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Typical PSA dispersion can be much improved in adhesive performance by adding tackifier dispersions. Especially the tack and peel on low surface energy sustrates like untreated PE and PP is affected positively, while cohesion is still sufficient for the application. When developing tackifier dispersions we need to walk a fine line between creating a stable final adhesive dispersion and not affecting the tackifier action negatively. In the current presentation we will show the nature and the action of the tackifier, the surfactant, and the influence of surfactant packages to come to a stable, fast running PSA dispersion which has excellent adhesive performance.
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Tackifier DispersionsCreating Stable, Fast Running Waterborne Adhesives
Evert SmitRonnie Zeeman
Wouter van der Meulen
34. MKVS
October 19-21 2009
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• 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
Content
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At Arizona Chemical we believe the key to success is through understanding our
customers’ businesses, working in close partnerships for mutual benefit.
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• 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
Our company
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Our locations
OuluSandarne
Niort
Chester le Street
Singapore
Almere
Valdosta
Jacksonville
Savannah
Panama City
Pensacola
Dover
Miami
Sales offices
Production sites
St. Petersburg
� 10 production sites, 5 sales offices
� US Headquarters in Jacksonville, FloridaEuropean headquarters in Almere, The Netherlands
Gersthofen
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Our raw material:Renewable resources from the forest
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SustainabilityBiorefining- A New Word for our Decades of Experience!
Renewable raw material
Refining and producing chemicals
Co-product of pulp production
Providing sophisticated products for the global chemical industry
PULP MILLArizona Chemical
Biorefinery:
“A facility that integrates biomass conversion processes and equipment to
produce fuels, power and added-value chemicals from biomass”Source: Wikipedia
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Arizona Chemical creates valuefrom the tree
CTO
CST
Kraft Process
CTO
Pul
p
CST
α-Pineneβ-Pinene
δ-3-Carene
TOFADTO
RosinPitch
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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
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The CTO and CST derivatives produced by Arizona Chemical in Oulu and Sandarne have a lower carbon footprint compared to substitutes
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Refinery Products: Value from the tree
Sylvalite ® RE 100 Comparable C5-C9 Resin
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Sustainable pine chemicals for daily life
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Green in Three Ways
TRUE BIOREFINERIESExtracting the most value from the biomass
TRUE BIOREFINERIESExtracting the most value from the biomass
LOW CARBON FOOTPRINTNordic refineries with demonstrated low footprint compared with similar operations
LOW CARBON FOOTPRINTNordic refineries with demonstrated low footprint compared with similar operations
CUSTOMERS’ GREEN ADVANTAGEAdditional environmental benefits as an enhancement to the biorenewable content
CUSTOMERS’ GREEN ADVANTAGEAdditional environmental benefits as an enhancement to the biorenewable content
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Creating a sustainable futurewith pine chemicals
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Tackifier Dispersions
For Pressure Sensitive Adhesive Dispersions
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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
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Why would an adhesive stick?
• What is the gain for the molecules?– Basic thermodynamics: Free Energy
∆∆∆∆G = H - T S∆∆∆∆∆∆∆∆
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Basic thermodynamics
∆∆∆∆G = H - T S∆∆∆∆∆∆∆∆
Entropy:order = loss(negative),thus bad
with polymer chains
Free energy:gain if negativevalue
Enthalpy:interaction = gain(negative value)
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Adhering to low surface energy substrates
•• NoNo possibilities for specific interactions– only Van der Waals
• The surface of PE is “liquid-like”– …and bonding to a liquid surface …
BulkBulk
TopTop
Very little interVery little inter--chain interactionchain interaction(just Van (just Van derder Waals)Waals)Small difference in free energy Small difference in free energy bulk and topbulk and top--layerlayerVery mobile chains (Very mobile chains (TgTg: : --90 C!)90 C!)Resulting in Resulting in ““ liquid floating topliquid floating top ””
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Tackifiers work by bridging the top…
BulkBulk
TopTop
Tackifiermolecules
∆∆∆∆G = H - T S∆∆∆∆∆∆∆∆∆∆∆∆G = H - T S∆∆∆∆∆∆∆∆∆∆∆∆G = H - T S∆∆∆∆∆∆∆∆
Small Molecules have little issue with
entropy!
Work almost like a surfactantBonding two phases…
Adhesive polymer
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Tackifying resins based on rosin
• Bonding– The molecule has 2 distinct areas
• Lipophilicenabling embedding in apolar areas
• Polar for interaction with the adhesive polymer
CH3
HO2 C
CH3
CH3
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Tackifying resins: Rosin derivatives
• Chemistry– The 2 functional groups also allow versatile modifications
• Esterification• Disproportionation• Hydrogenation• Polymerisation
or dimerisation• “Fortification”
CH3
HO2 C
CH3
CH3
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COO
COO OOC
OOC
C
Rosin Pentaerythritol Ester
CH2
CH2H2C
H2C
COO
COO
OOC
CH
CH2
CH2
GlycerolEster
Number of rosin molecules
Softening point,ºC
DiDi--esterester TriTri--esterester
2 3 4
liquid 85ºC 100ºC
TetraTetra--esterester
CH3
H3C
CH3
H3C
CH3
H3C
CH3
H3C
O
C
O
H2C
O
Diethylene Glycol Ester
CH2
O
CH2
H2C
O
Esterification – Rosin esters
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Rosin ester dispersions
Dispersion of a rosin ester in water with surfactant(s) and possibly other additives.
C O O
C O O
O O C
C H
C H2
C H2
Glycerol Ester
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Dispersing rosin esters
• In a dispersion the rosin ester is considered to be the oil phase
How does a rosin ester disperse in water?
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“Catastrophic Inversion”
Adding water and surfactant to molten rosin ester
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In real life
Catastrophic Inversion
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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
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Suspect Adhesive
Good Adhesive
25,000 sec25,000 sec --11 with a 20 micron gapwith a 20 micron gap- Suspect would run OK on Gravure or Curtain, but not on Slot-Die- Good adhesive runs well on all three
Shear stability in high speed coating
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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
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Shear Rate = 25,000 s -1, Gap = 10 micronsrunning
time
Old formulationNew formulation
low viscNew formulation
high viscMarket sample
Effect of surfactant package
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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!but this can be done!
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Comparison performance
Tack PE Tack Steel Peel PEPeel Steel
Shear
Neat system
Tackified system0
2
4
6
8
10
12
14Optimised surfactant package system
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Examples commercial grades
• Aquatac ® XR4316
– General purpose high solids product
– Designed for use on curtain coaters
• High mechanical stability• Low viscosity
– Good adhesion / cohesion properties with several polymers
– APEO free
• Aquatac ® XR4324
– Coater-ready when added to adhesive polymer
– Designed for use on curtain / gravure / slot die coaters
• Unique wetting package included
• High mechanical stability
• low viscosity
– Good adhesion / cohesion properties with several polymers
– APEO free
Copyright Arizona Chemical
Confidential
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Rosin Ester Dispersions
�Upgrade adhesive performance fordispersions
�Need for high solids content�Easy in use�Ever faster running coaters�“Green” – APEO free and renewable resource
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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:
LetLet ’’s work togethers work together
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Contact Details
Dr Evert SmitTechnical Leader Resins
Arizona ChemicalArizona ChemicalTransistorstraat 16
1322 CE Almere
The Netherlands
Mobile: +31 653 29 50 32
Office: +31 36 54 62 924
http://http://www.arizonachemical.comwww.arizonachemical.com
