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Tackifier Dispersions
- 1. Tackifier Dispersions Creating Stable, Fast Running Waterborne Adhesives Evert Smit Ronnie Zeeman Wouter van der Meulen 34. MKVS October 19-21 2009 1
- 2. Content • Introduction Arizona Chemical – Sustainable, Green and low Carbon Footprint • Rosin Ester Tackifiers – Their action – looking at molecular scale – Chemistries • Rosin Ester Dispersions – How are they made? • Stable adhesive dispersions with tackifiers – Testing at high shear • Performance • Conclusions 2
- 3. At Arizona Chemical we believe the key to success is through understanding our customers’ businesses, working in close partnerships for mutual benefit. 3
- 4. Our company • 10 Manufacturing facilities • Broad-based research and development • Regional headquarters in Jacksonville, Florida and Almere, Netherlands • 2 Research, Development & Technical Service labs – Almere, The Netherlands – Savannah, Georgia US 4
- 5. Our locations Oulu Sandarne St. Petersburg Chester le Street Almere Dover Gersthofen Pensacola Savannah Niort Valdosta Panama City Jacksonville Miami Singapore 10 production sites, 5 sales offices US Headquarters in Jacksonville, Florida European headquarters in Almere, The Netherlands Sales offices Production sites 5
- 6. Our raw material: Renewable resources from the forest 6
- 7. Sustainability Biorefining- A New Word for our Decades of Experience! Biorefinery: “A facility that integrates biomass conversion processes and equipment to produce fuels, power and added-value chemicals from biomass” Source: Wikipedia Renewable raw Co-product of pulp Refining and Providing sophisticated products material production producing chemicals for the global chemical industry Arizona PULP MILL Chemical 7
- 8. Arizona Chemical creates value from the tree TOFA CTO Pulp DTO Rosin Pitch CTO Kraft Process CST α-Pinene β-Pinene CST δ-3-Carene 8
- 9. Arizona Chemical- Biorefining in its Truest Sense “By producing multiple products, a biorefinery takes advantage of the various components in biomass and their intermediates therefore maximising the value derived from the biomass feedstock.” Source: Wikipedia 9
- 10. The CTO and CST derivatives produced by Arizona Chemical in Oulu and Sandarne have a lower carbon footprint compared to substitutes 10
- 11. Refinery Products: Value from the tree Sylvalite® RE 100 Comparable C5-C9 Resin 11
- 12. Sustainable pine chemicals for daily life 12
- 13. Green in Three Ways TRUE BIOREFINERIES TRUE BIOREFINERIES Extracting the most value from Extracting the most value from the biomass the biomass LOW CARBON FOOTPRINT LOW CARBON FOOTPRINT CUSTOMERS’ GREEN ADVANTAGE CUSTOMERS’ GREEN ADVANTAGE Nordic refineries with Nordic refineries with Additional environmental benefits as Additional environmental benefits as demonstrated low footprint demonstrated low footprint an enhancement to the biorenewable an enhancement to the biorenewable compared with similar operations compared with similar operations content content 13
- 14. Creating a sustainable future with pine chemicals 14
- 15. Tackifier Dispersions For Pressure Sensitive Adhesive Dispersions 15
- 16. Rosin Ester Dispersions • Upgrade adhesive performance for dispersions • Need for high solids content • Easy in use • Ever faster running coaters • “Green” – APEO free and renewable resource 16
- 17. Why would an adhesive stick? • What is the gain for the molecules? – Basic thermodynamics: Free Energy ∆ G = ∆ H - T∆ S 17
- 18. Basic thermodynamics ∆ G = ∆ H - T∆ S Free energy: gain if negative Entropy: value order = loss (negative), Enthalpy: thus bad interaction = gain with polymer (negative value) chains 18
- 19. Adhering to low surface energy substrates • No possibilities for specific interactions – only Van der Waals • The surface of PE is “liquid-like” – …and bonding to a liquid surface … Very little inter-chain interaction (just Van der Waals) Top Small difference in free energy bulk and top-layer Bulk Very mobile chains (Tg: -90 C!) Resulting in “liquid floating top” 19
- 20. Tackifiers work by bridging the top… Work almost like a surfactant Bonding two phases… Adhesive polymer Tackifier molecules Small Molecules have little issue with Top entropy! Bulk ∆ G = ∆ H - T∆ S 20
- 21. Tackifying resins based on rosin • Bonding – The molecule has 2 distinct areas CH3 • Lipophilic enabling embedding in apolar areas CH3 CH3 • Polar for interaction with the adhesive polymer HO2 C 21
- 22. Tackifying resins: Rosin derivatives • Chemistry – The 2 functional groups also allow versatile modifications CH3 • Esterification • Disproportionation CH3 CH3 • Hydrogenation • Polymerisation or dimerisation • “Fortification” HO2 C 22
- 23. Esterification – Rosin esters Number of rosin molecules 2 3 4 CH3 H3C CH3 CO O C H2 COO H2C CH2 OOC O COO CH C COO H2C CH2 OOC H3C H2 H2 CH2 C O C CH3 C C C O O H2 H2 OOC O H3C CH3 Diethylene Glycol Ester H3C Di-ester Glycerol Ester Tri-ester Tetra-ester Rosin Pentaerythritol Ester liquid 85ºC 100ºC Softening point,ºC 23
- 24. Rosin ester dispersions Dispersion of a rosin ester in water with surfactant(s) and possibly other additives. CO O C H2 CO O C H C H2 O O C G lycerol Ester 24
- 25. Dispersing rosin esters • In a dispersion the rosin ester is considered to be the oil phase How does a rosin ester disperse in water? 25
- 26. “Catastrophic Inversion” Adding water and surfactant to molten rosin ester 26
- 27. In real life Catastrophic Inversion 27
- 28. Adhesive dispersion • Typically acrylate polymer dispersion – Optimised for fast trouble free running • Add 20 – 40 % rosin ester dispersion – To improve tack and peel • BUT: Polymer – resin mixture can become sub-optimal for high speed running – … if not carefully designed re surfactant package – Final dispersion mixture needs to be stable at high shear stresses 28
- 29. Shear stability in high speed coating Suspect Adhesive Good Adhesive 25,000 sec-1 with a 20 micron gap - Suspect would run OK on Gravure or Curtain, but not on Slot-Die - Good adhesive runs well on all three 29
- 30. Optimised surfactant packages • Make the total adhesive – tackifier dispersion mixture stable – even at high loading, at the high shear stresses seen at high coating speeds • Prevent sedimentation 30
- 31. Effect of surfactant package Old formulation New formulation low visc New formulation high visc Market sample Shear Rate = 25,000 s-1, Gap = 10 microns running time 31
- 32. Adhesive performance • Surfactant undoubtedly has impact on adhesive performance – It counteracts the “surfactant action” of the resin – Hence negative for both peel and shear – Lower surfactant level should be better – …need careful balance for optimal stability but this can be done! 32
- 33. Comparison performance 14 Optimised 12 surfactant package 10 system 8 6 4 2 0 Tackified system Tack PE Neat system Tack Steel Peel PE Peel Steel Shear 33
- 34. Examples commercial grades • Aquatac® XR4316 • Aquatac® XR4324 – General purpose high solids – Coater-ready when added product to adhesive polymer – Designed for use on curtain – Designed for use on curtain / coaters gravure / slot die coaters • High mechanical stability • Unique wetting package • Low viscosity included • High mechanical stability • low viscosity – Good adhesion / cohesion – Good adhesion / cohesion properties with several polymers properties with several polymers – APEO free – APEO free Copyright Arizona Chemical Confidential 34
- 35. Rosin Ester Dispersions Upgrade adhesive performance for dispersions Need for high solids content Easy in use Ever faster running coaters “Green” – APEO free and renewable resource 35
- 36. Conclusions • It is possible to design optimal surfactant packages – Combining excellent high shear stability – …Without impeding adhesive performance • Rosin ester dispersion upgrade adhesive performance drastically • Ideally, each polymer – resin combination needs to be studied individually: Let’s work together 36
- 37. Contact Details Dr Evert Smit Technical Leader Resins Arizona Chemical Transistorstraat 16 1322 CE Almere The Netherlands Mobile: +31 653 29 50 32 Office: +31 36 54 62 924 evert.smit@azchem.com http://www.arizonachemical.com 37