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Improving

Waterborne
Acrylic Coatings
and Pressure
Sensitive
Adhesives
Bill McNamee – Research Manager
Contents

ƒ Principles of Non-migratory Surfactants (NMS)

ƒ Croda Product Range - MaxemulTM NMS

ƒ Coatings
ƒ Application work
ƒ Benefits

ƒ Pressure Sensitive Adhesives


ƒ Application work
ƒ Benefits

ƒ Conclusion
Non-migratory surfactants
Principles

ƒ Conventional surfactants - a necessary evil?


ƒ Essential components in emulsion polymer
systems
ƒ particle size control
ƒ colloidal stability

ƒ Physical adsorption through hydrophobic


interaction
Non-migratory surfactants
Principles

ƒ Conventional surfactants - a necessary evil?


ƒ Migratory products - do not remain within polymer
matrix
ƒ Effects on film properties
ƒ Surface effects
ƒ gloss, blocking resistance, adhesion, solvent
resistance
ƒ Bulk effects
ƒ water uptake, protection, pigment binding,
swelling
Non-migratory surfactants
Principles

ƒ Non-migratory surfactants
ƒ Contain reactive group capable of polymerisation
ƒ Able to covalently link to the particle surface during polymerisation
ƒ Irreversibly grafted through covalent linking
ƒ permanent protective barrier gives superior colloidal stability
ƒ homogeneous distribution of surfactant improves dry film
properties
Contents

ƒ Principles of Non-migratory Surfactants (NMS)

ƒ Croda Product Range - MaxemulTM NMS

ƒ Coatings
ƒ Application work
ƒ Benefits

ƒ Pressure Sensitive Adhesives


ƒ Application work
ƒ Benefits

ƒ Conclusion
Maxemul™
Anionic NMS – Maxemul 6106, 6112

ƒ Chemical description
ƒ Modified alcohol ether phosphates
ƒ Varying PEO chain length
ƒ M6112 > M6106
ƒ Supplied in acid form
ƒ require pre-neutralisation
ƒ allows formulation flexibility
ƒ Electrosteric stabilisers
ƒ Efficient during particle nucleation and growth
stage

(EO)n-OPO3H
Maxemul™
Non-ionic NMS – Maxemul 5010, 5011

ƒ Chemical description
ƒ Alkenyl / Carboxy functional hydrophobe
ƒ Varying PEO chain length
ƒ Maxemul 5010: 25 EO (HLB 13.1)
ƒ Maxemul 5011: 34 EO (HLB 16.1)
ƒ Steric stabilizers

(EO)n-X

COOH
Contents

ƒ Principles of Non-migratory Surfactants (NMS)

ƒ Croda Product Range - MaxemulTM NMS

ƒ Coatings
ƒ Application work
ƒ Benefits

ƒ Pressure Sensitive Adhesives


ƒ Application work
ƒ Benefits

ƒ Conclusion
Maxemul™ Anionic NMS: Nucleation
Efficiency

Maxemul 6112, Nucleation efficiency

90
Particle size (nm)

80

70 Control (Sat)
60 Maxemul 6112

50

40
Batch pzn @ 10% TS
0 2 4 6 8 10 12 14 16 18 20 22
Surfactant concentration (phm) Demineralised water to 1000
BA/MMA/MAA 48.8/49.9/1.3 100
KPS 0.3
Maxemul 6112 is dissolved in DI water at NaHCO3 0.15
20 % solids, used in acid form Demineralised water 15
Max 6112 var
1000
Maxemul™ Anionic NMS
Application work in Coatings

ƒ Acrylic terpolymer, BA/MMA/MAA (48.8/49.9/1.3)


produced in a seeded semi-continuous
polymerisation
ƒ Typically 45 % polymer solids, 145 nm particle
size
ƒ Benchmarked vs conventional and alternative NMS
ƒ Conventional linear alcohol ether phosphate
(SAT)
ƒ Conventional isobranched alcohol ether
phosphate (ISO)
ƒ Allylic functional NMS
ƒ Propenyl functional NMS
ƒ Nomenclature: M6112/2.5 ≣ M6112 at 2.5 parts per
hundred monomer
Maxemul™ Anionic NMS
Reaction kinetics / Surfactant Incorporation

ƒ Final conversion for Maxemul 6112 determined on a


seeded semi-continuous acrylic emulsion

ƒ Unreacted surfactant separated from polymer via


ultracentrifugation and quantified via P-analysis
ƒ 10 % free surfactant found in aqueous phase
ƒ Lower than conventional and other NMS
technologies

ƒ Significant impact on polymer molecular weight


obtained
Maxemul™ Anionic NMS
Reaction kinetics

ƒ Polymer molecular weights lower with Allylic and Propenyl functional NMS
ƒ Due to degradative chain transfer

500
Mol Wt (g/molx1000)

450 Mn
400 Mw
350
300
250
200
150
100
50
0
Pr eny .5

en .5

.5
Pr eny 5
Pr lly l 5
SA 3.5
61 .5

61 .5

.
A /2.

2
M 2 /1

M 2 /2

op l/2

/3
op l/1
op ic/
/
T

yl
12
1

1
61
M
Maxemul™ Anionic NMS
Colloidal Stability

ƒ MaxemulTM grafted reactive surfactants


also improve the colloidal stability 165
(dispersion stability) of the latex 160

Particle Size (nm)


ƒ Stability measured by analysis of 155
particle size (QELS) before and after
stress tests 150
ƒ Latices show excellent shear and 145
freeze/thaw stability 140
ƒ Latices resist high levels of solvents
135
(ethanol and butyldiglycol)
130
M6112/2.5 SAT/2.5
Before Shear After Shear
Maxemul™ Anionic NMS
Dry film properties - Superior water repellency

100 100
Transmission haze

80 80

Water Uptake (%)


60 60

40 40

20 20

0 0
0 1 2 24 0 5 10 15 20

Immersion time (hrs) Immersion time (days)


M6112/2.5R M 6112/2.5
M6112/2.5R M6112/2.5
ISO/2.5 SAT/2.5 SAT/2.5
[M6112, KPS initiated, M6112R, t-BPB initiated]
Maxemul™ Anionic NMS
Dry film properties - Superior water repellency

ƒ Appearance after immersion in water


ƒ Rapid whitening of film containing conventional emulsifier
ƒ Film containing NMS hardly whitens (as surfactant remains evenly
distributed in polymer upon drying)
ƒ Maxemul 6112 (1 week) Conventional (1 day)
Maxemul™ Nonionic NMS:
Colloidal Stability

Vac/VeoVa10
Effect of surfactant on colloidal stability
Synperonic NP20 Maxemul 5011

30 35

Particle volume (%)


Particle volume (%)

25 30
25
20 Initial
Initial 20
15 Freeze/thaw
Sheared 15
10 Sheared
10
5 5
0 0
-1.5 -0.5 0.5 1.5 -1.5 -0.5 0.5 1.5
log Particle size (µm) log Particle size (µm)
Mastersizer E
F/T (+23/-20°C) failed with NP20
Sheared for 30 Min at 3000 rpm
Maxemul™ NMS
Barrier Properties – Acrylic Film

ƒ Barrier properties determined by use of water (vapour) transmission


test

Upper part
of G cell

Film

Water container
(G cell)

ƒ The two parts of cell are screwed together with polymer film in
between [J. Appl.Polym. Sci.,56,823 (1995)]
Maxemul™ NMS
Barrier Properties – Acrylic Film

Water Transmission Rates


Air Upper

High water diffusion rates with conventional


surfactants usage suggests poor protective
properties of the film

Substrate Lower

Water transmission rates


Lower interface Upper interface
Nonyl Phenol 30EO 14.11 183.5
Sodium Lauryl Sulfate 13.6 103.4
Maxemul 5010 9.84 35.77
Maxemul 5011 13.92 34.31
Atomic Force Microscopy (AFM)
Effect of residual surfactants on Acrylic films

Film surface contaminated with Film surface with Non-migratory


conventional surfactant (NP30) surfactants

Acrylic latex
stabilised with
NP30 (l) or
Maxemul 5011 (r)
Atomic Force Microscopy (AFM)
Effect of residual surfactants on Acrylic films

Film surface with conventional Film surface with Non-migratory


surfactants after water washing surfactants after water washing

Acrylic latex
stabilised with
NP30 (l) or
Maxemul 5011 (r)

Film surface of conventional system after water washing shows pinholes where
surfactant micelles were; protective properties are affected
Maxemul™ NMS usage
Benefits in Coatings

ƒ Formulation
ƒ Pigment wetting and binding
ƒ Coalescent acceptance (higher solvent resistance
enables use of harder copolymers and coalescent
levels)
ƒ Film Properties
ƒ Scrub resistance
ƒ Due to better pigment wetting (gives improved
binding power) and better water resistance
originating from film with less hydrophilic spots
ƒ Water repellence
ƒ Lower water diffusion rates through the film due
to absence of hydrophilic domains and micropores
ƒ Faster drying
ƒ Particles do not flocculate during film formation
and water evaporation rate remains constant
Maxemul™ NMS usage
Benefits in Coatings

ƒ Film Properties
ƒ Salt spray resistance
ƒ Lower water diffusion rates through the film due
to absence of hydrophilic domains and micropores
ƒ Better adhesion of the polymer onto the substrate
as the interface is not contaminated with
surfactant
ƒ Barrier properties, stain resistance
ƒ Lower water diffusion rates through the film due
to absence of hydrophilic domains and
micropores. Reduces the transport of
watersolubles from the substrate to the film
surface and gives better stain resistance
ƒ Blocking resistance
ƒ Conventional emulsifiers accumulate at film
surface and attract water which plasticises the
film surface, leading to poor blocking resistance
Contents

ƒ Principles of Non-migratory Surfactants (NMS)

ƒ Croda Product Range - MaxemulTM NMS

ƒ Coatings
ƒ Application work
ƒ Benefits

ƒ Pressure Sensitive Adhesives


ƒ Application work
ƒ Benefits

ƒ Conclusion
Maxemul™ Anionic NMS
Application work in Pressure Sensitive Adhesives (PSA)

ƒ BA- and 2-HEA rich copolymers produced in a


seeded semi-continuous polymerisation
ƒ Typically 45 % polymer solids, 125 nm particle
size

ƒ Benchmarked vs conventional and alternative NMS


ƒ Conventional alcohol ether phosphate (A3232)
ƒ Allylic functional NMS
Maxemul™ NMS in PSA
Adhesive properties, shear strength

ƒ Tensile Strength (kN) or in-plane


cohesion failure
ƒ Test conditions
ƒ films obtained from a 60/40
PSA/Ethanol mix
ƒ applied on polyester substrate
ƒ cured for 5’ at 120°C and 24hrs at
ambient
ƒ contact area: 20mm x 20mm, 5 kg
loaded for 60 sec
Maxemul™ NMS in PSA
Adhesive properties, shear strength

ƒ Effects of film thickness and polymer composition


ƒ wet film thickness 50-200 µm, dry films obtained from a 60/40 PSA/Ethanol mix
ƒ [Surfactant] = 3.21 phm
ƒ Higher shear strength for Maxemul 6112 vs allylic NMS

BA/MMA/MAA/HEA

300

250
Max load (N)

Allylic NPEs
200
M6112

150

100
50

0
10

15

20

Wet film thickness


Maxemul™ NMS in PSA
Adhesive properties, shear strength
ƒ Effects of film thickness and polymer composition
ƒ wet film thickness 50-200 µm, dry films obtained from a 60/40 PSA/Ethanol mix
ƒ [Surfactant] = 3.21 phm
ƒ Higher shear strength for Maxemul 6112 vs conventional
BA/MMA/MAA

300
250
Max load (N)

200
M6112 3.21 HEA free
150
A3232 HEA free
100
50
0
50

0
10

15

20

Wet film thickness


Maxemul™ NMS usage
Benefits in Pressure Sensitive Adhesives

ƒ Less foaming
ƒ Less surfactant in the water phase (due to grafting) reduces foaming
ƒ Faster application speed
ƒ Shear forces acting on the latex particles can not displace the grafted
surfactant - shear stability is good, even at low surfactant levels
ƒ Weatherability (non-whitening)
ƒ Less water diffusion in the film due to absence of hydrophylic domains
and micropores improves whitening resistance in humid conditions
ƒ Removability
ƒ Low levels of oligomers are generated as the Maxemuls show low
tendency for chain transfer reactions, lower tack and better
removability results
ƒ Cohesive Strength
ƒ Better cohesive strength of the adhesive due to absence of surfactant
micelles and microvoids
Contents

ƒ Principles of Non-migratory Surfactants (NMS)

ƒ Croda Product Range - MaxemulTM NMS

ƒ Coatings
ƒ Application work
ƒ Benefits

ƒ Pressure Sensitive Adhesives


ƒ Application work
ƒ Benefits

ƒ Conclusion
Maxemul™ NMS
Conclusion

ƒ Surfactant able to covalently link to the


particle surface during polymerisation
ƒ Gives superior colloidal stability, shear, freeze
/ thaw stability, pigment and solvent
acceptance
ƒ Yields superior dry film properties
ƒ Appearance
ƒ Protection
ƒ Adhesion
ƒ Dramatically improves end use properties of
emulsion polymers for coatings and adhesives
Improving
Waterborne
Acrylic Coatings
and Pressure
Sensitive
Adhesives