How structural order boosts performance...fluorinated block copolymers . with excellent...

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





1.2.3.4.

Conclusion5.


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


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


Content





1.2.3.4.

Conclusion5.


■ 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!


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!


■ 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)


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


Content





1.2.3.4.

Conclusion5.


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


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


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.


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.


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


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


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.


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


Content





1.2.3.4.

Conclusion5.


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%


1st

2nd



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.


Content





1.2.3.4.

Conclusion5.


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


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.


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


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