Weather Resistant Oligomers

Sartomer Company, Inc. Exton, Pennsylvania USA

Sartomer Company, Inc. Oaklands Corporate Center Tel:610-363-4100

502 Thomas Jones Way

Exton, PA 19341

800-SARTOMER (800-727-8663) Fax: 610-363-4140 Web: www.sartomer.com

5005 07/05

ABSTRACT A series of aliphatic urethane acrylate oligomers were UV cured and examined for response to accelerated weathering. Gloss retention, yellowing index, tensile strength, break elongation, and tensile modulus were determined as a function of accelerated weathering duration. Preliminary spectroscopic data is also presented. Several high performance oligomers passed 3000 hours QUV accelerated weathering exposure with excellent retention of both physical appearance and mechanical properties. Possible degradation mechanisms will be proposed and related to the chemical structures of these oligomers. INTRODUCTION Even though it is a relatively new technology, Ultraviolet (UV)/Electron Beam (EB) curing has already enjoyed a healthy growth in numerous industrial applications, such as coatings, adhesives, inks, and electronics. Fast curing (usually less than 1 second), excellent film properties, and essentially no volatile organic compounds (VOCs) are the major benefits. In contrast, conventional solvent-borne thermal curing processes are under increasing pressure from regulatory agencies to limit the amount of solvents emitted into the environment. In recent years, major advances have been made in raw material and equipment designs, which make this unique technology available for new industrial applications. Accompanying exciting developments such as low skin irritation acrylate monomers1, low viscosity oligomers, cationic chemistry2, and kinetic monitoring of the photopolymerization process3, is a theme of increasing interest in the current UV/EB curing industry: the study of the weathering resistance of radiation-cured films. By careful experimental design and systematic evaluation, highly weather resistant oligomers, monomers, photoinitiators, and stabilizers can be identified. Based on a better understanding of the chemical and mechanical changes that occur during the complicated weathering process, UV/EB cured coatings for long term exterior applications can be realized.

A laboratory accelerated QUV weathering device was used in this study. For industrial coatings, the most reliable and widely accepted weathering data is gathered by exposure of up to five years in a harsh outdoor environment (e.g. Florida or Arizona). However, the long exposure time required to evaluate coating durability hampers the need to study the chemical changes based on a wide range of formulation components. As a result, it is a common practice in todays coating industry to develop new chemistry and make significant formulation modifications based on the data from laboratory accelerated weathering tests4. The very nature of their high density crosslinking makes UV cured films resistant to radiation, chemical and thermal treatment. From previous work by other investigators on the weatherability of UV cured coatings5, 6, 7, 8, 9, 10, the following general observations can be made: (1) Aromatic epoxy and aromatic urethane acrylates are inferior to aliphatic urethane acrylates in weathering resistance. (2) The photo resistance of UV cured films can be markedly enhanced by the addition of adequate photostabilizers, mainly UV absorbers and HALS. (3) Low functionality and non-ether-containing monomers have better gloss retention. (4) Photoinitiators of -hydroxyacetophenone derivatives offer high reactivity in photocuring and low color development. (5) For nonlight-absorbing polymers, the backbone chemical structure greatly influences a coatings weathering pattern. Radical induced oxidation and photolysis have been proposed as two of the major mechanisms accounting for degradation. This paper will focus on the accelerated weathering performance of a series of commercial aliphatic urethane oligomers with vastly different backbone structures. Results of the evaluation will provide further insights into the fundamentals of weatherability of UV cured coatings.

EXPERIMENTAL QUV Accelerated Weathering Tester A QUV Accelerated Weathering Tester equipped with QFS-40 lamps (UV-B) from Q-Panel Company was used in this study. The QFS-40 lamps have a substantially higher energy output between 270 nm and 323 nm compared to the spectrum of natural sunlight.

The QUV is programmed to operate in a cycle of 8 hours UV radiation at 60C, followed by 4 hours dark condensation at 40C. Lamps are replaced after 400 service hours to ensure constant UV radiation dosage. Formulation and Materials A total eleven oligomers were used in the weathering study. The backbone structures and physical properties for these oligomers are listed in Table 1. The typical formulation for the oligomers studied is as follows:

Table 1. Oligomers: General structure and properties

Oligomer CN120 CN980 CN981 CN982 CN963 CN964 CN965 CN966 CN132 CN133 CN983
* EA: Epoxy Acrylate ** UA: Urethane Acrylate

General Structure Bisphenol A EA* Aliphatic UA** Aliphatic UA Aliphatic UA Aliphatic UA Aliphatic UA Aliphatic UA Aliphatic UA Diacrylate Triacrylate Diacrylate

Polyol Type Aromatic Ether Ether/Ester Ether/Ester Branched Ester Branched Ester Branched Ester Branched Ester Aliphatic Aliphatic Urethane

MW M=1000 1.1-1.3 M 1.6-1.8 M 2.6-2.8 M 5.4-5.6 M -

Viscosity cps @ 60C 2,300 19,600 6,300 9,375 55,000 18,300 11,200 57,000 970 @ 25C 18,600 @ 25C 5,100

Component Oligomer HDDA SR1129

Weight % 80 20 5 (on resin)

thickness. This is very important because film thickness is a very critical factor in determining a coatings weathering performance. UV Curing System A Fusion Model F440 UV curing unit was used. For gloss and yellowing measurement, both 0.5 mil and 5 mil samples were cured by passing one 300 W/in D bulb, followed by one 400 W/in H bulb, at a conveyor speed of 50 fpm (feet per minute). Each sample was exposed twice using this curing condition. For mechanical properties and spectroscopic measurements, 5 mil wet films were cast on aluminum Q-Panels and initially cured under one 300 W/in H bulb at 200 fpm. The semi-cured films were then cut into 0.5 inch wide strips. Finally, fully cured films were obtained by passing the strips under one 300 W/in D bulb, followed by one 400 W/in H bulb, at a conveyor speed of 50 fpm. Again, a total of two passes were used.

HDDA, hexanediol diacrylate, is a difunctional monomer with excellent solvency and weathering resistance as concluded from a previous study10. Esacure KIP100F (oligo[2-hydroxy-2-methyl-1-[4methylvinyl) phenyl] propanone]), is an -hydroxyacetophenone type unimolecular photoinitiator known for its non-yellowing properties. HDDA, Esacure KIP100F and all oligomers are commercial products from Sartomer Company. Wet Film Preparation One-half mil and five mil wet films were cast on mill finished aluminum Q-Panels using various drawdown rods. Great care was taken to obtain films with uniform

Gloss Measurement 60 gloss was measured using a Micro-Tri-Glossmeter from BYK-Gardner. Gloss retention was calculated by dividing gloss readings at specified time intervals by gloss reading at time zero. Yellowing Measurement The yellowing property of a film is expressed by a yellow index which is calculated by following equation: YI=[(1.28*X-1.06*Z)/Y]*100 where X, Y, Z are the tristimulus coordinates. The values for X, Y, and Z were obtained using a Hewlett Packard 8452-A Diode Array UV-Vis Spectrometer equipped with a Reflectance Spectroscopy Accessory from LapSphere. The UV-Vis is operated by a Window Color software program which gives Tristimulus, Hunter Lab, CIELAB, and POLAR Coordinates. FTIR A Nicolet Magna 550 FTIR Spectrometer equipped with a Baseline Horizontal ATR accessory was used. 5 mil film strips were used for data collection. Mechanical Properties Test Tensile strength, break elongation, and tensile modulus were determined using a Thwing-Albert tensile tester with a strain rate of 0.5 in/min. For each sample, at least 5 specimens were tested and an average value was reported. RESULTS AND DISCUSSION Weatherability of Aliphatic Urethane Acrylates with Polyester Backbones Oligomers CN963, CN964, CN965, and CN966 belong to the same class of aliphatic urethanes. They are derived from the same type of branched polyester polyol, with only the molecular weight of the polyol varying. The molecular weight relation between CN963, CN964, CN965, and CN966 is approximately 1:2:3:5. Because the polyol backbone is the only variable, this class of oligomers provides a

good base to study the effect of the polyol backbone structure on the weathering performance of the films. Figure 1 gives gloss retention vs QUV exposure time for this class of oligomer. The very clear pattern from the graph is a dramatic improvement in gloss retention as the molecular weight of the polyester polyol decreases. This observation is in total agreement with previous findings by this laboratory for a closely related system. To explain this observation, it is necessary to carefully examine possible modes of chemical modification occurring both in the films surface and bulk. In a QUV accelerated weathering chamber, high energy UV radiation, moisture, oxygen and temperature are the primary factors for film degradation. The combination of these factors could result in complex degradation pathways. Figure 1. Effect of molecular weight on gloss retention

Gloss Retention vs Time 80% Oligomer + 20% HDDA + 5% SR1129

%Gloss Retention

100 90 80 70 60 50 40 0 2 5

CN964 CN965 CN963 Film Thickness 0.5 mil

CN966

12 16 20 24 28

Hours QUV X100

From a macroscopic point of view, chain scission and crosslinking (Scheme 1) are mainly responsible for the change in a polymers physical properties in weathering5. Chemically, both free radical induced and non-free radical reactions, such as hydrolysis of ester linkages could be the cause for chain scission and crosslinking.

Scheme 1. Chain crosslinking and scission

g kin slin s o Cr
Sc is s

io n

Scheme 2. Free radical photo-oxidation

Crosslinked Polymer Matrix Residual Radicals From Curing

hv or R

O2

ROO RH hv ROOH

Termination Product

Chain Branching

RO + OH

The above analysis, based on previous studies by others,4, 5 suggests two possible factors contributing to the gloss and yellow index change for this class of oligomers. First, the degree of crosslinking in a UV cured film is partially affected by the concentration of acrylate functionality in a formulation. On a unit volume basis, the lower molecular weight CN963 has a higher acrylate concentration, thus a higher degree of crosslinking upon curing. This highly crosslinked network greatly reduces the rate of oxygen and moisture uptake and retards the rate of surface oxidation and photolysis. The degree of possible ester hydrolysis is also low. This is evidenced by a much smaller number of water spots for CN963 and CN964 compared with their higher molecular weight counterparts, CN965 and CN966. As a result, considerable gloss was retained even after 3000 hours QUV exposure. Secondly, a long branched polyester polyol, CN966, has more secondary and tertiary hydrogens available for abstraction by radicals. This hydrogen abstraction process may cause radical coupling between polymer chains and lead to excessive crosslinking at the film surface causing micro-cracks. These micro-cracks change the surface morphology and result in lower gloss readings. For the same class of oligomers, the yellow index data follows a similar trend. For half mil films, CN 963 retains a very low yellow index over the course of weathering, while CN966 reaches a fairly high value (Figure 2). In such an inherently non light-absorbing system, both oxidation and photolysis are important degradation processes. Chromophores, such as hydroperoxides or ketones formed during oxidation, could be UV sensitized and react with other labile hydrogen sources in the presence of oxygen. This may result in the formation of highly colored quinoid (by oxidation, as presented in Scheme 3) and conjugated products (by coupling). In CN963, the low molecular weight polyester backbone provides a limited number of labile hydrogens for abstraction. The high crosslink density also slows down the migration of the residual photoreactive groups onto the film surface. These all help minimize yellowing.

Scheme 2 shows a typical free radical photooxidation process. The primary step in weathering induced degradation of aliphatic urethane acrylates involves the formation of free radicals by the interaction of the crosslink matrix with light or heat. Residual free radicals from the UV curing process could also be a source of free radicals. Once these free radicals have been formed, they react with oxygen to form peroxy radicals. Peroxy radicals can abstract hydrogen from the polymer matrix to form hydroperoxide and a new carbon centered free radical, R. This cyclic process will continue until two free radicals are coupled. This coupling termination causes excessive surface crosslinking. Some of the ultimate products of photooxidation reactions are alcohol, ester, acid and other carbonyl compounds. As a result, chain scission and crosslinking occur.

Figure 2. Effect of molecular weight on yellowing

Yellow Index vs Time 80% Oligomer + 20% HDDA + 5% SR1129

13
Yellow Index

CN966

CN965

CN963 CN964

8 3

Film Thickness: 0.5

-2 0 2 5 8 12 16 20 24 28
Hours QUV X100

Crosslinking of residual double bonds dominated during the initial QUV exposure. As the double bond concentration decreased, the other competing degradation mechanisms started dominating and determined physical property changes at later stages of weathering. On the other side, flexibility suffered from this same crosslinking; hence, films broke at a lower elongation. Compared with polyether polyol urethane acrylates which will be discussed later, the change in elongation (for CN964, from 28% at initial to 22% at 3000 hours QUV) for this class of oligomers is still very gradual. Significant elongation was still conserved. The impact resistance follows the same trend, as shown in Figure 5 for tensile modulus vs time. Figure 3. Effect of molecular weight on tensile strength
Tensile Strength vs Time 80% Oligomer + 20% HDDA + 5% SR1129 Film Thickness: 5 mil
Tensile Strength, psi

Scheme 3. Formation of colored quinoid

R Polymer Matrix Oxidation C O RH R C OH R

9998 7998 5998 3998 1998 -2 0 100 500 1000

Hours QUV
CN966 CN964 CN965 CN963

Ketone R C OH O2 R C OH OH R' O R C OH

Figure 4. Effect of molecular weight on elongation

H R'

R, R': Labile H Containing Species

Break Elongation%

Break Elongation vs Time 80% Oligomer + 20% HDDA + 5% SR1129 Film Thickness: 5 mil

Figures 3, 4, 5 show tensile strength and elongation data vs QUV exposure time. All oligomers show an increase in tensile strength with aging. This is due to the well known fact that even in fully cured films, there are still substantial residual acrylate double bonds. Upon QUV weathering, these residual acrylates continue to crosslink. This contributes to the increase in tensile strength. It is interesting to note that for CN963, the tensile strength starts declining and eventually levels off after the first 500 hours of exposure. A similar trend was observed for other oligomers in this series.

30 24 18 12 6 0 0 100

CN965

CN963

CN964

500

1000

Hours QUV

Figure 5. Effect of molecular weight on tensile modulus

Tensile Modulus vs Time 80% Oligomer + 20% HDDA + 5% SR1129 Film Thickness: 5 mil
Tensile Modulus 190000 140000 90000 40000 -10000 0 100 500 Hours QUV 1000
CN963

color development. The mechanism for the difference in gloss retention still remains unclear. Figure 7. Effect of film thickness on gloss retention
Gloss Retention vs Time 80% Oligomer + 20% HDDA + 5% SR1129

CN964

%Gloss Retention

CN965 CN966

100 90 80 70 60 50 40 0

CN965 5 mil CN966 5 mil

CN965 0.5mil CN966 0.5mil

Figure 6 shows FTIR spectra for CN964 before weathering and after 1000 hours of QUV exposure. The increase of the peak around 3600 cm-1 and the broadened peak at 1750 cm-1 suggest the formation of hydroxyl and carbonyl groups, resulting from the radical photooxidation process. Hydrolysis of the ester backbone is not likely a major process. Otherwise, a reduction in tensile strength due to chain scission should be observed. The fairly significant peak shifts around 1000 cm-1 and 1500 cm-1 also suggest a modification of the polyester backbone. Work is ongoing to explore possible chemical modification mechanisms. Figure 6. FTIR spectrum of CN964 before and 1000 hours after QUV
2.0 1.8 1.6 1.4 1.2 A b s o r b a n c e 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800

10

12

Hours QUV X100

It should be made clear that the designed QUV exposure time for all films was 3000 hours. However, some films failed at earlier stages. The films either delaminated or degraded so severely that no meaningful data could be collected, and the test was stopped. It can be tentatively theorized that weathering degradation is really a multi-mechanism chemical process. The observed physical properties at certain stages of weathering are likely to be impacted collectively by several competing mechanisms. Much more work needs to be done to gain a quantitative understanding of the multi-mechanism degradation process. Figure 8. Effect of film thickness on yellowing
Yellow Index vs Time 80% Oligomer + 20% HDDA + 5% SR1129

1000 hours 500 hours 100 hours 0 hours

Wavenumbers (cm-1)

13 Yellow Index 8 3 -2 0 1 2 4 5 6 8 10 12 14 16 18
Hours QUV X100
CN965 5 mil CN965 0.5 mil

Finally, film thickness also plays a very important role in the accelerated weathering. CN965 and CN966 provide examples, as shown in Figure 7 and Figure 8. Thick films have better gloss retention but poorer yellowing resistance than thin films. The higher photoinitiator concentration in thick films explains the
8

Weatherability of Aliphatic Urethane Acrylates with Ether or Ether/Ester Polyol Backbones CN980, CN981, and CN982 are aliphatic urethane acrylates, where CN980 has a pure polyether polyol backbone and CN981 and CN982 have ether and ester polyol backbones. As shown in Figure 9, Both CN981 and CN982 have excellent gloss retention. CN982 passed 3000 hours QUV. CN981 passed 2400 hours with 90% gloss retention and is expected to reach 3000 hours with great film properties. This weather resistant oligomer also has unique properties, such as low viscosity, fast curing, and good pigment wetting. Figure 9. Effect of ether/ester polyol on gloss retention
Gloss Retention vs Time 80% Oligomer + 20% HDDA + 5% SR1129

CN980, with a pure ether backbone, shows a rapid loss in gloss retention even though the film survived 2200 hours. The -hydrogen of ethers are well known to be labile for abstraction by radicals. The high content of ether linkage in CN980 causes excessive surface crosslinking (Scheme 4) and micro-cracks, which lead to lower gloss readings. Data from Figure 10 also show an increase in tensile strength for all three oligomers, which again is due to the crosslinking of residual double bonds. It is worthwhile to point out that upon weathering, this class of oligomers becomes rigid more rapidly than their ester counterparts. All three oligomers start with greater than 30% elongation. Elongation quickly dropped to less than 5% after 500 hours (Figure 11). Extra crosslinking due to the ether linkage is the major cause for the dramatic loss of flexibility. Figure 10. Effect of ether/ester polyol on tensile strength
Tensile Strength vs Time 80% Oligomer + 20% HDDA + 5% SR1129 Film Thickness: 5 mil
Tensile Strength, psi

%Gloss Retention

100 90 80 70 60 50 40 0

CN982 CN980

8000
CN981

0.5 mil Film

CN981

6000 4000 2000 0 0 100 500 Hours QUV 1000

CN982

12

16

20

24

28

Hours QUV X100

CN980

Scheme 4. Oxidation and crosslinking of ether linkages

O H O C H O O O C H H O C H H C H H C H O n C H H H C H O n O2 n O C O O C H O n H H H C H H C H H C H n n n C H H n O2 O O C H O O C H C n H C H n

Figure 11. Effect of ether/ester polyol on elongation

Break Elongation vs Time 80% Oligomer + 20% HDDA + 5% SR1129 Film Thickness: 5 mil
Break Elongation%

O 2 O O C H

42 36 30 24 18 12 6 0 0

CN982 CN981 CN980

100 500 Hours QUV

1000

Preliminary Weathering Evaluation of Some New Specialty Oligomers CN983 is a low viscosity pure urethane acrylate. CN132 and CN133 are aliphatic difunctional and trifunctional acrylates, respectively. Both are very low viscosity. Without ester or ether backbones, this new generation of oligomers is expected to have superior weathering performance, provided the oligomers are formulated properly. Figure 12. Yellowing resistance of new specialty low viscosity oligomers
Yellow Index vs Time 80% Oligomer + 20% HDDA + 5% SR1129

provide superior weathering resistance. It can be concluded that with judicious selection of formulation components, UV curable coatings with excellent weathering resistance can be achieved. Work is ongoing to systematically study the effect of structure, as well as component ratio, on weathering performance. ACKNOWLEDGMENTS The author wishes to acknowledge all colleagues in Sartomer Company for their support during the course of this work. Special thanks go to Mr. Tim Cauffman and Mr. Henry Miller for helpful and creative discussions. REFERENCES 1. H. C. Miller, RadTech88 Asia, Proceedings, pp 499, 1988. 2. J. V. Crivello, in Radiation Curing in Polymer Science and Technology, Vol II, pp 435, J. P. Fouassier and J. F. Rabek (ed), 1993. 3. C. Decker and K. Moussa, J. Polym Sci., Polym Chem. Ed., 28, 3429, 1990. 4. D. R. Bauer, J. of Coatings Technology, Vol. 66, No. 835, pp 57, 1994. 5. L. R. Gatechair, in UV Curing: Science & Technology, pp 285, S. P. Pappas (ed) Stamford (U.S.A.): Technology Marketing Corp., 1985. 6. T. E. Cauffman, RadTech94 North America Proceedings, pp 229, 1994. 7. C. Decker, K. Moussa, and T. Bendaikha, J. Polym Sci., Polym. Chem. Ed., 29, 739, 1991. 8. R. S. Tu, Proceedings of Radiation Curing V, pp 117, Sept 23-25,1980. 9. G. Genskens, in Degradation & stabilization of Polymers, Applied Science Publisher, 1977. 10. N. Rounds, J. Plamondon, and A. Kohr, RadTech86 North America Proceedinds, 1986. KEYWORDS Weathering resistance, Oligomer, Low viscosity oligomers, Aliphatic urethane acrylate, Gloss retention, Yellowing, QUV, Tensile strength, Tensile elongation, Tensile Modulus, UV curing
10

Yellow Index

18 13 8 3 -2 0
CN133

CN120

Film Thickness 0.5 mil CN963 CN132

CN983

12

16

20

24

28

Hours QUV X100

Compared with CN963, the best weathering resistant oligomer in this study, CN132, CN133, and CN983 show very little color development. This is shown in Figure 12. For comparison, CN120, an aromatic epoxy acrylate, shows substantial color development, as expected. Thin films of CN132 and CN133, and a thick film of CN983 cracked or delaminated at early stages of QUV exposure due to embrittlement. This problem can be solved by modifying the formulation to increase the films inherent flexibility. CONCLUSION Weathering is a multi-mechanism degradation process. Aliphatic urethane acrylates show great resistance to accelerated weathering. For polyester polyol extended acrylates, low molecular weight oligomers, such as CN963, give higher gloss retention and superior yellowing resistance. The mechanical properties of this class of oligomers are also well conserved during accelerated weathering. Aliphatic urethane acrylates with properly balanced ether and ester polyols, such as CN981 and CN982, also perform well in the 3000 hours QUV test. Preliminary data indicate the new generation of low viscosity aliphatic oligomers will

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