**5. Biocides approved by the EU for use in the textile industry**

Biocides which can be used in the textile industry belong to biocidal compounds category II and to group 9 on the list of biocidal compounds (under Directive 98/8/EC), and include 134 active substances. The active substances in category II which can be used in the textile industry belong to eight groups of chemical compounds: inorganic compounds, compounds of nitrogen, phenol and their derivatives, compounds of halogens and their derivatives, oxidizing compounds, alcohols, aldehydes, organic acids and their derivatives (Table 2).

Mechanisms of action on microorganisms depend on the type of compound, and often take multiple routes. Biocides cause disturbance of the functioning of the cytoplasmic membrane and cell wall, inactivation of proteins, slowing of DNA synthesis, and many other types of damage to the cells of microorganisms (Brycki, 2003).

Examples of commercial preparations containing the listed chemical compounds, which are currently used frequently in the textile industry, are listed in Table 3. On the international market many firms also offer ready-made fibres with antimicrobial properties, containing biologically active substances – examples of these are given in Table 4.

However, the mass use of chemical preparations and ready-made fibres containing biologically active substances lead to an increase in microorganisms' resistance to biocides. There are also increased requirements in terms of high effectiveness against a wide spectrum of microorganisms. For this reason new solutions are constantly being sought – new compounds or mixtures of compounds, and methods for stabilizing them and applying them to fabrics. The development of new technologies related to the production of fibres with antimicrobial action has proceeded particularly rapidly in the last decade. An overview of selected research into production and antimicrobial activity of natural and artificial fibres containing biocides is presented in Table 5. Extensive data concerning polymeric materials can be found in the survey paper by Munoz -Bonilla and Fernandez- Garcia (2011).

Among the biocides used in both natural and artificial fibres, there is a high level of interest in quaternary ammonium salts and phosphonium salts. The role of biological agent is played by the fibre additive chitosan, as well as antibiotics tetracycline, cephalosporin, vinyloimidazol, ciprofloxacin, and antifungal clotrimazol, ketokonazol. There has recently also been great interest in inorganic nanoparticles as agents with antimicrobial properties.

Effective at low concentration Doesn't change the properties of

Degradable after use

**Biocide** 

Stable Cheap

There are few active compounds that meet all of these requirements, and therefore work is

Biocides which can be used in the textile industry belong to biocidal compounds category II and to group 9 on the list of biocidal compounds (under Directive 98/8/EC), and include 134 active substances. The active substances in category II which can be used in the textile industry belong to eight groups of chemical compounds: inorganic compounds, compounds of nitrogen, phenol and their derivatives, compounds of halogens and their derivatives, oxidizing compounds, alcohols, aldehydes, organic acids and their derivatives (Table 2).

Mechanisms of action on microorganisms depend on the type of compound, and often take multiple routes. Biocides cause disturbance of the functioning of the cytoplasmic membrane and cell wall, inactivation of proteins, slowing of DNA synthesis, and many other types of

Examples of commercial preparations containing the listed chemical compounds, which are currently used frequently in the textile industry, are listed in Table 3. On the international market many firms also offer ready-made fibres with antimicrobial properties, containing

However, the mass use of chemical preparations and ready-made fibres containing biologically active substances lead to an increase in microorganisms' resistance to biocides. There are also increased requirements in terms of high effectiveness against a wide spectrum of microorganisms. For this reason new solutions are constantly being sought – new compounds or mixtures of compounds, and methods for stabilizing them and applying them to fabrics. The development of new technologies related to the production of fibres with antimicrobial action has proceeded particularly rapidly in the last decade. An overview of selected research into production and antimicrobial activity of natural and artificial fibres containing biocides is presented in Table 5. Extensive data concerning polymeric materials

can be found in the survey paper by Munoz -Bonilla and Fernandez- Garcia (2011).

Among the biocides used in both natural and artificial fibres, there is a high level of interest in quaternary ammonium salts and phosphonium salts. The role of biological agent is played by the fibre additive chitosan, as well as antibiotics tetracycline, cephalosporin, vinyloimidazol, ciprofloxacin, and antifungal clotrimazol, ketokonazol. There has recently also been great interest in inorganic nanoparticles as agents with antimicrobial properties.

still being done to find substances for use in fabrics with the desired properties.

**5. Biocides approved by the EU for use in the textile industry** 

biologically active substances – examples of these are given in Table 4.

Fig 1. Features of good biocide for nonwovens

Safe for people,

damage to the cells of microorganisms (Brycki, 2003).

The obtaining of nanoparticles of metals or nanostructured fibres has, thanks to the increase in surface area, led to the achievement of new characteristics desirable in the textile industry, and significantly greater effectiveness in destroying microorganisms. High activity have: TiO2 nanoparticles, metallic and non metallic TiO2 nanocomposites, titania nanotubes (TNTs), silver nanoparticles, silver-based nanostructured materiale, gold nanoparticles, zinc oxide nanoparticles and nano-rods, copper nanoparticles, metallic and inorganic dendrimers nanocomposite, nanocapsules cyclodextrins containing nanoparticles. New methods of obtaining such fibres with the addition of nanoparticles are constantly being developed, and the stabilization of nanoparticles on the surface of fibres is also of great importance (Dastjerdii et al., 2009; Dastjerdi & Montazer, 2010, Silver, 2003).

One of the conditions which a biocide is required to satisfy is its safety, and therefore much attention is currently being paid to substances of natural origin which are not toxic or allergic and are easily biodegradable. Some natural dyes and substances extracted from plant seeds and fruit contain active substances which slow the development of microorganisms and can be used to produce biologically active fabrics (Table 6).


Microbial Degradation of Woven Fabrics and Protection Against Biodegradation 277

2-hydroxy-biphenyl

antifungal activity

antibacterial activity

Tiobendazol

Tolcide C30 2'-(thiocyanomethylthio) benzothiazole Table 3. Chemical preparations with antimicrobial activity used in the textile industry

**Bioactive nonwovens/ producer Antimicrobial properties of nonwovens** 

Fibra K/ Asach Chemical Ind.Co (Japan) viscose silk with colloidal sulfur with

Rhovyl' AS/ Rhovyl (France) PVC with antibacterial activity Table 4. Nonwovens with antimicrobial activity (available on the global market)

Quaternary ammonium salts

Quaternary ammonium salts

2,2 '-dihydroxy-5, 5'-dichloro-diphenylmethane

natural origin fibers such as cotton with antibacterial and antifungal activity

polyacrylic fibers with antibacterial and

polypropylene with antibacterial activity

polyamide with antibacterial activity

polyester with antibacterial activity

**Antimicrobial activity Author, year** 

Jantas & Górna, 2006;Kanazawa et al., 1994; Kim et al., 2010

Kenawy et al., 2002;

Kenawy & Mahmoud, 2003; Nurdin et al., 1993

active against *Staphylococcus aureus, Escherichia coli*

active against *S.aureus, E.coli, Pseudomonas aeruginosa, Bacillus subtilis, B.cereus, Shigella* sp.*, Salmonella typhi,* 

**Chemical preparations (trade name) The active substances**  Nuodex zinc naphtenate Zinc naphthenate Nuodex copper naphtenate Copper naphtenate

Preventol GD Preventol O extra Preventol R80 & R50

Sanitized BSC Sanitized DET 8530

Co. (Japan)

(Germany),

Polyurethane, Polyglicidyl methacrylate

Acords (England)

(based on: McCarthy, 1995; Evans, 1996)

Navaron/ Taogoesei Chemical Industry

Amicor AB, Amocor AF, Amicor Plus /

Gymlene/F.Drake Fibres (England), Microban/ Filament Fiber (USA)

Rhodia/ Rhodia Technical Fibres

Livefresh/ Kanebo (Japan)

 Bacterkiller/ Kanebo (Japan), Kuraray/ Kuraray (Japan) ,

Trevira Bioactive / Trevira (Germany)

**Nonvowens Antimicrobial** 

Cotton phosphonium salts

**agents** 

alginatequaternary ammonium complex

quaternary ammonium salts with aliphatic triisocyanate, phosphonium salts

with alkyl chains; chloroacetyl chloride,

naphtylacetic acid,

Huvis Corp. (Korea),


Table 2. Biocides used in protection of nonwovens and their antimicrobial activity (based on: Brycki, 2003)


**Mechanisms of antimicrobial** 

intracellular components from cell

the low molecular masses

Transformation of sulfhydryl groups to di sulfide bridges in protein - protein deactivation

Inhibition of DNA replication, denaturation of proteins

Inhibition of DNA replication, denaturation of proteins (by joining the amino groups), dysfunction of cytoplasmic membrane and cell wall, outflow of the low molecular masses intracellular components

Inhibition of DNA replication, denaturation of proteins, damage and dysfunction of cytoplasmic membrane and cell wall, outflow of

the low molecular masses

intracellular components from cell

**activity** 

from cell

bacteria membrane and cell wall, outflow of

**activity** 

gram positive, gram negative bacteria, viruses

gram positive, gram negative bacteria

gram positive (including *Mycobacterium tuberculosis,* and bacterial spores), gram negative bacteria, viruses,

gram positive, gram negative bacteria

Table 2. Biocides used in protection of nonwovens and their antimicrobial activity (based on:

Actifresh RT-87-11 Alkaline mixture of halogenated organic compounds

Biocide PB 940 2,2 '-dihydroxy-5 ,5-dichloro-diphenyl-monosulfide

**Chemical preparations (trade name) The active substances**  Afrotin ZNK 10 & ZNL Zinc pyridinate

Armesan A Phenyloxy-chloro-phenol

Esterol 100 CD; Mystox LPL Pentachlorophenol laurate

Kathon LM 2-octyl-4-isotiazolino-3-one Metanit 55-61 Carbendazim + diuron

Densil P Dithio-2, 2'-biobenzomethylamide

Fungitex ROP Dichlorophen Bis (chlorohydroxyphenyl) methane GivGard DXN 6-acetoxy-2 ,4-dimethyl-1 ,3-dioxane

Myacide 2-bromo-2-nitropropane-1 ,3-diol Myacide SP 2,4-dichloro-benzyl alcohol

Cuniculate 2419-75;Mystox 8 8- copper quinolinate

**The active substances Antimicrobial** 

and calcium hypochloride, sodium chlorate, chlorine dioxide; organic: chloroarylamides, halohydantoin,

peracetic acid, , peroxyoctanoic acid, hydrogen peroxide, 2-

propan-2-ol, 2-phenoxyethanol,

chloroisocyanuric acid

**Oxidizing compounds** 

benzyloxymethanol, 2,4 dichlorobenzyl alcohol-

formaldehyde, dialdehydes glyoxal, glutaraldehyde, orthophthalic aldehyde

**Organic acids and their** 

aliphatic: carboxylic acids: formic, glycolic, lactic, nonanoic; aromatic acids: benzoic, salicylic karbaminic

butanone peroxide

**Alcohols** 

**Aldehydes** 

**compounds** 

Brycki, 2003)


Table 3. Chemical preparations with antimicrobial activity used in the textile industry (based on: McCarthy, 1995; Evans, 1996)


Table 4. Nonwovens with antimicrobial activity (available on the global market)


Microbial Degradation of Woven Fabrics and Protection Against Biodegradation 279

active against *E.coli,* depended on the structure and content of pyridinium groups, not bactericidal, but

active against *S.aureus, E.coli, K.pneumoniae*

*E.coli, P.aeruginosa*

*T.mentagrophytes* 

*A.niger*

*C.tropicalis*

*S.aureus,* 

*vulgaris,* 

active against *C.albicans, Penicillium funiculosum, P.mycetomagenum, Aspergillus niger, A.repens* 

> active against *E.coli, K.pneumoniae, C.albicans,*

active against *E.coli, S.aureus, C.albicans,* 

active against *E.coli, B.subtilis, K.pneumoniae,* 

active against *E.coli,* 

active against *E.coli, K.pneumoniae, Proteus* 

*Proteus vulgaris, P.aeruginosa*

bacteriostatic

*E.coli,*

triclosan active against *S.aureus, E.coli*

cephalosporin active against *S.aureus,* 

Table 5. Nonwovens with antimicrobial agents (based on the scientific researches)

**Nonvowens Antimicrobial agents Antimicrobial activity Author, year**

**Antimicrobial activity Author, year** 

Tan et al., 2000

Ren et al., 2009

Goetzendorf-Grabowska et al.,

Gupta et al., 2007,

Bucheńska et al., 2003

Prusty et al.,

Khan et al., 2011

Singh et al., 2005

Han & Yang,

Gupta et al.,

2005

2004

2010

Struszczyk et al.,

2004

2008

2003

**Nonvowens Antimicrobial** 

Polypropylene , polypropylene with

Poly(L,L-lactide) on

Polypropylene, polyacrylonitryle

Poly(ethylene terephtalate)

Polyamide, polypropylene, polyester

cotton

viscose

**agents** 

4-vinyl pyridine, radiation-induced

Cotton N-halamine active against *S.aureus,* 

tetracycline hydrochloride, vinyloimidazol, ciprofloxacin

clotrimazol, ketokonazol

*citrifolia; Terminalia catappa, Artrocarpus heterophyllus, Tectona grandis* (contain of: flavonoids, quinonoids, indigoids, tannins)

*catechu* (main component

*lacca, Quercus infectoria, Rubia cordifolia, Rumex maritimus*

*lacca, Mallotus philippinensis, Punica granatum, Quercus infectoria, Terminalia chebula,* 

Silk Dyes from plants *Morinda* 

Wool Dyes Catechu from *Acacia* 

catechin)

Wool Dyes from *Acacia catechu, Kerria* 

Wool Dye curcumin from *Curcuma* 

*Rheum emodi* 

Cotton Dyes from *Acacia catechu, Kerria* 

*longa*


*Trichophyton rubrum, Candida albicans, Aspergillus flavus, Fusarium oxysporium*

polypropylene with glycidal methacrylate, βcyclodextrin, quaternary ammonium –chitosan complex active against *Lactobacillus plantarum*,

*S.aureus, E.coli;*  polypropylene with chitosan active against *S.aureus, E.coli, Proteus vulgaris,* not effective against: *Klebsiella pneumoniae, P.aeruginos;.*  polypropylene-cotton with chitosan active against *Fusarium oxysporum, Verticillium alboatrum, Alternaria alternata, Clavibacter michiganensis, Pseudomonas solantacearum*

Cotton chitosan active against *S.aureus* Lim & Hudson, 2004

*faecalis*

*E.coli,*

Nylon, silk nanosilver active against *S.aureus* Dubas et al.,2006

copper (CuO) active against *Staphylococcus epidermidis* 

*albicans*, *C.tropicalis*, *S.aureus, E.coli,* 

*K.pneumoniae, Streptococcus* 

active against *S.aureus,* 

active against *S.aureus, E.coli, P.eruginosa*

**Antimicrobial activity Author, year** 

Abdou et al., 2005; Kim et al., 2010

Gorensek & Recelj, 2007; Hipler et al., 2006; Sachinvala et

Montazer et al., 2011

Jain & Pradeep, 2005; Lala et al., 2007; Radetic et al., 2008, Yu et al., 2003

Abdou-Neel et al.,

2005

al., 2007

**Nonvowens Antimicrobial** 

Polypropylene, Polypropylene-

cotton

**agents** 

glycidal

chitosan,

methacrylate, βcyclodextrin, quaternary ammonium – chitosan complex,

Cotton silver, nanosilver active against *Candida* 

nanotitanium dioxide photoinduced

nanosilver, lidocaine, gold, zinc oxide nanotitanium dioxide

Wool silver and

Poliacrylonitryle, poli(N-vinylpyrrolidone), PVC, cellulose acetate, Poliester,

Polycaprolactone Polyurethane, Polipropylene

Phosphate glass

fiber


Table 5. Nonwovens with antimicrobial agents (based on the scientific researches)


Microbial Degradation of Woven Fabrics and Protection Against Biodegradation 281

\*needle-punched nonwoven; polypropylene-silver (in the form of master batches) + acrylic fiber-biocide

Microorganisms sensitive to the action of biocides are bacteria – Gram-positive cocci and Gram-negative bacilli. The most resistant organisms, with high survival rates, include sporeforming bacteria and moulds (Majchrzycka et al., 2010). This is because the activity of biocides added to fabrics is dependent on the physiological state of the microorganisms: the most sensitive are cells in a phase of vegetative growth, while resistance is shown by

**Organic contaminants** present on the fabric may reduce the biological effect. Proteins are substances that protect microorganisms, sugars and fats may be a source of food and lead to the development of microorganisms, and moreover those compounds may react with the biocides, reducing their effectiveness. Research into antimicrobial activity in the presence of artificial sweat (inorganic compounds) did not reveal any significant effect on the bioactivity

Increased **temperature** generally strengthens the antimicrobial activity of chemical agents, due to the increased reactivity of the active substances as well as synergy between the

Increased **humidity** strengthens the antimicrobial activity of fabrics containing biologically active substances. The presence of water makes it possible for the biocide to penetrate into the cells of microorganisms in the form of ions, and for these to act effectively. Hence fibres with **hydrophilic** properties containing biocides will be more effective than hydrophobic fibres containing the same active substances (Gutarowska et al., 2010). Comparative studies on the antimicrobial action of hydrophobic PAN fabrics containing quaternary ammonium salts and the same fabrics containing biocide on an inorganic medium – perlite – with hydrophilic properties showed a significant improvement in the biocidal effectiveness of hydrophilic fabrics with added perlite (Table 8). Bioactivity improved with increasing

*N* where *N*0—the number of microorganisms on the sample of the textile material for time *<sup>t</sup>*

**Mean SD** 

**Microorganisms Nt After 6 h of incubation** 

= 0, *N—*the number of microorganisms on the sample of the textile material for time *t*<sup>n</sup>

incubation with bioactive nonwoven\* (based on Majchrzycka et al., 2010)

endospore of bacteria and the spores of moulds (Gutarowska et al.,2010).

destructive effects of the substance and temperature (Brycki, 2003).

Table 7. Microorganisms Survival Index (Nt) for various microorganisms after 6 hours

SD – standard deviation

0

of fabrics (Majchrzycka et al., 2010).

Nt:

*t N*

*N*

*Escherichia coli* 0.000 0.000 *Pseudomonas aeruginosa* 0.001 0.000 *Klebsiella pneumoniae* 0.001 0.000 *Staphylococcus aureus* 0.000 0.000 *Micrococcus flavus* 0.000 0.000 *Bacillus subtilis* **0.550 0.348**  *Candida albicans* 0.000 0.000 *Aspergillus niger* **0.036 0.006**  *Penicillium chrysogenum* **0.004 0.001** 


Table 6. Nonwovens with natural origin antimicrobial agents (based on the scientific researches)
