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Antimicrobial finishes
Two different aspects of antimicrobial protection
INTRODUCTION

  • Two different aspects of antimicrobial
    protection provided by chemical finishes
    can be distinguished
  • The first is the protection of the
    textile user against
  • pathogenic or odour causing
    microorganisms (hygiene finishes).
  • The second aspect is the protection of
    the textile itself from damage caused by
  • mould, mildew or rot producing
    microorganisms.
INTRODUCTION

  • The growth of microorganisms on
    textiles can lead to
  • functional, hygienic and aesthetic
    difficulties (for example staining).
  • The most trouble-causing organisms are
    fungi and bacteria.
  • Under very moist conditions, algae can also
    grow on textiles but are troublesome only
    because
  • they act as nutrient sources for fungi and
  • bacteria.
INTRODUCTION

  • Fungi cause multiple problems to
    textiles including
  • discoloration, coloured stains, and fibre
    damage.
  • Bacteria are not as damaging to
    fibres, but can produce
     – some fibre damage,
     – unpleasant odours
     – and a slick, slimy feel.
  • Often, fungi and bacteria are both
    present on the fabric in a symbiotic
    relationship.
INTRODUCTION

 • Substances added to fibres, such as
   lubricants, antistats, natural-based
   auxiliaries (for example size, thickener
   and hand modifiers) and dirt provide
    – a food source for microorganisms.
 • Synthetic fibres are not totally immune to
   microorganisms, for example
    – polyurethane fibres and coatings can be damaged
 • Wool is more likely to suffer bacterial attack
   than cotton,
 • and cotton is more likely than wool to be
   attacked by fungi.
INTRODUCTION

• Antimicrobial finishes are particularly important for industrial
  fabrics that are exposed to weather.
• Fabrics used for awnings, screens, tents, tarpaulins, ropes,
  and the like, need protection from rotting and mildew.
• Home furnishings such as carpeting, shower curtains,
  mattress ticking and upholstery also frequently receive
  antimicrobial finishes.

• Fabrics and protective clothing used in areas where there
  might be danger of infection from pathogens can benefit from
  antimicrobial finishing. These include hospitals, nursing
  homes, schools, hotels, and crowded public areas.
INTRODUCTION

• Textiles in museums are often treated with
  antimicrobial finishes for
   – preservation reasons.
• Sized fabrics that are to be stored or shipped
  under conditions of high temperature (~ 40 °C
  or 100 ºF) and humidity
• require an antimicrobial finish to retard or
  prevent microbial growth fuelled by the
  presence of warp size.
• Textiles left wet between processing steps for
  an extended time often also need an
• antimicrobial treatment.
Properties of an effective antimicrobial finish


    • The growth rate of microbes can be
      astoundingly rapid.
    • The bacteria population, for
      example, will double every 20 to 30 min
      under ideal conditions (36–40 °C or 77–
      98 °F, pH 5–9).

    • At this rate, one single bacteria cell can
      increase to 1 048 576 cells in just 7
      hours.
    • Therefore, antimicrobial finishes must be
      quick acting to be effective.
Properties of an effective antimicrobial finish


    •   In addition to being fast acting, a number of other
        important criteria can be listed for antimicrobial
        finishes.
    •   The antimicrobial must kill or stop the growth of microbes
        and must maintain this property through multiple cleaning
        cycles or outdoor exposure.

    •   The antimicrobial must be safe for the manufacturer to apply
        and the consumer to wear.

    •   The finish must meet strict government regulations and have
        a minimal environmental impact.

    •   The antimicrobial finish must be easily applied at the textile
        mill, should be compatible with other finishing agents, have
        little if any adverse effects on other fabric properties
        including wear comfort, and should be of low cost.
Mechanisms of
antimicrobial finishes
two types based on the mode of attack on
microbes
Mechanisms of antimicrobial finishes


• a variety of chemical finishes have been used to
  produce textiles with demonstrable antimicrobial
  properties.

• These products can be divided into two types
  based on the mode of attack on microbes.
• One type consists of chemicals that can be
  considered to operate by a controlled-release
  mechanism.

• The second type of antimicrobial finish consists
  of molecules that are chemically bound to
  fibre surfaces.
controlled-release mechanism


• The antimicrobial is slowly released from a
  reservoir either on the fabric surface or in the
  interior of the fibre.
• This ‘leaching’ type of antimicrobial can be
  very effective against microbes on the fibre
  surface or in the surrounding environment.
• However, eventually the reservoir will be
  depleted and the finish will no longer be
  effective.
• In addition, the antimicrobial that is released to
  the environment may interfere with other
  desirable microbes, such as those present in
• waste treatment facilities.
Molecules that are chemically Antimicrobial finishes
bound to fibre surfaces


• These products can control only those microbes
  that are present on the fibre surface, not in the
  surrounding environment.
• ‘Bound’ antimicrobials, because of their
  attachment to the fibre, can potentially
          – be abraded away
          – or become deactivated
          – and lose long term durability.
Mechanisms of antimicrobial finishes


    • Antimicrobial finishes that control the
      growth and spread of microbes are
      moreproperly called biostats, i.e.
      bacteriostats, fungistats.

    • Products that actually kill microbes
      are biocides, i.e. bacteriocides,
      fungicides.

    • This distinction is important when
      dealing with governmental
      regulations, since biocides are strongly
      controlled.
Mechanisms of antimicrobial finishes

• The actual mechanisms by which antimicrobial finishes control
  microbial growth are extremely varied, ranging from
        • preventing cell reproduction,
        • Blocking of enzymes,
        • reaction with the cell membrane (for example with silver ions) to the
          destruction of the cell walls
        • and poisoning the cell from within.
•   An understanding of these mechanisms, although important for
    microbiologists, is not really a requirement for the textile
    chemist who applies and evaluates the effectiveness of
    antimicrobial finishes.
Chemistry of
antimicrobial finishes
Antimicrobials for controlled
release
Bound antimicrobials
Antimicrobials for controlled release


• Many antimicrobial products that were formerly
  used with textiles are now
• strictly regulated because of their toxicity and
  potential for environmental damage.Products
  such as
   – copper naphthenate,
   – copper-8-quinolinate,
   – and numerous organo mercury compounds fall into this
     category.
Antimicrobials for controlled release – Limited Use
materials


 Other materials that still have limited
  use in specialised areas include
 tributyl tin oxide (deleted in many
  countries, Fig. 15.1a),
 dichlorophene (Fig. 15.1b)
 and 3-iodo-propynyl-butyl carbamate
  (Fig. 15.1c).

 These products typically show a very
  broad spectrum of activity against
  bacteria and fungi, but suffer from
  application and durability problems
Antimicrobials for controlled release –
General Type
• Some more useful products of this same general
  type include
  1. benzimidazol derivatives,
  2. salicylanilides
  3. and alkylolamide salts of undecylenic acid (particularly
     effective against fungi).


• Application of these materials with resin
  precondensates can improve durability to
  laundering, but also deactivation by reaction with
  the resin may occur.
Antimicrobials for controlled release -
    Formaldehyde
•   A widely used biocide and preservation product is formaldehyde.
•   Solutions of formaldehyde in water, called formalin, were
    used for disinfection and conservation,
•   for example, of biological samples for display. Bound
    formaldehyde is
               – released in small amounts from common easy-care
                 and durable press finishes
•   Therefore these finishes include – at least until they are
    washed – a small antimicrobial side effect.
•   This can also be true for some quaternary compounds,
•   for example wet fastness improvers and softeners.
•   But for more effective requirements specific antimicrobial
    finishes are necessary.
Antimicrobials for controlled release-
TRICLOSAN
• One of the most widely used antimicrobial products today is
• 2,4,4'-trichloro-2'- hydroxydiphenyl ether, known more
  commonly as ‘triclosan’ (Fig. 15.1d).
• Triclosan finds extensive use in mouthwashes,
  toothpastes, liquid hand soaps, deodorant products,
  and the like.
• Although it is effective against most bacteria, it has poor
  antifungal properties.
• Triclosan is also important as a textile finish, but since its
  water solubility is very low, aqueous application requires
  use of dispersing agents and binders.
Antimicrobials for controlled release-Quaternary
Ammonium Salts


        • Quaternary ammonium salts have
          been found to be effective antibacterial
          agents
              • in cleaning products
              • and for disinfecting swimming pools
              • and hot tubs.


        • However, their high degree of water
          solubility limits their use as textile
          finishes.
Antimicrobials for controlled release-ORGONO
SILVER

• Research into controlled-release
  antimicrobials continues with
• organo-silver compounds and silver zeolites,
• which are promising candidates for textile finishes.
• Silver ions, for example, incorporated in glass
  ceramic, have
   – a very low toxicity profile
   – and excellent heat stability.
• These principles are also used for fibre
  modification, an alternative to the antimicrobial
  finishes with high permanence.
Antimicrobials for controlled release – FIBER
 MODIFICATION

• In recent years a variety of antimicrobial modified fibres have been
  developed,
   – including polyester,
   – nylon,
   – polypropylene
   – and acrylic types.
• An example of these fibre modifications is the incorporation of 0.5–2 %
  of organic nitro compounds (for example based on 5-nitrofurfural)
  before primary wet or dry spinning.
• Regenerated cellulosics can be modified with carboxylic or sulfonic acid
  groups,
    – followed by immersing in a solution of cationic antimicrobials which are then
    – fixed to the cellulose by salt bonds.
Antimicrobials for controlled release – MICRO-
ENCAPSULATION

     • A novel approach to the controlled
       release of antimicrobials is
     • micro-encapsulation.
     • These capsules are incorporated either in
       the fibre during
        – primary spinning
        – or in coatings on the fabric surface.
Chemistry of
antimicrobial finishes
Antimicrobials for controlled release

Bound antimicrobials
Bound antimicrobials

• Several antimicrobial finishes that function at fibre
  surfaces have been commercialised.
• One popular product is based on octa-decyl-
  amino-dimethyl-trimethoxy-silyl-propyl-
  ammonium chloride (Fig. 15.2a).
• This material can be applied by either exhaust or
  continuous methods.
Bound antimicrobials

• After application, a curing step is required to form
• a siloxane polymer coating on the fibre surface.

• This coating immobilises the
   – antimicrobial part of the molecule (the quaternary nitrogen)
   – and provides the necessary durability to laundering.
Bound antimicrobials

• Another bound finish has been developed with
• PHMB, poly-hexa-methylene biguanide (Fig.
  15.2b).
• PHMB can also be
   – either pad
   – or exhaust applied.
• This chemical has the proper molecular structure to
  bind tightly to fibre surfaces, yet still be an
  effective antimicrobial.
Bound antimicrobials

   • The antimicrobial effect of
   • cationically charged materials is
     thought to involve interaction of the
      – Cationic molecule with anionic phospholipids
        in the microbe’s cell walls.


   • This interaction is believed to increase
     the permeability of the cell walls to the
     point of cell death.
Bound antimicrobials


• A new and novel approach to bound antimicrobials
  was recently introduced.
• Cotton reacted with
• methylol-5,5-dimethyldyantoin
• is then treated with hypochlorite
• to form chloramines in the fibre (Fig. 15.3).
Bound antimicrobials

• These chloramine sites have antibacterial activity
• and can function as renewable antimicrobial agents by
• continued treatment with hypochlorite through household
  bleaching and washing after reacting with bacteria (Fig. 15.4).

 Problems with using higher
 concentrations of chloramines
 include
 yellowing with heat (for example
 ironing)

 and cellulose ibre damage
 especially significant strength loss,
 caused by oxy- and
 hydrocellulose
 (generated by hypochlorous acid
Bound antimicrobials -- CHITOSAN

•   Another novel approach is the
    application of chitosan.
•   This modified biopolymer
•   is manufactured from
    inexpensive natural waste.

•   Chitin from crustacean shells
    (e.g. from crabs) is converted
    to chitosan by alkaline
    treatment.

•   Chitin is an analogue of
    cellulose with N-acetyl groups
    instead of hydroxy groups in
    position 2 (Fig. 15.5).
Bound antimicrobials -- CHITOSAN
• Alkali splits most of them (75–95 %), generating free amino groups that
  provide
   – Fungistatic
   – and bacterostatic effects.
• This mild antimicrobial activity may be amplified
   – by methylation of the amino groups
   – to quaternary trimethylammonium structures.
• Chitosan can be applied by
   1. microencapsulation
   2. or by reactive bonding to cellulose
   3. and by crosslinking of chitosan.
• The advantages of the antimicrobial finish with chitosan include
   1. high absorbency properties,
   2. moisture control,
   3. promotion of wound healing,
   4. non-allergenic,
   5. non-toxic
   6. and biodegradable properties.
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Anti microbial

  • 1. Antimicrobial finishes Two different aspects of antimicrobial protection
  • 2. INTRODUCTION • Two different aspects of antimicrobial protection provided by chemical finishes can be distinguished • The first is the protection of the textile user against • pathogenic or odour causing microorganisms (hygiene finishes). • The second aspect is the protection of the textile itself from damage caused by • mould, mildew or rot producing microorganisms.
  • 3. INTRODUCTION • The growth of microorganisms on textiles can lead to • functional, hygienic and aesthetic difficulties (for example staining). • The most trouble-causing organisms are fungi and bacteria. • Under very moist conditions, algae can also grow on textiles but are troublesome only because • they act as nutrient sources for fungi and • bacteria.
  • 4. INTRODUCTION • Fungi cause multiple problems to textiles including • discoloration, coloured stains, and fibre damage. • Bacteria are not as damaging to fibres, but can produce – some fibre damage, – unpleasant odours – and a slick, slimy feel. • Often, fungi and bacteria are both present on the fabric in a symbiotic relationship.
  • 5. INTRODUCTION • Substances added to fibres, such as lubricants, antistats, natural-based auxiliaries (for example size, thickener and hand modifiers) and dirt provide – a food source for microorganisms. • Synthetic fibres are not totally immune to microorganisms, for example – polyurethane fibres and coatings can be damaged • Wool is more likely to suffer bacterial attack than cotton, • and cotton is more likely than wool to be attacked by fungi.
  • 6. INTRODUCTION • Antimicrobial finishes are particularly important for industrial fabrics that are exposed to weather. • Fabrics used for awnings, screens, tents, tarpaulins, ropes, and the like, need protection from rotting and mildew. • Home furnishings such as carpeting, shower curtains, mattress ticking and upholstery also frequently receive antimicrobial finishes. • Fabrics and protective clothing used in areas where there might be danger of infection from pathogens can benefit from antimicrobial finishing. These include hospitals, nursing homes, schools, hotels, and crowded public areas.
  • 7. INTRODUCTION • Textiles in museums are often treated with antimicrobial finishes for – preservation reasons. • Sized fabrics that are to be stored or shipped under conditions of high temperature (~ 40 °C or 100 ºF) and humidity • require an antimicrobial finish to retard or prevent microbial growth fuelled by the presence of warp size. • Textiles left wet between processing steps for an extended time often also need an • antimicrobial treatment.
  • 8. Properties of an effective antimicrobial finish • The growth rate of microbes can be astoundingly rapid. • The bacteria population, for example, will double every 20 to 30 min under ideal conditions (36–40 °C or 77– 98 °F, pH 5–9). • At this rate, one single bacteria cell can increase to 1 048 576 cells in just 7 hours. • Therefore, antimicrobial finishes must be quick acting to be effective.
  • 9. Properties of an effective antimicrobial finish • In addition to being fast acting, a number of other important criteria can be listed for antimicrobial finishes. • The antimicrobial must kill or stop the growth of microbes and must maintain this property through multiple cleaning cycles or outdoor exposure. • The antimicrobial must be safe for the manufacturer to apply and the consumer to wear. • The finish must meet strict government regulations and have a minimal environmental impact. • The antimicrobial finish must be easily applied at the textile mill, should be compatible with other finishing agents, have little if any adverse effects on other fabric properties including wear comfort, and should be of low cost.
  • 10. Mechanisms of antimicrobial finishes two types based on the mode of attack on microbes
  • 11. Mechanisms of antimicrobial finishes • a variety of chemical finishes have been used to produce textiles with demonstrable antimicrobial properties. • These products can be divided into two types based on the mode of attack on microbes. • One type consists of chemicals that can be considered to operate by a controlled-release mechanism. • The second type of antimicrobial finish consists of molecules that are chemically bound to fibre surfaces.
  • 12. controlled-release mechanism • The antimicrobial is slowly released from a reservoir either on the fabric surface or in the interior of the fibre. • This ‘leaching’ type of antimicrobial can be very effective against microbes on the fibre surface or in the surrounding environment. • However, eventually the reservoir will be depleted and the finish will no longer be effective. • In addition, the antimicrobial that is released to the environment may interfere with other desirable microbes, such as those present in • waste treatment facilities.
  • 13. Molecules that are chemically Antimicrobial finishes bound to fibre surfaces • These products can control only those microbes that are present on the fibre surface, not in the surrounding environment. • ‘Bound’ antimicrobials, because of their attachment to the fibre, can potentially – be abraded away – or become deactivated – and lose long term durability.
  • 14. Mechanisms of antimicrobial finishes • Antimicrobial finishes that control the growth and spread of microbes are moreproperly called biostats, i.e. bacteriostats, fungistats. • Products that actually kill microbes are biocides, i.e. bacteriocides, fungicides. • This distinction is important when dealing with governmental regulations, since biocides are strongly controlled.
  • 15. Mechanisms of antimicrobial finishes • The actual mechanisms by which antimicrobial finishes control microbial growth are extremely varied, ranging from • preventing cell reproduction, • Blocking of enzymes, • reaction with the cell membrane (for example with silver ions) to the destruction of the cell walls • and poisoning the cell from within. • An understanding of these mechanisms, although important for microbiologists, is not really a requirement for the textile chemist who applies and evaluates the effectiveness of antimicrobial finishes.
  • 16. Chemistry of antimicrobial finishes Antimicrobials for controlled release Bound antimicrobials
  • 17. Antimicrobials for controlled release • Many antimicrobial products that were formerly used with textiles are now • strictly regulated because of their toxicity and potential for environmental damage.Products such as – copper naphthenate, – copper-8-quinolinate, – and numerous organo mercury compounds fall into this category.
  • 18. Antimicrobials for controlled release – Limited Use materials  Other materials that still have limited use in specialised areas include  tributyl tin oxide (deleted in many countries, Fig. 15.1a),  dichlorophene (Fig. 15.1b)  and 3-iodo-propynyl-butyl carbamate (Fig. 15.1c).  These products typically show a very broad spectrum of activity against bacteria and fungi, but suffer from application and durability problems
  • 19. Antimicrobials for controlled release – General Type • Some more useful products of this same general type include 1. benzimidazol derivatives, 2. salicylanilides 3. and alkylolamide salts of undecylenic acid (particularly effective against fungi). • Application of these materials with resin precondensates can improve durability to laundering, but also deactivation by reaction with the resin may occur.
  • 20. Antimicrobials for controlled release - Formaldehyde • A widely used biocide and preservation product is formaldehyde. • Solutions of formaldehyde in water, called formalin, were used for disinfection and conservation, • for example, of biological samples for display. Bound formaldehyde is – released in small amounts from common easy-care and durable press finishes • Therefore these finishes include – at least until they are washed – a small antimicrobial side effect. • This can also be true for some quaternary compounds, • for example wet fastness improvers and softeners. • But for more effective requirements specific antimicrobial finishes are necessary.
  • 21. Antimicrobials for controlled release- TRICLOSAN • One of the most widely used antimicrobial products today is • 2,4,4'-trichloro-2'- hydroxydiphenyl ether, known more commonly as ‘triclosan’ (Fig. 15.1d). • Triclosan finds extensive use in mouthwashes, toothpastes, liquid hand soaps, deodorant products, and the like. • Although it is effective against most bacteria, it has poor antifungal properties. • Triclosan is also important as a textile finish, but since its water solubility is very low, aqueous application requires use of dispersing agents and binders.
  • 22. Antimicrobials for controlled release-Quaternary Ammonium Salts • Quaternary ammonium salts have been found to be effective antibacterial agents • in cleaning products • and for disinfecting swimming pools • and hot tubs. • However, their high degree of water solubility limits their use as textile finishes.
  • 23. Antimicrobials for controlled release-ORGONO SILVER • Research into controlled-release antimicrobials continues with • organo-silver compounds and silver zeolites, • which are promising candidates for textile finishes. • Silver ions, for example, incorporated in glass ceramic, have – a very low toxicity profile – and excellent heat stability. • These principles are also used for fibre modification, an alternative to the antimicrobial finishes with high permanence.
  • 24. Antimicrobials for controlled release – FIBER MODIFICATION • In recent years a variety of antimicrobial modified fibres have been developed, – including polyester, – nylon, – polypropylene – and acrylic types. • An example of these fibre modifications is the incorporation of 0.5–2 % of organic nitro compounds (for example based on 5-nitrofurfural) before primary wet or dry spinning. • Regenerated cellulosics can be modified with carboxylic or sulfonic acid groups, – followed by immersing in a solution of cationic antimicrobials which are then – fixed to the cellulose by salt bonds.
  • 25. Antimicrobials for controlled release – MICRO- ENCAPSULATION • A novel approach to the controlled release of antimicrobials is • micro-encapsulation. • These capsules are incorporated either in the fibre during – primary spinning – or in coatings on the fabric surface.
  • 26. Chemistry of antimicrobial finishes Antimicrobials for controlled release Bound antimicrobials
  • 27. Bound antimicrobials • Several antimicrobial finishes that function at fibre surfaces have been commercialised. • One popular product is based on octa-decyl- amino-dimethyl-trimethoxy-silyl-propyl- ammonium chloride (Fig. 15.2a). • This material can be applied by either exhaust or continuous methods.
  • 28. Bound antimicrobials • After application, a curing step is required to form • a siloxane polymer coating on the fibre surface. • This coating immobilises the – antimicrobial part of the molecule (the quaternary nitrogen) – and provides the necessary durability to laundering.
  • 29. Bound antimicrobials • Another bound finish has been developed with • PHMB, poly-hexa-methylene biguanide (Fig. 15.2b). • PHMB can also be – either pad – or exhaust applied. • This chemical has the proper molecular structure to bind tightly to fibre surfaces, yet still be an effective antimicrobial.
  • 30. Bound antimicrobials • The antimicrobial effect of • cationically charged materials is thought to involve interaction of the – Cationic molecule with anionic phospholipids in the microbe’s cell walls. • This interaction is believed to increase the permeability of the cell walls to the point of cell death.
  • 31. Bound antimicrobials • A new and novel approach to bound antimicrobials was recently introduced. • Cotton reacted with • methylol-5,5-dimethyldyantoin • is then treated with hypochlorite • to form chloramines in the fibre (Fig. 15.3).
  • 32. Bound antimicrobials • These chloramine sites have antibacterial activity • and can function as renewable antimicrobial agents by • continued treatment with hypochlorite through household bleaching and washing after reacting with bacteria (Fig. 15.4). Problems with using higher concentrations of chloramines include yellowing with heat (for example ironing) and cellulose ibre damage especially significant strength loss, caused by oxy- and hydrocellulose (generated by hypochlorous acid
  • 33. Bound antimicrobials -- CHITOSAN • Another novel approach is the application of chitosan. • This modified biopolymer • is manufactured from inexpensive natural waste. • Chitin from crustacean shells (e.g. from crabs) is converted to chitosan by alkaline treatment. • Chitin is an analogue of cellulose with N-acetyl groups instead of hydroxy groups in position 2 (Fig. 15.5).
  • 34. Bound antimicrobials -- CHITOSAN • Alkali splits most of them (75–95 %), generating free amino groups that provide – Fungistatic – and bacterostatic effects. • This mild antimicrobial activity may be amplified – by methylation of the amino groups – to quaternary trimethylammonium structures. • Chitosan can be applied by 1. microencapsulation 2. or by reactive bonding to cellulose 3. and by crosslinking of chitosan. • The advantages of the antimicrobial finish with chitosan include 1. high absorbency properties, 2. moisture control, 3. promotion of wound healing, 4. non-allergenic, 5. non-toxic 6. and biodegradable properties.