Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
105()2(~8
The present inventlon provides
an organLc solvent-free flameproofing composltion which
is dispersed in water and which contains as component
(a) 50 to 700 g/kg of a brominated cycloalkane with 7 to 12
ring carbon atoms and 4 to 6 bromine atoms bonded to these
ring carbon ~toms, as component
(b) 0.1 to 300 g/kg of a dispersant7 as optional component
(c) 0 to 30 'kg of a protective colloid
and, as component
(d) water to a total bulk of 1 kg.
This flameproofing agent is-intended primarily for providing
synthetic fibrous material, above all textiles, of polyester
or polyamide with a flameretardant finish.
Component (a) can consist of both solid and liquid brominated
cycloalkanes. However, solid compounds, i.e. those which are
in the solid aggregate state at temperatures up to 20~C, are
preferred Particularly suitable compounds are those with a
melting point between ~0 and 200C, in particular between
100 and 190C.
Exal~ples of cycloalkanes which can be used as component (a)
are: 1, 2, 3, 4, 5, 6-hexabromocycloheptane, above all 1, 2,
3, 4- or 1, 2, 4, 6-tetrabromocyclooctane or, in particular,
1, 2, 5, 6, 9, lO~hexabromocyclododecane (abbreviated herein-
after to HBCD). Preferably HBCD is used by itself as active
substance.
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m ese compounds are known and are manufactured by methods
which are known per se.
Suitable dispersants as component (b) are, for example, the
conventional dispersants used in the dyestuffs and textile
industry: lignin sulphonates, ar~matic sulphonic acids, sa-
turated-aliphatic dicarboxylic acids which are substi~uted
by long-chain alkyl radicals, condensation products of aromatic
sulphonic acids and formaldehyde, alkylphenol/ethyleneoxy
adducts, fatty acid, fatty amine or fatty alcohol/ethyleneoxy
adducts, sulphated substituted benzimidazoles, sulphonated
fatty acid amides. Good results are obtained above all with
lignin sulphonates, with ethyleneoxy adducts of alkylphenols,
fatty amines, fatty alcohols or fatty acids and, in parti-
cular, with substituted benzimidazoles or with condensation
products of aromatic sulphonic acids and formaldehyde.
It is preferable to use those dispersants which at elevated
temperatures, e.g. at 180 to 220C, do not produce any yellow-
ing of the treated substrate or which at most only result in
a yellowing which can be removed in the washing-off. In other
words, the dispersants either must not decompose at elevated
temperature of they should form only soluble or volatile de-
composition products. The amount of dispersant used is pre-
ferably between 1 and 60 percent by weight, based on the
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amount of HBCD. Particularly good results are obtained with
1 to 50, above all 1 to 2~ and especially 1 to 4, percent by
weight of dispersant, based on the amount of HBCD.
The storage stability can be increased if the aqueous suspen-
sions or dispersions also contain a protective colloid as com-
ponent (c). Suitable protective colloids are those convention-
ally used in the art a e.g. polyvinyl alcohol, polyvinyl pyrro-
lidone, methyl cellulose, carboxymethyl cellulose, hydroxy-
ethyl or hydroxypropyl cellulose, gelatins, acid casein, starch
paste or polymers of monomers of the acrylic acid series, for
example polyacrylic acid, ethyl acrylate or methylmethacrylate
copolymers. Good results are obtained above all with poly-
vinyl alcohol, hydroxyethyl cellulose and, especially, with
carboxyme~hyl cellulose.
The aqueous preparations contain as a rule 5~ to 7G0 g/kg,
preferably 2~D to 7Q~ g/kg, in particular 20~ to 5~0 g/kg, of
brominated cycloalkane; 0.1 to 3Q~ g/kg, preferably 0.2 to
~00 g/kg, especially 5 to 4~ g/kg, of dispersant; ~ to ~0 g/kg,
preferably 0 to 10 g/kg of protective colloid. The preparations
are bulked to 1 kg with water.
The component (a) is desirably ground as an aqueous dispersion
in the presence of a dispersant in such a manner that the
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particles have an average diameter of 1 to 30u, preferably
1 to 2~u. Good results are obtained above all with disper-
sions in which the particle size is 1 to lQu, especially 1
to 5~. The particle size has no actual influence on the flame-
retardant finishes, but it does have an influence on the sta-
bility of the dispersions.
m e brominated cycloalkanes wet only poorly, so that they are
advantageously not suspended in water until directly before
use, but already beforehand. Pure suspensions, however, are
relatively unstable and the component (a~ precipitates rapidly.
A dispersant is therefore added to the preparation according
to the invention, since this prevents a rapid sedimentation
of component (a). This sedimentation can be prevented almost
completely by the further addition of a protective colloid.
The protective colloids can be incorporated into the dis-
persion before or after the grinding.
If need be, such dispersions can be converted into solid
c~mmercial forms by drying them in known manner, for example,
in a spray dryer or in a conventional paddle dryer. These
solid forms can be reconverted into dispersions at any time.
The grinding of the solid component (a) is effected in con-
ventional devices suitable for such a purpose, e.g~ in a glass
ball mill, a sand mill or in a corundum disc mill.
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It is a fur~her object of the invention to provide a method
of providing synthetic materials of polyester or polyamide
with a flame-retardant finish using an organic bromine com-
pound, which comprises treating these materials with the aqu~-
ous flameproofing agent according to the invention and sub-
jecting the treated materials to a heat treatment, the pro-
cedure being carried out in such a manner that, after the
heat treatment, the add-on of component (a) on the treated
fibrous material is ~.5 to 7 percent by weight, based on the
weight of the treated material.
The flameproofing agent, which is in the form of a concen-
trated aqueous emulsion, above all, however, of a concen-
trated aqueous suspension, is diluted with water to provide
a treatment liquor in such a manner that, having regard to
the liquor pick-up by the fibrous material to be treated,
the add-on of component (a~ is ensured.
According to the invention, the procedure to be followed is
preferably that the fibrous ma,erial is dried after the treat-
ment with the aqueous flameproofing agent and optionally then
subjected to a heat treatment at elevated temperature. A suit-
able method consists in drying the treated material at tem-
peratures up to 1~C, e.g. 70 to 10~C, and subjecting it
to a heat treatment of over 10~C, e.g. 1Q~ to 22~C or, in
.
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particular, 15C to 22~C, i.e. carrying out a thermosol
treatment.
The thermosol process is carried out preferably at 175 to
220C and lasts normally from 1~ ~Q 2Q~ seconds, preferably
from 20 to 10~ seconds. Particularly good results are obtained
with treatment times of 1~ to 6~ seconds.
Preferably the process is carried out in such a manner that,
depending on the nature of the fibrous material and its sur-
face weight, and by diluting the flameproofing agent with
water, the add-on of component (a) on the fibrous material is
.5 to 5.3 percent by weight, or especially 0.5 to 4.5 per-
cent by weight, based on the weight of the treated fibrous
material.
The polyester and polyamide fibrous materials which can be
provided with a flame-retardant finish according to the in-
vention can be in any desired stage of processing, i.e. they
can be treat2d as staple fibres or endless filaments, as woven
or knitted fabrics, dyed or undyed, or as textiles which have
already been further processed. Preferably, however, they are
always in the form of textile fibrous material.
The flameproofing agent which contains the component (a) can
be applied to the fibrous material by conventional methods,
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e.g. by spraying, printing, preferably by exhaustion or,
especially, by padding.
Preferably polyester fibrous materials are finished. Such
materials are preferably those derived from terephthalic acic,
e.g. poly(ethylene glycol terephthalate) or poly(l,4-cyclo-
hexylene-dimethylene terephthalate). Polyester fibres which
can be finished e~ectively according to the invention are
described, for example, in US patents 2 465 319 or 2 9~1 446.
Examples of polyamide fibres are those of poly-2--caprolactam,
polyhexylmethylenediamine adipate or poly-~J-aminoundecanoic
acid.
According to the invention, there are obtained on polyester
and polyamide fibrous materials permanent flame-retardant
finishes which are also retained after several washes or dry
cleanings. The finishes also have the advantage that the
handle of the finished fibrous materials does not have an
oily feel as is often the case when known agents are used.
Furthenmore, the tendency of the fabric to dry and wet soiling
is greatly reduced. The fastness to light and rubbing of dye-
ings is scarcely affected.
A particular advantage of the process according to the inven-
tion, however, resides in the fact that improved flame-re-
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~ V5~208
tardant finishes are obtained with the application of smaller
amounts of flameproofing agent.
In addition, the flame-retardant finish according to the in-
vention does no~ have any de~rimental effect on the mechanical
properties of the treated fibrous materials. In particular, ~he
good handle properties of the treated fabrics are scarcely
impaired owing to the small amount of flameproofing agent ap-
plied. The same also applies to the low stiffness in fleY.ure
and the high tear strength of the finished fibrous materials.
Even printed fabrics can be treated according to the invention
without the quality of the print being in any way thereby
impaired.
me fl~eproofing agents according to the invention can also
be used simultaneously with dyes or fluorescent brighteners,
so that it is possible to dye or treat with fluorescent brigh-
teners and to flameproof in one process.
.
Good res~lts are also obtained when using smaller amounts of
dispersant~ e.g. ~.1 to 3 percent by weight, based on the
treatment liquor, so that no washing-off is necessary.
~n the following manufacturing directions and Examples, the
parts and percentages are by weight.
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105(~ 8
Manuacturing Directions for Dispersions
A. 22~ g of H~CD are dispersed in a solution of 8 g of a con-
densation product of naphthalenesulphonic acid and formalde-
hyde in 172 g of water and the dispersion is ground in a glass
ball mill to an average particle size of l~u. After termina-
tion of the grinding, 4~ g of a 5% solution of carboxymethyl-
cellulose (degree of etherification = ~.85; viscosity of the
1% solution = 1~-2~ cP) are added to an stirred into the for~
mulation. A readily flowable, storable dispersion is obtained
which, onsettling, gives an easily stirrable sediment.
B. 222 g of HBCD are dispersed in a solution of 4.4 g o~ the
sodium salt of l-benzyl-2-heptadecyl-benzimidazole-disulphonic
acid in 174 g of water and the dispersion is ground in ~ sand
mill to an average particle size of 5u. After termination of
the grinding, 44 g of a l~/o solution of a polyvinyl alcohol
(degree of hydrolysis = 88%; viscosity of the 4% solution
= 20 cP) are aclded to the dispersion which is then thoroughly
mixed. A readily pourable and dilutable, storable dispersion
is obtained.
. 222 g of HBCD are dispersed in a solution of 8.8 g of the
sodium salt of l-benzyl-2-heptadecyl-benzimidazole-disulphonic
acid in lil g of water and the dispersion is ground in a cor-
undum disc mill to an average particle size of lOu. Then 44 g
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of a 1~% solution of a hydroxyethyl cellulose (degree of sub-
stitution ~ 2.5; viscosity of the 2% solution = 150-400 cp)
are stirred into the resultant dispersion. A readily pourabl~
and dilutable dispersion is obtained.
D. 6ao g of HBCD are dispersed in a solution of 3~ g of a
condensation product of naphthalenesulphonic acid and formalde-
hyde in 6~0 g of water and the dispersion is ground in a gl~ss
ball mill to an average par~icl~ size of 5u. After the dis-
persion has been dried in a paddle dryer and subsequently
ground, or after it has been spry dried, there is obtained a
powder which can be redispersed in water.
E. The procedure of Direction B is carried out except that
200 g of HBCD, 4 g of the same dispersant, 2 g of carboxy-
methyl cellulose and 194 g of water are used. A r~adily pour-
able and dilutable dispersion is obtained (diameter of the
particles: lOu).
F-. 5 g of a dispersant are dissolved in 25 g of water. To this
solution are poured in 10 g of HBCD and 50 g of glass beads
(diameter: lmm). Stirring is performed for 24 hours. The dis-
persion i5 afterwards separated from the glass beads and the
particle size determined. A fine dispersion of HBCD is ob-
tained which is ready for use.
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Batch Dispersant Particle
size u
Fl condensation product of 1 mole of cresol 1-2
Q.l mole of 2-naphthol-6-sulphonic acid,
~.6 mole of sodium sulphite and 1.5 mole
of formaldehyde
F2 2.5 g of lignin sulphonate obtained from
acid wood pulp 1-2
2.5 g of lignin obtained from alkaline
wood pulp
. F3 lignin sulphonate obtained from wood pulp 1-2
4 lignin sulphonate obtained from acid wood
pulp 1-2
G. 200 g of HBCD are ground to a fine, readily pourable and
dilutable dispersion (particle size 2 to 4 u~ in a solution
of 2 g of oleylmethyl tauride (sodium salt) as dispersant in
198 g of water in accordance with Direction A.
.
H. The procedure of Direction G is carried out except that 2 g
of dioctyl sulphosuccinate (sodium salt) are used as disper-
sant. The particle size of the resultant readily pourable and
dilutable dispersion is 1 to 4 u.
I. 10 g of HBCD, 38 g of water and 2 g of an adduct of 1 mole
of 4-nonylphenol and 35 moles of ethylene oxide as dispersant
are processed with 5~ g of glass beads as in Direction F to
a fine dispersion which is ready for use. Particle size:
1 to 4 u.
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J. The procedure of Direction I is carried out except that
39 g of water and 1 g of an adduct of 1 mole of laurylamine
and 4 moles of ethylene oxide are used. A fine dispersion
which is ready for use is obtained. Particle size: 1 to 4 u.
K. The procedure of Direction I is c~rried out except that
39 g of water and l g of an adduct of mole of oleic acid and
4 moles of ethylene oxide are used. A fine dispersion which
is ready for use is obtained. Particle size: 1 to 4 u.
. 18~ g of 1,2,3,4-tetrabromocyclooctane, 36 g of a conden-
sation product of naphthalenesulphonic acid and formaldehyde,
384 g of water and 4~ g of glass beads (diameter: 1 mm) are
stirred to a dispersion. The dispersion is separated from the
glass beads to yield a dispersion which is ready for use and
having an average particle size of 1 to 3 u.
M. The procedure of Manufacturing Direction I is carried out,
except that 180 g of lg2,5,6-tetrabromocyclooctane are used.
A dispersion which is ready for use and having an average
particle size of 1 to 3 u is obtained
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113S~)2~)8
E X ~ M P L E
,
Polyester fabrics with a weight per unit area of 150 g/m2 are
padded with -the aqueous treatment liquors according to Table
I, dried for 30 minutes at abou~ 80C and subseqllently sub-
jected to a thermosol treatment over the course of the time
indicated at 2~C.
The degree of thermosolation indicates the amount of product
present on the fibrous material after the thermosol treat-
ment (based on the amount originally taken upj.
The fabrics are then washed for 5 minutes at 60~C in a liquor
which contains per litre 2 g of anhydrous sodium carbonate
and 1 g of a condensation product of 1 mole of p-nonylphenol
and 9 moles of e~hylene oxide. The fabrics are subsequently
rinsed and clried.
.
The degree of fixation indicates the amount of product which
is present on the fibrous material after the wash (based on
the amount taken up after the thermosol treatment).
In the subsequent rapid wash, the fabrics are agitated for
2 or 4 hours at 95C in a liquor which contains 5 gJl of
Na3P04 and 1 g of p.isooctylphenylpolyethoxyethanol. The li- --
quor ratio is 1:40.
~n the other hand, a number of the fabrics are washed for
- 14 -
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lQ~020~
45 minutes at 60C in a domestic washing machine in a liquor
which contains 4 g/l of a household detergent (SNV 198 861 -
Wash).
me indivldual fabric samples are then tested for their flame
resistance (vertical test DIN 53 9~6, ignition tine: 6 se-
conds).
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andle Rating: ~ = unchanged
1 = a trace stiffer than
2 = somewhat stiffer than
3 = sti~f
4 = very stiff
~) corrected application, i.e. dispersant allowed for.
Instead of one of the indicated treatment liquors it is also
possible to use the product of Direction D in redispersed form
and similarly good results are obtained.
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)26~8
E X A M P L E 2
,
The same procedure is carried out as in Example 1 using treat-
ment liquor E, but a synthetic polyamide 66 fabric (surface
weight 1i7 glm2~ is finished instead of a polyester fabric.
The liquor pick-up is lOC~/o~ the concentra~ion of the HBCD dis-
persion is 11~ g~kg of liquor, but otherwise the conditions
are the same:
% add-on after drying 5.8untreated
% add-on after thermosol trèatment 5
% add-on after washing-off 4.2
% degree of thermosol treatment 86
% fixation without thermosol treatment 84
% fixation with thermosol treatment 72
handle after washing-off 1/4
flame resistance
before thermosol treatment
combustion time in secs. ~ 14
tear length in cm 7 9
after thermosol treatment
combustion time in secs O 14
tear length in cm 7 9
after washing-off
combustion time in secs. 0 14
tear length in cm 7 9
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E X A M P L E 3
Polyester fabric with a weight per unit area of 162 g/m is
padded for 3Q minutes with the aqueous liquors according to
Table II and dried at about 8~C and subsequently subjected
to a thermosol treatment for 20 seconds at 200lCo The liquor
pick-up is about 60%.
The washing-off is effected as in Example 1. The fabric is
subsequently washed up to 40 times over the course of 45 mi-
nutes at 6~C in a domestic washing machine in a liquor which
contains 4 g/l of a household detergent (SNV 198 861 ~ Wash).
The fabric is then tested for its flame resistance (Vetical
Test DIN 53 9~6, ignition time: 3 seconds).
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E X A M P L E 4
Polyester fabrics with different weights per unit area are
padded with treatment liquors which contain variable amounts
of the dispersion according to Direction ~. The fabrics and
the amounts of ~he dispersions used are indicated in Table III.
The fabrics are dried at 80C for 3~ minutes and subsequently
subjected to a thermosol treatment at 2Q0C over the course
.of 2~ seconds. me washing o~f is effected as indicated in -.
Example 1. The fabrics are subsequently washed up to 2~ times
for 45 minu~es at 6~C in a domestic washing machine in a li-
quor which contains 4 g~l of a household detergent (SNV 198
- 861 - Wash).
The individual fabrics are then tested for their flame resi-
stance (Vertical Test DIN 53 9~6, ignition time: 3 seconds).
l'he results are reported in Table III. The handle ratings
have the same meanings as in Example 1.
- 24 -
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V ~ H 8 u~
H I ~ / ;~ ~)
_ _ ~ .
~ ~9
HH V ~
l _~ ~ ~
~U 5_1 H C~ ~N ~ ~ C S ~
~ ~ ~ ~ ~ n
t~ ,_J ~1 H co H .
E-l -- v H
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V ~ H I ,_1~N ~ O ~.S)
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P l .~J H I Q C~
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a~ a) G) ~ g Q~ aJ
0 J~
- 26 -
: :.
l~S~;~Q~
E X A M P L E 5
A polyamide fabric with a weight per unit area of 177 g/m2 is
padded wi~h a treatment liquor which contains variable amounts
of dispersion A according to Direction A. The drying~ the ther-
mosol treatment, the washing-off and the single wash in the
domestic washing machine are carried out as indlcated in Exam-
ple 4. The same applies to the test of the flame resistance
and the evaluation of the handle.
The results are reported in Table IV.
- 27 -
, , : , ~ . ~ . . .
- - , : : - ~ : : : ;
osa~
--~
- - ~ - ~ -
O H ~ r O ~ H
.~ .
~ . ~ ~ ~ ~
H h H u~ ~ ~ ~ ~ D ~
tl~
~ _ ~. ~
~ S~
~ ~ ~ ~'
r-l rl
. ~1 ~10 0 ~
O h ~ v ~
,,~ ~ ~ X X
~ ~ ~ 4~
o o ~o ~ ~.
S~ ~ td
~0 ~
S
- 28 ~
,
.~
.
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', `' " ' ' - ',
~5020
__
. ~
0 ~
H HH r-l 00 C~l 00
~ ~ ..
H ~ U )
,D H ~> oo U~ oo
.
E~ _ _ ~
t) t~
a) a)
ca co
. .~ ~ ~0 ~ ~. '~.
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'bO ~ ~ bO
u
. E ~
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_ ~ ,~ . . ... .. .
29
,
l~SOZ~8
E X A M P L E
Polyester fabrics wlth a weight per unit area of 15~ g/m are
padded with the aqueous treatment liquors according to Table
V, dried for 3~ minutes at about 80C and subsequently sub-
jected to a thermosol treatment for 6~ minutes at 2~0C. The
fluorescent brightener used in treatment liquors I to IV has
the formula
~ ~C Ir~ c ~
The dye used in treatment liquors V to IX has the formula
OH
~2) ~ N = N ~ -N = N ~
C113
I I
. 2 2 CH2 O-R,
wherein R represents 5G% hydrogen and 5~% -C-CH3.
After the fabrics have been padded they are given a washi.ng-off
as in Example l and tested for their flame resistance ~Vertical
Test DIN 53 906, ignition time 3 seconds) and for their mecha-
nical properties. The handle is rated as indicated in Example l.
- 3~ -
,
': ' '
-
ll~SO;~
In addition, the stiffnes in flexure is measured in the ASlMD-1388-64 T test and the tear strength in the SNV Test 198461.
The results reported in Table V show that fabrics can be si-
multaneously dyed, brightened and ~lameproofed with scarcely
any impairment of the good mechanical properties.
- - 31 -
.
. ~ . - . -
105~208
~ ~ ~ ~ ~7 ~ . _
~ .
b~ , , ,
JJ ~
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H I ILr~
H ~)
~ ~ I I I I ~ ~ I
1_1 O1~
~ L" ~ ~ ^ ^ ^00 ~ 0
O ~ r~r~
,~ ~ O 1~
~ 3 ~ ~
a~ .IJ H I I I ~ I
r-l t~ H ,_1
,f~ S
td tO ~-I C
. H U)
00
~1 H O 1~ I r 1
_ ~
~ ~0 . \-01 4 ,~ ~
~ O ' S~
1~ o ~
~
U ,~ ~ ~dU ~
t O~I-rl r~ :1 4 ~ ~ o ~ ~
o o~ C` O
~r~ ~ U
~ ~ X lJ X
~¢ O ) ~0 Q.) a~ 1:4 P
~r~ g
~ O~-IC~ ~ ~I) ~ ~ rl ~1 ~1 ~1 ~ ~ a)
~ Ua~ -~ O ~ ~ ~0 ~
.,~
Or~ h ~ r~ o O O r~ C~
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. ~ r~ ~ ~0 0q~ Or~ ~ ~ . -
o
. ~ o o ~ o ~ ~ ~
..- ~o
- 32 -
.
`:
`
l~S02Q8
~a ~o
. ~ C~
_~ ~.
~ sulnq ,_~\N '~
. ~: ~ ~ __~__1
sulnq ~ ~
H ~_ ~__
~ ~ O~ ~ ~ o~
_
~4 ~ ~ 00
~ ~ _
rl ~ t~ 1
~_ .__~
. H sulnq ,~N
~ H . _~
--1 t~ H S uln q ,~N ~ 0 ~ ~^
IJ H ___ ~
E~ ~ ~ ~ ~
.~ ~ _ ~
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. ~ , ~
. ~ V
a) 4~ ~ td
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O ~ ~ ~ ~ ~. ~: -
~ a~
~ ~ ~ O ~
, , _ , . ~ ~ ~ __
- 33 -
:` :
:: :
~lISOZ08
E X A M P L E 7
Polyester fabric (5 g) with a weight per unit area of 15Q g/m2
is treated by the exhaustion process in a HT apparatus under
a gauge pressure of about 5 for 1 hour at 140C with 101 g of
a treatment liquor I or with 101.25 g of a treatment liquor
II of the following composition:
treatment liquor I: 1 g of a dispersion according to Direc-
tion A
1~0~ g of water
treatment liquor II: 1 g of a dispersion according to Direc-
tion A
lQQ g o~ water
0.25 g of a mixture which consists of a
dodecylbenzenesulphonate-triethanolamirle
salt and an adduct of castor oil fatty
acid and ethylene oxide and is dissolved
in a solvent mixture of trichlorobenzenes,
diphenyl, xylene, m-hexanol and ethylene
glycol.
In contrast to Example 1, a washing-off is not carried out in
this Example. After the termination of the treatment, each of
the fabrics is washed 20 times in a domestic washing machine
for 45 minutes at 60C in a liquor which contains 4 g/l of a
household detergent (SNV 198 861 - Wash).
- 34 -
~ . .
~: :
- .
- , . . i
. .; .. .
,
- .
:~50208
The add-on of HBCD on the fabric samples is determined be-
fore and after the washes. After the washes, the flame re-
sistance is also tested in the DIN 53 906 Vertical Test at
an ignition time of 3 seconds.
The results are reported in Table VI.
- 35 -
.. : ,
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~_~ ~ ~
~ ~ 1 ~
,a ~ ~ ~ ~D
c~ ~ ~ H I~ `J C~
E-l t~,l ~r~ u) ~ ' -:
__ ~ ~
a ., 5
- 36 -
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