81 Biocides for the Coatings Industry 81.1 Introduction 81-1 81.2 In-Can Preservatives 8-1 K. Winkowski 81.3. Dry-Film Preservatives. 81-2 SP Corp. References 81-3 81.1 Introduction Microorganisms are ubiquitous in the environment. Many of them have simple requirements for growth that can be met by most waterborne coatings. Adding an in-can preservative will protect these coatings inthe wet state during storage and transport. Altera coating has been applied and dried, most waterborne and solvent-borne coatings are susceptible to colonization by fungi or algae. The addition of a dey-film preservative (fungicide or algaecide) will ensure long-term performance of the coating 81.2 In-Can Preservatives Industrial water-based formulations usually require protection against microbial spoilage. Examples of such formulations include latexes, emulsions, paints, adhesives, caulks, and sealing mastics. Microbial contaminants can be introduced by water (process water, wash water), raw materials (latex, filles, pigments, ete), and poor plant hygiene. Bacteria are the most common spoilage organisms, but fungi and yeasts are sometimes responsible for product deterioration, Among the most common contaminants, are Aeromonas sp., Bacillus sp., Desulfovibrio sp., Escherchia sp. Enterobacter sp, and Pseudomonas sp Microbial growth is usually manifested as a loss in functionality and may indude gas formation, pH changes, offensive odor, and changes in viscosity and color." Spoilage of the water-based products, which can go unnoticed until the product reaches the consumer, can result in significant economic loss to the ‘manufacturer. Good plant hygiene and manufacturing practices, when combined with the use of a compatible broad spectrum biocide, will minimize the risk of microbial spoilage of the coating? In selecting an in-can preservative, cost effectiveness, compatibility, stability, handling, and eco-toxicity are important factors to take into account. Intrinsic properties ofthe coating, such as pH, viscosity, redox potential, and the presence of certain ingredients may also alfect the electiveness of biocides. The best way to determine the efficacy of a biocide in a specific formulation is by performing an in-can challenge test. While there are several methodologies available to evaluate the efficacy of in-can preservatives? they allinvolve testing of preserved and unpreserved samples ofthe test coating when challenged with a battery of microorganisms and then monitoring the samples for the presence of viable microorganisms and changes in the coating properties. Typical use levels for in-can preservatives are in the range of 0.05 to 05 weight percent.812 Coatings Technology Handbook, Third Edition TABLE SLI Examples of In-Can Preservatives ‘Active Ingredient Type Product Name Adamante Busan 1024, Dowell 75 Aldehyde Biocheck 80, Ucarcide 250, Nuosept 145, Nuosept 210 Amide Biochek 20 Amino acid adducts Nuowepe Hiloatane “Tekeamer 38 AD ydantoin derivative Biockeck 240, Dantogard,Toysan 395 Isathiazlinone Actcde RS, Busan 1174, Kathon LX, Mergal KIA, Nuosept 495, armel D22, Proxel GXL Oxazlidine Bohan CS 1135, Canguad 327, Nuosept 9, Thoysan 192 Chlorinated phenol Preventol CMK Tiazine Boban GK, Congard 454, Vancide TH Blends of actives Actcides,Prosls, Mergals,Nuosepts, Rocmas et ‘A wide range of in-can preservatives are available. They are usually added as eatly as possible in the production process and include adamants, aldehydes, amides, amino acid adducts, halogenated alkanes, imidazolinones, sothiazolones, oxazolidines, phenolics, and triazines. Table 81.1 shows alist of typical produets 81.3 Dry-Film Preservatives Both water-based and solvent-based coatings are susceptible to the colonization of fungi and algae upon drying, The type of microorganisms that can colonize the coating will depend on several factors, including, the moisture content of the susface, the presence of nutrients, the substrate, and the type of coating.‘** For example, the moisture content of the surface is affected by factors such as climatic conditions (amount of rainfall, dew, humidity, temperature, and time ofthe year) as well as local conditions surfaces sheltered. from winds and shaded areas will contain higher moisture content). The presence of nutrients may include constituents of the coating (such as polymers, thickener residues, etc), biodegraded substances produced by other microorganisms (eg., complex substrates may be attacked by a succession of micto- organisms), or simply material deposited on the coating from the atmosphere, such as dirt. The substrate is also of importance. It provides, for example, a suitable pH environment. In this regard, fungi favor ‘more acidic conditions, such as those provided by wood. Algae, on the other hand, favor more alkaline conditions, such as those provided by masonry. Last, the type and properties of the coating (water repellency, hardness, chalking, and roughness) will also play an important role in determining which type of microorganism could colonize the coating, ‘On exterior surfaces, Aureobasidivm pullulans and Alternaria sp. are common fungal isolates. In general, fungi found on exterior surfaces are able to withstand high temperatures and dry conditions, are tolerant to UV exposure, and can adhere well to surfaces.” On interior surfaces, the fungi Aspergillus sp. and Penicillium sp. are frequently isolated. Algae are mainly isolated from exterior surfaces. Green. algae species (Chlorella sp. or Stchococeus sp.) are usually isolated in temperate regions. Trentepohlia sp. (which can be orange or green in color) is very common in tropical regions. Blue-green algae ( Gloeocapsa sp. Nostoc sp.) have been isolated from various regions. Several blue-green algae (Calothri-sp. Sytonema sp.) are black in color and are, thus, easily mistaken for fungal discoloration, ‘The geowth of microorganisms on coatings, also known as defacement, not only affects the appearance of the coating (discoloration), but it may also compromise its performance (biodeterioration). Fungi can penetrate coatings, resulting in cracking, blistering, and hampering the coatings’ adhesion properties, thus leading to decay or corrosion of the underlying substrate. Algae colonies, which seem to grow more rapidly on porous substrates such as stucco, cement, and bricks, may be able to hold water. The freezing and thawing of this entrapped water may induce cracking or may increase the permeation properties ofBiocides for the Coatings Industry 813 TABLE 81.2 Examples of Dry-Fil Biocides Active Ingesent Product Name ‘encimidazte ‘Maal BM, Prevntol BCM, Metsol TK100 CCaybamic aid derivatives Fungitel 420, Polyphase PUT, Omacide IPBC. 20 Chorothaonit ‘Aatcide C98, Busan 1192, Nuocide 960, [wothiazalinone ‘Acticide 45, Skane MB, Rezone 2000 Dyridine N-oxide derivatives Zinc Omadine ‘Thiszole Busan 1030, Preventol CR ‘Thiophialimide FFangivol 11, Prevent AS, Vanide 89 Traine algaccdes) __Irarol 1071, Nuocde 107 lends of actives Actcides, Megas, Nuocides,Polyphass, et the coating, leading to failure. Also, the presence of water may encourage colonization by other micro: organisms, which, in turn, may cause biodeterioration.” "There ate several dry-film fungicides and algaecides in the market. Dry: film fungicides should be UV stable and resistant to leaching. Typical use levels for dry-film biocides are in the range of 0.5 to 2.0 percent by weight. As with the in-can preservatives, performance and compatibility with a specific coating formulation should be tested. Accelerated laboratory tests are usually recommended to test outdoor coatings.# These tests involve coating an inert surface that is then inoculated with various fungal or algae species. The surface is then rated periodically, and the percent of surface covered by microbial growth is rated. Long-term outdoor exposute studies on test fence can also be conducted.” For interior coatings, the Envizonmental Chamber test is recommended, ‘The most common fungicide active ingredients in the market include benzimidazoles, carbamic acid derivatives (eg., PBC), chlorothaloni,isothiazolones (eg, OTT), pyridines-N-oxide derivatives, thiaz oles, and thiophthalamides (eg, fopet). The most common algaecides include S-triazines and urea derivatives (eg., Diuron). Table 81.2 shows a lst of typical products including several available blends. References 1. J.Gillat, JOCCA, 10, 387-392 (1992), 2. K. Winkowshi, PCT, 7, 60-66 (2002). 3. K.Winkowski, ECY, 1-2, 85-91 (2001), 4. S. Bussjaeger, G. Daisey, R. Simmons, S. Spindel, 8. Williams, J. Coat. Technol, 71, 67-69 (1999) 5. JA. Dupont, Mod. Paint and Coat, 11, 38-48 (1978) 6. 1.C. Wright, Biadeteriration, VI, 637-643 (1986). 7 8 9. 0. 1 R.A. Zabel and F. Terracina, JCT, 4, 42-46 (1978). ASTM D5590-94, Annual Book of ASTM Standards, 06.01, pp. 608-611. ASTM D5589-97, Annual Book of ASTM Standards, 06.01, pp. 604-607, ASTM D3436-86, Annual Book of ASTM Standards, 06.01, pp. 362-364, ASTM D3273-86, Annual Book of ASTM Standards, 06.01, pp. 474-476.