How structural order boosts performance Lars HoffmannTechnical Marketing Formulation Additives
ETCC 2018, AmsterdamJune 27 2018
Content
Applications for Easy-to-Clean surfaces
Additives based on CFRP fluorinated acrylates
Performance benefits
Characterization of functional surfaces
1.2.3.4.
Conclusion5.
June 2018 | Formulation Additives2
Content
Applications for Easy-to-Clean surfaces
Additives based on CFRP fluorinated acrylates
Performance benefits
Characterization of functional surfaces
1.2.3.4.
Conclusion5.
June 2018 | Formulation Additives3
Anti-Icing
4 June 2018 | Formulation Additives
Where do we need persistent surface and how do we clean them?
Water Repellence
Chemical Resistance
Anti-Fingerprint
Self-Cleaning
Anti-Graffiti
Stain Resistance
Anti-Dirt Pickup
Easy-to-Clean
The fear of soiling and the miracle of cleaning
Soiling
AttackDirt & Stain
Forces
Temperature, Humidity, Radiation, Oxygen
Hydrophilic, Hydrophobic, Basic, Acidic, Organic
Surficial, Immersive, Destructive
Cleaning
Cleaning Agents
Organic Solvents, Water, Steam,
Special Cleaners
Process
Easy-to-Clean
Self-Cleaning
Automated and manual: High Pressure Water Jet,
Brushes, Textile
5 June 2018 | Formulation Additives
Which properties are important for functional surface with favorable cleanability?
Resistance and
CleanabilitySurface
Morphology
Chemical Nature
Surface Polarity
HydrophilicHydrophobicSmooth, Rough,
Micro-structure
Glass Transition Temperature [Tg]
Network Density
Durability: Temperature, Radiation, Chemical
Attack, Biological Attack
6 June 2018 | Formulation Additives
Content
Applications for Easy-to-Clean surfaces
Additives based on CFRP fluorinated acrylates
Performance benefits
Characterization of functional surfaces
1.2.3.4.
Conclusion5.
June 2018 | Formulation Additives7
■ Reaction temperature range: 100°C – 150°C
■ Special nitroxide regulator required for acrylates
Nitroxide Regulator Persistant Radical+ monomersX
R O NR'
R''O N
R'
R''R *+*
T
O NR'
R''R R O N
R'
R''
T
* *+
8
Nitroxide mediated controlled radical polymerization (NMP or NOR)
NOR Mechanism
June 2018 | Formulation Additives
9
Fluorinated block copolymers created by CFRP technology
A-block Resin Compatible Block B-block Surface Active Block
Compatible with paint systems:■ Resins■ Solvents
Acrylates of different polarity and solubility
Example: F-functional Acrylates
Resin and solvent specific!
Surface active!
June 2018 | Formulation Additives
10
A new approach for highly surface active cross linkable additives
CURRENT
Example:■ Efka® FL 3600,
3777■ Hydropalat®
WE 3370, 3500
Example: Efka® WE 3050
HO-R
NEW
Cross linkable function Resin and solvent specific
Surface active!
June 2018 | Formulation Additives
■ SIMS samples the first monolayer (information depth 1-2 nm)■ Offers chemical and molecular information (MS)■ With high sensitivity (down to ~ppm)■ No quantification without standard (signal matrix dependent),
albeit a qualitative trend derived in most cases.■ Either cations are anions are transferred by the ion optics into
the ToF-Unit of the spectrometer. Every sample therefore offers a set of spectra, one covering all cationic species formed, the other covering all anionic species formed.
+hv e-
Atoms. molecules.Secondary Ions
Sampling depth~ 1 nm
Penetration depth~ 10 nm
Primary ion beam~10 keV (Bi+, Bi3+..)
11
Principle of Secondary Ion Mass Spectrometry (SIMS)
June 2018 | Formulation Additives
Sputter Source(Ar1500
+-Cluster)
AnalysisGun
The surface is analyzed via an Analysis Gun. The material is then removed by sputtering.
The newly formed surface is analyzed again, and the procedure is repeated.
After profiling the peak intensity of masses, this is then graphed against sputtering time, which enables layer composition across the material.
Remark: ■ The amount of material removed by the sputter source is dependent on a variety of parameters. ■ No direct conversion of sputter times into depth values is therefore possible. ■ Calibration by a separate measurement of the crater depth at the end of the profiling is always needed.
12
SIMS depth profiling - dual beam approach
1 2 3
Bulk
Layer 1Layer 2
Sputter Time
Peak
Inte
nsity
June 2018 | Formulation Additives
Content
Applications for Easy-to-Clean surfaces
Additives based on CFRP fluorinated acrylates
Performance benefits
Characterization of functional surfaces
1.2.3.4.
Conclusion5.
June 2018 | Formulation Additives13
Application tests - characteristics of selected additives
Type/Name Chemical CharacteristicsHydroxyl Number(mg KOH/g)
Structural Design
GM 31 Fluorinated hydroxyl-functional block copolymer 96
GM 35 Fluorinated block copolymer (without OH groups) No OH-groups
GM 144 Fluorinated hydroxyl-functional copolymer, random 155
SL 31 Organically modified polysiloxane No OH-groups
HO-R
EO/P
O
EO/P
O
14 June 2018 | Formulation Additives
HO
-R
Name Description Content [%]
Joncryl® 510 Hydroxy functional polyacrylate 50.2
Basonol® HPE 1170 B Hydroxy functional hyperbranched Polyester 9.0
DBTL, 5% active in BuAc Catalyst 0.13
Xylol Solvent 28.47
Solvenon® PM Solvent 12.2
Total 100
Basonat® HI 190 B/S HDI Isocyanurate 27.4
Remark: Hydroxyl content of the additives were not considered by the stoichiometric calculation
15
Application tests - recipe of sb 2pack PU test system
June 2018 | Formulation Additives
Surface energy and contact angle measurements
020406080
100120140160
Ref
eren
ce
SL31
0,1
SL31
0,8
SL31
1,5
GM
31 0
.1
GM
31 0
,5
GM
31 1
,5
GM
31 2
,5
GM
144
0,1
GM
144
1,5
GM
35 0
,5
GM
35 1
,5
GM
35 2
,5
w/oadditive
mod. PDMS hydroxy F-Acrylate, block hydroxy F-Acrylate, random
F-Acrylate, block
Con
tact
Ang
le
CA (Water) CA (Diiodomethane)
Remark: selected additives in an SB 2pack polyurethane clear coat.
16
Fluorinated hydroxyl-functional block copolymer shows low surface energy even at low dosage.
June 2018 | Formulation Additives
108 104 102 99
0
20
40
60
80
100
120
0
5
10
15
20
25
30
35
40
without cleaning 1st Cleaning cycle 2nd Cleaning cycle 3rd Cleaning cycle
Con
tact
Ang
le W
ater
Surf
ace
Ener
gy [m
J/m
²]
polar fraction [mN/m] disperse fraction [mN/m] Contact angle water
17
Persistency of low energy surface effect after cleaning cyclesLow surface energy remains after three cleaning cycles. This further confirms persistent cross linking of the fluorinated hydroxyl-functional block copolymer
Remark: SB 2pack PU system with 0.5% GM31.
June 2018 | Formulation Additives
Sample 1Reference
Sample 20,1% GM35
16.00u - O- -MC: 16; TC: 9.826e+004
42.00u - CNO- -MC: 41; TC: 4.660e+005
19.00u - F- -MC: 38; TC: 3.947e+005
292.97u - C7F11- -MC: 14; TC: 7.915e+004
Sample 30.1% GM31
Remark: Ion mapping of O, CNO, F, C7F11: Lighter areas correspond with a higher signal intensity, while darker areas correspond with lower to none signal intensity.
High surface activity
Exudation?
18
Ion mapping of surface activity and weathering resistance by ToF-SIMS analysis - before weathering
June 2018 | Formulation Additives
Poin
t-to-
Poin
t Nor
mal
izat
ion
-210
-310
-410
-510
-610Sputter Time [s]140120100806040200
1) Focke-001
C N O-
C N O-CNO-
F-
F-F-
1) Reference w/o additive
2) 0.1% GM35
3) 0.1% GM31
Distinct stratification of
fluor component
Top Depth
■ Both fluorinated copolymers prove distinct stratification.
■ F-intensity shows strong decrease in concentration from the top.
19
ToF-SIMS depth profile of SB 2pack PU coating - before weathering
June 2018 | Formulation Additives
O- normalized to totalMC: 0; TC: 4.887e+002
CN- normalized to totalMC: 0; TC: 6.047e+002
F- normalized to totalMC: 0; TC: 9.710e+000
C7F11- normalized to totalMC: 0; TC: 1.274e+000
Sample 1Reference
Sample 20.1% GM35
O- normalized to totalMC: 0; TC: 5.609e+002
CN- normalized to totalMC: 0; TC: 5.129e+002
F- normalized to totalMC: 0; TC: 6.755e+002
C7F11- normalized to totalMC: 0; TC: 1.124e+002
Sample 30.1% GM31
Contamination while weathering
Exudation washed off
Still high surface activity
20
Ion mapping of surface activity and weathering resistance by ToF-SIMS analysis - after weathering*
Remark: Ion mapping of O, CNO, F, C7F11: Lighter areas correspond with a higher signal intensity, while darker areas correspond with lower to none signal intensity. *After 500h WOM-CAM 180.
June 2018 | Formulation Additives
Poin
t-to-
Poin
t Nor
mal
izat
ion
-210
-310
-410
Sputter Time [s]24020016012080400
1) Focke-001
C N O-
C N O-CNO-
F-
F-F-
1) Reference w/o additive
2) 0.1% GM35
3) 0.1% GM31
Top Depth
Strong F-signal strength after weathering
■ The fluorinated hydroxyl-functional block copolymer exhibits persistent F-signal strength after weathering. This indicates covalent bonding into the resin matrix.
21
ToF-SIMS depth profile of SB 2-pack PU coating - after 500h WOM-CAM 180 weathering
June 2018 | Formulation Additives
Content
Applications for Easy-to-Clean surfaces
Additives based on CFRP fluorinated acrylates
Performance benefits
Characterization of functional surfaces
1.2.3.4.
Conclusion5.
June 2018 | Formulation Additives22
GM310.5%
GM312.5%
GM315.0%
Referencew/o additive
Before cleaning After cleaning with organic solvent
Remark: SB 2pack PU clear coat, two stain/cleaning cycles
23
Anti-Graffiti testing with felt-tip pen Offers strong dewetting with durable resistance and improved cleanability.
GM310.5%
GM312.5%
GM315.0%
Referencew/o additive
1st
2nd
June 2018 | Formulation Additives
Referencew/o additive
GM310.5%
GM311.5%
GM312.5%
Easy-to-Clean testing with standardized dirt
Remark: SB 2pack PU clear coat contaminated with standardized dirt, cleaning with low pressure water jet
24
Fluorinated hydroxyl-functional block copolymer shows improved cleanability.
June 2018 | Formulation Additives
Content
Applications for Easy-to-Clean surfaces
Additives based on CFRP fluorinated acrylates
Performance benefits
Characterization of functional surfaces
1.2.3.4.
Conclusion5.
June 2018 | Formulation Additives25
Benefits of functional CFRP based fluorinated acrylatesDistinct surface activity with low surface energy Cross linkable by certain functionality
Covalent bonded into the resin matrix
Air
Liquide
HO
-R
+ Polyisocyanatesor
MF-resins
Air
Resin Matrix
June 2018 | Formulation Additives26
Conclusion
CFRP technology enables customized modular design leading to hydroxyl functionalized fluorinated block copolymers with excellent compatibility and co-reactivity for enduring surface modification.
Their cross-linkability results in a long-lasting effect and makes them ideal for achieving “easy-to-clean” effects in automotive and industrial top coat formulations.
Their high surface activity results in extraordinary low surface energies even at low dosage levels.
The conclusion is that hydroxyl-functional, fluorinated block copolymers represent a new and innovative class of surface additives to achieve excellent hydrophobization effects and improved cleaning properties in SB 2k PU top coats.
27 June 2018 | Formulation Additives
Credits
Thank you to the following colleagues for their contribution:
■ Dr. Sascha Oestreich■ Dr. Ralf Knischka■ Dr. Ulrich Tritschler■ Dr. Sabine Hirth■ Armin Petzhold■ Andrea Schamp■ Marc Dennis Focke
28 June 2018 | Formulation Additives