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Formulating cost-efficient &

low to zero VOC alkyd based coatings


using
polymeric surfactants technology
APAC Coatings show, Jakarta
June 23-24th, 2010 J. Grade,
Application Manager
Croda Coatings and Polymers

Croda Plc

Croda is a leading global supplier of speciality chemicals


Personal care
Lubricants
Polymer additives
Crop care
Homecare and cleaning
Coatings and Polymers

Coatings and Polymers product offerings


Building blocks from oleochemical and synthetic origin for
condensation polymerisation
Surfactants used as process aids during resin manufacture
Surfactants as formulation aids
Surfactants in alkyds and alkyd based coatings

Alkyd resins
Popular binders for wood and metal
protective coatings

Simple chemistry, Fatty acid modified polyesters


Well established, long history
Excellent balance between cost/performance
High gloss finish/ Excellent protective properties
Largely from renewable resource

Solvent-borne

VOC compliant alkyds


Drivers for change
Origin

Organic solvents are flammable


Organic solvents catalyse photochemical synthesis of ozone in lower
regions of the atmosphere.
OPS (Organo Psycho Syndrome), irreversible damage of the short
term memory.

Change driven by

legislation (e.g.Deco paints directive)


Distribution sector (safety, green image, carbon footprint)

EEC directive 2004/42/CE

VOC or Decorative Paints directive


Stricter VOC - regulations (Volatile Organic Compounds) at EU level
Further amendments expected for 2013 - 2015

More stringent national regulations

Indoor air quality

Maximum VOC content limit values


for paints and varnishes (EU)

(*) DIRECTIVE 2004/42/CE OF THE


EUROPEAN PARLIAMENT AND OF THE
COUNCIL of 21April 2004; annex II

Technology options

Conventional
alkyd
Solventborne
alkyds

Waterborne
alkyds

Jan 2010

High solids alkyds

Water reducible
alkyds

Water in oil alkyds

Urethane modified alkyds

Alkyd emulsions

Technology options

Conventional
alkyd

Drawbacks of
high solids alkyds
Waterborne
Jan 2010
alkyds

Solventborne
alkyds
High solids alkyds

Water in oil alkyds

Softer films
Water reducible
alkyds
Faster yellowing
Slow drying

Urethane modified alkyds

Higher cost
Alkyd emulsions

VOC compliant alkyds


Water in oil alkyds
Partial replacement of solvent
and/or resin with water

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%

water
solvent
alkyd

W/O alkyd
Conventional

High solids

W/O alkyd

Surfactant stabilised
Water+ Surfactant
Pigments
Polymer

LoVOCoat
polymeric W/O stabilisers
LoVOCoat Form 100/ LoVOCoat Stable 100

Surfactant/co-surfactant combination
Liquid products, 20% active matter
Recommended ratio Form100/Stable 100 60:40
Recommended concentration 15.5% min. on water

Use of polymeric surfactant combination


guarantees
Fine droplet size
An excellent shelf life and tropical storage without
phase separation
High water loading with low formulation viscosity
Minimal effect on flow, drying time or dry film
properties

LoVOCoat
the W/O concept

starting formulation
W/O alkyd

Ref
Formulation

Ref
Water (1% MgSO4)

06.33.045

LoVOCoat Form 100

3.05

LoVOCoat Stable 100

1.95

Long oil alkyd, 78% in Exxsol D40


Properties

31

64

Brookfield viscosity (mPA.s)

4200

Particle size (nm)

350

Storage stability

40C

5m

55C

3m

Surfactants supplied as 20% solutions


Recommended surfactant level min. 3.1% active matter, 15.5% as is on dispersed water phase
Recommended ratio LoVOCoat Form100:LoVOCoat Stable 100 60:40
Excellent storage stability, even at higher temperatures
Viscosity reduction vs high solids alkyd (formulations above use the same conventional alkyd)
Optimisation of emulsification conditions is key to guarantee a small droplet size

LoVOCoat
the W/O concept

Via direct emulsification

Water
phase

Resin phase

The emulsifiers are dissolved in the oil phase.


A watersoluble salt or polymer is added to the water as osmotic pressure regulator
Water is added to the oil phase with high shear stirring, a water in oil emulsion is formed
Typical surfactant level, down to 3% surfactant, active matter on dispersed water phase
Emulsification using high mechanical shear or low speed emulsification in a viscous continuous
phase

LoVOCoat
Water incorporation strategies

Water in solvent
pre-emulsion
Rotor stator mixer

Let down
Mixing at low
shear with
finished paint

Water in alkyd
pre-emulsion
Dissolver

Let down
Mixing at low
shear with
pigment
concentrate

Water in pigment
concentrate
Dissolver

Let down
Mixing at low
shear with
remaining alkyd

LoVOCoat Polymeric surfactants


for W/O emulsion stabilisation
Conventional surfactant

Polymeric surfactant

Pigment

Low MW hydrophobes,C18max
Weak hydrophylic interaction,
easy desorption

Pigment

Polymeric hydrophobe
Strong hydrophylic interaction, irreversible
adsorption, thick steric barrier

W/O alkyds
Effects of stabiliser
LoVOCoat vs conventional W/O technology
Effects on viscosity

Effects on formulation stability


(40C)

12000
18
16
14

8000
LoVOCoat

6000

Conventional

4000

Stability (weeks)

Brookfield Viscosity (mPa.s)

10000

LoVOCoat stability >16W

12
10

LoVOCoat
Conventional

8
6
4

2000

2
0

0
20%

25%

32.60%

Water content (%)

20%

25%

32.60%

Water content (%)

W/O emulsions with polymeric surfactant technology have significantly lower viscosities and better
shelf life vs oligomerics. All formulations have 50% L.O.Alkyd, from 20 to 32.6% of a 1% MgSo4
solution, 8% surfactant on water and Exxsol D40 to the balance

W/O alkyds
Effects of stabiliser
LoVOCoat vs conventional W/O technology

Approx. 50% polymer


20% W/O emulsion
LoVOCoat, 3.1% a.m.
30d at 50degC

Approx. 50% polymer


20% W/O emulsion
Comp., 3.1% a.m.
7d at 50degC

W/O emulsions with polymeric surfactant technology have significantly lower viscosities and better
shelf life vs oligomerics. All formulations have 50% Polymer solids, approx. 20% water in oil, 3.1%
stabiliser active matter on water (1% MgSO4)

W/O alkyd formulations


Effects on rheology

Flow properties are unaffected with up to 25% water incorporated (resin dependent). All formulations
have 50% L.O.Alkyd, from 20% of a 1% MgSo4 solution, 8% surfactant on water and Exxsol D40 to the
balance (cone & plate rheometer)

W/O alkyd formulations


Effects on rheology
LoVOCoat vs conventional W/O technology
16
14

Viscosity (Pa.s)

12
10
Conventional

LoVOCoat

6
4
2
0
0.01

0.1

10

100

1000

Shear rate, log(1/s)

Oligomeric stabiliser shows viscosity increase at low shear rates which will affect levelling of the
coating. LoVOCoat technology only shows this rheology at high water loading (32% and high surfactant
level (8% on water). All formulations have 50% L.O.Alkyd, 20% of a 1% MgSO4 solution, 8% surfactant on
water and Exxsol D40 to the balance

Drying times

Measured with a BK drying time recorder at standard conditions, 23C, 50%


R.H.

Leveling

basic trace

rippled film -

surface trace

dry

W/O alkyd formulations


Effects on drying time, clearcoat
Conv. 8%
W/O alkyd
3.1% surf

levelling
basic trace
ripped film
surface trace

W/O alkyd
6.2% surf
W/O alkyd
8% surf
Reference
0

10

BK drying time (hrs), 50% alkyd, 32% water, 3.1 to 8% surfactant, active matter on dispersed
waterphase, solvent to the balance
Only moderate increase; stabilisers have no effect on drying; slower drying for oligomeric stabiliser

W/O alkyd formulations


Effects on dry film properties
Hardness Gloss 60

Transmittance

Surf conc

Process

4W

4W

4W

reference

21

96

93,3

W/O alkyd

18

97

92,6

8% surfactant, active matter on dispersed water phase


Konig hardness, gloss and transmittance measured
The transmittance measurement on the clear film is a measure
of its transparency. It is the ratio of transmitted light to the
incident light.

W/O alkyd formulations


Effects on drying time, Formulations

BK drying time (ASTM 5895), hrs

Brookfield Viscosity
(DV-II, 30rpm, spindle 18 Ambient)

1) Sikkens Cetol TGL Plus

20% water

250

mPa.s

200

10% water

150
100

0% water

50
0

0
0% water
Visco 24hrs RT

10% water
Visco 1 w eek RT

20% water
Visco 1 w eek 50 C

Cetol TGL Plus (Akzo), varnish, 440g/l VOC


Results show a reduction in drying time with water added!

2
leveling

4
basic trace

8
ripple

10
surface trace

12

W/O alkyd formulations


Effects on drying time, Formulations
Brookfield Viscosity
(DV-II, 30rpm, spindle 18 Ambient)

BK drying time (ASTM 5895), hrs

400
20% water

mPa.s

300
200

10% water

100
0% water

0
0% water
Visco 24hrs RT

10% water
Visco 1 w eek RT

20% water
Visco 1 w eek 50 C

Rubbol AZ PLUS, white pigmented high gloss trim paint (Akzo)


Results show a reduction in drying time with water added!

2
leveling

6
basic trace

8
ripple

10

12

14

surface trace

W/O alkyd formulations


Effects of ageing on drying time
Rubbol AZ plus High Gloss Finish (Max 300 g/ l VOC)
leveling
basic trace
20% 8 w k 50C

ripple
surface trace

0% 8 w k 50C

20% w ater

0% w ater

0,00

2,00

4,00

6,00

8,00

10,00

12,00

14,00

Time (hrs)

Rubbol AZ PLUS, white pigmented high gloss trim paint (Akzo)


Ageing at elevated temperatures causes a moderate increase in drying time

W/O alkyd formulations


Effects of formulation ingredients

PVC (%)
Volume solids (%)
VOC (g/l)

13.66
64.78
258.46

14.43
51.15
224.40

14.43
49.88
239.23

Ti-Pure R-902+
Lovocoat Form 100
Exxsol D40

30.49
3.01
12.28

25.71
2.53
10.36

25.20
2.48
10.15

Uralac HS233 Q-85


Lovocoat Form 100
Lovocoat Stable 100

52.22
0.00
0.00

41.32
1.56
1.00

40.49
1.53
0.98

Water, 1% MgSO4
Octa-Soligen 141 Z
MEKO
Butylglycol
Total

0.00
1.77
0.23
0.00
100.00

16.09
1.25
0.18

15.77
1.22
0.17
2.00
100.00

100.00

W/O alkyd formulations


Effects of formulation ingredients
5
Pa.s

Resin free grind, surfactant stabilised


Zephrym 3300B (anionic) or LoVOCoat Form 100 (polymeric)
15% PVC, approx. 65 vs 50% volume solids
Butylglycol for further viscosity reduction

4,5
4
3,5
3

2,5

Zephrym 3300B, no water

2
1,5

LoVOCoat Form 100, 16% water


LoVOCoat Form 100, no water

LoVOCoat Form 100, 16%


water, 2% BG

0,5
0
0

100

200

300

400

500

600

700

800

1/s

1.000

Shear Rate

US 200 plate/plate Rheometer, MP 31 (50mm,0) d=1 mm

W/O alkyd Emulsifiers


Performance benefits
LoVOCoat polymeric surfactant technology
Allows for high water level incorporation
Excellent tropical storage stability
With minimal impact on drying rate and dry film properties

Formulation of VOC compliant alkyd based coatings


Based on conventional SB alkyds
No resin development required
Complementary to HS alkyd development
Improved drying time for HS alkyds

Formulation flexibility
Cost savings without compromise

Technology options

Conventional
alkyd
Solventborne
alkyds

Waterborne
alkyds

Jan 2010

High solids alkyds

Water reducible
alkyds

Water in oil alkyds

Urethane modified alkyds

Alkyd emulsions

Please visit our website at


www.crodacoatingsandpolymers.com

Technology options

Water reducible alkyds


Poor shelf life,
hydrolysis in the can
Solventborne
Poor barrier properties
alkyds
Low polymer solids

Conventional
alkyd

High solids alkyds

Urethane modified alkyds


Good shelf life
Water in oil alkyds
Hard films
Expensive

Waterborne
alkyds

Jan 2010
Water reducible
alkyds
Urethane modified alkyds

Alkyd emulsions

Alkyd emulsions
Total replacement of solvent with water

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%

water
surfactant
solvent
alkyd

Conventional

High solids

Alkyd emulsion

Alkyd emulsion
Surfactant stabilised

Alkyd emulsions

Developing alkyd emulsions using external emulsifiers

The technology offers the following performance benefits:


Conventional alkyd resins can be used

Emulsification rather then diluting in solvent


No polymer development required
No co-solvent required
Higher polymer solids (>50%)

Cost savings from solvent elimination

Preferred production method:


The phase inversion technique
Stirred pot, low stirring speed
Low investment cost, low energy cost

Going waterborne
Simple emulsification process

Procedure
The emulsifiers are preferably
dissolved in the resin phase.
Water is added to the oil phase
while stirring -> formation of a
W/O emulsion.
After reaching the inversion point
(surpassing viscosity maximum):
spontaneous inversion from a W/O
to an O/W emulsion upon further
addition of water.
Water
phase

Oil phase

O/W

Going waterborne role of the


surfactant

The role of the surfactant


Interfacial tension reduction
Facilitates droplet formation

Stabilisation of formed polymer particles


Protection against coalescence
Control of shelf life

Limitations of conventional surfactant technology


Poor affinity to the oil/water interface
Risk of preferential adsorption in pigmented systems
High surfactant levels are required

Plasticization of film surface


Lower efficiency of associative thickeners

Going waterborne
Emulsifier selection

Our leading edge alkyd emulsifiers, product offerings:


Maxemul 7101, nonionic polymeric emulsifier, 100% a.i.
All long & medium oil alkyds, up to emulsification temp. to 85C

Maxemul 7102, nonionic polymeric emulsifier, 100% a.i.


For high temperature emulsification close to 100C

Maxemul 7201, anionic emulsifier, 100% a.i.


Oil soluble, most versatile

Going waterborne
Formulation optimisation
alkyd emulsion
pbw
Long oil alkyd
KOH

relative to A.V.

Surfactant

5-8% on resin

Water

50-55

up to 100

Emulsions stabilised by a combination of anionic and nonionic polymeric emulsifier


Process and formulation optimisation is critical for succesful formulating
Anionic/nonionic surfactant ratio
Surfactant level on resin, 6% on resin on average
Neutralisation of the resin
Stirring speed, approx. 250-300rpm and stirrer design
Emulsification temperature, dependent on resin viscosity
Speed of water addition
Emulsions have excellent storage stability, >2 yrs at ambient temperature
No compromise on dry film properties

VOC compliant alkyds


Alkyd emulsions, particle size
Medium oil alkyd emulsion
Particle size after 1 month ageing at 40 and
50degC

Resin
Water
KOH
Maxemul 7101
Maxemul 7201

pbw
47.17
49.77
0.23
1.42
1.42

Particle Size Distribution

10
Volume (%)

8
6
4
2
0
0.01

0.1

10

Particle Size (m)


20673-77/1 ~40 1 month, 08 October 2007 14:21:51
20673-77/1 ~50 1 month, 08 October 2007 14:16:20
20673-77/1 ~RT 1 month, 21 September 2007 11:14:00

100

1000

3000

VOC compliant alkyds


Alkyd emulsions, dry film properties

Beck Kller drying time recording


Conventional solventborne alkyd vs alkyd emulsion

Set
Time

Touch
Dry

Through
Time

%Cobalt Stage1 Stage2 Stage3


Solventborne
Maxemul
7101/7201

Discontinuous
Track

0.02

<10min

6.5

7.25

Stage4
14.7517.5

0.02

<10min

11-15

Final
Through
Time

Stage
5
23
17

VOC compliant alkyds


Alkyd emulsions, dry film properties
Konig hardness development

Conventional solventborne alkyd vs alkyd emulsion

25
Knig pendulum hardness / s

20
15
10

Conventional solvent
borne alkyd coating

Non-VOC water borne


alkyd coating

0
0

Time / weeks

Going waterborne - the Maxemul


benefits

Maxemul advanced surfactant technology for alkyd resin emulsification


allows for total elimination of solvents in water borne alkyd based
coatings

No compromise on performance versus conventional alkyd coatings


No solvent emissions at workplace
No alkyd resin development work required
Minimal investment costs
Cost savings from solvent elimination
Formulation of zero-VOC coatings, easy to handle and apply

Please visit our website at


www.crodacoatingsandpolymers.com