N-methyl-1,2-benzisothiazol-3(2H)-one (MBIT) New Solution for In-can Preservation Surface Coatings Association Australia (SCAA) Conference August 24-26, 2011 Gek Mui Ho, Emerentiana Sianawati
Outline Why a new Active Industry Trends Evolution of Microbial Contamination Biocides Tool Box and its Gaps Key requirement of a new biocide product MBIT Introduction Benefit Products Design MBIT based products Performance Validation Paints with bacteria, mold and yeast problem Latex with bacteria, mold and yeast problems Case study 1 Latex with wild strain problem Case study 2 Colorants bacteria, yeast and mold problems Case study 3 CaCO 3 slurry difficult to preserve Conclusions 2
Why a New Active? Industry Trends Demand for lower levels of VOC and residual monomer and expanded use of non synthetic/natural based raw materials. New regulations reduce the number of biocidal actives available. Preservative options (706) notified in-can-preservatives (50) Remaining by 2015 25-30? Eco-label and EH&S restrictions (CMIT, Bronopol, FARs) Greater scrutiny of certain chemical substances through laws such as REACH in the EU, and GHS initiative More discerning customer preferences driven by ecolabels, green chemistry and internet-based research 3
Why a New Active? Industry Trends Outcome Substrates have higher microbial susceptibility, harder to eradicate and preserve. Emergence of wild strains (various Pseudomonas sp), mold, and yeast. Customers experience more microbial contamination Limited BiocidesTool Box Eco and EH&S compliant biocides have performance gaps. 4
Why a New Active? Evolution of Microbial Contamination common perception: area susceptible for contamination 3 4 5 6 7 8 9 10 11 Fungi/Yeast Bacteria reality: ph 3 4 5 6 7 8 9 10 11 all microorganisms opportunistically + time + time ph 5
Evolution of Microbial Contamination Substrates have higher susceptibility to mold and yeast Fungi challenge (day) 0 Cycle I 7 Cycle II 14 Cycle III Sample streak (day) 0 2 3 7 9 10 14 16 17 SM Architecture Paint (ph 8.3) CL Int. Architecture Paint (ph 8.7) WB Teak Coating (ph 7.9) Challenge 1 (5 x 10*7 CFU/ml) 5 4 5 5 Challenge 2 (5 x 10*7 CFU/ml) 5 5 5 Challenge 3 (5 x 10*7 CFU/ml) 5 5 5 5 5 5 5 5 4 5 5 5 5 5 1 5 5 2 5 5 Adhesive (ph 6.7) 5 1 1 0 5 5 5 5 5 Ext Paint (ph 8.7) 5 0 0 0 5 5 5 5 5 Score Level of Fungal Contamination 0 No contamination 1 Trace contamination 2-5 Moderate to heavy contamination 6
Yesterday Biocides Tool Box Yesterday s traditional biocidal actives for wet state preservation applications MIT / BIT / CMIT / Bronopol / HCHO bacteria mould yeast Microbial Contamination
Current - Biocides Tool Box Limited actives and spectrum Activities Microorganisms are ubiquitous and very adaptive MIT / BIT / CMIT / Bronopol / HCHO bacteria mould yeast Microbial Contamination
N- Methyl Benzisothiazolin-ne (MBIT) Broad Spectrum replace old biocides MBIT an effective bactericide and fungicide for wet state preservation applications MIT / BIT / + MBIT bacteria mould yeast Microbial Contamination
New Biocide Formulations Key requirements Low-VOC Complies with new regulations and ecolabels Composition restrictions Formaldehyde-free heavy-metal free, Bronopol-free (regions specific, limited cases) CMIT-free (regions specific) Effective against bacteria, yeast and mold Closes performance gaps of current formulations 10
MBIT Introduction MBIT a novel biocidal active ingredient O S N CH 3 N-methyl-1,2-benzisothiazol-3(2H)-one CAS-Registry-Nr.: 2527-66-4 11
Structural similarities -Isothiazolone based bactericides and fungicides O Cl O Cl S N CMIT broadband Cl S N DCOIT fungicide O O S N MIT bactericide S N OIT fungicide O NH S BIT bactericide O N CH 3 S Methyl-BIT broadband Bu-BIT fungicide O N S
BIOBAN MBIT Benefits SUPERIOR PRESERVATION Broad Spectrum Activity bacteria, mold and yeast The only globally registered active for high ph systems with excellent activities against yeast and mold MBIT formulations close performance gaps of current formaldehyde-free formulations Effective at relatively low use levels VERSATILITY ph stability from 2 to 10 Higher solubility in water than 1,2 Benzosiothiazolin-3-one (BIT) Can be formulated with other key actives Highly Compatible in aqueous systems SUSTAINABILITY Favorable human and environmental toxicity profiles expected similar to BIT biocide Aligned with green chemistry principles 13
MBIT Products Design MBIT/isothiazolinone synergistic blend Cl O S N S N O Chloro methyl isothiazolin-one (CMIT) Methyl isothiazolin-one MIT O NH S 1,2 Benzisothiazolin-one BIT O N CH 3 S Methyl-BIT Broad spectrum (bacteria, mold, yeast) Very good against environmental strains Stable in oxidizing environment Stability ph < 8 R43- labeling for > 15 ppm (Europe only) Broad spectrum bactericide Broad ph Stability ph 2-12 Stable in reducing environment Weak against fungi and yeast Broad spectrum bactericide Broad ph Stability ph 2-12 Stable in reducing environment Elevated dose for Pseudomonas sp kill Weak against fungi Broad spectrum (bacteria, yeast, fungi) Broad ph Stability ph 2-10 Stable in reducing environment Elevated dose for Pseudomonas sp kill Synergistic Blends
Synergism between MIT and MBIT Minimal Inhibitory Concentrations (MIC) values for MIT and MBIT versus bacteria and fungi individually Yeast C. albicans (ATCC #10231) MIC at 48 hours Mould A. niger (ATCC #16404) MIC at 72 hours MIC (MIT) MIC (MBIT) SI MIC (MIT) MIC (MBIT) SI 175 0 1.00 400 0 1.00 0 8 1.00 0 60 1.00 50 1 0.41 100 10 0.42 Pseudomonas P. aeruginosa (ATCC #15442) MIC at 72 hours Staphylococcus S. aureus (ATCC #6538) MIC at 24 hours MIC (MIT) MIC (MBIT) SI MIC (MIT) MIC (MBIT) SI 25 0 1.00 60 0 1.00 0 200 1.00 0 8 1 10 60 0.70 15 3 0.63 Example: 50/175 + 1/8 = 0.41 15
Formulating using MBIT Advantages Being soluble in water MBIT can be formulated as stable, flow-able clear liquid rather than a more viscous dispersion Solvent and VOC-free
MBIT Based Products MBIT/MIT -CMIT, FR Free -Solvent free - Effective against - environmental strains, - yeast, mold 17
MBIT Performance Validation Coating and Raw Material Preservation 18
MBIT / MIT Blend Performance Efficacy against bacteria and mold/yeast Challenge test of an exterior wall paint (pure acrylic) ph 8 Biocide active, ppm MIT BIT MBIT TOTAL Bacteria Mold/yeast BLANK 38 38 76 50 50 100 75 75 150 38 28 66 50 38 88 75 56 131 19
MBIT / MIT Blend Performance Paint susceptible to yeast and mold MBIT offers superior protection against fungal contamination Test Materials Biocides # successive challenges to pass against ppm, actives Bacteria Yeast Mold Paint #2, ph > 8 MBIT: MIT 87.5 6 6 6 131.25 6 6 6 175 6 6 6 BIT:MIT 100 0 1 6 150 5 1 6 200 6 6 6 Paint #1, ph < 8 MBIT: MIT 87.5 6 6 6 131.25 6 6 6 175 6 6 6 BIT:MIT 100 0 1 6 150 5 1 6 200 6 6 6 20
MBIT / MIT Blend Performance Efficacy against mix of microbes Challenge test of a styrene acrylate binder, ph 8.5 Mixed inoculum: bacteria, mold, and yeast Biocide Active, ppm # Inoculations MIT BIT BNPD MBIT TOTAL 1 2 3 4 5 # passing BLANK 0 25 25 0 50 50 0 100 100 3 25 25 50 2 50 50 100 3 100 100 200 4 25 25 50 0 50 50 100 0 100 100 200 4 25 20 45 4 50 40 90 5 100 75 175 5 21
Case Study 1: Latex Preservation Wild strains problem LAB STRAINS 200 160 Latex 2 Latex 3 Latex 4 Latex 5 120 80 40 0 (BIT+ZPT)plus MBIT:MIT BIT BIT:MIT WILD STRAINS 500 400 Latex 2 Latex 3 Latex 4 Latex 5 300 200 100 0 (BIT+ZPT)plus MBIT:MIT BIT BIT:MIT 22
Case study 2 COLORANTS Yeast & mold problem Efficacy Against Bacteria Effective Concentration, ppm Active 500 400 300 200 100 Efficacy Against Yeast/mold 0 Blue Yellow Red BIT BIT + MIT MBIT MBIT+MIT Effective Concentration, ppm Active 500 400 300 200 100 0 FAIL BIT BIT + MIT MBIT MBIT+MIT 23
Case study 3 CaCO 3 Slurry Difficult to preserve BIOCIDE ppm a.i. Challenge 1 Cycle I Cycle II Cycle III Cycle IV Day 28 Day 1 Day 7 Day 8 Day 14 Day 15 Day 21 Day 22 Control - No Biocide 4 4 4 4 4 4 4 4 BIT 500 4 4 4 1 2 4 2 4 250 4 4 4 4 4 4 1 4 125 4 4 4 4 4 4 4 4 BIT:MIT 250 4 2 3 2 4 1 2 1 125 4 3 4 2 4 1 2 2 62.5 4 4 4 3 4 2 4 4 MBIT:MIT 250 2 1 1 1 1 1 1 1 125 2 1 2 2 4 0 2 1 62.5 2 2 3 2 3 1 2 1 MBIT 500 4 0 0 0 0 0 0 0 250 4 1 1 1 0 0 0 0 125 4 1 1 1 1 0 0 1 Challenge 2 Challenge 3 Challenge 4 24
CONCLUSIONS Industry trends change the landscape of in-can preservation systems Products become more susceptible to microbial contamination The emergence of hard to eradicate wild strains including mold and yeast Limited biocides available performance gaps MBIT:MIT Product Fill the gap of current standard ICP options Efficacious in paints and raw materials at average concentration of lower than 100 ppm actives. Effectively eradicate wild strains isolated from contaminated products and during plant hygiene audit 25
Thank you for your attention! 26