UV Stabilization of Organic Coatings

Mervin G. Wood, Ph.D.

Technical Expert
JPCL Webinar
November 11, 2015

Outline
Ultraviolet Component of Light Sources
Degradation and UV Light
Ultraviolet Absorbers (UVA)
Hindered Amine Light Stabilizers (HALS)
Weathering Test Methods

Conclusions

Ultraviolet Component of Light Sources

UV-C Region (up to 280 nm)
Found only in outer space
Filtered out by Earths atmosphere
UV-B Region (280 to 315 nm)
Responsible for polymer damage

Absorbed by window glass to 290 nm

UV-A Region (315 to 400 nm)
Also responsible for polymer damage
Dose is proportionally higher than C or B
3

Ultraviolet Component of Light Sources

Natural Sunlight*
Miami, Florida (June 17, 1983)
1.8

Irradiance (Watts/sq. meter)

1.6
1.4

UVC

1.2

UVB

UVA

0.8
0.6
0.4

Visible

0.2
0
250

270

290

310

330

350
Wavelength (nm)

370

390

410

430

450

Increasing Energy per photon

Energy = h=hc/

Shorter = Higher Energy per photon, lower intensity (fewer photons in solar radiation)
Longer = Lower Energy per photon, higher intensity, higher total energy in sunlight
*UV-B will increase with altitude

Degradation and UV Light

Degradation and UV Light

Light Energy
Energy can be...
absorbed
reflected
scattered

transmitted
Absorbed energy can...
cause photolysis of polymers, impurities
be transferred from one molecule to another
be emitted as heat or light
6

Degradation and UV Light

Absorbed UV light can break bonds

UV-B
UV-A

/ nm

Bonding

Type

Bond Energy

230

-C-C-

Aromatic

520 kJ/mol

286

R-O-H

Alcohol

420 kJ/mol

290

R-CR2-H

prim. / sec. / tert. H

410 / 395 / 385 kJ/mol

310

C-O-H

Alcohol

385 kJ/mol

320

-C-O-

Ether

365 - 390 kJ/mol

340

R-CH2-CH3

Aliphatic

335 - 370 kJ/mol

350

-CR2-Cl

aliphatic Chloride

330 - 350 kJ/mol

360

-CH2-NR2

Amine

330 kJ/mol

400

-O-O-

Peroxide

270 kJ/mol

References: Morrison Boyd, Lehrbuch d. Org. Chemie, 3rd Ed., VCH, 1985
7

Degradation and UV Light

Absorbed UV light can break bonds

Degradation and UV Light

Mechanism of photo-oxidation
DT, h

Initiation

Polymer-P

Propagation /

P + O2

Branched chains

Auto catalytic
Chain reaction
Termination /
Recombination

POO + PH

fast
slow

free radicals (P, PO, HO, HOO,...)

POO
POOH + P

PO + PH

POH + P

HO + PH

H2O + P

POOH
2 POOH

DT, h
DT, h

PO + OH
PO + POO + H2O

P + P

P-P

P + POO

POOP (Peroxide bridge)

PO + PO

POOP (Peroxide bridge)

P + PO

POP (Ether bridge)

Ultraviolet Absorbers (UVAs)

10

UV Absorbers
UVAs How they work
Prevent polymer degradation by absorbing light and converting to heat
Tautomeric mechanism allows long-term activity
Subject to Beer-Lambert Law thickness dependent
Not very efficient in highly pigmented systems

11

UVAs Degradation and UV Light

R

R*

ROO

O2

PH

ROO

ROOH + P

h or D
RO

UV Absorbers work here

.OH

HALS work here

12

UV Absorbers
Benzotriazole UVA Mode of Action
-

R1

R1

h
D
R2

Enol form (S0)

R2

Keto form (S1)

Energy dissipation
Conversion of the absorbed UV light
takes place in the excited singlet state

13

UV Absorbers
Beer-Lambert Law
A = ebc
where A = absorbance
e = molar extinction coefficient
b = path length

c = concentration of UV absorber
Absorption (A) = -log T
T = Transmission

Competitive absorption of harmful UV light

14

UV Absorbers
Governed by Beer-Lambert Law
Extinction Coefficient
UVA Concentration
Film Thickness
Range of Absorption

290 nm 400 nm
Properties
Compatibility
Regeneration
Photopermanence
15

UV Absorbers Various Commercial Classes

Oxanilide

Benzotriazole
Cyanoacrylate

Benzophenone

Triazine
16

UV Absorbers UV absorbance spectra

of UVA types
1.50

UV-A

UV-B

VIS

Absorbance

c = 20 mg/liter in Toluene(Xylene), path = 1cm

1.00
Cyanacrylate
Oxalanilide
Benzophenone
Benzotriazole
0.50

Triazine

0.00
290

310

330

350

370

390

410

430

Wavelength / nm

Cyanoacrylates, Oxalanilides absorbs efficiently only in UV-B

Benzotriazoles show best spectrum coverage
17

UV Absorbers Photopermanence
110

30mm Clear Coat with UVA + 1% N-Alkyl HALS on fused quartz plates
(% UV-A determined at 345nm)

UV-A retained / %

100

98.2%
94.2%

90

89.6%
83.9%

80

Decreasing Photopermanence
70

76.2%

0.8% Triazine C
1.5% Triazine B
1.5% Triazine A
1.5% Benzotriazole B
1.5% Benzotriazole A

60

50
0

500

1000

1500

2000

2500

Xe-WOM CAM 180 exposure / hrs

Photopermanence = f(UVA type, Mw)

18

UVAs Synergy with HALS

Polyester Urethane Clearcoat/Bronze Metallic Basecoat, XeWOM = J2527
100

90
80

20 Deg Gloss

70
60

Unstabilized

50

2% UVA
1% N-Alkyl HALS

40

2% UVA/1.5% N-Alkyl HALS

30
20
10
0
0

500

1000

1500

2000

2500

3000

3500

4000

Hours
19

UV Absorbers Proper UV Absorber

Choice
Substrate Sensitivity

UV wavelength sensitivity of resin binder or underlying resin

UV wavelength sensitivity of pigment

Sensitivity of color change (yellowing or pigment fading) for resulting article

Environmental Factors

Environmental conditions

Interior versus exterior

Duration of service (warranty)

Formulation Details

Solventborne, waterborne, 100% solids or UV cured

Basecoat/clearcoat, monocoat, etc.

20

Hindered Amine Light Stabilizers (HALS)

21

Hindered Amine Light Stabilizers

Photostabilization with HALS
Regenerative
Effective in maintaining physical properties
Effective in pigmented as well as low Pigment to Binder (P/B) ratio
formulations
Not thickness dependent

22

Hindered Amine Light Stabilizers

How much effect can HALS have?
1% HALS

X 10,000
Unstabilized

X 1,000

2% HALS

X 10,000
Unstabilized

Scanning electron micrographs

of a white polyester
polyurethane after 1300 hours
QUVB (313 nm)

HALS Function in Coatings

Gloss retention
Reduce cracking
Reduce chalking

X 10,000
23

HALS Degradation and UV Light

R

R*

ROO

O2

PH

ROO

ROOH + P

h or D
RO

UV Absorbers work here

.OH

HALS work here

24

Hindered Amine Light Stabilizers

Mechanism of Action Modified Denisov Cycle
R

H
R C O N

Oxidation
N R

N O

O
R' C

O O

or
O
O
R' C
O H
or
R' O

C
R

R
O
C

O
O-

O
H

R' O

C R
R

R'
H
25

Hindered Amine Light Stabilizers

HALS Basicity
Piperidine

pKb
5.0

Alkyl Piperidine

5.1

A l k y l P i p e r i d i n e / AO h y b r i d

5.5

A l kox y P i p e r i d i n e

9.6

R1 = Head Group

R2 = Backbone

Activity
Basicity
Compatibility

Solubility/Compatibility
Equivalent Weight
Basicity
26

HALS Weathering Performance of HALS Type

HSTSA Clearcoat/Silver Metallic Basecoat, Weathering = South FL
100
90
80

20 Deg Gloss

70
60
Unstabilized

50

2% UVA/1% N-Acyl HALS

2% UVA/1% N-Alkyl HALS

40

2% UVA/1% N-OR HALS

30
20

HSTSA = High Solids

Thermoset Acrylic

10

0
0

10

20

30

40

50

60

70

Months
27

Weathering Test Methods

Natural Weathering

Accelerated Weathering

Florida
Arizona
Australia
Other

QUV-B (for high altitude simulation)

Xenon with various light filters
QUV-A (for terrestrial simulation)
Many others

Substrate Weathering Considerations

Environmental Factors
Interior versus exterior
Environmental conditions & pollutants
Duration of service (warranty)
28

Conclusions
UV Absorbers ...
Competitively absorb UV light to hinder radical initiation
Regenerate
Retard color change in low P/B formulations
Shield polymer from UV light and degradation

Exhibit synergism with HALS

29

Conclusions Continued
Hindered Amine Light Stabilizers ...
Terminate free radicals to prevent further chain reactions
Are effective in high pigmented as well as low P/B formulations
Regenerate
Are not thickness dependent

Reduce cracking and loss of tensile properties

Exhibit synergism with UVAs

30

Acknowledgements
Many thanks to Lori Boggs and Diane Langer for their contribution and
support

31

While the descriptions, designs, data and information contained herein are presented in good faith and
believed to be accurate, they are provided for guidance only. Because many factors may affect processing
or application/use, BASF recommends that the reader make tests to determine the suitability of a product for
a particular purpose prior to use. NO WARRANTIES OF ANY KIND, EITHER EXPRESSED OR IMPLIED,
INCLUDING, BUT NOT LIMITED TO, WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A
PARTICULAR PURPOSE, ARE MADE REGARDING PRODUCTS DESCRIBED OR DESIGNS, DATA OR
INFORMATION SET FORTH, OR THAT THE PRODUCTS, DESCRIPTIONS, DESIGNS, DATA OR
INFORMATION MAY BE USED WITHOUT INFRINGING THE INTELLECTUAL PROPERTY RIGHTS OF
OTHERS. In no case shall the descriptions, information, data or designs provided be considered a part of
BASF's terms and conditions of sale. Further, the descriptions, designs, data, and information furnished by
BASF hereunder are given gratis and BASF assumes no obligation or liability for the descriptions, designs,
data or information given or results obtained all such being given and accepted at the reader's risk.

BASF Corporation, 2015

32