environmental considerations in the selection of dry film biocides

Pharma&Biotech

Environmental Considerations in The Selection of Dry Film Biocides

Dilipraj T K / Lonza Inc. (Arch Chemicals Division)

MicrobialControl

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 Need for both long term and broad spectrum protection of the

paint film

Fungicidal Algaecidal Fungicidal/Algaecidal

Octyl Isothiazolinone (OIT) Diuron Zinc Omadine™ (ZnOM)

Dichloro Octyl Isothiazolinone (DCOIT) Irgarol

N-butyl Benzisothiazolin (BBIT) Terbutryn

Iodo Propynyl Butylcarbamate (IPBC)

Chlorothalonil (CTL)

Carbendazim (BCM)

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

Group A Low Water Solubility

Group B Medium Water Solubility

Group C High Water Solubility

Zinc Omadine™ (ZnOM) 0.008 gm/L Diuron 0.035 gm/L Octyl Isothiazolinone (OIT) 0.48 gm/L

Chlorothalonil (CTL) 0.0006 gm/L DCOIT 0.014 gm/L N-butyl Benzisothiazolin (BBIT) 0.7 gm/L

Carbendazim (BCM) 0.008 gm/L Terbutryn 0.025 gm/L Iodo Propynyl Butylcarbamate (IPBC) 0.168 gm/L

Irgarol 0.007 gm/L

7

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?


O O O OO O O O O O O OO O O O O O O OO O O O O O O OO O O O

O O O O O O O O O O O O O O O O O O O O O O O

O O O O O O O O OO O O O O

O O OO O O O O

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


If the fungicide has too low a water solubility, then not enough fungicide is pulled from the reservoir to prevent defacement

No growth Light growth Moderate growth Heavy growth







Irgarol 0.007 gm/L

O X O X O X O XX O X O X O X O X X X XX X X X X X X XX X X X X X X XX X X X

O O X O X O X OO X X X X X X X X X X X X X X X X X X X X X X X X X

O O X X XO X X X X X X X X X X X X X X X X X X X X X

O O X X O X X X X X X X X X X X X X X X X X X

9


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







Irgarol 0.007 gm/L

O X O X O X O XX O X O X O X OO X O X O X O XX O X O X O X OO X O X O X O XX O X O X O X OO X O X O X O XX O X O X O X O

O O X O X O X OO X X O X O X X O X O X O X X O X O X X O X O X O X X O X O X X O X O X O X X O X O X

O O X X O XO X X X O X X O X X X X O X X O X X X X O X X O X X X X O

O O X X O X X X X X X X X X X X X X X X X X X

10

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 supplemental algaecide

Challenges Faced by a Coatings Formulator:Developing a strategy for dry film protection

Troy Troy Troy Thor Thor

Troysan™ 663 Troysan™ 678 Troysan™ 662 Acticide™ PA Acticide™ PM

9.0% BCM3.0% IPBC

15.0% Diuron

15.0% BCM5.0% IPBC

12.0% BCM4.0% IPBC

4.0% Irgarol™

11.8% CTL6.0% OIT

19.0% Diuron

14.0% CTL

19.0% Diuron

Dow Dow Ashland Ashland Lanxess

Rocima™ 63 Rocima™ 65 Fungitrol™ 2010 Fungitrol™ 2002 Preventol™A14D

7.5% BCM2.7% OIT

20.0% Diuron

9.0% BCM5.0% DCOIT 3.5% Irgarol™

20.1% CTL10.1% IPBC

48.0% CTL

6.0% Irgarol™

10.0% BCM3.0% OIT

22.0% Diuron

Data Source; NPIRS http://npirspublic.ceris.purdue.edu/ppis/

11

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

Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings

12

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 Labeling Requirements

T = Skull and crossbonesN = Dead fish and tree

R46 = May cause heritable genetic damageR52 = Harmful to aquatic organismsR53 = May cause long term adverse effects in the aquatic environment

R60 = May impair fertilityR61 = May cause harm to the unborn child

R51 = Toxic to aquatic organisms

Carbendazim must be listed on the labelas a hazardous ingredient at levels >0.1%

* EU/DDP classification

Carbendazim Level %

Symbol Indication of Danger

R and S Phrases (On Label)

<0.1 None None None 0.1 - 0.25 T Toxic R46, S53, S45 MSDS Phrase; Mutagen Cat 2

0.25 -0.5 T Toxic R46, R52/53, S53, S45 MSDS Phrase; Mutagen Cat 2

0.5 - 2.5 T Toxic R46, R60, R61, R52/53, S53, S45 MSDS; Mutagen Cat 2, Reprotox Cat 2*

2.5 - 25 T N Toxic Dangerous for the environment

R46, R60, R61, R51/53, S53, S45, S60,S61 MSDS; Mutagen Cat 2, Reprotox Cat 2*

Carbendazim potentially requires both health hazard and environmental hazard labels

14

Comparison of EU and GHS Criteria

Category 1 T R46 Category 2 T R46 Category 3 Xn R68

Substances known to be mutagenic to man.

Substances which should be regarded as if they are mutagenic to man.

Substances which cause concern for man owing to possible mutagenic effects.

EUCriteria

GHSCriteria

Category 1 Category 2

Category 1A Category 1B

Chemicals know to induce heritable mutations in germ cells of humans.

Chemicals which should be regarded as if they induce heritable mutations in germ cells of humans.

Chemicals which cause concern for man owing to the possible that they may induce heritable mutations in germ cells of humans.

Table 3.5.1Cut-off values/concentration limits of ingredients of a mixture classified as germ cell mutagens that would trigger classification of the mixture

Ingredient classified as: Cut-off/concentration limits triggering classification of a mixture as:

Category 1 mutagen Category 2 mutagen

Category 1 mutagen > 0.1%

Category 2 mutagen > 1.0%

Under GHS, Carbendazim falls into the more serious Category 1 classification

15


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 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 Labeling Requirements

R50/53 : Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment

R51/53: Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment

R52/53 Harmful to aquatic organisms, may cause long-term adverse effects in the aquatic environment

Concentration % Classification

0.1 - 0.6 R52/53

0.6 - 1.0 N; R51/53

1.0 - 2.5 N; R51/53

2.5 - 10.0 N; R50/53

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

N = Dead fish and tree

18


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, Diuron falls 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 (with OIT) 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

US Test Site EU Test Site India Test Site S. Asia 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

ActiveAgent

Biocide Product ActiveAgent

Biocide Product

ZnOM Zinc Omadine™ ZOE Antimicrobial OIT Isocil™ WT Fungicide

Zinc Omadine™ Powder Antimicrobial IPBC Omacide™ IPBC 40 Fungicide

Zinc Omadine™ FPS Antimicrobial Omacide™ IPBC 30 Fungicide

CLT Densil™ C40 Antimicrobial Omacide™ IPBC 20 Fungicide

Omacide™ IPBC 100 Fungicide

BBIT Densil™ DN Antimicrobial

Densil™ DG45 Antimicrobial

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

0

1

2

3

4

5

6

7

8

9

10

North Vertical Wood - Flat- 12 Months

Low Dosage

Medium Dosage

High Dosage

Densil™

ZOD

Antim

icrobial

ZnOM

/ OIT / D

iuron

ZnOM

/ IPB

C / D

iuronZnO

M / IP

BC

/ Diuron

Control

(no fungicide or algaecide)

Rating Description10 No Fungal Growth9 Trace8 Slight6 Moderate4 Pronounced2 Severe0 Complete Coverage

Panel Study - Test Fence Results Summary

24

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

North Vertical HP - Flat- 24 Months

Low Dosage

Medium Dosage

High Dosage

ZnOM

/ OIT / D

iuron

ZnOM

/ IPB

C / D

iuronZnO

M / IP

BC

/ Diuron

Densil™

ZOD

Antim

icrobial


Panel Study - Test Fence Results Summary

Control

(no fungicide or algaecide)

25

Panel Study - Test Fence Results Photographs

DENSIL™ ZODDS 6338

3 ACTIVE BLENDMID DOSAGE

AVG = 7.034 MONTHS

BLANKNEG CTRLAVG = 4.6

34 MONTHS

POS CTRLMID DOSAGE

AVG = 4.934 MONTHS

DS 6338 alt.3 ACTIVE BLEND

MID DOSAGEAVG = 7.0

34 MONTHS

DS 63862 ACTIVE BLEND

MID DOSAGEAVG = 6.0

34 MONTHS

Photos were taken at 33 months

Ratings shown are for 34 months

Panel Photos from S. Florida Test Fence Lab made standard acrylic flat paint Primed southern yellow pine Exposure 90 North vertical


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

Thank You!

environmental considerations in the selection of dry film biocides

Documents