Novecare 18/06/2006

CHALLENGING BOUNDARIES
Phosphorus Flame Retardants for Textiles
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
Introduction
18/06/2006 Novecare CHALLENGING BOUNDARIES
Stenter
Winch Dyeing
machine
Flame retardants are prevalent in many aspects of our lives
In upholstered furniture
Curtaining
Car seating
The work place
Transportation
How Do Textiles Burn?
18/06/2006 Novecare CHALLENGING BOUNDARIES
Fire
Oxygen +
Textile (fuel)
+
=
Ignition
source
How Do Textiles Burn?
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Stenter
Cellulose decomposes (in oxygen) to tarry
depolymerization products, notably levoglucosan
Then to volatile combustible products such as alcohols,
aldehydes, ketones and hydrocarbons
Flammable gases ignite
After flaming, the carbonised residue slowly oxidises
(smoulders) until it has been consumed
Winch Dyeing
machine
How Do Textiles Burn?
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Thermal degradation of Cellulose
O
CH
2
OH
OH
OH
O
O
O
OH
OH
O
CH
2
OH
350
0
C
O
HO
OH
OH
O
CH
2
Levoglucosan
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
18/06/2006 Novecare CHALLENGING BOUNDARIES
The Action of a Phosphorus Flame Retardant
There are Potentially Four ways of Disrupting Combustion
Removal of heat or application of cooling. Achieved
by treating the material with heat absorbing materials.
Increase in pyrolysis temperature i.e. glass fibre,
aramids, carbon fibres
Elimination of oxygen from combustion zone i.e.
halogens
Prevent evaporation i.e. form char - Phosphorus
The Action of a Phosphorus Flame Retardant
18/06/2006 Novecare CHALLENGING BOUNDARIES
Stenter
Winch Dyeing
machine
Application of ignition source
Formation of phosphorus pentoxide and phosphoric
acid
Dehydration of cellulose occurs
Dehydration reduces the temperature of
decomposition (275-325C as opposed to 375C for
untreated cotton)
Evolution of levoglucosan inhibited
Flammable tars and gases reduced, char increased
Formation of protective layer of char
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The Action of a Phosphorus Flame Retardant
Synergistic Effect of Nitrogen
Nitrogen catalyzes the cellulose phosphorylation
The retention of phosphorus in the char may be aided
by nitrogen
Release of nitrogen gas which dilutes the flammable
gases and reduces flaming
Higher levels of nitrogen may allow lower levels of
phosphorus in the flame retardant
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
Flame Retardant Selection
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Application
Application method
Performance requirements
Fabric composition
Fabric construction, weight
Fabric must still behave like untreated material
COST
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
Classification of Textile Flame Retardants
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Phosphorus containing flame retardants
O
P OR
3
R
1
O
OR
2
P
R
1
O
O
O R
2
R
3
P
R
1
O
O
O R
2
R
3
Phosphate Phosphonium Phosphonate
R
2
P R
4
R
1
R
3
Cyclic
Classification of Textile Flame Retardants
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Another method of classifying textile FRs is
according to
their durability to washing:
Durable Resistant to 50 or more washes
Semi-Durable Resistant to a water soak
Non-Durable Resistant to no washing
Classification of Textile Flame Retardants
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Dialkylphosphonopropionamide
Co-reacted with an amino resin and an acid curing catalyst
Pad, dry, heat cure followed by alkali wash
H
2
C CHCONH
2 +
(CH
3
O)
2
P
O
H
(CH
3
O)
2
P
O
CH
2
CH
2
CNH
2
O
(CH
3
O)
2
P
O
CH
2
CH
2
CNHCH
2
OH
O
HCHO
Durable Flame Retardants (Top Treatments)
Classification of Textile Flame Retardants
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Durable Flame Retardants (Top Treatments)
Tetrakis(hydroxymethyl)phosphonium
chloride marketed under the PROBAN
trademark by Rhodia and is available
only under licence
Applied to cotton and cotton synthetic
blends by pad, dry, ammonia cure and
hydrogen peroxide oxidation
Durable to repeated washing
(HOCH
2
)
3
P
+
CH
2
NHCNHCH
2
P
+
(CH
2
OH)
3
O
CL
-
CL
-
NH
3
NHCH
2
PCH
2
NHCNHCH
2
PCH
2
NH
CH
2
NH
CH
2
NHCH
2
PCH
2
NHCNHCH
2
PCH
2
NH
CH
2
NH
CH
2
O
O
O
2
H
2
C P CH
2
CH
2
O
Classification of Textile Flame Retardants
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Flame Retardants for Polyester fabrics (Top Treatments)
Cyclic Phosphonate Ester based
products may be used
Applied by pad, dry, heat cure
process
Durable to washing
Phosphorus FRs lower the
melting point of polyester fabrics
allowing the fabric to melt away
from the ignition source more
easily
C
CH
3
O
H
3
CP
O
O P
CH
3
OCH
3
O
x
2-x
Classification of Textile Flame Retardants
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Non-Durable Flame Retardants (Top Treatments)
Non-durable APPs used
End-uses include furnishings, filter fabrics, disposable protective clothing
(NH
4
.PO
3
)n
(HPO
3
)n + nNH
3
H
3
PO
4
Degradation of APP
Classification of Textile Flame Retardants
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Non-Durable Flame Retardants (Top Treatments)
Need for more sophisticated flame retardants for higher processing
speeds and more demanding applications
Phosphonates generally have higher thermal stability than APPs
allowing higher processing speeds
Flame Retardants capable of being processed at temperatures of over
130C have been developed by Rhodia and marketed under the
AMGARD trademark
Some of the AMGARD products are based on phosphonate chemistry
which generally have higher thermal stability than APPs
Classification of Textile Flame Retardants
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Semi-Durable Flame Retardants
Used for items not normally washed but may be subjected to water soak
or dry cleaning
Ammonium polyphosphates may be used
End uses include upholstery and curtains
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
Inherent Flame Retardant Fibres
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Phosphorus containing FR additive can be incorporated into the spinning
dope during manufacture of viscose fibres
Polyester fibres can also be given FR properties by inclusion of
phosphonic acid based derivative
Inherent Flame Retardant Fibres
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C
O
P
O
CH
3
CH
3
S
O P
O
C
O CH
3
CH
3
S
Viscose spinning bath additive for flame retardant rayon
Cl
OCH
2
P
O
Cl
OCH
2
C
P
O
OCH
2
OCH
2
Spirocyclic pentaerythritol di(phosphate acid monochloride additive for
polyester
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
Methods of Application
18/06/2006 Novecare CHALLENGING BOUNDARIES
Drying Area
Mangle Rollers
Pad
Mangle
Stenter
Fabric roll
Fabric roll
Methods of Application
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Pad trough
Padding
(full
impregn
ation) Fabric
Mangle rollers
Lick
Roll
Low
viscosity
paste
Fabric
Knife or
squeegee
Foam or
paste
Fabric
Screen coating (back-
coating)
Mesh -screen
Steel
support
roller
Methods of Application
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Paste
Fabric
Knife
Steel
roller
Steel
roller
Knife
over air
(Back-coating)
Paste
Steel roller
Fabric
Knife
Knife over
roll
(Back-coating)
Methods of Application
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Pad Mangles
Methods of Application
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Stenter
Drying
Methods of Application
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Textile Coating Machines
Methods of Application
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Winch Dyeing
Machine
Wet Processing (Dyeing) machines
Jig Dyeing machine
Jet Dyeing Machine
Methods of Application
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Wet Processing (Dyeing) machines
Continuous Wash Ranges
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
Flammability Standards and Testing
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Standards and testing are vital in ensuring that the flammability
performance of a fabric is satisfactory for a specific end-use
Flammability testing must be carried out in accredited test laboratories
using recognised flammability test methods
There are a range of national and international flammability standards
Flammability Standards and Testing
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Protective Clothing (woven & or knitted) for use in the European Community
EN 533: 1997 Index 3, EN 531: 1995 para 6.2.2 EN 470: Part 1: 1995 para 6.1
after 50 washes at 75C (according to EN 10528 Standard wash).
UK Sheeting & Blankets
BS7175 Ignition sources 0, 1 & or 5 when tested on top of & or below the test
fabric, after 200 washes at 74C.
UK Curtaining
BS 5867 Part 2 Type B after 50 washes at 74C.
Mattress Ticking
BS 7175 Ignition sources 0, 1& or 5 when tested on top of & or below the test
fabric, after 3 washes at 74C.
UK Upholstery
BS 5852 Part 1 Ignition sources 0 & 1 after a water
soak treatment BS 5651.
Flammability Standards and Testing
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EN 532 standard for work wear
Flammability Standards and Testing
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BS 7175 on Continental quilts
Crib 5 test
Flammability Standards and Testing
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EN 348 standard for work wear
Flammability Standards and Testing
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DOC FF3-71 standard for childrens sleepwear
Summary
18/06/2006 Novecare CHALLENGING BOUNDARIES
Introduction
How Do Textiles Burn?
The Action of a Phosphorus Flame Retardant
Flame Retardant Selection
Classification of Textile Flame Retardants
Inherent Flame Retardant Fibres
Methods of Application
Flammability Standards and Testing
HSE Considerations
Conclusions
HSE Considerations
18/06/2006 Novecare CHALLENGING BOUNDARIES
In recent years all chemicals are coming under increased scrutiny,
especially halogen containing flame retardants
Further pressure from REACH proposals (the Registration, Evaluation
and Authorisation of Chemicals) in the EU due to become operational
in spring 2007
High customer expectation in terms of safety of chemical finishes
Ecolabels such as ko-Tex (or Blue Angel) whereby the endorsement
confers safe toxicological and environmental profiles of the relevant
chemicals
Conclusions
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Ever increasing pressure on chemical manufacturers to produce finishes
which have a good tox and environment profile, and are cost and
performance effective
General move away from halogen containing flame retardants
Challenge for the future will be to develop more efficient flame retardant
finishes in terms of application and also performance
Also multi-function finishes for textiles where flame retardant
performance is imparted along with other properties, e.g. antimicrobial,
soil/stain resist
Reference: R Padda and G Lenotte, General Trends in Textile Flame Retardants, Speciality Chemicals Magazine, 2005, 43-44.
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