Novel solutions to improve the

Performance of
Automotive Coatings
Rüdiger Mertsch, Rainer Lomölder,
Wernfried Heilen, Tobias Unkelhäußer, Kirstin
Schulz

Evonik Industries AG
Agenda

• Scratch resistance by Polytrialkoxysilanes

• How to achieve Matted OEM Clear

Coatings

• Levelling and Flow Improvement by

additives

• Summary

Page | 2
Agenda

• Scratch resistance by Polytrialkoxysilanes

• Matted OEM Clear Coatings

• Levelling Improvement by additives

• Summary

Page | 3
What is meant by
“Scratch resistance“ at the moment?

to prevent … to achieve… (also after weathering)

 Scratch resistance is an individual impression of the improvement

of a mechanical surface damage.

Improvement is judged based on

 Visibility of scratches Scratch resistance is measured via
 Magnitude of scratches reflectometer (Loss of gloss)
 Number of scratches

Page | 4
 Silane technology based clearcoats
could become the new standard

 Chemical resistance, an issue in the past,

has been successfully addressed by 2K-PUR
technology

 CeramiClear® has been a technical

breakthrough regarding scratch resistance
(~10 years ago)

 Major OEMs have already or are going to

implement silane technology based clearcoat
systems

 German premium car manufacturer is

“technically excited” and “convinced that
silane technology will become the standard
within the next 10 years”

Page | 5
Chemical background:
VESTANAT® EP-M 95 is a core element
of our new technology

 Isocyanates react with diols or polyols forming urethanes bonds

O
O
Me
HO
2 Si
Si N C O + R OH

Me O
O
O
O
Me
Me VESTANAT® EP-M 95
O
O
O
O Me
O H
O
O
Me
R O N Si
Si
Si
Si N O Me
H O
O
O
Me O
O
O
O

Me

 Aliphatic urethanes are well-proven in coating materials, show favorable

properties (high flexibility and hardness) and are uncritical e.g. in terms of
yellowing behaviour

Page | 6
 Two promising approaches for
Si-PUR hybrids crosslinking

Approach A:
NISO-technology: Crosslinking of polyols (transesterification)

Polyol Polyalkoxysilane / e.g. VESTANAT® EP-M 95

Approach B: Boosting of 2K PUR systems (self-condensation)

Polyalkoxysilane /
Polyol Polyisocyanate e.g. VESTANAT® EP-M 95
December 6, 2012 | Scratch resistant clear coats based on poly-trialkoxysilanes Page | 7
VESTANAT® EP-M 95:
Modification of 2K PUR Clearcoats

VESTANAT® EP-M 95 2K PUR

Me
H
O
O O
O Me

O
O
O H

Si N C Polyol
Me
Si Si N O R O N Si

O
O
Me

Me
O
O O
H O O
O
Me

Interpenetrating networks

Scratch 2K PUR
resistance characteristics
(e.g. Hardness and
flexibility at the same
time)
Page | 8
Formulation aspects: Approach B
(Boosting of 2K PUR systems)

 Boosted 2K PUR Formulation with VESTANAT® EP-M 95

Scratch Resistant Clearcoat Formulation

(100% M95 added onto solid content [66%])

31.7% by wt. Setalux 1767 (Acrylic Polyol)

12.7% by wt. VESTANAT® HT 2500 L
2.8% by wt. VESTANAT® EP-CAT 11
33.9% by wt. VESTANAT® EP-M 95
9.1% by wt. Butyl Acetate
9.1% by wt. Xylene
0.7% by wt. TEGO GLIDE® 410, stabiliziers
50/50 70/30 90/10

Ratios individually adjustable!

Page | 9
VESTANAT® EP-M 95 „boosted“ 2K PUR-
System

Catalyst: 0,5% VESTANAT® EP-CAT 11

Curing conditions: 22‘ 140°C
System: Setalux 1767 / VESTANAT® HT 2500 L

Dosage VESTANAT® EP-M 95

0% 10 % 30 % 50 % 100 %

Hardness [König] 1d 171 174 164 162 143

Erichsen Cupping [mm] 8,0 8,5 7,0 6,0 7,0

Impact, direct [inch Ibs] > 80 > 80 > 80 > 80 80

Acid Etch (20 % H2SO4,

47 / 65°C 48 / 67°C 44 / 62°C 40 / 61°C 46 / 71°C
1st impact / destroyed)

• Slight decrease of hardness with increasing amount VESTANAT® EP-M 95

• Slight decrease of flexibility with increasing amount VESTANAT® EP-M 95
• Acid etch on comparable level
Page | 10
 Improvement of scratch resistance by
addition of VESTANAT® EP-M 95

35
Setalux 1767 // HT 2500 L ; T 1890 L
Setalux 1767 // HT 2500 L
30

25
Loss of gloss 20°

20

15

10

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

Dosage VESTANAT® EP-M 95 [%]

 Advantages: „Plug-in“ –Technology and individual adjustment of properties is possible

Page | 11
The new silane technology clearcoats
shows excellent properties
Both approaches ensure:

 High hardness and flexibility

 Very good appearance and no haze

 High scratch resistance and gloss retention

 Sandability (car refinish)

Coated panels after Crockmeter test

DIN EN ISO 105-X12, 10 double rubs, 3M polishing paper 9 mic/81330

Page | 12
Agenda

• Scratch resistance by Polytrialkoxysilanes

• How to achieve Matted OEM Clear

Coatings
• Levelling and Flow Improvement by
additives

• Summary

Page | 13
How to achieve matted OEM Coatings
Targets for a OEM matted clear coat:

1. Similar gloss at different film thicknesses

2. No influence on gloss during application & drying

3. Excellent chemical stability and durability

4. High transparency of the clear coating

Page | 15
Gloss Measuring System - Reflectometer

Source of Light
20°

60°
Detector

85°

Page | 16
Influence of Film Thickness vs. Gloss @
60° (OEM based on ACEMATT ® 3300)

Source of Light
20°

60°
30 Detector

85°

20
60° Gloss

10

0
32 36 41 48
Film Thickness [µm]

Page | 17
Influence of Film Thickness vs. Gloss @
85° (OEM based on ACEMATT ® 3300)

Source of Light
20°

60°
80 Detector

85°

60
85° Gloss

40

20

0
32 36 41 48
Film Thickness [µm]

Page | 18
Influence of Flash Off Time
(Curing at 80°C / 30 Min.)

50

40
60° Gloss

30
30‘ 60°C
20

10

0
0 15 30 45
Flash off time in min.

Page | 19
„Jacksonville“ Weathering“

The “Jacksonville” weathering test is

a special outdoor exposure test that
can only be performed from mid-May
to the end of August in Jacksonville,
Florida. This area has a history of
above-average acid rain content and
is used as a benchmark for acid rain
and industrial environment testing for
automotive finishes. This fourteen
weeks performed test is required by
the car manufacturers, before a new
car lacquer finish is introduced.

Page | 20
„Jacksonville“ Weathering“
Gloss reduction of the unmatted Clear Coating

95

90

85

80

75
Gloss 20° Gloss 60° Gloss 20° Gloss 60°
1 year 1 year

Clear coat

Page | 21
„Jacksonville“ Weathering of Matted
Clear Coatings

70
60
50
40
30
20
10
0
Gloss 60° Gloss 85° Gloss 60° 1 Gloss 85° 1
year year

Competitor 1 Competitor 2 OK 520 TS 100 3300

Page | 22
Change of Gloss according
ADF-Test

Zero Sample ACEMATT® 3300

3D-Säule 2
ACEMATT® 3300
ACEMATT® OK 520
30

20
60° Gloss

10

0
27 56 84
[Days]
Page | 23
Influence of Matting Agents on the
Chemical Influence of Resistance
(2c PU formulation based on Macrynal SM 510 and D`Dur N75 / Stress time 24h)

Matting Agent Gloss @ Super- Diesel 1% 1% Sodium Bird

60° Sulphuric hydroxide excrement
Benzin
acid
Without 92 0 0 0 0 0

ACEMATT® 3300 24 0-1 0 0 1-2 0

ACEMATT® OK 520 24 1 0 0 2 0

Silica gel 23 2 0 0 -1 2-3 0

(Competitor)

Clear coat from the 29 2 0 0 2 0

market

Rating:
0 = very good
5 = poor
Page | 24
Polishing (Sonax® Xtreme polish 6 Wax 3
progressive)
OEM Clear coat based on ACEMATT® 3300)

80

60
85° gloss

40

20

0
0 2 4 6
Polishing Cycles

Page | 25
Agenda

• Scratch resistance by Polytrialkoxysilanes

• How to achieve Matted OEM Clear

Coatings
• Levelling and Flow Improvement by
additives
• Summary

Page | 26
Flow & Leveling
Go for the Perfect Finish
The Perfect Finish
Needs a Bit of Everything

Slip
Leveling

Flow

Substrate
wetting
substrate

|
Acrylate-based TEGO® Flow

Polyacrylate levelling agents

TEGO® Flow 300, 370, ZFS 460

• Excellent leveling
• Excellent recoatability
• No surface tension reduction
• No slip

H
OC3H5

O OH O O O O
x

y z

|
Mode of Action
Acrylate-based Flow Additives

|
Structural Parameters Determine
Properties of Organomod. Siloxanes

2 2
1

1 Length of polydimethylsiloxane chain

→ silicone character (surface activitiy, slip, incompatibility)

2 Type and degree of organic modification

→ Polarity, solubility and compatibility

|
Glide Additives Improve other
Properties, too

Substrate Flow & Slip

wetting Leveling
Promotion
Short chain TEGO® Wet
polysiloxane

Medium chain TEGO® Flow

polysiloxane

Long Chain TEGO® Glide

polysiloxane

|
Measuring Slip

The force which is needed to

pull 500g over the coating
surface, is measured

The lower the value, the

better the slip properties.

|
Strong Slip with TEGO® Glide
No Slip with Acrylate-based Flow

180

160

140

120
Slip Value (cN)

100

80

60

40

20

0
Blank 0,1% Wet 270 0,1% Flow 425 0,1% Glide 450 0,1% Glide 410 0,1% Flow 300 0,1% Flow 370

Good reduction of friction only with Polyether siloxanes

with a long siloxane chain.
|
Coating: 2p-PUR HS Synocure 9293 + Desmudur 3360
 Surface Tension Reduction by Siloxane-
based Products – especially TEGO® Glide

28

27

26
Static surface tension (mN/m)

25

24

23

22

21

20
Blank 0,1% Wet 270 0,1% Flow 425 0,1% Glide 450 0,1% Glide 410 0,1% Flow 300 0,1% Flow 370

|
Coating: 2p-PUR HS Synocure 9293 + Desmudur 3360
Different Levelling depending on the
Additive Used
Blank

Acrylic Polymer Polyether siloxane

Short Wave Long Wave

|
Coating: 2p-PUR HS Synocure 9293 + Desmudur 3360
Leveling Strongly Depends on Additive
Dosage

0.1 % TEGO Wet 270 0.3 % TEGO Wet 270

Short chain polyether

siloxanes need higher
dosage.

0.1 % TEGO Glide 450 0.3 % TEGO Glide 450

Longer chain polyether
siloxanes need lower
dosage.

Avoid overdosage!

|
Coating: 2p-PUR HS Synocure 9293 + Desmudur 3360
Contamination Test –
Evaluation of Crater Prevention

Substrate: Black Coil Coating

Contaminant: 1% Grease in Solvent Naphta
Recoated with 2p-HS-Clear Coat

|
Coating: 2p-PUR HS Synocure 9293 + Desmudur 3360
Surface Tension Reduction Is
Essential for Crater Prevention

Blank 0.1% TEGO Flow 370

0.3 % TEGO Wet 270 0.1% TEGO Glide 410

Best crater prevention with powerful surface tension

reducers, e.g. TEGO Glide 410
|
Coating: 2p-PUR HS Synocure 9293 + Desmudur 3360