Note: Descriptions are shown in the official language in which they were submitted.
WO9l/~307 PCT/AU~/00275
- 1 - Z045629
'': "'
',, ',
" "
' ' :. ;'
FIRE RETARDANTS ~;
' '~' ' ~'
Thl~ lnventlon relates to flre retardant
compo~ltlons whlch have partlcular appllcatlon as 1re
retard~nt agent~ ln:
~ 1) Plastlc materlals (such as polyurethanes, epoxy
r-sln~, and other thermoset, thermoplastic materlals) and
precursor thereof.
(2) Flre retardant coatlngs (lncluding polymerlc ~;~
coatlngs) such as paints. ~;
t3) Surface treatments to improve the flre ;~
retardancy of textlle yarns and flbre~, ln both synthetlc
and natural flbres and ln blends thereof.
Tho lnventlon 19 based on an unexpected synerglstic
or potentlatlng lnteractlon between two hitherto known ~ -~
cla~se~ of flre retardant~, namely (1) halogenated ~,,
phosphates; and (11) phenol substltuted wlth one or more
30 halogen atoms. In partlcular, the comblnatlon of ~;;;
components (1) and (li) produces a flre retardant having
slgnlflcantly superlor fire retardant propertles than
elther of the fire retardants alone, or basgd on a mere
comblnatlon of thelr known propertles.
Accordlng to one aspect of ~he lnventlon, there ls
provlded a flre retardant composltion whlch comprises:
(i) at least one halogenated phosphate; and ; ;
~ ,, ,',:
i .
.~,,,,~,
. '~'
W O 91/00307 PC~r/AU90/00275
- 2 - 2 0 4 5 6 2 9
(ii) at least one phenol substituted with one or
more halogen atoms.
Component (i) may be any halogenated phosphate which
exhlblts fire retardant properties. For example,
component ~i) may be selected from
2-chloroethanol phosphate:
1-3-dlchloro-2-propanol phosphate;
l-chloro-2-propanol phosphate:
2-3-dl-bromo-1-propanol phosphate;
oligomerlc chloroalkyl phosphonates,
bls(2-chloroethyl)2-chloroethyl phosphonate;
trlchloroethyl phosphate (~CEP)
trlchloropropyl phosphate (TCPP)
dlmethyl monophosphate (DMMP).
15 TCEP and TCPP are partlcularly preferred.
Component (il) may be selected from compounds
containlng one or more phenol rlngs whlch are substltuted
wlth one or more halogen groups, preferably bromlne
atoms. Compounds having a slngle phenol ring are
20 pre~erred i~ 2,4,6 tribromo phenol (TBP) ls partlcularly
preerred.
~n a partlcularly preferred aspect of the lnventlon
there 15 provlded a composltlon whlch comprises a mlxture
o~:
25 (a) TCEP and/or TCPP: and
(b) TBP.
The preclse weight ratlo of component (i) to
component (ii) ls generally unlmportant. For example,
the ratlo of component (1) to component (il) may be from
1:0.45 to 1:1.25. Component (i) i9 generally a liquid,
; and component (li) a solid. In a preferred embodlment of
thls lnventlon, component (11) ls added to component (1)
to form 8 gaturated or substantlally saturated solutlon,
where the ratlo of component (1) to component (11) ls
35 about 1:0.86. A dlluent may be added to the mixture to
3 allow component ratios greater than those that form a
~aturated solutlon.
SU~STITUTE Sl-IEET j
,.. , . .. ,... . . ......... , , , ,: ...................... ., ;. .
,.. ,.. ~ . .... , - : ,., ~ . . : :- , - ,
WO91/00307 PCT/AU90/00275
3 2045629
. :
The fire retardant compos~tion of the invention is a
liquid and does not appear to undergo any reactions at ;
temperatures at least up to 73C. At about 73C the
composltlon may change colour from a clear liquid to a
darker colour (possibly due to bromine release). There
appears to be an endothermic reaction at about 110C.
The flre retardant composltion i9 soluble in organ~c
~olvents such as methanol, ethanol, propanol, butanol,
~tc.; and ls generally lnsoluble ln agueou~ solutlons.
Aqueous solutlons may be prepared using commercial
emul~lfiers such as Teric (a reg~stered trademark of ICl
Australia Pty. Ltd.) and uslng technlques as descrlbed ln
the examples set out below.
When used as a flre retardant in plastics or resins~
the 1re retardant is blended wlth the components used to
form the re~in. For example, in the production of
urethane resln~ or foams, the flre retardant may be mixed
with a polyol component (i.e. a hydroxyl containing
polymer, see Encyclopedia of Chemlcal Technology, 3rd
Editlon, Vol. 11, p. 88, John Wlley and Sons, 1981) prlor
to mlxlng of the polyol wlth an lsocyanate to glve a
polyol blend. The polyol blend may, for example, contaln
from 5 to 80% of the flre retardant composition as
herelnbefore descrlbed. Ths components of the polyol
blQnd are sultable for storage for a considerable period
of tlme, i.e., up to six months or more, even at elevated
¦ temperatures.
The polyol blend may additionally contaln one or
~ 30 more basic materials, (such as an lnorganlc or organlc
j base, for example an amlne, such as trimethyl amine).
When present, the base generally comprises from 0.01% to
15% (wt/wt) of the polyol blend. The polyol blend may
also contaln glycerol, silicone, water, CFC, an amine ;~
catalyst and a tin catalyst.
Alternatively, the fire retardant composition may be
mixed wlth both the polyol and isocyanate at the same
'~
' UL.STITUTE S~EET
,: ""',:
WO 91/00307 PCr/AU90/00275
2045629
,
time, to form a polyurethane polymer such as a
polyurethane foam.
The amounts of reactants used in the preparation of
ursthane oams on a weight basis may vary considerably
according to well known methods in the art.
Conventlonslly, the proportlons of polyol and isocyanate
are selected to provide approxlmately equal amounts
(molar equivalents) of hydroxy and lsocyanate
functlonalities, with isocyanate being in slight excess.
The flre retardant of the lnventlon may constltute from 1
to 50% (wt/wt) of the reaction mixture.
Particular advantages associated with the use of
flre retardant composltions of the lnventlon ln the
productlon of polyurethanes are as follows:
1. The flre retardant enables high levels of flre,
retardancy to be achleved by the addltlon of the flre
retardant lnto the precursors of polyurethane foam
polymers.
2. The flre retardant exhlblts plastlclslng
effects whlch ln part enable cell structures in foams to
be ea~lly modlfled and controlled.
3. The flre retardant ls readily soluble ln
commerclally available foam prepolymer~ and as such acts
as a vlsco~lty modlfler.
4. Polyol blends contalnlng the flre retardant of
thl~ lnventlon are relatlvely stable.
The applicant has addltlonally found that where the
flre retardant composltlon of thls lnventlon is used ln
the productlon of polyurethane foams, chlorofluorocarbons
(CFCs) may be reduced or omltted from the reactlon
mlxture. The flre retardant in accordance with thls
lnventlon enables polyurethane foams to be controlled
durlng thelr blowlng phase utlllslng carbon dloxlde gas,
formed as a reactlon between water and lsocyanate, as a
blowlng agent, enabllng the ellmlnatlon or reductlon of
CFCs and other volatlle agents. In thls lnstance, the
flre retardant of this invention also reacts as a
I Sl.IBSTITUTE S~EET_,
- ,,
~........ . . . . . : . .. ~
` .` . . , ~ - ~ . -
,, , . :. : - ~
.. , ,:. ~: . - - . -
W09l/~307 PCT/AU90/0027~
204S629
- 5 -
reaction temperature modifier to o~ercome the excessive
rapid exotherm generated in polyurethane foams when the
isocyanate components in the foam are reacted wlth water
to form carbon dioxlde.
In accordance wlth another aspect of the present
lnventlon, there is provided a polyol blend whlch
comprlses a polyol and a fire retardant composltion as
hereinbefore described, which i8 free of CFCs. Such
polyol blends are generally used in the productlon of
polyurethane foams where the blends are reacted with an
lsocyanate to form the polymer, wlth carbon dioxlde
productlon ln the reactlon belng the expandlng gas.
In yet another aspect of the inventlon, there is
provided a polyol blend which comprlses a polyol, a flre
retardant as herelnbefore descrlbed, and low levels of
CFCs. As used hereln, the term "low levels" refer~ to
0.1% to 17% (wt/wt) of CFC ln the polyol mlx.
Conventional polyol formulation~ generally contain 25%
(wt/wt) CFCs or more. CFCs have been implicated in the
depletion of the ozone layer, and hence the use of low
levels ls advantageous. Polyol blends contalnlng low
levels of CFCs may also contaln glycerol, slllcone,
water, an amlne, and a tin catalyst. The polyol blend
may contaln from 5 to 80% of the fire retardant
25 composltlon as hereinbefore described. ~';
Thls lnvention also relates to polyurethane foams
whlch lncorporate flre retardants as descrlbed herein;
and further relates to polyurethane foams when produced
by the reactlon of a polyol blend contalning a flre
retardant, wlth an isocyanate containlng compound.
In accordance wlth another aspect of this lnventlon,
the flre retardant compositlons described hereln may ~e ;
incorporated lnto polymeric materials such as polyvinyl ,
chloride (PVC), polyester, polyamide, polyimide,
polypropylene, polyethylene, nylon, phenolic resin and
acetal resin. Such polymeric materlals may contain from
0.1 to 50% (wt/wt) of the fire retardant compositlon of
,
j SUBSTITUTE SHEET j
,
W091/00307 PCT/AU90/0027
204S629
,
thls invention. The fire retardant of this invention is
simply addsd to the various reaction mixtures which give
rise to above polymeric material. The fire retardant is
thus incorporated into the polymeric matrix. The fire
retardant may react to some extent with the components of
the reaction mixtures, as long as polymerization or
conventional properties of the polymers are not adversely
effected.
The fire retardant of this lnvention may also be
lncorporated into a pulp of cellulose or llke flbres for
the productlon of paper, cardboards, etc. Such material
exhlblts flre retardant propertles.
When used as a flre retardant coatlng or surface
treatment, the flre retardant composition may be dlluted
wlth an organlc solvent to form, for example, a mlxture
contalns 1~ to 90% (wt/wt) flre retardant, and then
~prayed onto a surface whlch 19 deslred to be coated. On
evaporatlon of the organlc solvent, a stable surface
coatlng remalns. In the treatment of exposed tlmber
products, for example, the flre retardant may be
lncorporAted lnto conventlonal wood stalns to yleld a
decoratlve surface. In another lnstance, for example,
composltlon~ of thls lnventlon may be applled to
furnishlng~, drapes, carpets, tents, screen cloths, etc
to lmp~rt flre retardancy. In such cases a staln
release, deodorant and the llke may be added to the
mlxture. The term "deodorants" used hereln refers to any
compound or number of compounds whlch have an odour
reduclng effect, or whlch lmpart a pleasant smell to the
human and/or anlmal nose. Deodorants or odour modlflers
are descrlbed, for example, ln the Encyclopedla of
Chemlcal Technology, 3rd Edltlon, Vol. 16, pp. 297-305,
John Wlley & Sons, 1981.
In the case of surface treatments of textiles, yarns
and fabrlcs lt is generally preferred to use an aqueous
fire retardant. Thls is formed by the combination of the
compound with a commercial emulsifying agent (such as ICI
.',
i SUeSTlTUTE SHEE~J
: '
., ~
WO91/00307 PCT/AU90/0027~
~ 7 ~ 20A5629
Teric 200), which is then diluted with water and applied
to the fabric or textiles. Application may be by
immerslon and nip roller to achieve pick up weights of
between 20 -90i~. Usually a high temperature treatment
(CUch as about 100C-250C) of the fabric followY
application of the compound to stabilise both the
compound and the fabric. The resultant cloth exhibits a
high degree of flre retardancy. (See Example ).
Partlcular advantages associated wlth the use of the
flre retardant compositlons in relation to fabrlc
appllcatlons of the lnventlon are;
1. A good "hand" of feel of the fabrlc. Many flre
retardants effect the feel of fabrlcs causlng them to
eel stlff or "woody".
2. Good llght-fastness, the treated fabrlc
exhlblts uv stablllty well in excess of requlred
standards. ''~'
3. A hlgh level of wash retentlon, agaln well ln
excess of standards.
4. Ease of applicatlon, that ls requlring a single
treatment.
In accordance wlth another aspect of thls lnventlon, ;~,
there 18 provlded a flre retard~nt composltlon as deflned
heroln, whlch addltlonally comprlses one or mor~ of the "
~ollowlng:
(1) a deodorant:
~11) staln release compound; ;;
(ill) wood staln or palnt;
(lv) volatlle organlc solvent and/or lnorganlc
solvent; and/or
(v) emulslfylng agent.
In accordance wlth a further aspect of this
lnventlon, there 19 provlded textiles; yarns; fabrlcs;
tlmber; wood-contalnlng products; or articles such as
carpets, screen cloths, drapes or furnlshlngs; which have
been treated wlth a flre retardant composltion as
described hereln. By the term "treatment" is meant
, "'",
; ~ '
;'' ~ '
;.~i! ., - .; ,' " ~ ; ' ' ' ~ ' ;
W O 91/00307 PC~r/AU90/0027~
- 8 - 2045629
appllcatlon by spraying, dipping, painting and other
methods well known in the art for the application of fire
retardants.
A number of embodiments of the present invention
will now be further described, with reference to the
followlng, non-llmlting example. It is to be understood
that the followlng examples ln no way restrict the
inventlon to those compounds, composltlons and methods
speciflcally exempllfled, whlch are detalled ~y way of
representative example only.
E~ 1 .
preDar~ on of Fire Retardant ComDositions:
Reagents:
(i) Trichloropropyl phosphate (TCPP) and
trlchloroethyl phosphate (TCEP) were obtalned
commerclally from Akzo Chemicals under the trade names
FYROL Pcf and FYROL Cef respectively. Both TCPP and TCEP
are llqulds at amblent temperatures.
(il) Trls 2,4,6 tribromophenol and Bls 2,4,6
Tribromophenol (TBP) were obtalned from elther Great
Lake~ Chemlcal Company, West Lafyette, Indlana, U.S.A. or
from ~romlne Compounds Llmlted, Beersheva, Israel. These
compounds are flaky sollds at amblent temperatures.
Flre retardant composltlons were prepared by mlxlng
the bromlnated phenol wlth one or both of chlorlnated
phosphates, untll all the bromlnated phenol 19 dlssolved
thereln. Warmlng the chlorlnated phosphate, for example
to 70-C, promotes solubllity of the brominated compound.
Where TCPP and TCEP are used ln combinatlon, the weight
ratlo ls usually 1:1 however thls may vary.
A range of flre retardant composition were prepared
wherein the welght ratlo of chlorlnated phosphates (TCPP
and TCEP) to bromlnated phenols was from 1:0.45 to
1 35 1:1.25. For Examples 2 to 6 listed below a near
saturated solutlon of fire retardant was prepared by
dlssolvlng 80g of TBP in lOOg o~ TCPP.
.;
j SU6STITUTE SHE~T I ~ :
.,
WO91/00307 PCT/AU90/00275
- 9 - 2045629
E$AMPLE 2
Polyol Blends ( stability of blends containing fire
retardant):
The followlng components were mixed together in a
standard commerclal mixer, or beaker, to give a common
polyol blend:
- 31.5g Polyol - Daltolac 140 (trademark of ICI
Chemlcal Industrles Llmited) '~
- 2.29g Glycerol
- 0.67g Slllcon - Dow Cornlng DC 193
- 0.44g Amlne - Dabco 33LV (33~ trlmethyl amlne)
- 0.4g Water
- 0.04g Tln - Dabco T12 catalyst (Dibutyl tin -
dllaurate)
- 14.57g CFC - Dupont Freon 11 ;
- 53.00g Flre retardant composltlon of Example 1.
Polyol blends contalning no CFCs were prepared by
deletlng the CFC component ln the above mlx, and ralsing
the amount of water to 2.44 g.
The above formulations contain 50.5% (wt/wt) fire
r-tardant. Formulations the same as above (in the
pre~ence and absence of CFC) were prepared which contain
from 5 to 63~ (wt/wt) fire retardant.
The above polyol formulations were stable, and could
bo stored for at leaQt 60 days at elevated temperatures
of 60-C without any noticeable deleterious effects.
Parameters checked lnclude changes in both the vlscoslty
and the colour of the blend and, when reacted wlth an
lsocyanate, changes in the reaction time proflles of,
Cream, Rlse & Gel times (as descrlbed in the Polyurethane
Handbook, Hansen Publishers, New York, 1985, Ed. ~unter
Oertel), when compared wlth fresh blends of the same
formulatlon. No notlceable changes were observed.
. . ,, ;;
t 35
,1 ,
~ ,
,,~ ' .
i
,~ ~ ' ;'
. -- . .
W091/~307 PCT/AU90/00275
- lo - 2045629
E~AMPLE 3
A Standard Polyurethane Blend wlth Varying Levels of Fire
Retnrdant (E~ample 1) Compared to a Commonly UsQd Fire
Rstardant (FYrol Pcf):
Polyurethane foams are prepared by reacting a
hydroxyl-containlng polymer (polyol) with a
polyfunctional isocyanate as shown in Scheme A, where (1)
19 polyfunctlonal lsocyanate, ~2) a polyol, and (3) a
polyurethane
Scheme A:
O O
OCN - R - NCO ~ HO - R ' - OH C - NH - R - HNC - OR ' - O
(1) (2) (3)
whsreln R and R' are alkyl, alkoxy or the llke optionally
subqtltuted wlth one or more substltuents.
A detailed revlew of polyurethanes 18 to be found in
Polyureth~ne Elastomers, by C. Hepburn, Applled Science
Publlshers, 1982, whlch ls lncorporated herein by
reference.
Polyurethane foams were produced by mixlng the
polyol formulations with a polyisocyanate, SUPRASEC 5005
(a dilsocyanato-diphenylmethane), obtained from ICI
Australia Operations Llmlted. The amount of lsocyanate
used to react wlth the polyol was calculat~d by
determining the total equivalents of hydroxyl groups ln
the polyol formulation, according to methods well known
ln the ~rt, and described for example in Polyurethane
Elastomers by C. Hepburn, Supra.
Conventionally, the isocyanate is used in very
slight excess. An index of x 1.05 is commonly used.
Thus, the polyol blend of Example 2 would be mixed in a
commercial mixer with 56 g of lsocyanate. (Suprasec 5005)
The following formulations were produced:
3a 3b 3c 3d
Daltolc 140 31.5~ 31.50 31.50 31.50
Glycerol 2.29 2.29 2.29 2.29
Sllicone 0.67 0.67 0.67 0.67
~,
; SU~STITUTE SHEET j
. - ,
-
WOgl/00307 PCTtAU90/0027i
~' '
- 11 - 2045629 . .
3a 3b 3c 3d
(cont) (cont) (cont) (cont)
Amlne 0.44 0.44 0.44 0-4
Tln 0.04 0.04 0.04 0.04
Water 0.44 0.44 0.44 0.44
CFC (Fll)14.57 14.57 14.57 14.57
Example 1 0 0 5.60 0
Fyrol Pcf 0 5.60 0 21.00
Isocyanate56.00 56.00 56.00 56.00
1 0 "'
3e 3f 3g 3h
Daltolc 140 31.50 31.50 31.50 31.50
Glycerol 2.29 2.29 2.29 2.29
Slllcone 0.67 0.67 0.67 0.67
Amlne 0.44 0.44 0.44 0.44
Tln 0.04 0.04 0.04 0.04
Water 0.44 0.44 0.44 0.44
CFC (Rll)14.57 14.57 14.57 14.57
Example 121.00 0 31.00 53.00
Fyrol Pcf 0 31.00 0 0
Isocyanate56.00 56.00 56.00 56.00
* All quantlties are ln grams.
Formulatlon 3a contalns no flre retardant.
Formulatlon~ 3c, 3e, 3g and 3h contaln lncreaslng amounts
of tho flre retardant composltlon of thls lnventlon.
Formulatlons 3b, 3d and 3f contaln lncreaslng amounts of
tho commerclally avallable flre retardant Fyrol Pcf
(trlchloropropyl phosph~te).
On reactlon the varlous formulatlons gave rlse to
polyurethane foams.
TE8TS
Limited O ygen Index ANSI/ASTM D 2863-77:
~hls test, ls an Australian and Internatlonal
Standard of flammability (see Polvurethane Hand~ook, Ed.
Gunter Oertel, 11985, Carl Hanser Verlag, pp. 495-496).
'~
13~
~, ' .
~ ;t~83~7 P(~/A'~
,
- 12 - 2045629
3aslcally, the test measures the % of oxygen that will
support candlelight combustion. The lower the ~ oxygen
index the more flammable is a material.
R0sults:
~ Oxygen Index
Blend 3a, (no fire retardant) 19.5
Blend 3b ~5.6g)(Conventlonal formulatlon) 22.5
Blend 3c (5.6g) 23.0
10 Blend 3d (21g)(unstable foam) 23.5
Blend 3e (21g) 24.6
Blend 3f (31g)(unusable foam) 25.0
Blend 3g (31g) 27.5
Blend 3h (53g) 28.5
These results show that foams produced uslng
conventional flre retardants have a lower percentage
oxygen lndex, and thus are more flammable than those
foams produced utllislng the flre retardant compositlon
of thl~ lnventlon. It ls to be noted that small
lncreases in the percentage in oxygen lndex correspond to
slgnlflcant increases ln flre retardancy. For example, a
dlfference of 0.5 ~n the percentage oxygen lndex between
formulatlon 3b (contalnlng a conventlonal flre retardant)
and formulatlon 3c ~contalnlng the flre retardant
compo~ltlon of this lnventlon) 18 lndlcative of a
slgnl1cant decrease ln flammablllty of the foam produced
by composltlon 3c.
The lncrease ln flre retardancy observed ln foams
contalnlng the flre retardant composltlon of Example 1 ls
belleved to result from a synerglstlc interactlon between
the components of the flre retardant, namely TCPP and ;
TBP. ;~
~he foam produced from blends 3b, 3d and 3f, was ;
inferlor when compared to foams produced using the same
level of the flre retardant of the lnventlon, insofar as
flammablllty and stablllty are concerned.
Formulations according to blends 3b, 3d and 3f were
''' ' ''~:
:, ,
! SUBSTITUTE SHEET ! : :~ ~
~ ,., .. ~
WO91/00307 PCT/AU~/00275 ~ -
- 13 - 2045629
also produced, where the fire retardant Fyrol Pcf was
replaced with halogenated phosphates, trichloroethyl
phosphate (TCEP), and dimethylmono phosphate (DMMP), and
wlth trlbromophenol (TBP). The percentage oxygen lndex
of the foams produced uslng halogenated phosphates
generally corresponded to those obtalned uslng the flre
retardant Fyrol Pcf (TCPP). The 4Oams produced uslng T8P
were of very poor quallty and possessed a very low
percentage oxygen index, below about 19.
These results show that the combination of a
halogenated phosphate and a phenol substltuted with one
or more halogen atoms interact synergistlcally to produce
foams havlng decreased flammabillty, when compared to
foams produced uslng elther of the components alone.
These results are surprlsing and unexpected.
The formulation of Example 1 was advantageous as
~table foams could be produced in the presence of large
quantltles of 1re retardant (see blends 3g and 3h). In
contra~t, formulatlons contalnlng more than 21 g of Fyrol
Pcf or other halogenated phosphates were physlcally
infsrlor ~poor dlmenslonal stabllity and low closed cell
count) and gave rlse to unstable foams. Foams produced
uslng the flre retardant TBP were of very poor quallty
and were generally unstable regardless of the amount of
T~P used.
The improved stabllity of foams produced uslng the
flre retardant composition of Example 1 was unexpected,
partlcul~rly as the independent components of the flre
retardant of Example 1 dld not glve rlse to stable foams
when large quantities were used (blends 3d and 3f).
Large quantities of the fire retardants of this
invention may be incorporated into polyurethane foams
without disturbing their structure. This is advantageous
as foams which are highly flame resistant may be
35 produced. ;
, . ~ , .
SUe~TlTUTE SHEET i
., .
WO91/00307 PCT/AU90/00275
- 14 - 2045629
E~AMPLE 4
Soluble Fire Retardants:
The fire retardant composltlon of Example 1 was
dlluted ln methanol to glve 20% (w/w) flre retardant
composltlon. Thls material was sprayed onto needled
polypropylene (a rlbbed wall coverlng manufactured by
Melded Fabrlcs Pty Ltd of Melbourne) and allowed to dry.
Dry pick up welght was 15.7%
The materlal was then washed 10 times wlth hot water
contalnlng a detergent.
The treated materlal exhlblts excellent fire
retardancy as measured by ASTM method FMVSS 302, a
horlzontal burn test ~see - Internatlonal Plastlcs
Flammabillty Handbook, Author Jurgen Troltzsch, publlshed
by Hanser Publlshers ISBN 3-446-13571-5, Section
8.3.1.2). In thls test, a slab of materlal 8 lnchQs x 3
lnCheJ wa8 held horlzontally ln a flame ~nd the rate of
burn back mea~ured. Results classlfy samples ln this test
a~ "8elf Extlnguishlng". ~he treated materlal dld not
burn.
In contrast, non-treated materlal was completely
consumed by flame, which rapldly spread down the strlp of
material.
Needled polypropylene treated ln the same manner
25 (includlng washlng) as above, wlth equlvalent amounts of ;~
TCPP, TCEP, DMMP or T3P shows slgnlflcant burn back ;~
(about 83 mm/mlnute) and consumptlon of material.
.;' ',,: ',',':
~AMPLe 5
Flre ~etard~nt Co~tina For Timber:
ln thls example samples of 6mm Plywood (200mm by
200mm) were thoroughly drled by placlng them in an oven
at 60 Deg C for 24 hours prior to the test. One half of
each sample is liberally coated on both sides wlth a
mixture comprising 20 parts of Example 1 and 80 parts of
l,l,l,trichloroethane (solvent) and allowed to dry.
Other samples were also made at the same tlme and in a
. ,:'"'",;,'~
';~
_ , .
, SUBSTITUTE SH~ET ~
. .. . . .
WO91/00307 PCT/AU90/0027
- 15 - ~0456Z9
similar manner using no fire retardant, and equivalent
amounts of the fire retardants TCEP, TCPP, DMMP and TBP.
After drying the samples were cut into 10mm wide strips
50 that the sample size is 6mm by 10mm by 200mm wlth
approxlmately one half of the sample (10 by 100mm) having
a coatlng of flre retardant. The samples were then held
downwards at an angle of 45 Deg wlth the untreated end in
the lower acpect. The untreated end of each sample was
llt. ~urning i8 observed as the flame travels upward.
~n the case of those samples treated wlth the flre
retardant of Example 1, burnlng ceased upon the flame
reaching the treated area. In all the other samples
tested, complete burnlng took place wlth the sample~
belng consumed.
E~AMPLE 6
As ~ Sur~ce Trentment for Te~tlles:
In one example a mlxture is formsd with 85% of the
flre retardant compound (Example 1) and 15% Terlc 200
(IC~). The Terlc 200 is heated to 50 Deg C to llqulfy it
and the flre retardant 15 910wly added whllst the
temperature ls kept at 50 dec C. Thl~ ls then allowed to
cool. Thls mlxture ls further added to water at the
rate of 200 grams per lltre, wlth constant agltatlon.
The fabrlc to be treated 19 lmmersed ln the solutlon and
run through nlp roller~ to glve a plck up welght of
between 40 to 100% (usually 70%). In some lnstances a
st~ln relea~e, deodorant, uv stablllser or other
treatment m~y be added to the mlxture. The wet fabric ls
i 30 then stretched and exposed to hot alr at between 120 and
160-C for several mlnutes.
TESTS
Austral~an Standard 1530 (parts 2 & 3) TESTS FOR
FLAMMABILITY OF MATERIALS AND SIMULTANEOUS DETERMINATION
OF IGNITION, FLAME PROPAGATION, HEAT RELEASED AND SMOKE
IND B
Thls is an Australlan standard test (for a detailed
.. . .
'VBSTITUTE SHEE~r i
.,
~i
WO91/00307 PCT/AU90/00275
2045629
- 16 -
reference, see International Plastics Flammabillty
Handbook, Author Jurgen Troitzsch, published by Hanser
Publlshers ISBN 3-446-13571-5 Section 8.2.16 which is
incorporated hereln by reference) and in the~e examples
testlng was carried out at the Australlan Wool Testlng
Authorlty Ltd. North Melbourne, Vlctoria, Australia.
In one sample tested agalnst the AS 1530 part 2 test
(a vertlcal burn test, flame applied to the bottom of a
strlp of materlal) ths followlng test results were
obtalned:
Sample: Woven fabrlc comprlslng 65% polyester and 35%
cotton havlng a nomlnal mass of 220 grams per square
metre, colour navy.
Dry plck up welght of flre retardant actlve ~;;
lngredlents as per Example 6 was 10.8%
Reeults: (AWTA test # 7-428445-fn)
Treated Untreated Result ranae ;~
Speed Factor 0 44 0-60
20 Sproad Factor 0 23 0-40 ~;
Heat Index 1 12 0-Upwards
Flammablllty Index 1 85 0-lOO
In these tests, hlgh values reflect undeslrable i~
r-sults. It ls cl~ar from the above data that treatment
wlth the flre retardant ls most advantageous. ;
In another sample tested agalnst the AS 1530 part 3
tost (~ample moved towards a radiant heat source) the
followlng test results were obtalned: ~'
Sample: Woven fabric comprisiny 100% wool having a
nominal mass of 388 grams per square metre and a
thlckness of 1.3 mm.
Dry pick up weight of fire retardant active
ingredients as per Example 6 was 11.3%.
The test ls a comparison between unwashed materlal
and materlal washed ten times wlth hot water and
detergent.
,.... .................................................................. .... ... .....
¦ SUBSTITUTE SHEET ! -`
. , ...
W O 91/00307 PC~r/A U90/00275
- 17 - 20~5629
Results: (AWTA test # 7-428995 fn)
UnwashedWashed Result range
Ignitability 0 0 0-20
Spread of flame 0 0 0-10
5 Heat evolved 0 0 0-10
Smoke developed 5 4 0-10
Number of speclmens tested ~ 6
Number of specimens ignited ~ 0
Agaln, these results sho~ that the treated material
aftsr w~shlng ls still highly fire resistant.
The described compositions and meth~ds have been
adv~nced merely by way of explanation and many
modlflcatlons m~y be made thereto wlthout departlng from
the splrlt and scope of the inventlon whlch lncludes
every novel feature and comblnatlon of novel features
hereln dl~closed.
~. . ~
.~ S~5BSTITUTE SHEET i
