new developments – environment friendly … and haasshilip kumar.pdfnew developments –...
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New Developments – Environment Friendly Adhesive Systems
Shilip Kumar – Business Manager Rohm and Haas (India) Pvt. Ltd.
August, 2008
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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
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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
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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
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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)
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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
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Dry
Pro
duct
s
Generally 2 layer laminates
Adhesives – Applications
High Performance
Mainly SB, New SL
Medium Performance-SB, SL,
WB (lower end)
General Performance - SB, WB, SL
Liqu
ids
Ret
ort
Typically 3 layer laminates 4 layer complexlaminates
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Laminating Adhesives : How They Stack Up
Good
Fair
Low
Economics Safety, Odor Risk Cure Time*
* - Slitting, heat sealing
Processing
Low
Low
High
High
Low Easy
Fair Easy
Fair
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Key Regulations : Adhesives in Food Packaging
21 CFR 175.105 To cover laminates subjected to room temp applications (49°C and below).
21 CFR 177.1390Laminate structures for use at temp of >121°C (retortable laminates)
21 CFR 177.1395Laminate 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
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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.
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Solvent-Free New Developments
• Fast cure • Retort / Boil in Bag • Extremely Low Monomer (ELM)
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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-FreeTMC-411 & 5 days
with Mor-FreeTM C-132-1Products 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
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Pot Life of MF 75-164/C-411 at 100:40 Mix RatioPot Life For Mor-Free L 75-164/C-411
0.00
2000.00
4000.00
6000.00
8000.00
10000.00
12000.00
14000.00
16000.00
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
Visc
osity
, cp 25°C
38°C43°C49°C
Pot life at 38° C 30mins
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Pot Life of MF 75-164/C-132-1 at 100:63 Mix RatioPot Life For Mor-Free L 75-164/C-132-1
0.00
2000.00
4000.00
6000.00
8000.00
10000.00
12000.00
14000.00
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
Visc
osity
, cp 25°C
38°C43°C49°C
Pot life at 38° C 43mins
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Comparative Bond Strength Development
Bond Strength Development in PET/PE
0100200300400500600700800900
MF403A/C-411 MFL75-164/C-411 MFL75-164/C-132-1
Avg
.Loa
d in
gm
s/25
mm
4hrs 8hrs 24hrs 48hrs 26days
Bonds develop rapidly in 8hrs
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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-FreeTM C-
411)• A solvent free product that can be used for hot fill applications and has
FDA 177.1395.• Room temperature application and cure.
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Solvent-Free for Retort Laminates
• Mor-FreeTM 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
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Physical Properties – Mor-FreeTM 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
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Bond Strength study
0
500
1000
1500
2000
2500
Pre-RetortBond
Post RetortBonds
Bond
s - P
eak
Load
(GLI
)
PetSiOX/Nylon/440CPPDupontLBT/SiOxNylon/440CPPPETAlOx/Nylon/440CPP
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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
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Amines may be formed as follows:
Isocyanates react with water
R - NCO + H20intermediate stage, carbon dioxide splits off
R - NH2
corresponding amine is formed
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Amines may be formed as follows:
Polyurethanes can hydrolyse(especially under sterilization conditions)
R`- O - CO - NH - R + H2Ointermediate stage, carbon dioxide splits off
R`- OH + R - NH2
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1 component
2 comp MDI based
Hybriddifferent NCO´s
ELMExtremely Low Monomer
Aliphatic0 %
0.1 %
> 10 %
Aro
mat
ic N
CO
leve
l
Historical Developments in Solvent-Free Technology
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Solvent Free ELM Adhesives - Specific Advantages
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
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 ELM ProductsMor-FreeTM 415+CR88-551
Mor-FreeTM ELM415+CR88-554
Mor-FreeTM ELM415+CR87-550
Superior Properties• Universal product tailored to
application needs with choice of co-reactant
• Good adhesion to films, metallizedfilms and aluminum foil
• Superior chemical and heat resistance with hot fill
• Extremely good sealability
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0,00
1,002,00
3,004,00
5,00
6,007,00
8,009,00
10,00
1 3 7 14 18 22 29Days
µg/1
00 m
l/4 d
m²
Aliphatic Polyurethane
ELM 415 A + CR 88-554
Hybrid Polyurethane
NCO/OH Polyurethane
Mor-Free ELM Solvent-free AdhesivesFood Contact & Migrations
Old Limit 2002-72/EC20 ppb
Decay example of Primary Aromatic Amines
in a OPA printed – PE Laminate
New limit 01/07/200810 ppb
TR
EN
D
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Acrylic WBDL For Flexible Packaging
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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.
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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
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Water Based Acrylic vs Solvent Based UrethaneWater 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
Energypropagates
crack
Energydeformsadhesive
High adhesion/Moderate cohesion
Moderate adhesion/High cohesion
vs.
Polyurethane :
Acrylic :
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Robond - How it works
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Shear vs. Laminate Bond Strength
0
200
400
600
800
Green BondStrength
Cured BondStrength
Green ShearStrength
Cured ShearStrengthB
ond
Stre
ngth
(gra
ms
/ 25m
m) S
hear
Str
engt
h (k
N/m
2) Robond 1K GP Adhesive
Solvent Based MP Urethane
Robond 2K MP Adhesive
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32
Factors to Consider
1. Cylinder2. Pump3. Dryer – Air velocity, Volume of air, Exhaust4. Nip temperature and pressure5. Smoothing Bar6. Ink compatibility wet-out
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Cylinder – Different Cell Geometries
Pyramid Quad Channel Quad (QCH)
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Smoothing Bar
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Smoothing Bar
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Pump selection
• Critical to minimize foaming• Select pumps with minimum shear• Do not use ink pumps, centrifugal or
gear pumps• Recommendation:
– peristaltic or – diaphragm
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The RobondTM L Family
Robond L-90DRobond L-90D
General PurposeGeneral Purpose
Robond L-208 / CR-3ARobond L-208 / CR-3A
Medium PerformanceMedium Performance
Robond LAcrylic Dry Bond
Laminating Adhesives
* Robond L-168A – New Development
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Concerns with WBInk 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.
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Robond L-168A overcomes ink and substrate wetting issues
With General WB With Robond L-168APoor wetting 100% wetting
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Robond L-168A overcomes ink and substrate wetting issues
With General WB With Robond L-168APoor wetting 100% wetting
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Conclusion
Environment Friendly WB adhesives a viable option forGP & lower end MP applications.
Newly developed product will address Ink wet-out relatedissues.
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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
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Thank you for the kind attention.