0,00 20 ppb 10 ppb Decay example of Primary Aromatic Amines in a OPA printed PE Laminate Old Limit 2002-72/EC New limit 01/07/2008 1 3 7 14 18 22 29 Days Aliphatic Polyurethane ELM 415 A + CR 88-554 Hybrid Polyurethane NCO/OH Polyurethane TREND

Acrylic WBDL For Flexible Packaging

Water Based Acrylic Adhesive Chemistry Very Different from SB/SL PU Systems An emulsion polymer made by free radical polymerisation of acrylic monomers on water. High MW polymer particles finely suspended in water. Appearance : Opaque white Particle Size : 0.05 1.0 microns Molecular Weight : 500,000 1,000,000 is typical Very flexible Laminate bond strength is related to the deformation energy required to separate the laminate.

WB Adhesives - Benefits User Friendly Easy Mixing / No Viscosity Adjustment Cost effective No Adhesive wastage Better Optics No VOC or DG Issues Safer, Greater Regulatory Compliance Faster Processing No WIP Shorter Time to Market Performance Equivalent to Medium Performance PU Systems

Water Based Acrylic vs Solvent Based Urethane Water Based Acrylic Very High Molecular Weight Low Viscosity (Particles) High Application Solids Solvent Based Urethane Low Molecular Weight Viscosity increases dramatically with increasing molecular weight (Chains) Low Application Solids Polyurethane : High adhesion/ Moderate cohesion Energy propagates crack Acrylic : vs. Moderate adhesion/ High cohesion Energy deforms adhesive

Robond - How it works

Shear vs. Laminate Bond Strength Bond Strength (grams / 25mm) Shear Strength (kn/m2) 800 600 400 200 0 Robond 1K GP Adhesive Solvent Based MP Urethane Robond 2K MP Adhesive Green Bond Cured Bond Strength Strength Green Shear Strength Cured Shear Strength

Factors to Consider 1. Cylinder 2. Pump 3. Dryer Air velocity, Volume of air, Exhaust 4. Nip temperature and pressure 5. Smoothing Bar 6. Ink compatibility wet-out 3 2

Cylinder Different Cell Geometries Pyramid Quad Channel Quad (QCH) 3 3

Smoothing Bar

Pump selection Critical to minimize foaming Select pumps with minimum shear Do not use ink pumps, centrifugal or gear pumps Recommendation: peristaltic or diaphragm

The Robond TM L Family Robond L Acrylic Dry Bond Laminating Adhesives Robond L-90D General Purpose Robond L-208 / CR-3A Medium Performance * Robond L-168A New Development

Concerns with WB Ink wettability Universal Ink wet-out is an issue Wet-out problem can be resolved using an Inline corona treater. Corona Treater cleans the surface of the printed film of waxes, low molecular weight compounds,.. New Product to address this concern Robond L-168A Robond L-168A has good wettability shown promising results on a wide variety of Ink systems.

Robond L-168A overcomes ink and substrate wetting issues With General WB With Robond L-168A Poor wetting 100% wetting

Conclusion Environment Friendly WB adhesives a viable option for GP & lower end MP applications. Newly developed product will address Ink wet-out related issues.

Rohm and Haas Company - Leading supplier of adhesives and coatings for the flexible packaging industry A comprehensive product portfolio for all bonding needs Adhesives for paper, film and foil lamination - General purpose through high performance. - Water-based, solvent-based, solvent-free energy curable. Heat-and cold-seal coatings - Solvent-based, water-based, barrier, dispersions. Primers Extrudable Tie Layer resins

Thank you for the kind attention.