Tackifier Dispersions

Creating Stable, Fast Running

Waterborne Adhesives Evert Smit
Ronnie Zeeman
Wouter van der Meulen

34. MKVS
October 19-21 2009 1
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
At Arizona Chemical we believe the key to
success is through understanding our
customers businesses, working in close
partnerships for mutual benefit.

3
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
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
Our raw material:
Renewable resources from the forest

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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

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Arizona Chemical creates value
from the tree

TOFA
CTO
Pulp

DTO

Rosin
Pitch
CTO
Kraft
Process
CST

-Pinene
-Pinene
CST
-3-Carene

8
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

11
Sustainable pine chemicals for daily life

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Green in Three Ways

TRUE
TRUE BIOREFINERIES
BIOREFINERIES
Extracting
Extracting the
the most
most value
value from
from
the
the biomass
biomass

LOW
LOW CARBON
CARBON FOOTPRINT
FOOTPRINT CUSTOMERS
CUSTOMERS GREEN
GREEN ADVANTAGE
ADVANTAGE
Nordic
Nordic refineries
refineries with
with Additional
Additional environmental
environmental benefits
benefits as
as
demonstrated
demonstrated low
low footprint
footprint an
an enhancement
enhancement to to the
the biorenewable
biorenewable
compared
compared with
with similar
similar operations
operations content
content

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Creating a sustainable future
with 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
Free energy:
gain if negative Entropy:
value order = loss
(negative),
Enthalpy:
thus bad
interaction = gain
with polymer
(negative value)
chains

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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

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 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

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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

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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

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 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 C H2
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 85C 100C

Softening point,C

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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

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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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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

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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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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
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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!

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Comparison performance

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Optimised
12 surfactant
package
10 system
8

0 Tackified system
Tack PE Neat system
Tack Steel
Peel PE
Peel Steel
Shear

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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
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
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:
Lets work together

36
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

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