Training Biocides Formulation TechnologiesJanuary 16th 2011, Sametime MeetingFrank Bienewald, Jürgen Wiethan, EMD/DF, Grenzach, GermanyJanuary 16th 20121AgendaBiocides – General Introduction Overview BASF Biocide Product Portfolio Main FT Applications and more Technical Details of ProductsJanuary 16th 2012CONFIDENTIAL / INTERN2What is a Biocide ?There are various different legal and scientific definitions There is potential for overlap and for grey areasExample Definition - from 98/8/EC (EU Biocidal Products Directive) Biocidal products: Can be active substances or preparations Can contain one or more active substances Are intended to destroy, deter, render harmless, prevent the action of, or otherwise exert a controlling effect on any harmful organism Act by chemical or biological meansJanuary 16th 2012CONFIDENTIAL / INTERN3Why do we use Biocides ?• Visual growth • Odour generation • Colour changes • Viscosity changes • Corrosion • Leads to economic loss • Possible health effects - pathogensJanuary 16th 2012CONFIDENTIAL / INTERN4Biocide Market TrendsAwareness of health / hygiene (avian influenza, MRSA, SARS….) Water-based products increasing (paints, adhesives etc.) Water re-use (e.g. paper production, industrial water treatment) Negative opinions of certain biocides (e.g. parabens, formaldehyde, triclosan). Often not scientifically based. Increasing regulation leading to reduced number of AIs Labelling restrictions on common AIsJanuary 16th 2012CONFIDENTIAL / INTERN5Biocides – Trends, Needs, Claims BiosecuritySpa baths Precautions against SARS MRSA – hospital “superbug” Legionella bacteriaDecontamination of anthrax infected buildingJanuary 16th 2012E.coliCONFIDENTIAL / INTERN6Biocides – Trends, Needs, Claims Household HygieneBathroom and toilet cleaningOdour controlBuilt in hygienic surfacesMould preventionJanuary 16th 2012CONFIDENTIAL / INTERN7Biocides – Trends, Needs, Claims Household ArticlesJanuary 16th 2012CONFIDENTIAL / INTERN8Biocides – Trends, Needs, Claims Maintaining Efficiency in IndustryMarine foulingMembrane foulingBiomass in a deaerator (oil production)Microbially induced corrosionJanuary 16th 2012Slime in paper productionCONFIDENTIAL / INTERN9Product OverviewJanuary 16th 2012INTERN10Overview BASF Biocide Product PortfolioActive Substance Application AreaHuman Hygiene Private and Public Health Area Medical, Man, Industry Swimming Pool Air-Conditioning Chemical Toilets/Waster Others Veterinary Hygiene Food and Feed Hygiene In-can Preservatives Metal Working Fluids Film Preservatives Plastic & Textile Materials Masonry Construction Materials Liquid Cooling Systems Slimicides (Industrial Processes) Paper Pulp Mineral Oil Marine antifouling January 16th 2012TCS = Triclosan (Irgasan DP300), HP = Tinosan HP100BNGADZHTGLCDPEXFMTCSXHPIrgaguardIrgarolXX XX XX XX XX XXX X XX X X X X X X X X X X X X X X X X X X X X X X XXXX X X XX X X X X X X X XCONFIDENTIAL / INTERN11Products IProtectol BN Effective bactericide Preservation useNO2 HO Br OHProtectol PE Cosmetic preservation In-can preservation (incl. household products) and disinfection uses Metalworking Fluids (also solvent properties)O OHProtectol GA 50 Fast acting biocide Disinfection and water preservation usesH OJanuary 16th 2012Protectol GL Disinfection and water preservation uses Useful co-biocide (e.g. combination with GA)O HCONFIDENTIAL / INTERNH OO H12Products IIProtectol FM Formaldehyde-free Broad spectrum activity Biodegradable with attractive environmental and safety profile Disinfection usesAseptrol Products based on delivery of chlorine dioxide (ClO2), strong biocide at very low concentrations Tablet technology for uses in water solutions (disinfection) Sachet technology for release of ClO2 gas to the atmosphere (odour-control and disinfection) Fits best with small to medium sized applicationsH OOHCl OJanuary 16th 2012O13CONFIDENTIAL / INTERNProducts IIIIrgasan DP300 / Irgacare MP Broad-spectrum biocide with longlasting activity PC, oral care uses, hand disinfectantsTinosan HP100 Broad-spectrum biocide with longlasting activity on treated surfaces Uses in laundry care, surface cleaners and disinfectantsOH O Cl Cl ClCl O ClOHJanuary 16th 2012CONFIDENTIAL / INTERN14Products IVProtectol DZ Effective biocide Readily biodegradableProtectol HT Formaldehyde releaser Alkaline pH stableS H3C N NS CH3HON NNOHOHJanuary 16th 2012CONFIDENTIAL / INTERN15Products VIrgarol 1051 Algicide Uses in marine antifoulingH N N N N NH SIrgaguard B range Silver zeolites and silver glass Uses in plastics, textile fibresSilver-Zinc Zeolite Silver-Zinc GlassJanuary 16th 2012CONFIDENTIAL / INTERN16“Biocide Map” - FT ApplicationsActive Substance Application Area In-can Preservatives Metal Working Fluids Plastic & Textile Materials Slimicides (Industrial Processes) Paper Pulp Mineral Oil X X X X X X X X X X BN X GA X DZ X HT X X GL PE X X X FM X IrgaguardJanuary 16th 2012CONFIDENTIAL / INTERN17ApplicationsJanuary 16th 2012INTERN18Industrial PreservationJanuary 16th 2012INTERN19Preservation Applications Products Requiring PreservationProducts most at risk: – Have a high water content – Are formulated with a final pH of 2-10 – Have a high organic content (natural or synthetic) – Are used or stored in environments with a high ambient temperature Industrial Products • Water based paints and polymer dispersions • Adhesives, sealants, fillers, lithographic solutions and inks • Pigment and mineral slurries Cosmetic Product Preservation • Skin creams, lotions, shampoos, conditioners, shower gels and wet tissues Household Products • Dishwashing liquids, cleaners and liquid polishesJanuary 16th 2012CONFIDENTIAL / INTERN20Arch (now Lonza)Protectol BN•Good combination active ingredient with CIT/MIT, BIT (compensating weaknesses of BN against fungi)•Use in blends to remove R43 labelling requirements for CIT•Effective against Pseudomonas strains (problem for BIT)•Regulatory approvalsProtectol GA•May be used for quick “knock-down”e.g. for mineral slurriesProtectol HT•Formaldehyde releaser with good high pH stability•Good combination partner for BIT•Regulatory approvalsProtectol DZ•Broad spectrum control. Use in e.g. starch based systems and paper additivesSpecialist formulators of preservatives for industry:•Clariant•Schülke & Mayr•Thor•ISP•Arch (now Lonza)•DowSingle actives are frequently combined because of their unique advantages A formulation(blend) can be used to obtain optimal antimicrobial protection e.g. broad spectrum activity, long term stability, low toleranceBIT -good fungicide, but gaps in antibacterial activityBronopol -excellent bactericide, but poor fungicideBIT/Bronopol formulation -excellent broad spectrum activityMetalworking Fluids80% Mineral Oil8% Emulsifiers8% Corrosion Inhibitors 3% Biocide/Fungicide 1% AntifoamArch (now Lonza) Arch (now Lonza)Arch (now Lonza)Broad spectrum antimicrobial performanceWidely accepted (in Europe)Cost effective alternative to formaldehyde release technologiesCompatible with other active ingredients and raw materialsEasy to use, readily incorporated into a variety of formulation typesExcellent solvent properties and coalescing abilitiesBiodegradableNon-irritating and non-sensitising at in-use levelUse in concentrate at typically 10%–Concentration typically around 1% in final fluid–Use in conjunction with fungicide and optionally further bactericideOil & Gas ExplorationStimulate production of oil from reservoir Prevent contamination of oil reservoirS formation (oil souring)Packing fluidOil & Gas Production Products and CompetitorsApplication Injection and Production Product Glutaraldehyde Glutaraldehyde THPS Quats Muds and Fluids Preservation Bronopol Bronopol DBNPA Glutaraldehyde Glutaraldehyde Various formaldehyde releasers Protectol BN Bioban Dow Antimicrobial Protectol GA 50 Ucarcide Brand Protectol GA 50 Ucarcide Tolcide Supplier BASF Dow Rhodia Akzo, Rhodia, Lonza BASF Dow Dow BASF DowJanuary 16th 2012CONFIDENTIAL / INTERN31Oil & Gas Production BASF ProductsProtectol GA50 (some Protectol GA24) • Fast acting, broad spectrum biocide • Disinfects and preserves • Cost effective vs. THPS • Safe to handle with appropriate procedures • Good environmental profile (e.g. biodegradable) Protectol BN • Long lasting preservative bactericide • Cost effective vs. DBNPA • Good tox profile • Easy to handleJanuary 16th 2012CONFIDENTIAL / INTERN32Pulp & PaperJanuary 16th 2012INTERN33Pulp and Paper Biocide use in Pulp and PaperApplication Areas for Paper Industry Biocides - Slimicides – prevention of slime build-up in process - Mineral Slurries – preservation of slurriesJanuary 16th 2012CONFIDENTIAL / INTERN34Pulp and Paper No/Wrong Biocide use in Pulp and Paper…Loss of production Reduction in quality Microbiological corrosion Loss of additives Gas production Off spec and rejected PaperJanuary 16th 2012Unscheduled breakage Slime spots, holes, odour Damage to metals, stainless steel Reduce additive effect, plug lines H2, H2S or methane creating the potential for explosions Cost of re-working & loss of product / customersCONFIDENTIAL / INTERN35Pulp and Paper Papermaking ProcessBiocidesBiocides BiocidesJanuary 16th 2012CONFIDENTIAL / INTERN36Pulp and Paper Products and CompetitorsApplication Slimicides Product Glutaraldehyde Glutaraldehyde Isothiazolinones Isothiazolinones DBNPA Bronopol Dazomet MBT Mineral Slurry Preservation Isothiazolinones Isothiazolinone Bronopol Various formaldehyde releasers Brand Protectol GA 50 Piror Kathon Acticide Dowicil Protectol BN Protectol DZ Busan Kathon Proxel Protectol BN Preventol Bodoxin Supplier BASF Dow Dow Thor Dow BASF BASF Buckman Dow Arch (now Lonza) BASF Lanxess BodeJanuary 16th 2012CONFIDENTIAL / INTERN37Pulp and Paper BASF ProductsPaper slimicide use is a core application for BN and GAProtectol BN / Myacide AS/S • Highly effective against Pseudomonas types (BIT shows resistance) • Good efficacy against slime forming bacteria (vs. competitive products) • Cost effectiveness vs. competitor products (DBNPA, Isothiazolinone etc.) • Very effective in combination with isothiazolinones • Regulatory approvals Protectol GA50 / Myacide GA • “Quick kill” biocide • Broad efficacy spectrum • Cost effectiveness / efficacy vs. competitor products (THPS, Peracetic acid) • Regulatory approvalsJanuary 16th 2012CONFIDENTIAL / INTERN38Pulp and Paper BASF ProductsProtectol DZ The most important benefits are its rapid speed of kill and broad spectrum of activity. Paper Mill Process Water Protectol DZ is very active at low doses within the paper industry. For use as a slimicide it should be dosed at 50g to 150g per tonne of finished paper. Bulk Pulp As a preservative for bulk pulp and paper mill auxilliaries (e.g. mineral slurries) 100500ppm Protectol DZ is recommended.January 16th 2012CONFIDENTIAL / INTERN39Plastic and Textile MaterialsJanuary 16th 2012INTERN40Synthetic (plastic) surfaces are often an ideal support for microbial growth supported by appropriate environmentalconditions (humidity, temperature, nutrients)Microbial growth can lead to●hygiene problems (microbial contaminations →infections)●staining, discoloration, odor●material destruction, loss of physical propertiesAntimicrobial technologies mainly based on built-in additives with a more or less adjustable release behaviour (antibacterial ones are often silver-based as for example IRGAGUARD®fromBASF)IRGAGUARD®-Antimicrobial solutions based on inorganic Silver-Technology-Training Biocides / Formulation Technologies -Jürgen Wiethan, E-EMD/DF, January2012Appearance of Irgaguard®White to off-white powder MasterbatchSilver-Zinc Zeolite Silver-Zinc GlassB 5000silver-zinc zeoliteB 512020% masterbatch of B 5000 in LDPEB 6000silver-glass / zinc-zeoliteB 7000silver-zinc-glassB 762020% masterbatch of B 7000 in PETCGX 51-505silver-glass#EB 50-98020% masterbatch of CGX 51-505 in PET# # preliminary product status (not listed yet)* continuously enhanced and expandedMultiple kill mechanismInactivation of enzymesgroups)Direct binding to DNS (inhibition of replication)Damage of cell structure and cell membranelow risk of microbial resistanceEfficacy: BacteriaGram positive Bact.Suitability for transparent applicationsnoyesyesnoEFSASML(0,05mg/kg)SML(0,05mg/kg)* PT 2 ~ disinfection, PT 7 ~ film protection, PT 9 ~ fibers & polymers (BPD-Evaluation process still under examination)Recommendation of use as active substance*•0.3% –1,5% IRGAGUARD B 5000/7000•0.2% –1,2% IRGAGUARD B 6000•0.3% –1,5% CGX 51-505Recommendation of use as masterbatch*• 1.5% –7.5% IRGAGUARD B 5120 (20% MB of B5000 in LDPE)• 1.5% –7.5% IRGAGUARD B 7620 (20% MB of B7000 in PET)• 1.5% –7.5% EB 50-980(20% MB of CGX 51-505 in PET)* depending on polymer type and additives, target application, target organisms etc.。