Tackifier Dispersions

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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

evert.smit@azchem.com

http://http://www.arizonachemical.comwww.arizonachemical.com