Post on 14-Dec-2015
transcript
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?
Challenges Faced by a Coatings Formulator:Considering biocide solubility and spectrum
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
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
No growth Light growth Moderate growth Heavy growth
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
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
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
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
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
Challenges Faced by a Coatings Formulator:Consumer perceptions about label warnings
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 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 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 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, 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
Rating Description10 No Fungal Growth9 Trace8 Slight6 Moderate4 Pronounced2 Severe0 Complete Coverage
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
Rating Description10 No Fungal Growth9 Trace8 Slight6 Moderate4 Pronounced2 Severe0 Complete Coverage
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