Oxylink Performance additive. For better waterborne Coatings.

Detlef Burgard Bhler PARTEC GmbH

Outline
1. Introduction Buhler and Micronisers Australasia

2. Issues for Solvent & Water based paints

3. Nanotechnology for waterborne coatings i. Nano-dispersions ii. Surface Modification & Functionality 4. OxylinkTM i. Resin type ii. Wood iii. Metal iv. Plastics v. Cost Savings vi. Customer feedback

Buhler.
Corporate profile.

Buhler is the global specialist and technology partner for plant design & construction and services for the food Industry and production of high-grade functional products. The Groups core technologies are mechanical and thermal processs engineering for producing - foods, - specialty foods, - coating and die cast components. Buhler is the competent partner in consulting, technology, development, project management, and customer service. Annual sales: CHF 1.9 billion Number of employees: 7,700 Active in over 140 countries; Manufacturing sites worldwide: Americas: USA, Brazil Europe: Germany, Switzerland, Spain Africa: South Africa Asia: China, India

Micronisers Australasia.
A small innovative Australian Company

Unique process for the manufacture of nano ZnO for UV protection in personal care and industrial applications Patented additive for the modification and improvement of physical properties of crystalline polymers

TGA/ APVMA facility for the production of active pharmaceutical ingredients and veterinary scheduled products in to fine powders for improved functionality and bioactivity
Main international customers include Buhler Partec, Ciba BASF, Elanco Animal Health Ely Lily, Croda & BYK Chemie

Collaboration with Nanokote Pty Ltd / Nanogate GmbH for nano enhanced coating technologies
Collaboration with Sonic Essentials Pty Ltd for nano enhanced foliar sprays and seed coatings

Issues for Solvent and Water Based Coatings how to become GREEN ?
GOVERNMENT LEGISLATION INDUSTRY TARGETS

SED: Solvent Emission Directive Directive 99/13/EC in force from 31-10-2005 Emission control tightened from 31-10-2007 Directive 2004/42/CE in force from 01-01-2007

NEC: National Emission Ceiling National Emission Ceiling fixed from 2010 NECs tightened up to 2020

CAFE: Clean Air For Europe Clean Air For Europe - thematic strategy due July 2005 EC data (IIASA Report) suggests large reduction beyond SED

World wide regulations have the potential to reduce VOC by about 4 Mt/a *

Source: SpecialChem - Jun 1, 2009

Water borne coatings are GREEN but they have some limitations

not resistant against moisture not stable against chemical attack not blocking resistant difficult to process hard to dry generally of lower quality than solvent borne alternatives

A lot of these arguments are based on preconception, but there

is also some truth

Thus, there is a continous need to improve the performance of waterborne coatings

How can Nanotechnology help with these issues ??

Some principals to understand:

- A true nano system in any specific application may not relate to primary particle size! - Selection of the correct nano particle or carrier - Stable system - Compatible system - Targeted functionality

Nanoparticles and dispersions when is it real???

Both systems based on 30 nm ZnO

Oxylink

Common In situ agglomerated particle size of simple nano dispersions

What is Oxylink ?
ZnO containing mixture of nano particles in aqueous dispersion Solid content: Density: Viscosity: pH: 40 wt.%* 1.5 g/ml* 4 mPas* 8.5*

TM

Particle size distribution*

*: typical values, no specifications

Simple nanodispersions with pure nano ZnO have potential problems..

Generation of reactive oxygen species (ROS) by interaction of UV with pure zinc oxide particles can result in interactions with the substrate causing a degradation of the substrate, loss of color & no UV protection

UV

O2

O2-

Oxide Nano Particle

e- electron

OH
3.2 eV hole h+

OH radical

H2O
Past experiments by Micronisers with nano dispersions of ZnO in paints gave no advantage and in some instances negative results
Courtesy of Deakin University ARC Linkage Grant

Ready to use surface modified and stabilized nanodispersions are needed in first place!!!!
Surface modification of nanoparticles ensures compatibility to solvent, formulation and resin

CH
O COOH

CH

OH

CnH2n+1 NH2
Tailored properties by reaction with reactive surface -OH groups hydrophobic / hydrophilic, acidic / alkaline; - potential, polymerizable, etc.

L
L = complexing ligand

Dispersions of surface modified nanoparticles: Production by Chemomechanical processing

& = Know-How Package

Chemistry: Surface Modification

Agglomerated nanoparticles, Incompatible with matrix and processing

Agitator Bead Mill

Process: Comminution and Dispersion

De-agglomerated nanoparticles, surface modified and compatible with matrix and processing (tailor-made)

Targeted Functionality - Oxylink nanoparticles lead to increased cross linking in water based coatings ..
Film formation without and with Oxylink nanoparticles*

Stable dispersion: droplets of resin in water droplets carry reactive groups

Application and drying: water evaporates resin droplets stack physical drying (no chemical bonding)

Coalescence: resin droplets merge continuous film forms

resin droplet: polymer chain

Oxylink nanoparticles are stabilized in coating formulation

nanoparticles connect reactive groups higher network density results in increased chemical resistance O

H2N

COOH CH CH2 Oxylink nanoparticle

C
O

O C O

* Educated guess. Exact mechanism waits to be explained scientifically. Source: Team working hypothesis.

Increased cross linking should lead to better performance

Chemical properties

Resistance against solvents e.g. MEK, IPA MEK double rub resistance IPA double rub resistance Water permeation Blocking resistance

Mechanical properties

- Adhesion (Crosscut, tape) - Abrasion resistance (Taber 100; 200 Cycles)

Optical properties

- Gloss (60)
Processing parameters

- Drying time

Improved solvent resistance for a range of waterborne resins - Pure dispersion + coalescence agent only
according to ASTM D 5402
250 control MEK double rubs 200 150 100
End point detection: coating destroyed

Oxylink

50
0 Acrylic Styrene acrylic self crosslinking acrylic Acrylic urethane hybrid

Significant improvement due to Oxylink

Oxylink shows better performance than wax additives: Higher versatility and better humidity resistance
Pure dispersion + coalescence agent only
180 160 MEK double rubs 140 120 100 80 60 40 20 0 Control wax dispersion 1 Oxylink wax dispersion1 + Oxylink

Resin base: Acrylic resin Worleecryl 1 7641

140 120 MEK double rubs 100 80 60 40 20 0 control wax dispersion 1 wax dispersion 2 wax dispersion 3 wax dispersion 4 Oxylink

Coatings exposed to 100 % humidity at 40 C

Resin base: AC 337 ER Acrylic resin Primal 2

Slovent resistance: Wax additives work for special formulations only Oxylink good performance in different resins

After drying left: Wax additive right: Oxylink

WOODCOATINGS - Oxylink in Fully formulated waterborne acrylic

EXTERIOR TRANSLUCENT HIGH BUILD STAIN BASED ON PRIMAL AC-337 ER (HBST)
Incredients Primal AC-337 ER *1 (45.5%) TegoFoamex *2 825 Water Texanol *3 Aqueous ammonia (28%) Water OXYLINK TM *4 Acrysol RM-12W *1(19%) Water g 655.1 2 100.8 23.1 2.7 201.6 6.95 6.75 1

EXTERIOR TRANSPARENT WOOD GLAZING BASED ON WORLEECRYL 7461 (WG)

Incredients Worleecryl 7461*5 water Dow Corning Add. 65 water: Ethylen glycol 1:1 Acrysol RM 5000 *1 Dow Corning Add. 57*6 OXYLINK TM*4 water 42 3 5 11 9 g 762 166 02

*1 Rohm & Haas, USA,*2 Evonik Tego Chemie GmbH, Germany, *3 Eastman Chemicals ltd, UK, *4 Bhler PARTEC, Germany *5 Worle-Chemie GmbH, Germany ,*6 Dow Corning, USA

WOODCOATINGS - Gloss (60) remains unchanged

High gloss as a consequence of compatibility between Oxylink and resin matrix
90 80 70 with Oxylink without Oxylink

Gloss (60)

60 50

40
30

20
10 0

WG

HBST

WOODCOATINGS Solvent resistance significantly improved with Oxylink

OxylinkTM concentration: 0.9 wt.% (solids/solids) End point detection: coating destroyed

OxylinkTM concentration: 0.9 wt.% (solids/solids) End point detection: Starting of gloss decline

with Oxylink without Oxylink

160 140 Solvent double rubs 120 100 80 60 25

MEK

IPA
solvent double rubs 20

MEK
15

IPA

10

40
20 0 WG HBST WG HBST

0 WG HBST WG HBST

WOODCOATINGS Oxylink accelerates drying: Faster processing means higher productivity

OxylinkTM concentration: 0.9 wt.% (solids/solids) Time to drying stage 4 (= overworkable) significantly reduced
60 without Oxylink with Oxylink

TM

50

Drying time (hrs)

40

30

20

10

WG

HBST

WOODCOATINGS Oxylink improves blocking resistance: Faster processing and broader application
OxylinkTM concentration: 0.9 wt.% (solids/solids) According to Richtlinie 6, IFT Rosenheim (0 = best; 5 = worst)
5
HBST with Oxylink HBST without Oxylink

TM

4 Blocking rating

0 Humidity wood Humidity plastic Temperature wood Temperature plastic

WOODCOATINGS Overall properties significantly improved

EXTERIOR TRANSPARENT WOOD GLAZING BASED ON WORLEECRYL 7461 (WG)

WG

With Oxylink

Without Oxylink 58,8 100

Gloss retention solvent rub, MEK

Drying time (tack free)

100

Drying time Gloss (60 ) Gloss retention IPA rub Gloss retention MEK rub Blocking resistance Adhesion (Crosscut, tape) MEK double rub Water permeation Average

100 98,5 100 100 100 100 100 94,7 99.2

80

Blocking resistance
60

40

45,5 15,4 100 100

Gloss retention solvent rub, IPA MEK double rub resistance

20

Water permeation

Adhesion (Crosscut, tape)

27,3
Gloss (60)

100
without Oxylink with Oxylink

68.4

WOODCOATINGS - Overall properties significantly improved

EXTERIOR TRANSLUCENT HIGH BUILD STAIN BASED ON PRIMAL AC-337 ER (HBST)

HBST

With Oxylink

Without Oxylink
Blocking resistance

Drying time (tack free)

100

Drying time Gloss (60 )

100 100

41,7 98,8

80

Abrasion resistance

60

40

Gloss retention IPA rub

Blocking resistance Abrasion resistance Adhesion (Crosscut, tape) MEK double rub IPA double rub

100
100 100 100 100 100

40,9
20 81,2 100 34,4 82,1

Gloss retention solvent rub, IPA

20

Gloss (60)

MEK double rub resistance

Adhesion (Crosscut, tape)

IPA double rub resistance

Water permeation

Water permeation
Average

100
100

94,7
66

without Oxylink

with Oxylink

METAL COATINGS -Two waterborne systems were examined by an independend institute (ILF)
Acronal S 760, (BASF) two coat built up (primer + topcoat) self-crosslinking styrene acrylic latex Fully formulated pigmented coating Neocryl XK-86 (DSM NeoResins+) DTM metal coating Acrylic styrene copolymer emulsion Fully formulated pigmented coating One coat system

METAL COATINGS - following test protocol was applied to steel sheets; grade R 621
Property
Crosslinking and solvent resistance Corrosion protection

Method
MEK and IPA -double rub (ASTM D-5402) Salt spay test according to DIN EN ISO 9227, DIN EN ISO 46282, DIN EN ISO 4628-3, DIN EN ISO 4628-4, and DIN EN ISO 4628-5 Spot test, DIN EN ISO 2812-3 and DIN EN ISO 4628-2; 10 substances* CH for 300 h, DIN EN ISO 6270-2 and DIN EN ISO 4628 1000 h, Type II UV-A bulbs and humidity (DIN EN ISO 11507, process A), evaluation was done using DIN EN ISO 4628 Cross cut method according to, DIN EN ISO 2409 DIN 53150 Reflectivity at 60 and 85 according to DIN EN ISO 2813

Chemical resistance Humidity resistance Weathering resistance Adhesion Drying time Gloss

*: gasoline, water-butyl glycol 90/10, ethyl acetate-butyl acetate 1:1, sodium hydroxide solution (5 %), hydrochloric acid (10 %),

acetic acid (10 %), hand lotion Atrix, aqueous Marlon A 350 solution (50 %), artificial bird excrement and distilled water

METAL COATINGS Acronal Self crosslinking styrene acrylate coating can significantly be improved by Oxylink
MEK double rub

without Oxylink MEK double rub IPA double rub Chemical resistance Adhesion Drying time Gloss Corrosion protection (salt spray test) Weathering resistance Humidity resistance Average 28,3 66,7 92,0 100 100 100 100 80,0 28,7 77,3

with Oxylink 100 100 100 100 100 93,3 100 100 100 99,3
Weathering resistance

100

Humidity resistance

80

IPA double rub

60

40

20 0

Chemical resistance

Corrosion protection (salt spray test)

Adhesion

Gloss

Drying time

without Oxylink

with Oxylink

METAL COATINGS -Neocryl Acrylic styrene copolymer DTM coating can significantly be improved by Oxylink
MEK double rub

without Oxylink MEK double rub IPA double rub Chemical resistance Adhesion Drying time Gloss 22,9 60,2 82,3 100 100 100 88,9 71,4 0,0 69,5

with Oxylink 100 100 100 100 100 97,8 100 100 100 99,8
Weathering resistance

Humidity resistance

100 80 60 40 20 0

IPA double rub

Chemical resistance

Corrosion protection (salt spray test)

Weathering resistance Humidity resistance Average

Corrosion protection (salt spray test)

Adhesion

Gloss

Drying time

without Oxylink

with Oxylink

METAL COATINGS - Significant improvement of humidity resistance

With Oxylink Without Oxylink

Condensed humidity CH, 300 h; DIN EN ISO 6270-2, DIN EN ISO 4628

PLASTIC COATING - Metallic coating formulation - Starting point formulation for first Oxylink tests
Pigment paste Water Dissolve Disperbyk 192 Stapa Hydrolan IL 161, add while stirring Halox SZP 391 add while mixing Halox 515 add while mixing Diethylene glycol monobutylether add while mixing Let sit over night Homogenize with rotor stator device for 5 min Final coating E-700-Halox Water Ethylene glycolglycol-monobutylether Diethylenglycolglycol monobutylether Dowanol DPM, Dipropylene glycol monomethylether Mix ingredients and adjust pH to 9.0 with 2-Amino-2-Methylpropanol (AMP) Add pH=9 mixture to Neocryl A 662 while stirring Byk 346, add while stirring Drewplus SG-4552, add while stirring Pigment paste, add slowly while stirring 125 0.75 1.25 37.5 15.75 29 7.5 7.5 Ingr./g 59.1 1.5 39.4 1.18 1.18 0.788

PLASTIC COATINGS - Film application and blocking test

Coating applied via doctor blade on Leneta - film, wet thickness 200 m The coating was dried at room temperature (22 C) for a given time 5 cm x 5 cm samples were prepared Two respective samples were laid on top of each other (coated sides)

Sample stack is loaded with 2.5 kg for 24 hrs, either at 22 C or at 50 C

Afterwards, the two samples are separated by hand and rated according to the following scheme:

0 1 2

No visible change, no sticking Slight sticking, no damage Sticking, stains slightly visible

3
4 5

Blocking, film damaged, no delamination

Blocking, slight delamination Full blocking, servere delamination

PLASTIC COATINGS - high temperature blocking is improved by Oxylink

5

Drying conditions:

Blocking at 50 C

Temperature: 22 C Drying time: 48 hrs following the suppliers recommendations

Blocking test:

Temperature: 50 C Load: 2.5 kg/25 cm

0 1 2 3

wt.% Oxylink

PLASTIC COATINGS - Very strong synergy between Oxylink and PTFE wax: No blocking after very short drying time
Drying time 3 hrs instead of 48 hrs 0 = best 5 = worst

Dried at 22 C & Blocking test was done at 22 C

PLASTIC COATINGS - Samples after blocking test

Oxylink & Wax Control Wax Only

2% Oxylink Only

5
3%Oxylink Only 5
0 1 No visible change, no sticking Slight sticking, no damage Sticking, stains slightly visible Blocking, film damaged, no delamination Blocking, slight delamination Full blocking, servere delamination

Wax only

5
5

2 3

1% Oxylink Only

4 5

OXYLINK
Improved Quality of Water based coatings with Oxylink

Cost savings also possible

COST SAVINGS: less expensive resin plus Oxylink vs high cost resin for WG woodcoatings
Drying time (non sticking) IPA double rub resistance
100 80 60 40

Gloss (60)

Without Oxylink: Hybrid coating shows better performance than acrylic coating. Relative performance values: Hybrid coating Acrylic coating

MEK double rub resistance

20 0

Scratch resistance

Worleecryl 7461 Hybridur 870

93 71

Adhesion (Crosscut, tape)

Gloss retention solvent rub, IPA Abrasion resistance

Gloss retention solvent rub, MEK

Drying time (non sticking)

Performance of acrylic coating can be improved and is significantly better than hybrid coatings by addition of 1 % Oxylink. Relative performance values: Hybrid coating Acrylic coating plus Oxylink

IPA double rub resistance

100,0 80,0 60,0 40,0

Gloss (60) Worleecryl 7461 + Oxylink Hybridur 870 Scratch resistance

MEK double rub resistance

20,0 0,0

67 96

Adhesion (Crosscut, tape)

Gloss retention solvent rub, IPA Gloss retention solvent rub, MEK

Abrasion resistance

COST SAVINGS Oxylink provides better performance and lower costs (WG) 9
Price AUD/kg Hybridur 870 (via NRC)# Worleecryl 7461# Resin Cost Difference 8.47 5.94 2.53

8 7

Cost saving 21 %
Worleecryl 7461 plus Oxylink

6
Worleecryl 7461

Oxylink Price
Added cost 1% Oxylink

70.00
0.70

3
2 1

Potential Savings

$ 1.83/ kg

0
Formulation
Hybridur Worleecryl Oxylink 1% solids

Kg of resin
739 762 11

Price AUD per Kg

8.47 5.94 70

Hybridur 870

Cost per tonne

$6,259 $5,296 $963 $48,150

Savings per tonne of paint for resin system

#

European Prices for resins

Savings per 50 tonne of paint per year

COST SAVINGS - Comparison between Hybrid- and Acrylic coating Hybridur 870 vs. Primal AC 337 HBST woodcoating
Drying time (non sticking)
100

Without Oxylink: Hybrid coating shows better performance than acrylic coating. Relative performance values: Hybrid coating Acrylic coating

IPA double rub resistance

80 60 40

Gloss (60)

MEK double rub resistance

20 0

Scratch resistance

Hybridur 870 Primal AC 337

97 76

Adhesion (Crosscut, tape)

Gloss retention solvent rub, IPA Gloss retention solvent rub, MEK

Abrasion resistance
100

Drying time (non sticking)

Performance of acrylic coating can be lifted to the same level as hybrid coatings by addition of 1 % Oxylink. Relative performance values: Hybrid coating Acrylic coating plus Oxylink

IPA double rub resistance

80 60 40

Gloss (60)

MEK double rub resistance

20 0

Scratch resistance Hybridur 870 Primal AC 337 + Oxylink Gloss retention solvent rub, IPA

87 86

Adhesion (Crosscut, tape) Abrasion resistance

Gloss retention solvent rub, MEK

| |

COST SAVINGS Oxylink provides better performance and lower costs (HBST) 9
Price AUD/kg Hybridur 870 (via NRC)# Primal AC 337# Resin Cost Difference 8.47 5.70 2.77

8 7

Cost saving 24%

Primal AC 337 plus Oxylink

6
4
Primal AC 337 Hybridur 870

Oxylink Price
Added cost 1% Oxylink

70.00
0.70

3
2 1

Potential Savings

$ 2.03/ kg

0
Formulation
Hybridur Primal AC 337 Oxylink 1% solids

Kg of resin
739 649 8.0

Price AUD per Kg

8.47 5.70 70

Cost per tonne

$6,259 $4,259 $2,000 $100,000

Savings per tonne of paint for resin system

#

European Prices for resins

Savings per 50 tonne of paint per year

INTERIOR DECORATIVE CONCRETE SURFACE - Benefits

Results applicable to Asia for concrete rendered interior surfaces

Cost sensitive segement how to get improved performance at acceptable cost?

However, less expensive resins have lower performance
ACRYLIC RESIN EFFLORESCENT ALKALI RESIST WATER RESIST DIRT PICK UP

High Quality
Lower Quality

GOOD
POOR

GOOD
POOR

GOOD
POOR

POOR
GOOD

Use a less expensive resin & Oxylink

50% improvement in dirt pick up Significantly improved efflorescence control Improved alkali and water resistance Cost saving compared to expensive resin

COST SAVINGS Oxylink for interior decorative concrete surface 9

Price AUD/kg High Quality Resin 50% solids Lower Quality Resin 45% solids Resin Cost Difference 1.63

8 7

Cost saving 6 %

6
5
Low Quality
0.24

Oxylink Price
Added cost 0.2% Oxylink

70.00
0.14

3
2 1

Potential Savings

$ 0.10/ kg

0
Formulation
High quality resin Lower quality resin Oxylink 0.2% solids

Kg of resin
400 400 0.4

Price AUD per Kg

1.63 1.39 70

Low Quality plus Oxylink

1.39

High Quality

Cost per tonne

$652 $584 $68 $3400

Savings per tonne of paint for resin system

#

Asian Prices for resins

Savings per 50 tonne of paint per year

Oxylink - factors to consider to determine dose rate

Point of 100% reaction with available carboxyl groups which will differ with type and quality of resin Potential for Oxylink to react with other substrates and additives especially when exposed to UV light!

Free Oxylink
Performance Parameter

Oxylink Cross Linked

?
Dose Rate of Oxylink
Starting formulations indicate 0.8% to 1.2% dose rate; customer experience ranges from 0.2% to 5.0%

Positive Benefits Identified by Oxylink customer feedback: A lot of properties can be improved consistent with the effects of an extremely efficient crosslinking additive....
Corrosion protection 4% Alkali resistance 4% Dirt pick up 8% Crosslinking 4% UV stability 4% Hardness, Abrasion / scratch resistance 22 %

Humidity / water resistance 8% Blocking resistance 21 %

Chemical resistance 8%

Drying time 17 %

Conclusion

Oxylink can significantly improve the overall properties of waterborne coatings

TM

The gap between waterbornes and solvent borne

coatings becomes narrower and the hurdles for waterbornes become lower

As a consequence, nanotechnology can play an important role in bringing greener coatings forward

44 | 20.05.2009 |Dr. Detlef Burgard, Bhler PARTEC | Bhler