Light Stabilizers For Polyolefins

Products, Technology and Experience That Work for You

Additives

Value beyond chemistry

Ciba Additives
creates, develops, manufactures and markets products which preserve and enhance the performance and aesthetics of plastics, rubber, fibers, paints, coatings, photographic paper, inks, grease and oils. Cibas Additives business began with scientific breakthroughs in light stabilization in the 1950s and in antioxidants in the 1960s that allowed our customers to broaden the uses of plastics in outdoor and high performance applications. We introduced hindered amine stabilizers in the 1970s, and improved phosphite processing stabilizers and non-interactive hindered amines in the 1980s. The 1990s brought a new generation of processing, thermal, UV and integrated stabilization systems. These four decades of continuous performance improvements have laid the foundation for an even more innovative future. By consistently meeting and exceeding customer needs and expectations, Ciba Specialty Chemicals, a premier global specialty chemicals company, is committed to technological innovation and business growth.

Table of Contents

PROTECTION FROM THE ELEMENTS

KEEPING PACE WITH A CHANGING WORLD

LIGHT STABILIZATION OF FIBER AND TAPE

LIGHT STABILIZATION OF FILM

12

LIGHT STABILIZATION OF MOLDED APPLICATIONS

16

LEADING-EDGE RESEARCH AND DEVELOPMENT

21

DATA BANK

22

Protection From the Elements

Exposure to sunlight and some artificial lights can have adverse effects on the useful life of polyolefin products. UV radiation can break down the chemical bonds in a polymer. This process is called photodegradation and ultimately causes cracking, chalking, color changes and the loss of such physical properties as impact strength, tensile strength, elongation and other properties. To counteract these damaging effects on polyolefin performance, Ciba Specialty Chemicals offers a broad range of UV stabilizers designed to solve the degradation problems associated with exposure to sunlight. Although there are many types available, UV stabilizers can be catagorized by two general classifications ultraviolet light absorbers (UVA) and hindered amine light stabilizers (HALS).

ULTRAVIOLET ABSORBERS (UVA)

UVAs slow down the degradation process by preferentially absorbing harmful ultraviolet radiation and dissipating it as thermal energy. However, high concentrations of absorbers and sufficient thickness of the polymer are required before enough absorption takes place to effectively retard photodegradation. In some applications, combinations of UVAs and HALS create a synergistic interaction that may enhance light stability.

HINDERED AMINE LIGHT STABILIZERS (HALS)

HALS are very effective and efficient stabilizers for polyolefins. They do not absorb UV radiation, but act to inhibit degradation of the polymer. Significant levels of stabilization are achieved at relatively low concentrations. HALS high efficiency and longevity are due to a cyclic process wherein the HALS are regenerated rather than consumed during the stabilization process.

GENERAL SCHEME OF INHIBITION OF PHOTO-OXIDATION

Quencher

O2

H-Donor

R*

O2/h RH RO h HO ROOH

ROO

RH

UV-Absorber

HALS
Hydroperoxide Decomposer Radical Scavenger Quencher

Watts per square meter per nanometer

2.8

2.4

2.0

1.6

1.2 Xenon Arc Lamp

.8

.4

Sunlight

UV-A Fluorescent Sun Lamp 0.0 250 300 350 400 450 500 550 600 650 UV-B Fluorescent 800 Sun Lamp Wavelength in Nanometers 700 750

Accelerated weathering devices are used to determine the effects of sunlight on various substrates. This graph illustrates the spectral energy distribution as a function of the wavelength produced by a number of artificial light sources. The graph compares these energy outputs to sunlight. The closer the energy distribution to sunlight, the more reliable and accurate the results of the experiment. Accelerated weathering devices that emit larger amounts of the higher energy/shorter wavelength light do not provide as good a correlation with outdoor weathering as those instruments which emit wavelengths closer to the distribution of sunlight. In addition, it may lead to false conclusions regarding the performance of the light stabilizer and subsequently to the performance of the plastic article.

I SUNLIGHT AND ARTIFICIAL LIGHT SOURCES

A Comparison of Relative Spectral Energy Distribution

I SUNLIGHT (YELLOW)
Miami Average Optimum Direct Global Radiation Measured 45S, 3/20/84

I XENON ARC LAMP (GREEN)

As used in Atlas Weather-Ometer 6500 Watt Xenon Lamp with 2 Borosilicate Inner and Outer Filters, 340nm Control (35 W/m )

I UV-B FLUORESCENT SUN LAMP (RED)

As used in The Q-Panel Company Q-U-V Accelerated Weathering Tester as per ASTM-G-53.

I UV-A FLUORESCENT SUN LAMP (BLUE)

As used in The Q-Panel Company Q-U-V Accelerated Weathering Tester as per ASTM-G-53.

Keeping Pace With a Changing World

1957
Two-seater Karmann Ghia introduced. Frisbee fun for all. Tinuvin ultraviolet light stabilizers for polymers are introduced.

1960
Telestar launched. Tinuvin 326/327/328 light stabilizers give plastics their first real chance at surviving outdoors.

1966
Fiber optic telephone cable developed.

1969
Man walks on the moon in spacesuit light stabilized by Ciba.

1970s
Childproof safety tops offered. A revolutionary new class of Hindered Amine Light Stabilizers (HALS) is commercialized. Tinuvin 770, a low molecular weight HALS is introduced.

1979
Ciba introduces Tinuvin 765, a liquid hindered amine light stabilizer for plastics.

1980
Chimassorb 944, a high molecular weight HALS is launched.

1983
A new wave of Swiss watches. Tinuvin 622 achieves FDA clearance, the first hindered amine light stabilizer for use in food contact applications.

1985
Introduction of granular, freeflowing, non-dusting product forms for improved handling.

1989
Berlin wall falls. Breakthrough NOR HALS based on new chemistry is announced. Tinuvin 123 receives the R&D 100 Award as one of the most innovative new products of the year.

1991
Channel Tunnel operational. Chimassorb 119 , a new enhanced performance hindered amine light stabilizer for polypropylene fiber is launched.

1994
Ciba launches synergistic HALS systems Tinuvin 783/111/791 the sum is greater than the individual effects.

1995
Irgastab FS Systemsphenol-free stabilizer systems for low initial color and enhanced light stabilityare commercialized.

1998
The Beetle returns. Introduction of Chimassorb 2020, 2030, 2040 a new HALS line for the next century. Excellent UV Stability Low Volatility Superior Initial Color Excellent Heat Stability No Pigment Interaction

Light Stabilization of Fiber & Tape

POLYOLEFIN FIBER
Polyolefin fibers are versatile, economical, durable, stain resistant and lightweight. High performance hindered amine light stabilizers have expanded the number of applications for which polyolefin fibers can be employed carpeting and upholstery applications for home and business, in the latest automobiles, geotextiles, umbrellas, outdoor furniture and a variety of non-woven applications. Because of the high surface-to-volume ratio in fibers, it is critical to employ stabilizers with low volatility and high resistance to extraction. High molecular weight hindered amine light stabilizers (HALS), such as Tinuvin 622, Chimassorb 944, and Chimassorb 119 have long been recognized as the standard of performance. Responding to customer demands for improved performance under a variety of conditions, Ciba continues to drive the evolution of state-of-the-art technology. Listed below are the products which represent the latest in polyolefin fiber UV stabilization. Tinuvin 783 Tinuvin 783 is a high molecular weight, high performance HALS. It delivers superb cost-performance benefits with a level of UV stability equal or superior to other high performance HALS (Figure 1).

Figure 1 Light Stability of Polypropylene Fiber Sample: 10 Denier, White Pigmented PP Fiber Base Stabilization: 0.12% Fiberstab L 112 + 0.05% Ca-stearate Exposure: Atlas Weather-Ometer Ci 65 @ 65C, 0.5 W/m2 at 340 nm Test Criterion: Hours to 50% Retained Tensile Strength No Light Stabilizers

0.3% Tinuvin 622

0.3% Tinuvin 783

0.3% Chimassorb 944

0.3% Chimassorb 119 0 500 1000 Hours 1500 2000

Chimassorb 2020 Chimassorb 2020 is a high molecular weight HALS with a narrow molecular weight distribution. It has virtually no effect on pigment color yield and little effect on polymer processing. Chimassorb 2020 represents our continuing effort to bring the best performance and value in light protection. Figures 2 and 3 show the superior performance of PP fiber stabilized with the new HALS. Studies have shown when HALS and pigments are present together in high concentrations, such as melt compounded in concentrates or masterbatches, color strength may be compromised. Examination of test plaques with HALS and pigment concentrations under a microscope show the pigment to be less well dispersed, therefore yielding poorer color strength. HALS may either hinder the pigment dispersion or

Figure 2 Light Stability of Pigmented Polypropylene Fiber Sample: PP Homopolymer, 10 Denier, Red Pigmented Base Stabilization: 0.10% Irgastab FS 110 + 0.05% Ca-stearate Exposure: Atlas Weather-Ometer Ci 65 @ 65C, 0.5 W/m2 at 340 nm + Ovenaging at 110C Test Criteria: Hours to 50% Tensile Strength + Hours Air Draft Oven to Embrittlement No Light Stabilizers

Figure 3 Color Yield of Red Pigmented Polypropylene Fiber Sample: PP Homopolymer, 10 Denier, Red Pigmented Base Stabilization: 0.10% Irgastab FS 210 + 0.05% Ca-stearate Pigmentation: 0.2% Cromophtal Red BRN

No Light Stabilizers

0.25% Tinuvin 622 0.15% Tinuvin 622 0.15% Chimassorb 944 0.15% Chimassorb 119 0.15% Chimassorb 2020 750 500 250 0 50 100 150 200 250 0.25% Chimassorb 944

0.25% Chimassorb 119

0.25% Chimassorb 2020 0

Color Yield %

100

Hours to 50% Retained Tensile Strength Hours to Embrittlement

cause pigment agglomeration. However, this agglomeration is highly dependent on processing conditions (and not typically seen to this extent in production equipment). New generation HALS such as Chimassorb 2020 and Chimassorb 119 eliminate this effect of pigment agglomeration. Therefore color yield is not affected by the HALS and is independent of the processing conditions. Table 1 and the photograph of test plaques below compare the effects of these new generation HALS.

Table 1 Effects of HALS on Color Yield HALS Chimassorb 2020 Chimassorb 119 Chimassorb 944 Delta E (Ref. No HALS) 0.3 - 0.6 0.3 - 0.9 10.4 - 17.0

15% Flush of CPC Blue with 12.5% HALS in PP, Brabender Mixed and Let Down 50/1 in PP.

Color Yield Comparison of HALS/Pigment Concentrate in Polypropylene No HALS Chimassorb 944 Chimassorb 2020

Control
Base Stabilization: 4% TiO2 + 0.25% HALS Pigmentation: 0.3% Blue 15

12

0.2

PIGMENTED PP FIBER
Consumer-driven preferences create applications that need pigment lightfastness requiring protection from high levels of UV radiation. For polymers containing organic pigments, multifunctional degradation mechanisms are at work. Pigment degradation can affect polymer stability and polymer degradation can affect pigment stability. A multifunctional stabilization system is needed to minimize color change and maximize polymer lifetime. Tinuvin C 353 Tinuvin C 353 is designed to meet requirements of finer denier fibers and demanding outdoor applications such as outdoor carpeting, awnings, umbrellas and interior automotive fibers. Tinuvin C 353 provides enhanced performance over traditional high molecular weight HALS such as Chimassorb 119. Figures 4 and 5 show that in two different pigmented polypropylene fiber samples, Tinuvin C 353 provides excellent color and physical property retention.

Figure 4 Stabilization of Pigmented Polypropylene Fiber Sample: 5 Denier PP Fiber Pigmentation: 0.25% C.I. Pigment Blue, 15:1 Exposure: Atlas Weather-Ometer Ci 65 (SAE J 1885) Test Criterion: Color Change After Exposure 12 10 Delta E 8 6 4 2 0 0 200 400 600 Hours 800 1000 1200

Figure 5 Stabilization of Pigmented Polypropylene Fiber Sample: 5 Denier PP Fiber Pigmentation: 0.25% C.I. Pigment Red 144 Exposure: Atlas Weather-Ometer Ci 65 (SAE J 1885) Test Criterion: Days to Failure

1.25%

0.75%

0.25%

0 Chimassorb 119 Tinuvin C 353

50 Days

100

150

1.0% Chimassorb 119 1.0% Tinuvin C 353

POLYPROPYLENE TAPE
Slit tapes are often used in woven fabric applications for outdoor use, e.g. bags, intermediate bulk containers (big bags) and sacks. These applications can be nonfood (chemical sacks) or food-packaging applications such as rice, corn and flour bags. Other common outdoor applications for tapes are artificial turf and ropes. Tinuvin 791 Tinuvin 791 is a state-of-the-art thermal and light stabilizer for PP tapes. It is based on a synergistic combination of low molecular weight and high molecular weight HALS. Figure 6 shows this combination provides the most efficient and long-lasting protection against the detrimental effects of both heat and light. Tinuvin 791 also provides good long-term extraction resistance, color retention and water carry-over properties. Tinuvin 783 Figures 6 and 7 illustrate that Tinuvin 783 provides the best balance of low water carry-over properties with excellent light and thermal stability. It is also the product of choice when indirect food contact approval is needed. Tinuvin 783 is a synergistic combination of two high molecular weight HALS and provides very low color and superior extraction resistance.

Figure 6 Light and Thermal Stability of Polypropylene Tape Sample: PP Homopolymer (3rd Generation) Tapes, 50 micron (2 mil) Base Stabilization: 0.1% Irganox B 225 + 0.1% Ca-stearate Exposure: Florida 45 South + Ovenaging at 120C Test Criteria: kLys to 50% Elongation + Days to Embrittlement No Stabilization 0.1% Tinuvin 770 0.1% Tinuvin 791 0.1% Tinuvin 783 0.1% Chimassorb 944 600 400 200 kLys (Florida) 0 50 100 Days (Oven) 150

Figure 7 Water Carry-Over Behavior of Polypropylene Tape Sample: PP Homopolymer, 50 micron (2 mil) Base Stabilization: 0.15% Irganox B 215 + 0.02% DHT-4A / 0.09% Irganox HP 2225 + 0.02% DHT-4A Conditions: 50 m/min; Water Temperature 25C Test Criterion: Water Carry-Over (cm)

No Stabilization

0.1% Tinuvin 770

0.1% Chimassorb 944

0.1% Tinuvin 791

0.1% Tinuvin 783

0 5 10 15

cm 0.15% Irganox B 215 + 0.02% DHT-4A 0.09% Irganox HP 2225 + 0.02% DHT-4A

HIGH DENSITY POLYETHYLENE TAPE

HDPE tapes are used extensively for tarps, tents, wind breakers and nets. Typically in these applications, the final article is exposed to a high level of UV radiation. Whether pigmented or non-pigmented, these applications need an effective light and thermal stabilization package to meet the final customer requirements. Tinuvin 783 Tinuvin 783 is the stabilizer of choice for demanding outdoor exposure of HDPE tapes (Figure 8). This stabilizer imparts the optimum UV and thermal protection and is especially effective in pigmented tapes.

Figure 8 Light Stability of High Density Polyethylene Tape Sample: HDPE (Ti Catalyst, d=0.950), Tapes 50 micron (2 mil), Stretch Ratio 1:6 Base Stabilization: 0.15% Irganox B 215 + 0.1% Ca-stearate Exposure: Florida 45 South Test Criterion: kLys to 70% Tensile Strength

No Light Stabilizers 0.05% Tinuvin 622 0.05% Tinuvin 783 0.05% Chimassorb 944

0.1% Tinuvin 622 0.1% Tinuvin 783 0.1% Chimassorb 944

0 100 200 300 400 kLys (Florida) 500 600

11

Light Stabilization of Film

In thin section applications, such as films, many factors need to be considered when selecting the right stabilization system for specific application requirements. These include not only the resin/additive formulation but also other parameters such as processing conditions, presence of mineral fillers and pigments, film thickness and construction and the final application environment. In selecting additives, there are two main classes to consider: UV absorbers are a class of stabilizers limited by the Lambert-Beers law, A = bc, where absorbance A is a function of film thickness b. In films, UV absorbers are unable to fully absorb the UV radiation until it has penetrated through the surface layers where degradation begins. HALS offer an extremely efficient approach to UV stabilization. Unlike UV absorbers, HALS function by a radical trapping mechanism and are not constrained by the thickness of the film. Figure 9 illustrates the superior performance of Tinuvin 783, a high molecular weight HALS compared to a UV absorber. Table 2 illustrates the influence of film down-gauging (15050 micron) on the selection of the stabilizer concentration. The lifetime of the film is decreased by decreasing the film thickness from 150 to 50 micron, even if the concentration of the stabilizers is twofold. Thus an adjustment of the additive concentration is needed to retain the same durability properties when the film thickness is reduced. The bulk of LDPE, LLDPE and EVA is used in the manufacture of films for packaging, agricultural and construction applications. Agricultural films used for greenhouse covering, mulching and silage wraps represent the largest light stabilized PE and EVA applications.

Figure 9 Light Stability of Low Density Polyethylene Film Sample: 125 micron (5 mil) High Pressure LDPE Base Stabilization: 0.03% Irganox 1076 Exposure: Florida 45 South Test Criterion: kLys to 50% Retention of Initial Elongation

No Light Stabilizers

0.25% Tinuvin 783

0.25% Chimassorb 81 0 100 kLys 200 300

Table 2 Influence of Stabilizer Concentration and Film Thickness on Light Stabilization of Low Density Polyethylene Film Sample: LDPE Blown Film Base Stabilization: 0.1% Irganox B 900 2 Exposure: Atlas Weather-Ometer Ci65@65C; 0.35W/m at 340 nm Light Stabilizer 150 Micron (6 mil) Film No Stabilizer Tinuvin 622 + Chimassorb 81 Concentration Tinuvin 783 Concentration 650 4500 (0.15%+0.075%) 7500 (0.15%) Hours to 50% Residual Elongation 100 Micron (4 mil) Film 600 4000 (0.2%+0.1%) 7000 (0.2%) 50 Micron (2 mil) Film 500 3000 (0.3%+0.15) 5500 (0.3%)

12

CONSTRUCTION AND INDUSTRIAL FILM

Construction and industrial films used outdoors for extended periods of time, ranging from some months to a few years, require proper UV light protection in order to meet end-users requirements. Common applications are stretch films, shrink wraps, heavy-duty bags and pool covers. Tinuvin 783 Tinuvin 783 is widely used for LDPE, LLDPE and EVA films and has extensive indirect food contact clearances worldwide. It is an effective and versatile light and thermal stabilizer for films and delivers excellent cost/performance benefits. Figures 10 and 11 demonstrate that Tinuvin 783 provides superior UV stability in LDPE film compared to Chimassorb 944 and Tinuvin 622.

Figure 10 Light Stability of Low Density Polyethylene Film Sample: 200 micron (8 mil) LDPE Film Base Stabilization: 0.03% Irganox 1076 + 5% Kaolin Exposure: Florida 45 South; Aluminum Backing Test Criterion: kLys to 50% Retained Elongation

Figure 11 Light Stability of Low Density and Linear Low Density Polyethylene Film Sample: 50 micron (2 mil) LDPE/LLDPE (1:1) Blown Films Base Stabilization: 0.05% Irganox B 900 Exposure: Atlas Weather-Ometer Ci 65 @ 65C, 0.5 W/m2 at 340 nm Test Criterion: Hours to 50% Retained Elongation

Control

0.15% Tinuvin 622 0.15% Tinuvin 783

% HALS

0.3

0.15% Chimassorb 944

0.6

0.5% Tinuvin 622 0.5% Tinuvin 783

1.2 0 100 200 300 kLys Tinuvin 622 Tinuvin 783 Chimassorb 944 400 500 600 700

0.5% Chimassorb 944 0 2000 4000 Hours 6000 8000

13

Tinuvin 111
Tinuvin 111 is an excellent UV stabilizer with outstanding extraction resistance offering superior performance in polyethylene and polypropylene film. Tinuvin 111, based on a combination of low-interacting tertiary HALS, is especially suitable for films in contact with chemicals (e.g. pool covers and films exposed to acid rain). Figure 12 demonstrates its UV stabilization properties in PP film. Films such as vapor-barrier films or black pigmented films, when required to offer a long service life, also need an adequate level of long-term thermal stability (Figure 13). High molecular weight HALS, such as Tinuvin 783 and Tinuvin 111, have excellent thermal stabilizing properties and extraction resistance and are suitable for this type of application.

Figure 12 Light Stability of Polypropylene Film Sample: PP Homopolymer, Film 500 micron (20 mil) Base Stabilization: 0.1% Irganox B 225 + 0.1% Ca-stearate Exposure: Atlas Weather-Ometer Ci 65 @ 65C; 0.35 W/m2 at 340 nm Test Criterion: Hours to 50% Elongation

No Stabilization 0.1% Tinuvin 111 0.2% Tinuvin 111 0.1% Chimassorb 944 0.2% Chimassorb 944 0.1% Tinuvin 783 0.2% Tinuvin 783
0 1000 2000 Hours 3000 4000

Figure 13 Long-Term Thermal Stability of Polyethylene Film Sample: 200 micron (8 mil) LDPE Film Exposure: Oven Aging at 100C Test Criterion: Days to 50% Retained Elongation

0.05% Tinuvin 783

0.05% Irganox 1076

0.05% Irganox 1010

No Stabilizers 0 50 100 150 200 250 300 350 400 Days

14

CONSUMER PRODUCTS PACKAGING

Packaging films have become more sophisticated as consumer product manufacturers strive to add value. Some packaged goods need to be protected from harmful UV light which can induce oxidation and/or affect the taste and odor of the package contents. UV absorbers act by absorbing harmful UV light and dissipating it as thermal energy. When added to polyethylene (LDPE, LLDPE and HDPE) and polypropylene (e.g. BOPP) packaging film, UVAs can reduce the amount of UV light that passes through the film, thereby protecting the contents. Figure 14 shows how Tinuvin 326 and Chimassorb 81 reduce UV transmission in LLDPE films. Compared to ultrafine TiO2, an inorganic UV screener, Tinuvin 326 and Chimassorb 81 block more UV light (280nm-400nm) with less impact on the visible light (400nm-700nm) transmission. This means that films containing UV absorbers have better UV blocking properties and better clarity. A range of Tinuvin products with different UV absorption properties can be tailored to achieve optimal performance for specific applications.

Figure 14 UV Transmission Through 100 micron (4 mil) Linear Low Density Polyethylene Film Sample: 100 micron (4 mil) LLDPE Film Base Stabilization: 0.1% Irganox B 900 100 90 80 % Transmission 70 60 50 40 30 20 10 0 280 320 360 400 440 Wavelength (nm) 480 520

No Light Stabilizers 0.5% TiO2 0.3% Chimassorb 81 0.3% Tinuvin 326

AGRICULTURAL FILM
Agricultural films are used outdoors for extended periods of timefrom some months for mulch films to several years for greenhouse films. These films come in contact with pesticides, fungicides or soil fumigants. Some sulfur or halogen-containing pesticides can interact with light stabilizers and reduce their effectiveness. Stabilizers for agricultural films need to provide not only light stability but also chemical resistance. Tinuvin 111, Tinuvin 492, Tinuvin 494 and the new generation NOR HALS all have certain degrees of chemical resistance and are found to outperform conventional stabilizers. For more information on stabilizing agricultural films, please refer to our brochure TINUVIN High Performance Stabilizers for Agricultural Films.

15

Light Stabilization of Molded Applications

Thick section polyolefins are widely used in a variety of outdoor products such as house siding, window shutters, stadium seats, garden furniture, trash cans, bottle and fruit crates, toys, and interior and exterior automotive parts and many more. For many years, polypropylene and polyethylene were stabilized against the detrimental effects of UV radiation using a low molecular weight HALS such as Tinuvin 770. During the mid- to late-eighties combinations of high molecular weight HALS with low molecular weight HALS provided a better balance of UV stability, thermal stability and substrate compatibility. Some of the newest products for thick section polyolefins include Tinuvin 123 S, a solid, non-interacting, low molecular weight NOR HALS; Chimassorb 2020, a low volatility, oligomeric high performance HALS; Tinuvin 783, Tinuvin 791, Chimassorb 2030 and Chimassorb 2040, new HALS that exploit mixed HALS synergy; and Irgastab FS 210, Irgastab FS 410, Irgastab FS 811 and Irgastab FS 812, a family of phenol-free stabilizers that perform best in color critical applications.

POLYETHYLENE FOR CONSUMER APPLICATIONS

High density and linear low density polyethylene are widely used in consumer applications such as bottle and fruit crates, trash cans, toys, outdoor sporting and leisure goods and innumerable packaging items.

Figure 15 Performance of Tinuvin 783 in High Density Polyethylene Plaques Sample: 3.125mm (125 mil) HDPE Plaques Base Stabilization: 0.06% Irganox B 225 Exposure: 6000 Hours of Atlas Weather-Ometer Ci 65 @ 65C, 0.35 W/m2 at 340 nm Test Criterion: % Retention of Elongation % 80 70 60 50 40 30 20 10 0 Control Tinuvin 622 Chimassorb 944 Tinuvin 783

16

Tinuvin 783 Tinuvin 783, a high molecular weight HALS system, is recommended for polypropylene and polyethylene thick sections requiring food contact clearance. In polyethylene, Tinuvin 783 performs better at equal concentration, is more economical and has indirect food contact clearance at higher loadings than Chimassorb 944 or Tinuvin 622 (Figure 15). High production rates and low molding equipment costs coupled with the development of low volatility HALS have helped make rotational molding one of the fastest growing processing methods in the plastics industry. For rotomolded applications, Tinuvin 783 provides excellent long-term light stability, is less interacting than other HALS and very economical to use. Figure 16 shows Tinuvin 783 to be more effective than other HALS currently used in rotomolded polyethylene.

Figure 16 Light Stability of Rotomolded Linear Low Density Polyethylene Plaques Sample: 3.125 mm (125 mil) Butene-LLDPE Plaques, Rotomolded at 344C (650F) Base Stabilization: 0.05% Irganox 1010 + 0.02% DLTDP Exposure: Atlas Weather-Ometer Ci 65 @ 65C, 0.35 W/m2 at 340 nm Test Criterion: % Retained Impact Strength

0.2% Tinuvin 783

0.2% Tinuvin 622

0.2% Chimassorb 944

40 60 80 % Retained Impact Strength 1,000 Hours 6,000 Hours 12,000 Hours

20

100

17

POLYPROPYLENE FOR AUTOMOTIVE APPLICATIONS

Polypropylene homopolymers and copolymers for automotive applications have traditionally been stabilized with a combination of hindered phenolic/hindered phosphite process stabilizer and the hindered amine light stabilizer Tinuvin 770. Tinuvin 791 Recent studies show Tinuvin 791 provides better light stability and highly improved thermal stability compared to Tinuvin 770 (Figure 17). In organic pigmented applications, the addition of a benzotriazole ultraviolet absorber enhances light stability and helps prevent the pigment from fading. Tinuvin 326, Tinuvin 327 and Tinuvin 328 are equally effective UV absorbers in thick section polyolefins (Figure 18). Irgastab FS 210, Irgastab FS 410, Irgastab FS 811, Irgastab FS 812 Molded-in color polypropylene and impact modified polypropylene is replacing painted plastics in applications such as auto bumpers and interior and exterior trim. Ciba has developed a family of phenol-free stabilizer systems for these color critical applications. These phenol-free stabilizer systems are based on a new alkylhydroxylamine process stabilizer that helps achieve good process stability while also obtaining excellent initial color, color consistency, and color maintenance during end use. Cibas phenol- free stabilizers include Irgastab FS 210, Irgastab FS 410, Irgastab FS 811, and Irgastab FS 812. Table 3 shows that Irgastab FS 812 can provide dramatic improvement in light stability. In addition, using a phenol-free stabilizer system such as Irgastab FS 812 virtually eliminates gas fade discoloration, a phenomena that typically leads to a yellowing, pinking, or off-shade discoloration of articles stored in warehouses (Figure 19).

Figure 17 Light and Thermal Stability of Polypropylene Plaques Sample: 2 mm (80 mil) PP Plaques Base Stabilization: 0.15% Irganox B 215 + 0.1% Ca-stearate Exposure: Florida 45 South and Ovenaging at 120C Test Criteria: kLys to 50% Retained Tensile Strength + Days to Embrittlement

0.2% Tinuvin 770

0.2% Tinuvin 791

0.2% Chimassorb 944 600 400 kLys 200 0 200 400 Days 600

Figure 18 Typical Physical Property of Polypropylene Copolymer Plaques Sample: 2 mm (80 mil), PP Copolymer Plaques Base Stabilization: 0.1% Irganox B 225 + Ca-stearate Exposure: Florida 45 South Test Criterion: Increase in kLys to Surface Roughness 1.2 1.0 Surface Roughness 0.8 0.6 0.4 0.2 0

100 200 300 kLys Control 0.4% Tinuvin 770 + 0.2% Tinuvin 328 0.4% Tinuvin 791 + 0.2% Tinuvin 328

400

500

Table 3 Xenon Weathering of Molded-in Color TPO (PP/EPDM) UV Stabilizer System Red Pigmented TPO kJ to Onset Delta E at 2500 kJ of Chalking 1250 58.4 Blue Pigmented TPO kJ to Onset Delta E at 2500 kJ of Chalking 1920 22.5

0.1% Irganox B 225 / +0.4% Tinuvin 791 +0.2% Tinuvin 328 0.65% Tinuvin FS 812

4000

4.2

>4000

1.8

18

Figure 19 Gas Fade Resistance of Molded-in Color Thermoplastic Olefin (TPO) Phenolic System: 0.1% Irganox B 225 + 0.4% Tinuvin 791 + 0.2% Tinuvin 328 Phenolic Free System: 0.65% Irgastab FS 812 5

Tinuvin 123 S Car manufacturers strive to produce automobiles that will look and perform well for 10 years. For aesthetic and styling reasons, manufacturers often partially paint molded-in color polypropylene. Thus light stabilizers must provide long-term stability and must not interfere with the adhesion of coatings to the substrate. Tinuvin 123 S, a new, solid non-interacting NOR HALS, helps polypropylene producers achieve both outstanding long-term light stability and good adhesion to TPO surfaces. Figure 20 shows the dramatic protection this highperformance system provides in a molded-in color blue pigmented TPO composition compared to a traditional phenolic system containing Tinuvin 791.

Delta Yellowness Index

1 Phenolic Phenolic Free

2 3 4 5 Cycles in Gas Fade Chamber

Figure 20 UV Stability of TPO (PP/EPDM) Stabilization Systems

0.1% Irganox B 225 +0.4% Tinuvin 791 +0.2% Tinuvin 328 0.65% Irgastab FS 812 0.05% Irgastab FS 042 +0.29% Tinuvin 123 S +0.2% Chimassorb 119 +0.2% Tinuvin 328

Exposure: 2,500 kJ

Chalked

43.6%

72.5%

Exposure: 4,000 kJ

Chalked

7.6%

45.8% % Gloss Retained

Sample: 0.1% Ca-stearate + 15% Talc Pigmentation: Mixed Blue Pigment Exposure: Atlas Weather-Ometer Ci65 (SAE J 1960)

19

CONSTRUCTION/ARCHITECTURAL APPLICATIONS
Tinuvin 123 S The low basicity and non-interacting nature of Tinuvin 123 S allows it to function well in acidic environments such as applications containing halogenated flame retardants. Tinuvin 123 S is uniquely suited to protect flame retardant roofing and stadium seats from UV deterioration. These extremely demanding end uses require the most advanced, highest performing light stabilizer systems available. Figure 21 shows that a phenolic-free stabilizer system composed of Tinuvin 123 S with Chimassorb 2020 allows a blue pigmented TPO composition to maintain more than 50% of its initial gloss even after 7,000 kilojoules of weathering in an Atlas WeatherOmeter.
Figure 21 Light Stability of Blue Pigmented TPO (PP/Plastomer) Base Stabilization: 0.1% Ca-stearate with 15% Talc Pigmentation: 1.6% Mixed Blue Pigment Exposure: 7000 kJ Atlas Weather-Ometer (SAE J 1960) Test Criterion: % Gloss Retention 60 50 % Gloss Retention 40 30 20 10 0 0.1% Irganox B 225 + 0.4% Tinuvin 791 + 0.2% Tinuvin 328 0.05% Irgastab FS 042 + 0.29% Tinuvin 123 S + 0.2% Chimassorb 2020 + 0.2% Tinuvin 328

The performance of these novel light stabilizer systems has allowed polyolefin producers to enter markets previously dominated by engineering polymers or other non-plastic materials. They have also allowed manufacturers of polyolefin roofing, siding and window shutters to offer consumers extended warranties against failures due to premature weathering.

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Leading-Edge Research and Development

Cibas scientists, engineers and technicians concentrate on customer-oriented and cost-effective technological solutions from three major Research and Development centers and numerous Technical Service centers around the globe. The focus is on substrate protection, polymer properties and polymer design that help make our customers products better and more successful in the marketplace. Cibas extensive technical support laboratories focus on developing customer-specific solutions for product stabilization and are designed to provide advanced capabilities for solving customer problems. Breakthroughs are being made in multicomponent blends, light stabilization systems for flame retardant polypropylene fiber, lowcolor stabilization systems for fibers and plastics, new hindered amines and pesticide-resistant systems, among other areas. In addition to our state-of-the-art synthetic and analytical capabilities, we are uniquely equipped to produce and test samples which are directly relevant to our customers applications. We can make blown film, spun fiber, extruded tapes, and injection and rotational molded parts. We have one of the worlds largest accelerated weathering facilities. Our outdoor exposure and specialized greenhouse testing is second to none. For the past half century, Ciba Additives has worked with customers to develop and commercialize high performance additives and additive systems that improve the appearance and performance of a wide variety of plastics, elastomers and synthetic fiber products. We look forward to working with our customers to develop innovative polymer additives technology well into the next century.

CIBA ADDITIVES TECHNICAL SERVICE CENTERS WORLDWIDE

USA, St. Louis USA, Tarrytown Switzerland, Basel Singapore Canada, Toronto Brazil, Sao Paulo South Africa, Johannesburg Australia, Melbourne

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Data Bank
CHEMICAL NAMES OF LIGHT STABILIZERS FOR POLYOLEFINS
Additive Tinuvin 123 Tinuvin 234 Tinuvin 326 Tinuvin 327 Tinuvin 328 Tinuvin 622 Tinuvin 770 Chimassorb 119 Chemical Name bis-(1-Octyloxy-2,2,6,6,tetramethyl-4- piperidinyl) sebacate 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol 2-(5-Chloro-2H-benzotriazol-2-yl)-6-(1,1-dymethylethil)-4-methylphenol 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole 2-(2H-Benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol Dimethyl succinate polymer with 4-hydroxy-2,2,6,6,-tetramethyl-1-piperidineethanol bis(2,2,6,6-Tetramethyl-4-piperidinyl) sebacate 1,3,5-Triazine-2,4,6-triamine,N,N'''-[1,2-ethanediylbis[[[4.6-bis[butyl (1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1 propanediyl]]-bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)Chimassorb 944 Poly [[6-[(1,1,3,3,-tetramethyl butyl) amino]-s-triazine-2,4-diyl][[(2,2,6,6tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6,-tetramethyl-4-piperidyl) imino]] Chimassorb 2020 1,6-Hexanediamine, N, N-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine 192268-64-7 70624-18-9 CAS No. 129757-67-1 70321-86-7 3896-11-5 3864-99-1 25973-55-5 6544-7-77-0 52829-07-0 106990-43-6

LIGHT STABILIZER SYSTEMS

Product Tinuvin 111 Tinuvin 123 S Tinuvin 492 Tinuvin 494 Tinuvin 783 Tinuvin 791 Tinuvin C 353 Irgastab FS 210 Irgastab FS 410 Irgastab FS 811 Irgastab FS 812 Fiberstab L 112 Blend Composition Chimassorb 119:Tinuvin 622

CONVERSIONS
Micron/Mil 0 50 100 150 200 250 Micron

0 Tinuvin 123:Polypropylene Chimassorb 119:Oxides:Stearates Chimassorb 119:Oxides:Stearates Chimassorb 944:Tinuvin 622 Chimassorb 944:Tinuvin 770 Chimassorb 119:Tinuvin 234 Irgastab FS 042:Chimassorb 119 Irgastab FS 042:Chimassorb 944 Irgastab FS 042:Tinuvin 791 Irgastab FS 042:Tinuvin 791:Tinuvin 328 HP-136:Irgafos 168:Tinuvin 622 South Florida/ Kilolangleys ppm/%

8 2000

10 Mil 3000 ppm

0 500 1000

0 0.05 0.1 1

0.2

0.3 %

2 Yrs South Florida Exposure

140 280 Average Klys 1 Kilolangley = 1000 Langley 1 Langley = The amount of energy to heat one gram of water 1C when one square centimeter is exposed. 2 2 1 Langley = 1 Cal/cm min = 697.3 W/m

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PHYSICAL PROPERTIES OF LIGHT STABILIZERS FOR POLYOLEFINS

Additive Molecular Weight Melting Point C Specific Gravity @ 20C Tinuvin 123 Tinuvin 234 Tinuvin 326 Tinuvin 327 Tinuvin 328 Tinuvin 622 737.2 448 316 358 351.5 (283)n Mn>2500 Tinuvin 770 Chimassorb 119 Chimassorb 944 481 2286 (579)n Mn>2500 Chimassorb 2020 2600-3400 120-150 1.01 300 375 transparent, slightly yellow pellets 82-86 115-150 120-150 1.05 1.03-1.05 1.01 200 240 300 260 350 375 white granules light yellow granules off-white powder liquid 135-141 140-141 154-158 79-87 55-70 0.97 1.22 1.32 1.26 1.17 1.18 TGA, in N2 at 10C/min Temp. at Temp. at 1% Wt. Loss 160 265 200 180 190 275 10% Wt. Loss 265 315 245 235 230 335 pale yellow liquid light yellow powder light yellow powder pale yellow powder off-white powder off-white powder Appearance

IMPORTANT
The following supercedes Buyers documents. SELLER MAKES NO REPRESENTATION OR WARRANTY, EXPRESS OR IMPLIED, INCLUDING OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. No statements herein are to be construed as inducements to infringe any relevant patent. Under no circumstances shall Seller be liable for incidental, consequential or indirect damages for alleged negligence, breach of warranty, strict liability, tort or contract arising in connection with the product(s). Buyers sole remedy and Sellers sole liability for any claims shall be Buyers purchase price. Data and results are based on controlled or lab work and must be confirmed by Buyer by testing for its intended conditions of use. The product(s) has not been tested for, and is therefore not recommended for, uses for which prolonged contact with mucous membranes, abraded skin, or blood is intended; or for uses for which implantation within the human body is intended.

Chimassorb, Tinuvin, Fiberstab, Irgastab, Irganox, Irgafos and Cromophtal are registered trademarks of Ciba Specialty Chemicals. Photos on page 19 1997 GM Corp. Used with permission of GM Media Archives.

23

CHEMICAL STRUCTURES OF STABILIZERS FOR POLYOLEFINS

Tinuvin 123 S
O H17C8O N OC (CH2)8 O CO N OC8H17 and PP

Tinuvin 234
HO N N 70% 30% N.A. N

Tinuvin 326
HO N N CI N CH3

Tinuvin 327
HO N N CI N

Tinuvin 328
HO N N N C(CH3)2CH2CH3 C(CH3)2CH2CH3

Tinuvin 622
H 3C H O H H3C CH3 N CH2 CH2 O O C CH2 CH2 O C O CH3

CH3 n

Tinuvin 770
O HN O C (CH2)8 O C O NH

Chimassorb 119
R C4H9 N R= N N N N CH3 R R-NH-(CH2)3-N-(CH2)2-N-(CH2)3-NH-R

Chimassorb 944
H N H N

N N N CH3 NH C CH3 CH2 CH3 C CH3

(CH2)6

H9C4

CH3

CH3 n

Chimassorb 2020
C 4H 9 C4H9 N N N N C4H9 N C4H9 N H C4H9 N N H N C6H12 N N N N N C6H12 N N N C 4H 9 C 4H 9 N N H N H N C 4H 9 N C4H9

Irgastab FS 042
OH H37C 18 N CH37 18

N H n

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