Environmental Considerations in The Selection of Dry Film Biocides

1. Environmental Considerations in The Selection of Dry Film Biocides MicrobialControl Dilipraj T K / Lonza Inc. (Arch Chemicals Division)

2. Overview • Microbial control challenges for a coatings formulator • The value of biocides and the impact of the lack of protection • Challenges faced by a coatings formulator • Limited number of biocide active agents available • Need for long term and broad spectrum protection of the paint film • Biocide compatibility with the paint formulation • Concern about consumer perceptions opposite label warnings • Multi-region dry film biocide panel study • Lonza’s active agent offerings for dry film protection • The ZOE formulation of Zinc Omadine™ • Formulations for other active agents • Study experimental design • Summary of study results • Introduction of Densil™ ZOD and Densil™ FAZ • Support from Lonza

3. Challenges Faced by a Coatings Formulator:Compatibility • Challenges for a coatings formulator • Biocide compatibility with the paint formulation Paint film protection agents must……… be chemically stable & not affect paint application deliver long lasting compatible with paints (viscosity, drying etc.) film protection

4. Challenges Faced by a Coatings Formulator:Broad spectrum protection • Challenges for a coatings formulator • The value of biocides and the impact of the lack of protection • Challenges faced by a coatings formulator • Broad spectrum protection of the paint film • Interior • Wide variety of fungi • Concern about indoor air quality; airborne fungal spores • Frequent human contact with painted surfaces • Exterior • Wide variety of fungi • Defacement by algae • Increasing diversity of substrates

5. Challenges Faced by a Coatings Formulator:Limited biocide actives available • Challenges for a coatings formulator • Limited number of available biocide active agents • Needfor both long term and broad spectrum protection of the paint film

6. Challenges Faced by a Coatings Formulator:Considering biocide solubility and spectrum • Limited number of available biocide active agents • Need for long term and broad spectrum protection of the paint film • Active agents have different water solubility and different microbial spectrum • Why is water solubility important? Biocide Active Agents Grouped by Water Solubility

7. Challenges Faced by a Coatings Formulator:Considering biocide solubility and spectrum • Need for long term and broad spectrum protection of the paint film • Active agents have different water solubility and different microbial spectrum • Why is water solubility important? In the conventional model of a paint film there is a reservoir of fungicide active agent in the paint film, and there is also some fungicide on the surface of the paint. As rain falls on the surface of the paint film, it washes away the fungicide on the surface, however the fungicide at the surface of the film is replenished by new fungicide that is drawn from the reservoir in the paint film.If the fungicide has too high a water solubility, then the reservoir will be depleted and the coating will show defacement No growth No growth No growth Heavy growth

8. Challenges Faced by a Coatings Formulator:Considering biocide solubility and spectrum If the fungicide has too low a water solubility, then not enough fungicide is pulled from the reservoir to prevent defacement Heavy growth No growth Light growth Moderate growth

9. Challenges Faced by a Coatings Formulator:Considering biocide solubility and spectrum A combination of a less water soluble fungicide with a more water soluble fungicide gives more robust paint film protection. No growth No growth No growth No growth

10. Challenges Faced by a Coatings Formulator:Developing a strategy for dry film protection • Need for long term and broad spectrum protection of the paint film • Active agents have different water solubility and different microbial spectrum • Potential blend strategy • Less water soluble fungicide as a foundation • May include more water soluble co-fungicide • May include a supplementalalgaecide Data Source; NPIRS http://npirspublic.ceris.purdue.edu/ppis/

11. Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings • Challenges for a coatings formulator • Limited number of available biocide active agents • Concern about consumer perceptions opposite label warnings • For durable film protection, need a fungicide with low water solubility; Carbendazim, Chlorothalonil, Zinc Omadine™ • Carbendazim • Pluses • Stable over wide pH range • Good compatibility history with other paint ingredients • Minuses • Very limited activity against algae or bacteria • Gaps in anti-fungal spectrum – ex. Alternaria sp. • CLP / GHS labeling • EU Category 2 Mutagen => GHS Category 1B

12. Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings • Challenges for a coatings formulator • Limited number of fungicide and algaecide active agents • Concern about consumer perceptions opposite label warnings • Current situation in Europe • The European Union has now implemented the United Nations' GHS (Globally Harmonized System of Classification and Labeling of Chemicals) into EU law as the CLP Regulation • The CLP Regulation which came into force on the 20th January 2009 requires manufacturers to: Classify, Label and Package substances and mixtures according to CLP before placing them onto the market • Implementation for Substances - Dec 2010 • Implementation for Mixtures (Paint) - June 2015 • In 2015, in Europe, the CLP legislation will limit the fungicide and algaecide concentrations that can be in European paints without having warning statements on the paint cans • EU warning statements and risk phrases for Carbendazim • Health Hazard label • Environmental Impact label • GHS dosage thresholds

13. Carbendazim EU LabelingRequirements * EU/DDP classification R46 = May cause heritable genetic damage R52 = Harmful to aquatic organisms R53 = May cause long term adverse effects in the aquatic environment R60 = May impair fertility R61 = May cause harm to the unborn child R51 = Toxic to aquatic organisms Carbendazim potentially requires both health hazard and environmental hazard labels

14. Comparison of EU and GHS Criteria EU Criteria GHS Criteria Table 3.5.1 Cut-off values/concentration limits of ingredients of a mixture classified as germ cell mutagens that would trigger classification of the mixture Under GHS,Carbendazimfalls into the more serious Category 1 classification

15. Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings • Challenges for a coatings formulator • Limited number of available biocide active agents • Concern about consumer perceptions opposite label warnings • Fungicides with low water solubility; Carbendazim,Chlorothalonil, Zinc Omadine™ • Chlorothalonil • Pluses • Very low water solubility • Good anti-fungal spectrum plus some activity against algae • Minuses • Alkaline pH hydrolysis • Problematic compatibility history with other paint ingredients; pinking, yellowing • Chalking in colored paints • Very limited activity against bacteria • CLP / GHS labeling for Chlorothalonil – Health Hazard + Environmental Impact • Chlorothalonil is in IARC Group B2 => GHS Category 2 • Cat 2 ≥ 0.1% but <1.0% “Some authorities will chose to label…others would not normally require a label” • Cat 2 ≥ 1.0% “a label would generally be expected” Under GHS, Chlorothalonil falls into the less serious Category 2 classification

16. Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings • Challenges for a coatings formulator • Limited number of available biocide active agents • Concern about paint compatibility and consumer perceptions opposite label warnings • Need a fungicide with low water solubility; Carbendazim,Chlorothalonil, Zinc Omadine™ • Zinc Omadine™ • Pluses • Broad spectrum; Anti-fungal, Anti-algal, Anti-bacterial • Zinc Omadine™ ZOE formulation has good compatibility history with other paint ingredients • CLP / GHS labeling • Zinc Omadine™…. • is not a mutagen, is not a carcinogen, is not a skin sensitizer • EU CLP Labeling only for Environmental Impact • For ZOE, the EU threshold limit for labeling (6000 ppm ZOE) is above the typical ZOE use level • Minuses • Requires suppression of trans-chelation

17. Zinc Omadine™ ZOE Dispersion EU LabelingRequirements Zinc Omadine™ does not require health hazard labels, it requires environmental hazard labels only at ZOE dosages above 6000 ppm, and only in regions where environmental hazard labeling is required

18. Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings • Challenges for a coatings formulator • Limited number of available biocide active agents • Select Zinc Omadine™ as low solubility active agent for durable protection of the paint film • Need a supplemental algaecide? • In many situations Zinc Omadine™ alone has sufficient anti-algal activity • However, panel testing shows some situations where a supplemental algaecide helps • Available supplemental algaecides; Diuron, Irgarol™, Terbutryn • Consider cost effect – Diuron offers good value • Consider spectrum – Diuron contributes to anti-fungal activity • Consider CLP / GHS label • All algaecides will have Environmental Impact • Diuron – Health Hazard + Environmental Impact • Diuron is EU Category 3 => GHS Category 2 • Cat 2 ≥ 0.1% <1.0% “Some authorities will chose to label…others would not normally require a label” • Cat 2 ≥ 1.0% “a label would generally be expected” • On balance, Diuron is preferred Under GHS, Diuronfalls into the less serious Category 2 classification

19. Challenges Faced by a Coatings Formulator:Developing a strategy for dry film protection • Challenges for a coatings formulator • Limited number of available biocide active agents • Select Zinc Omadine™ as durable fungicide + Diuron as supplemental algaecide • Benefits from a co-fungicide with higher water solubility; OIT or BBIT or IPBC ? • Look at active combinations, and active ratios • DS 6337, DS 6338: Zinc Omadine™ + Diuron + OIT (Isocil™ WT Fungicide) • DS 6338 alt.: Zinc Omadine™ + Diuron + BBIT (Densil™ DN Antimicrobial) • DS 6372, DS 6373: Zinc Omadine™ + Diuron + IPBC (Omacide™ Fungicides) • Test under different conditions • Different paint types, Different substrates, Different exposure conditions • Consider cost effect • Evaluate overall performance • Zinc Omadine™ + Diuron + OIT performs better overall than the other two combinations • DS 6338 (withOIT) was the best performing ratio of these active agents => Densil™ ZOD • Formulating Densil™ ZOD with OIT concentrate avoids introduction of VOC

20. Panel Study – Experimental Design • Problem • Durable film protection in geographical areas with high algal pressure • Identify biocide options consistent with local regulatory environment • Background • Panel studies conducted in multiple regions – Project Bristle • Substrates, painting practices, etc. selected as appropriate for each region • Zinc Omadine™ as foundation, vary secondary algaecide inclusion, vary co-fungicides • Findings • Need different secondary algaecide or different co-fungicide for different global regions • Need different active agent ratios for different global regions • Results • Commercialize DS 6338 as Densil™ ZOD as a global product • Commercialize DS 6408 as Densil™ FAZ (alt. ratio; ZnOM/OIT/Diuron) for Asia • Commercialize other products for other regions India Test Site S. Asia Test Site US Test Site EU Test Site

21. Panel Study – Active Agents • Lonza’s biocide offerings for dry film protection • Broad spectrum antimicrobials • Durable film protection • Biocide formulations optimized for use in coatings

22. Panel Study – Zinc Omadine™ Formulation • Zinc Omadine™ ZOE Antimicrobial • Zinc Omadine™ provides durable dry film protection against both fungi and algae • Advantages of Zinc Omadine™ ZOE Antimicrobial • Biocide formulation optimized for use in coatings • The ZOE formulation has good compatibility history with other paint ingredients • The ZOE formulation contains proprietary Lonza technology to suppress Zinc Omadine™ trans-chelation • Broad range of pH stability; Excellent thermal stability • Zero VOC • Can be used for both Interior and Exterior paints • Interior paints are increasingly being rated for mold resistance • Zinc Omadine™ is familiar to consumers as the world’s leading anti-dandruff agent • Well established track record of safety in skin contact applications • Compliant with upcoming regulations • EU CLP trigger concentration for Environmental Hazard label above typical use level • No anticipated Health Hazard labeling post U.S. GHS implementation

23. Panel Study - Test Fence Results Summary Control(no fungicide or algaecide) Densil™ ZOD Antimicrobial ZnOM / IPBC / Diuron ZnOM / IPBC / Diuron ZnOM / OIT / Diuron

24. Panel Study - Test Fence Results Summary Densil™ ZODAntimicrobial Control(no fungicide or algaecide) ZnOM / IPBC / Diuron ZnOM / IPBC / Diuron ZnOM / OIT / Diuron

25. Panel Study - Test Fence Results Photographs • Panel Photos from S. Florida Test Fence • Lab made standard acrylic flat paint • Primed southern yellow pine • Exposure 90 North vertical POS CTRL MID DOSAGE AVG = 4.9 34 MONTHS BLANK NEG CTRL AVG = 4.6 34 MONTHS Photos were takenat 33 monthsRatings shown are for 34 months DENSIL™ ZOD DS 6338 3 ACTIVE BLEND MID DOSAGEAVG = 7.0 34 MONTHS DS 6338 alt. 3 ACTIVE BLEND MID DOSAGE AVG = 7.0 34 MONTHS DS 6386 2 ACTIVE BLEND MID DOSAGEAVG = 6.0 34 MONTHS

26. New Products from Panel Study • Introducing - Densil™ ZOD Antimicrobial • Three active dry film biocide blend for exterior coatings • Zinc Omadine™ as the durable less water soluble fungicide • OIT as the more water soluble co-fungicide • Diuron as the supplemental algaecide • EPA reg. # 1258-1345 • Use patterns: Paints and Stains, Masonry Coatings, Plasters, Caulks and Sealants, Stucco, Mastics, and Joint Cements • Advantages of Densil™ ZOD Antimicrobial • Combination of fungicides with different water solubility gives more robust paint film protection • Fungicide blend with secondary algaecide covers a broader range of coating scenarios • Biocide formulation optimized for use in coatings • Densil™ ZOD contains proprietary Lonza technology to suppress Zinc Omadine™ trans-chelation • Zero VOC • Expected to be compliant with upcoming U.S. regulations • Health Hazard labeling post U.S. GHS implementation expected to be above typical Densil ZOD use levels

27. New Products from Panel Study • Introducing - Densil™ FAZ Antimicrobial • Designed for use in high volume paints • Three active dry film biocide blend for exterior coatings • Proportions of active agents differs from Densil ZOD • Densil FAZ has higher ratio of Diuron / (Zinc Omadine™ + OIT) • Consider the impact of geography and climate • Some tropical environments have very high algal pressure • The concentration of algaecide needed may determine the overall biocide dosage required • Having different ratios available provides flexibility for variations in climate and paint formulation • Advantages of Densil™ FAZ Antimicrobial • Combination of fungicides with different water solubility gives more robust paint film protection • Fungicide blend with secondary algaecide covers a broader range of coating scenarios • Biocide formulation optimized for use in coatings • Densil™ FAZ contains proprietary Lonza technology to suppress Zinc Omadine™ trans-chelation • Zero VOC

28. Summary – Lonza Support • Lonza’s biocide offerings for dry film protection • Support from Lonza • Corporate level commitment to continual improvement in EHS areas • Strong global regulatory and toxicology expertise and support • Strong microbiological and analytical chemistry support • Newly opened Innovation Center in Alpharetta, Georgia • On-going exploration of leading edge technologies • Strong corporate focus on Material Protection and Industrial Solutions • Development of products that are consistent with current requirements but are also aligned with trends and anticipated future market needs

29. Thank You!