16.09.2008

Intern

Industrial BiocidesYour choice for Product Preservation

Q Edition 2009

Your Choice for Product Preservation

Content

Introduction Microbial Contamination Applications In-Can Preservation Product Overview In-Can Biocides Dry-film Preservation Product Overview Dry-film Biocides Product Overview Antimicrobial Development & Technical Support Shipping and Storage

Welcome to Clariant Clariant is a global leader in the production of fine and specialty chemicals with about 18,000 employees and an-nual sales of more than CHF 7 billion. It is domiciled and headquartered in Muttenz near Basel, Switzerland, and operates worldwide on 5 continents. The products and services are based on specialty chemicals which play a deci-sive role in clients manufacturing processes and upgrade their end products. Our employees recognize the chal-lenges that customers face, tailor the products to their exact specifications, and collaborate with them to come up with effective solutions. As part of Clariant`s acquisition of BTP in 2000, the activities of Nipa Laboratories were integrated into the BU Industrial and Consumer Specialities. Under the brand names Nipacide and JMAC Clariant offers a broad range of different actives and blends to solve nearly every microbial challenge a customer can imagine.

Madras(Chennai) India

Pontypridd, UK

SouzanoBrazil

Mt. Holly USA

+ several small production locations in LATAM, ASIA and Australia

Zhenjiang China

Introduction In order to meet the increasing demands for environmentally compatible products, organic solvents in formulations are more and more replaced by water-based systems. But the change from an organic solvent to water also brings the problem of microbial contamination. Irrespective of the type of aqueous substance, spoilage occur in closed containers or the outer surface of material. This can even result in the destruction of the top coating and render it useless for the intended purpose. For both economic and hygienic reasons the growth of microbes should be prevented by adding highly effective preservatives. The right choice of a suitable preservative depends on the nature of the suspected contamination (bacteria, fungi, yeast, algae), on the physico-chemical compatibility, on the eco-toxicological demand and on the desired storage condition of the final product. The aim of this brochure is to give you an overview of preservatives suitable for in-can preservation, dry-film pro-tection and antimicrobial systems as well as different applications, starting from paint formulations up to the area of construction blends. Afterwards, our technical team will be at your disposal to support you in choosing the ideal preservative for your application. Microbial Contamination Microorganisms

Since microorganisms occur everywhere, their destructive activity is basically unavoidable. The microbial growth in paint causes gassing, discoloration, liquefaction, emulsion breakdown, pH variation and odor inside the container. It can also result in surface disfigurement of the coating after it is applied on the wall. Microbial spoilage could also be the reason for undesired gelling and thinning. When polymer emulsions are spoiled, poor adhesion, odors, gassing and visual contamination of the dispersion due to microbial attack is seen. Thus microbial contamination has many adverse affects on product quality. This invariably leads to product failure, product recall and also has potential human health issues. Thus in order to achieve a specific shelf life it is often a requirement to ensure that raw materials and finished goods are free of microbial contamination. Bacteria

Bacteria are a large group of unicellular microorganisms, typically a few micrometres in length, which have a wide variety of shapes, ranging from spheres to rods and spirals. There are typically 40 million bacterial cells in a gram of soil and a million bacterial cells in a millilitre of fresh water; in all, there are approximately five nonillion (51030) bacteria on earth, forming much of the world's biomass. The bacterial cell is surrounded by a lipid membrane, or cell membrane, which encloses the contents of the cell and acts as a barrier to hold nutrients, proteins and other essential components of the cytoplasm within the cell.

Fungi (Moulds / Yeast)

Moulds include all species of microscopic fungi that grow in the form of multicellular filaments, called hyphae. In contrast, microscopic fungi that grow as single cells are called yeasts. Like all fungi, moulds derive energy not through photosynthesis but from the organic matter inside of which they live. Moulds reproduce through small spores. Some species of yeast are opportunistic pathogens, where they can cause infection in people with compromised immune systems. Algae

Algae are a large and diverse group of simple, typically autotrophic organisms, ranging from unicellular to multicellular forms. They are photosynthetic like plants, and "simple" because they lack distinct organs found in land plants. Algae are most prominent in bodies of water, but are also common in terrestrial environments.

Applications Paints & Coatings

An inadequate preservation of paints and surface coatings will lead to visual contamination. In-can bacterial con-tamination can lead to undesired liquefaction, odours, gassing and discoloration. At this stage the paint is generally beyond recovery. To avoid this, the addition of preserving biocides is absolutely necessary. Facades are usually made of mineral materials such as stucco and gypsum, as well as wood materials which favor the growth of micro-organisms. Once a painted surface is colonized by micro-organisms, the integrity of the paint is compromised, and it may result in undesirable color changes and loss of adhesion. Then substrates are vulnerable and breakdowns may result. Therefore surface coatings like exterior paints or interior paints for special applications such as bathrooms or kitchens require dry film protection. The choice of the correct biocide is depending on pH of the formulation as well as if it has to fulfill regulatory ap-provals like VOC contribution or Ecolabels. Our broad range of biocide products will help you to protect your individual formulation. Polymer Emulsions

The selection of a biocide for polymer emulsions depends on specific demands such as pH stability, thermal treatment, indirect food approvals and in particular the presence of specific Redox systems. Polymer emulsions based on styrene acrylates or SBR latex often have a high pH and therefore can reduce the per-formance of biocides containing e.g. CMIT / MIT. Hence BIT based systems are often the preservative of choice, like Nipacide BIT 10 W or Nipacide BIT AS 20. Strong reducing and oxidizing agents as initiators and post treatments to reduce free monomers may deactivate certain biocide types. It should be considered that BIT is sensitive to oxidizing agents and CMIT/MIT to reducing agents.

Construction Chemicals

Due to the variety of different chemical based systems used in the construction industry the selection of the appro-priate preservation system has to be evaluated. This depends on e.g. the plasticizer basis like ligninsulphonates, polynaphthalenesulphonates or polycarboxylates and the pH value. For systems with pH >9 and / or containing amines CMIT/MIT based products can not be used. Therefore we recommend Nipacide TBXB or our Nipacide BIT range. Adhesives

Due to the wide range of chemical types used as components of adhesives an incompatible biocide is likely to be deactivating or bring about chemical changes affecting the adhesive properties and performance. For the selection of the biocide it is important to consider, beside the possible alkalinity, whether a proteinic adhe-sive (e.g. caseins or N.R. latex) or starch based adhesives have to be protected. Caseins can deactivate CMIT/MIT based biocides, therefore BIT based systems like Nipacide BIT 10 W or Nipacide BIT AS 20 are preferred to be used. For starch adhesives we recommend to use products from our Nipacide BIT range as well as Nipacide TBXB.

In-Can Preservation An inadequate preservative which does not suppress bacterial or fungal growth will lead to visual contamination. Clariant`s in-can biocides will help you to prevent microbial growth in your product in a wet state during manufac-turing, storage and transportation. The right choice of biocide is necessary to reduce the risk of loss of product properties, discoloration, pH reduction and gas formation. 1,2-Benzisothiazolin-3-one (BIT)

Benzisothiazolinone is well known as a broad effective molecule with excellent chemical and thermal stability and can be used in neutral and even in alkaline systems with pH >9 and for processes even above >60C where other biocide actives like CIT/MIT already show a re-duced performance. BIT is relatively stable against reducing agents but starts to degrade in the presence of strong oxidizing agents like hydrogen peroxide. The material is widely used be-cause it overcomes the stability problems seen with other isothiazolinones. Typical use levels are between 200-400 ppm of active ingredient. BIT is also effective in acid systems i.e. adhe-sives and polymer emulsions that are attacked by microorganisms.

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5-Chloro-2-methyl-isothiazolin-3-one and 2-Methyl-isothiazolin-3-one (CMIT / MIT)

Another major isothiazolinone often used for in-can preservation is the mixture of Chloro-methyl-isothiazolinone and Methylisothiazolinone. This economic mixture is effective against gram-positive and gram-negative bacteria, yeast and fungi. Even at low concentrations usual treat rates are below 15 ppm active ingredient. Particular note should be taken with use levels >15 ppm because of labelling restictions with R 43 (sensitizing) e.g. in the European Union.

Bronopol (BNPD)

2-Bromo-2-nitropropane-1,3-diol is a highly active non-oxidizing biocide used in aqueous systems. Its low mammalian toxicity (at in-use levels) and exceptional activity against bacteria (especially the troublesome Gram-negative species) make it a popular preservative in many industrial applications such as paints, polymer emulsions and as cooling water disinfection plants. Bronopol has a relatively high organically bound content of AOX-relevant bromine. Deactivation and hydrolysis starts at a pH value of 8, thus limiting its use in paint formulations that have a pH of 8-9. In addition Bronopol sometimes leads to discoloration.

OH OHBr

NO O

1,2-Dibromo-2,4-dicyanobutane (DBDCB)

N

Br

N

BrDBDCB can be used for preservation for a wide range of formulations such as paints, polymer emulsions and adhesives. It shows a very good efficacy against bacteria as well as for fungi and yeast. The use is recommended in a pH range 4-9. It can start to degrade above 40C. Formaldehyde releasers (O- / N- formals)

Formaldehyde releasers have a long history as biocide because they are very effective against a broad range of organisms. They are extremely cost efficient, effective against a wide variety of organism and relatively stable. In addition they are useful as headspace protection for in-can uses.

Dry-film preservation Surface coatings may require dry-film protection when applied as interior paint for wet rooms such as bathrooms or kitchens. For exterior paints this is necessary because of environmental conditions like high humidity and UV light. An inadequate preservative which does not suppress fungal or algal growth will lead to visual contamination of the surface coating. Clariant`s dry-film biocides will be capable withstanding those conditions and will give your prod-uct a long life. 3-Iodopropynylbutylcarbamate (IPBC)

IPBC has an excellent toxicity profile and is extremely efficacious against fungi. Therefore it is the most commonly used product for coating systems and wood preservation. IPBC has exceptional activity against the fungus Alternaria, which has been found to degrade polymeric coatings.

I O N

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Zinc-pyrithione

Zinc-pyrithione is effective against moulds, yeasts and algae. It is a very low water soluble active (avoids wash-out from exterior paints by rain) with a broad application range in paints, adhesives and sealants. It can be used in a pH range 4-8,5 but in alkaline media it starts to convert into the water soluble alkali salt.

N

S

ZnN

S

O

O

Carbendazim

N

N

H

NHCO2CH3

Carbendazim is widely used as fungicide in paints and sealants. It shows an activity against a variety of fungi and yeasts but is less effective against algae. For exterior applications it is often combined with an algicide to provide a broader spectrum. It is very low water soluble and shows very good pH stability (2-12) as well as thermal stability. Diuron

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NCO

NCH3

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HDiuron is a broad spectrum algicide with low water solubility and moderate pH stability (3-10) for the dry film preservation of exterior coatings. It does not have good fungicidal performance and therefore has to be combined with a fungicide active to provide a comprehensive protection in exterior applications. Octylisothiazolin-3-one (OIT)

Octylisothiazolinone is mainly used as fungicide for interior paints where fungicidal protection is needed such as bathrooms or kitchens and as co-fungicide. For exterior coatings it is recommended to formulate OIT with additional fungicide actives due to higher water solubility of OIT compared to other dry film actives which results in loss of performance when exposed to leaching with water. It can be used in formulations with a pH range of 2-10.

SN

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Antimicrobial preservation Silver Technology (JMAC)

Silver has been known for centuries for its antimicrobial properties with exceptional benefits of having very low toxic effects. Clariant offers a technology based on the inorganic composite of silver chloride on titanium dioxide, delivering a preservative active with truly beneficial properties. The active species are silver ions which interact with the micro-organisms resulting in a range of effects from growth inhibition and loss of infectivity to cell death. Because of its excellent thermal and pH stability JMAC biocides can be used for preservation for a wide range of industrial applications such as emulsions, paints, sealants and adhesives. They are recommended as antimicrobial agents for use in hygiene coatings, paper and board, textile or plastics.

JMAC biocides are easy and safe to handle and show a very low impact on the environment. They are very eco-nomic biocide because it is already effective at ppm dosages and the silver ions are released over a long period of time.

Product Overview In-Can Biocides

Product Overview In-Can Biocides Continued

Product Overview Dry-film Biocides

Product Overview Antimicrobial

Development and Technical Support At Clariant we are constantly reviewing ways in which we can improve our preservatives to ensure that we keep pace with our customers requirements. Let our technical experts find exactly your preservative. Clariant gives: Technical Service Development Support Microbiology Testing Hygiene Audit Regulatory Support At our global network of well-equipped technical service laboratories, our dedicated and experienced team supports the full product range with shelf-life stability test, along with wet-state (in-can) and dry film biocide efficacy stud-ies. Clariant offers microbiological services for chemical plants and products. A microbiological audit is necessary, for example, when a customer discovers germs in his products and is unable to establish which vat, pipe or raw mate-rial is the source of contamination.

Shipping and Storage Particularly note should be taken on storage conditions of biocide products provided in Technical Data Sheets (TDS) or Material Safety Data Sheets (MSDS). To ensure shelf life and performance of our products storage between 5C and 40C is recommended. Use biocides safely. Always read the label and product information before use.