A Unique Class of Fluoroalkyl Silicones with

Synergistic BehaviorTom Cheung, Bob Ruckle,

Adam Horne, Steve Wilkowski Siltech Corporation; Toronto, Canada

Challenges from Staining, Fouling, Graffiti, Fingerprints, Chemicals....

Silicone Fluoropolymer Low surface energy Very low surface energy

Very good thermal flexibility

Marginal thermal flexibility

Good chemical resistance Very good chemical resistance

Marginal oil resistance-swelling Very good oil resistance

Very good water resistance Good water resistance

Low abrasion resistance Low abrasion resistance

High cost ($10/lb.) Very high cost ($80/lb.)

Effective at low use levels Effective at low use levels

Comparison of Selected Properties of Silicone and Fluoropolymers

Fluoroalkyl Silicone Variants

Silicone

Fluoroalkyl

Organic

By varying the number, length and type of fluoroalkyl and/or organic substituents covalently bound to the silicone we can control properties.

• Silicone provides slip, surface tension reduction, mar resistance, water resistance, flexibility.

• Fluoroalkyl provides these and oleophobicity, stain and chemical resistance.

• Organic provides miscibility.

Soluble Non-PFOS Fluorosilicones

Condensation Reactive Solvent Soluble Water Soluble

Non-Reactive Solvent Soluble

a b c

x

a b c

n

Reactive non-PFOS Fluorosilicones

Condensation Reactive◦ Urethane◦ Epoxy◦ Polyester

UV and Free Radical Reactive◦ Acrylate◦ Vinyl

Condensation Reactive

a b ca b c

Fluoroalkyl Silicone Variantsc b R

FPE >0 >0 (CH2)3(OC2H4)d(OC3H6)e OH

FS 0 >0 None

AFS >0 >0 CnH(2n) R’

AS >0 0 CnH(2n) R’

a b c

Silicone

Wt % Silicone

Wt % CF2

Wt % organic

Reactive Site

MW Type

FPE 2010 L L H OH 3000 fluoroalkyl polyether siliconeFPE 2110 L L H OH 7000

FS D2 M H 0% no 2000 fluoroalkyl siliconeFS J15 H M 0% no 14000

AFS G2-F H L M OH 3000alkyl,

fluoroalkyl silicone

AFS E3.5-F M L L OH 2000

AFS C7-F H L L OH/ACR 2000

AFS H418 M M M no 5000

AS OH C50 VH 0% L OH 12000 alkylsiliconeAS OH J10 H 0% M OH 8000

Comparison Silicones Design

Various silicones are evaluated for slip, COF, defects and mar, stain, and fingerprint and chemical resistance.

The overall design used four systems:◦ SB 2k Urethane◦ UV cured urethane acrylate◦ UV cured epoxy acrylate◦ Commercial flat white paint (post addition)

Experimental Design and Methods:

CoF (sled method)

Gloss (gloss meter)

Fingerprint (internal test method)

Stain (variations on standard and internal test methods)

ASTM D543 (chemical resistance)

ASTM D1308 (chemical resistance)

ASTM D870 (water absorption)

Test Methods Utilized

Gloss: SB Urethane

• FPE are most miscible, improve gloss• AFS type decrease gloss cause

defects

100

105

110

115

120

125

130

135

Control AFS G2 AFS E3.5 AFS C7AFS C7ACR FPE 2010 FPE 2110

Deg

ree

of G

loss

Fisheyes

Gloss: Urethane Acrylate

• FPE are most miscible, keep gloss• AFS, AS and FS types decrease gloss

020406080

100120

Control FS D2 FS J15 FPE 2010FPE 2110 AFS C7ACR AFS H418

Deg

rees

Defects

Slip: Urethane Acrylate

• All improve COF• AFS C7 is best

Control FS D2 FS J15 FPE 2010

FPE 2110

AFS C7ACR

AFS H418

0

0.5

1

1.5

2

2.5 M/H%SIL/%CF2

H/M L/L H/L M/M

Sta

tic

Kin

etic

Slip: SB Urethane

• All improve COF• AFS C7 structures are best

• ACR better than OH

Control AFS G2 AFS E3.5

AFS C7 AFS C7ACR

FPE 2010

FPE 2110

0.00.30.50.81.01.31.5

Sta

tic

Kin

etic

M/L%SIL/%CF2 M/L H/L L/L

Slip: Post-added to Paint

• All improve COF, more at 5%

• FPEs are very good

Control

1% AFS G2

5% AFS G2

1% AFS E3.5

5% AFS E3.5

1% AFS C7

5% AFS C7

1% AFS H418

5% AFS H418

1% FS D2

5% FS D2

1% FPE 2010

5% FPE 2010

1% FPE 2110

5% FPE 2110

0.500.550.600.650.700.750.800.850.900.95

Sta

tic

Kin

etic

Mar Resist: SB Urethane

• All improve mar resistance• FPE are better than expected

Control

AFS G2

AFS E3.5AFS C7

AFS C7ACR

FPE 2010

FPE 21100%

20%

40%

60%

80%

100%

0

2

4

6

8

10

Glo

ss R

etai

ned

Mar

Res

ist R

ating

Control FS D2 FS J15 FPE 2010

FPE 2110

AFS C7 ACR

AFS H418

0123456789

10Ra

ting

UV Epoxy Acrylate: Mar, Stain, Print

• All are improved over control• The high %CF2 FS D2 is not best

• FPEs are weak on fingerprint• AFS C7 ACR strong on all

Mar

Res

ist

Sta

in R

esis

tF

ing

erp

rin

t R

esis

t

Control FS D2 FS J15 FPE 2010

FPE 2110

AFS C7ACR

AFS H418

0123456789

10Ra

ting

UV Ureth Acryl: Mar, Stain, Print

Mar

Res

ist

Sta

in R

esis

tF

ing

erp

rin

t R

esis

t

• All are improved over control• The high %CF2 FS D2 is not best

• FPEs are weak on fingerprint• AFS C7 ACR strong on all

Control

1% AFS G2

5% AFS G2

1% AFS E3.5

5% AFS E3.5

1% AFS C7

5% AFS C7

1% AFS H418

5% AFS H418

1% FS D2

5% FS D2

1% FPE 2010

5% FPE 2010

1% FPE 2110

5% FPE 2110

0123456789

10

Mar and Stain: Post-added to Paint

• All improve mar resistance/ more at 5%

• Both %CF2 and %Sil help • Lesser improvement in stain/ 5%

better

Mar

Res

ist

Sta

in R

esis

tM/L

%SIL/%CF2

M/L H/L L/LM/HM/M

Control AFS G2 AFS E3.5

AFS C7 AFS C7ACR

FPE 2010

FPE 2110

0123456789

10

Stai

n Re

ist R

ating

Stain Resist: SB Urethane

• AFS C7 structures again perform well

HB

Pen

cil

Bla

ck

Mar

ker

Blu

e P

enci

lB

row

n C

rayo

nB

lac

k C

rayo

n

Stain Resist: Urethane Acrylate

• AFS C7 ACR and FPEs are effective

Control FS D2 FS J15 FPE 2010

FPE 2110

AFS C7ACR

AFS H418

0

2

4

6

8

10St

ain

resi

st R

ating

HB

Pen

cil

Bla

ck

Mar

ker

Blu

e P

enci

lB

row

n C

rayo

nB

lac

k C

rayo

nR

ed P

enci

l

Control FS D2 FS J15 FPE 2010 FPE 2110 AFS C7ACR

AFS H4180123456789

10

Ratin

gStain: UV Epoxy Acrylate

• Highest %CF2 is least effective• AFS C7 ACR and FPEs are effective

HB

Pen

cil

Bla

ck

Mar

ker

Blu

e P

enci

lB

row

n C

rayo

nB

lac

k C

rayo

n

Water Repellency: SB Urethane

AFS C7-2F

AFS D5-2F

AFS C7 ACR

AFS C7

AFS E3

.5

AFS G2

FPE 2

010

FPE 2

110none

AS C50

AS C50 ACR

AS J10

AS C7-0CT

AS D2

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0%

5%

10%

15%

20%

25%

Height/Radius

% CF2

Heig

ht/

Radi

us

% C

F2

• Highest %CF2 is most effective• AS type alone are very effective

Additive (1%) IPA

Vinegar Soap NH4OH HCl

Average

NormalizedRating

AFS E3.5 5 2 3 2 2 2.8 1.0FPE 2110 6 1 4 3 2 3.2 2.0AFS C7 6 4 5 2 3 4 4.0AS C7-OCT 6 2 4 6 4 4.4 5.3FPE 2010 7 3 5 1 6 4.4 5.3AFS G2 8 2 4 5 5 4.8 6.7AS C50 8 3 4 5 5 5 7.3AS C50 ACR 7 7 6 3 2 5 7.3C7-2F 6 5 5 5 4 5 7.3Control 8 4 5 5 4 5.2 8.0AS D2 8 2 7 6 5 5.6 9.3AS J10 7 6 6 6 3 5.6 9.3AFS C7 ACR 8 7 6 5 3 5.8 10.0

Chemical Resistance: SB Urethane

AFS C7 ACR and two AS types gave an improvement here

Summary Chemical: Post add

• AS C50 is best. • AFS C7 and FS D2 are next best• AFS C7 ACR is worst.

AFS C7 ACRAS D2AFS C7-2FAFS H418AFS D2

FPE 2110AS C50 ACR AS C7 OCTAFS E3.5AFS C7

ControlAFS D5-2FFPE 2010AFS G2AS C50

All AFS additives improve COF, mar and stain resistance and to a lesser degree fingerprint.

The FPE type are the most compatible. Surprisingly, they are also among the best for slip and mar resistance, but not for fingerprint resistance.

The very incompatible FA types are not as effective as expected for slip and mar. Formulation should help.

Increasing % CF2 is often not the best in performance.

Low CF2 content AFS structures are usually the best Post-added AFS have little effect on slip and gloss but do

affect mar and stain resistance. Use levels needed were up to 5% and more is usually

better.

Results

Higher use level is better for mar and stain. Best stain results are for waxy stains. Water repellency can be improved with high CF2 or high

silicone content additives. For chemical and water resistance performance varied

more depending on the coating system and use level.

AFS H418 - which has a balance of % Sil, %CF2, & %CH2 - gives a very good balance of properties.

AFS C7-F is often the best for slip, mar and stain resistance. FS J15, AFS H418 and AFS C7 give the best finger print

resistance

Results

Thank You

Fluorosil 2010 and Fluorosil 2110. These are very good for all but fingerprint resistance

Fluorosil ACR C7-F or Fluorosil OH C7-F are best overall including fingerprint resistance. They are not always compatible.

Use levels are up to 5% and more is better in most cases.

Recommendations