Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~os~s76
T~e inventiQn re~ates ~o a fireproofing ~Iqueous cc)mE)o~i-
tion which contain~
R halo en con~po~Ld of th~ formula
Am (1)
~erein m i8 an integer ~Erom 1 to 6~ and G ¢orreEporte~
to a radic~l of the ormu~a
~r ~r
f ~ ~C~2~n-1 ~2)
l ~2
,
~herein Ml and M;~ are ~ethyL or preferably hydroE~en~
n is 1 or 2, with the G-radi¢~ls E~eing, provi~ed th~t ~ ~-
an ineeger i~ro~ 2 to 6~ identica~ or dlferet~t froE
each other J~
A corresponds to ~n m-~alent ~dic~L of the ~olLo~ing
fon~lae 63~ to ~8~, na~e~ ~ ~
[1 ~--D~[l ~_ (3)
wherein 1~ reE~re~ents an ~sptl~ ly 12rominated 2- to IB-
lent l~lene h~vl~g ~r to ~ csrbon atomsi, ~ st~d t e~c~
repre~ent ~n lnteger frool 1 to 5, u repre~ents 1 or 2f
2 ~,
. ::. .- .. .. . , . .. ... ~ : .~ , - . . . , ~ , ,:, , - :::- . .
1081876
and the sum s~u is at least 3;
Ql rq_
~~ -0~~ _0 ~4)
Brq-1 Q2
. _ z~-L
~; ~herein Q~ and Q2 esel2 represent hydrogen or alkyl hai~ing .
1 or 2 carbon atoms, ~ repre~en~s an integer from 1 to 5, ~:.
S: a~d z represents ~ ~r 2; ~ ~
,
_ _ . , ';,
~: ~ ; . ~ 1 p-- 1 ,
~ ~ 2-P ~5)
:~ ~ .-oole . -',~ .
wherein ~p i 1 or 2;
æ
Y2~=~ . O)
~ ~ ~. . ~o -- .
1 0 81 ~7 6
in Xl, X2, Yl, Y2, Y3 and Y4 esch stand for hydrogen
bromine or chlorine, Zl and Z2 each represent hydrogen,
bromine or chlorine, or together they represent a
chemical bond, with the whole radical con~aining 2 to 8
halogen atoms;
- OC - HN - E - N~ - C0 - (7)
wherein E represents ethylene or methylene or -CH2-0-CH2-; or
- CO - N~2 (8);
(b) a dispersing agent;
(c) optionally a protective colloid; and
(d) water.
This fireproofing composition is used essentially for the
fireproofing of synthetic fibre material, particularly
textiles made from polyester or polyamide.
In the case of constituen~ a) compounds, these can be
both solid and liquid brominated compounds.
Solid compounds are however preferred, i.e. such
compounds which are in the so1id aggregate state up to 20C.
Preferred compounds as constituent (a3 are moreover tho8e
containing two identical G-radicals of the formula (l)
and hence correspond to the fqrmula
r ~ ~
. ~' ' ' . .
:: :
~081876
~ ~r Br ~
H - C - ¦ ~ (CH2)n-1 [A~ (9)
~fl M2 m
wherein A~ Ml, M2, m and n have the given meanings.
Among the halogen compounds of the formula (9)~ the
compounds preferred are those having a molecular weight
S of 200 to 1600, a bromine content of 40 to 82 per cent by weight
and a chlorine content of 0 to 30 per cent by weight.
Particularly preferred halogen compounds are those which
correspond to the formula
. ~ Br Br ~
11 - C - 1H - (CH2)n 1 1A1. ~ m (10)
Ml m
wherein Ml represents methyl or preferably hydrogen,
n represents 1 or 2, m represents an integer from 1 to 6,
and ~ corresponds to an m-valent radical of one of the
following formulae (11) to (14), namely
~ (OOC) ~ I _ 1 . - Dl - (COO) S ! - 1 - . (11)
'
wherein Dl represents a brominated alkylene having 2 to 4
carbon atoms and 1 to 4 bromine atoms, s' and t' each -
_ 5
. .
'
~, . . ~ . .. . . . . . . . . . . . . .. . . . . . ..
~ . .. . , .. . .. - .. : . - . .
~0818'76
represent 1 or 2;
C - O
- (CH2) - o _ (12)
~..
- wherein r is an integer from 1 to 10; or
- ~C)w ~ D2 (13)
wherein D2 represents a w-valent alkylene having 1 to 8
carbon atoms, and w represents an integer from 3 to 8.
Also preferred are bromine compounds corresponding
to the formula
~ Br ~r -
H - C - C~l ~ (C~2)n-i [~2] (14
M 1 . m
wherein Ml represents methyl or preferably hydrogen,
n represents 1 or 2, m represents an integer from 1 to 6, and
A2 corresponds to an m-valent radical of one of the
following formulae (15) to (18), namely .
- (OOC)t,_l - D 1 ~ ~C)t'-l (15)
wherein D'l represents a dibrominated alkylene having
~
,
" "' ' . " ,' ' . ' ' . ' '', ' '. . , ' '~. ' '' . ' "' ' '"', ',' ,' ., ' " .' ', . . ~ ' ' ' ,'' "
~ : .
1 0 81 87 6
2 to 4 carbon atoms, and t' represents 1 or 2;
- (C}I2)r, - C00 - (16)
wherein r' is an integer from 4 to 7; ~-
( 2)r" ~ (17)
wherein r" is 1 or 2; or
_ (ooC)w, - D 2 (18)
wherein D'2 represents a w'-valent alkylene having 1 to 6
carbon atoms, and wt represents an integer from 4 to 6.
Good results are obtained, in particular, with halogen
compounds which correspond to one of the following
10 formulae (19) to (26), namely
[ I 2 (C2)n-1 ~ ~ (OOC)t-_l D 1 (~)t'-l ]
wherein D'l represents a dibrominated alkylene having 2
to 4 carbon atoms~ Ml represents methyl or preferably
hydrogen, and n and t' represent 1 or 2;
. .
.
,_, . ~. ... . . .. . . . .. . . . .. . . . .
10~31876
-- Br Br
1 1H2 - (CH2)11 1 -~ [= D- ]] (20)
M1 2
wherein D'l, Ml and n have the given meanings;
- Br Br
H - I - C~2 - (CH2)n_l -~ [~(c~I2)r-1-ooc-~ (21)
Ml 2
wherein r" is 1 or 2, and Mland n have the given meanings;
5 [H-l - CH~(CH2)n_11 - ~_o ~ [ ~ _O (22)
wherein z is 1 or 2, and Ml and n have the given meanings; : - :
.. . .
L ll2 (CH2jn 1 ~~ (23)
. .
wherein Ml and n have the given meanings; ::
.
-
- 8 -
.:
,
.. .. . ~. . . -
1081876
[ M I ] 2 ~ I 1 ~
Xl, X2, Yl, Y2, Y3 and Y4 each stand for bromine,
chlorine or hydrogen, and Z'l and Z'2 each represent
bromine, or together they represent a chemical bond,
with the halogen compound containing 6 to 10 chlorine or
bromine atoms, and Ml and n having the given meanings;
r Br Br
(C~2)n-~ ~ [ 0C~ CI-12-(0-cl12)v l-~l-CO-~ (25)
Ml 2
wherein v is 1 or 2, and Ml and n have the given meanings;
or
Br Br
11 - C - 1~1 ~ (C~12)n-1 - CO - ~12 (26)
,Ml
wherein Ml and n have the given meanings.
.. . . .
'
1al81876
Of the halogen compounds of the formulae (19) to (26),
the compounds preferably used are those having a melting
point of between 70 and 200C, especially between 100
and 190C, and a bromine content of 56 to 79 per cent
by weight.
As examples of such compounds, mention may be made of the
halogen compounds of the formulae
Br Br Br Br Br Br
.CH2-CH-CH2-OOC-CH--CH-C00-CH2-lH-CH2 (27),
Br Br CH2-Br Br Br . .
1H -CH-CH2-OOC-C-CH2-C00 CH2 2 (28),
Br
Br Br Br Br Br Br
CH2-c~cll2-c~l-c~l-cll2-c~l2-c~ -CH-CH (29),
'
Br Br Br Br
1H2~ CH- CH2 - OOC- CH~ CH~ - (30),
..... .. .. . ; :
- 10 -
:
1~81~76
Br Br Br Cll Br Br Br
CH2-CH-CH2-0 - ~ 1 3 ~ 0-CH2-CH-CH2 (31),
Br C 3 Br-
Br Br . Br Br
: CEI2 C~l~CH2-OOC ~ COO-C~12-CIl-C~2 (32),
Br Br
Br ~ COO-CEI2-CEI-C~2
~ )
Br / ~ COO-C~12-C~I-CE~2
Br Br
Cl Br Br
Cl ~ C-CH2-CH-CH2
Cl~C ~ (34)'
Cl ~ COO-CH2-~CH-CH2
Cl Br Br
.
Br Br Br Br
CH2-CH-OC-NH-CH2-0-CH2-NH-CO-CH-CH2 (35)
Br Br Br Br
CH2-CEI-OC~NH-CH2-NH-CO-CH-CH2 (36),
. Br Br
.orCH2-CH-CO-NH2 (3.7).
- 11 -
'
.
,
.
~(~81876
The compounds of the formula (1) are as a rule used
on their o~m as active substance.
These compounds are known or are produced by known
methods, such as by bromination or etherification of -
acid esters or of their methylolamide derivatives.
The usual dispersing agents, e.g. those customary
in the dyestuff and textile industries, are suitable as
constituent (b). The followin.g may be mentioned as
examples: lignin sulphonates, aromatic sulphonic acids,
saturated-aliphatic dicarboxylic acids substituted with
longer alkyl radicals, condensation products from aromatic
sulphonic acids and formaldehyde, optionally sulphonated
al.kylphenol-, fatty acid-, fatty amine- or fatty alcohol-
ethylene oxide adducts or ammonium salts thereof, sulphated
substituted benzimidazoles and sulphonated fatty acid
amides. Good results are obtained, in particular, with
substituted benzimidazoles, and especially with ligni.n
sulphonates, with optionally sulphonated ethylene oxide
adducts from alkylphenols, fatty amines, fatty alcohols
or fatty acids, with the ammonium salts of these adducts
and with condensation products from aromatic sulphonic
acids and formaldehyde.
- 12 -
- ~ ,,: ,`, , . ' . ''. . .
. .. . . . . . ., .. ., : . , .
1(~81876
Dispersing agents preferably employed are those which
produce at elevated temperature, e.g. at 180C to 220C,
no yellowing of the treated substrate, or at most a
yellowing that is removable on subsequent washing. In
other words, the dispersing agents either should not
decompose at elevated temperature or should merely form
soluble or volatile decomposition products. The amount of
dispersing agent used is preferably between 1 and 60 per
cent by weight, relative to the halogen compound of the
formula (1). Particularly good results are obtained with
1 to 50, especially with 1 to 20 and in particular with
1 to 4, per cent by weight of dispersing agent, relative
to the halogen compound.
In order to increase storage stability, the aqueous
suspensions or dispersions can also contain a protective
colloid as constituent (c). The protective colloids normally
employed in industry are suitable, such as polyvinyl
alcohol, polyvinylpyrrolidone, methylcellulose, carboxy-
methylcellulose, hydroxyethyl- or hydroxypropylcellulose, -~
gelatine, acid casein, starch paste or polymers of
monomers of the acrylic acid series, such as polyacrylic
acid, e~hyl acrylate copolymers or methyl methacrylate
copolymers. Good results are obtained, in particular,
- 13 -
', ; ............................ '
.
.
1~8~8~6
with polyvinyl alcohol, hydroxyethyl.cellulose and
esp~cially with carboxymethylcellulose.
The aqueous preparations contain as a rule 50 to
700 g/kg, preferably 200 to 700 g/kg, particularly 200
to 500 g/kg, of halogen compound as constituent (a);
0.1 to 300 g/kg, preferably 0.2 to 200 g/kg, especially
5 to 40 g/kg, of dispersing agent as constituent (b);
and 0 to 30 g/kg, preferably 0 to 10 g/kg, of protective
colloid as constituent (c). In each case the amount is :
made up with water to 1 kg.
The constituent (a) is advantageously ground as an
aqueous dispersion in the presence of a dispersing agent :
in such a manner that the particles have a mean diameter
of 1 to 30 ~, preferably 1 to 20~u. Good results are
. .
obtained, in particular, with dispersions having a particle
size of 1 to lO~u, especially 1 to 5 ~u. The particle size
in itself has no effect on the attainable fireproofing
effects, but it does have an effect on the stability of
the dispersions.
The halogen compounds (constituent a)) have only poor :
wettability, so that they are advantageously suspended or
emulsified not just immediately before appli.cation but
- 14 -
. .
.- . ..... . .
.: , : , .: . - . .
1081876
some time previous to this. Pure suspensions, i.e. those
without an ad~ition of dispersing agent, are however
unstable, and ~he constituent (a) rapidly settles out,
an effect rendering impossible an application to fibre
materials. There is therefore according to the invention
always added to the aqueous preparation a dispersing
agent, since this prevents a rapid settling out of the
constituent (a). This sedimentation can, if necessary,
be prevented almost completely by the addition of a
protective colloid. The protective colloids can be incor-
porated into the dispersion either before or after grinding.
Stable dispersions of this kind càn, if required, be con-
verted by drying in a manner known per se, e.g. in a spray
dryer or in a normal paddle dryer, into solid commercial
preparations which can be redispersed at any time.
The grinding of the constituent (a), which is prefer-
ably in the solid state, is performed in conventional
apparatus suitable for such purposes, e.g. in a glass-ball
mill or in a sand mill or in a corundum disc mill.
The invention relates also to a process for the fire-
proofing of synthetic fibre materials consisting of polyester
or polyamide with the aid of a halogen compound of the
- 15 -
. :- . ' ' '
'
~081876
formula (1), in which process these materials are treated
with the aqueous fireproofing composition of the invention
and are subjected to a heat treatment, the procedure
being such that the deposit of the constituen~ (a) after
heat treatment, relative to the fibre material treated,
amounts to 0.5 to 19 per cent by weight.
The fireproofing composition, wllich is in the form of
a concentrated aqueous emulsion, particularly however in
the form of a concentrated aqueous suspension, is to
such an extent diluted with water to a liquor that, with
account being taken of the liquor uptake by the fibre
material to be treated, the required deposit of the
constituent (a) is ensured.
The process according to the invention comprises a
method whereby the fibre material, after treatment with
the aqueous fireproofing composition, is dried and,
optionally, subjected to a heat treatment at elevated
temperature. One suitable method consists in drying the
treated material at a temperature of up to 100C, e.g. at
70 to 100C, and then subjecting it to a heat treatment at
above 100C, e.g. at 100 to 220C, or especially at 150
to 220C, i.e. subjecting it to the thermosol treatment.
The thermosol treatment is preferably performed at
- 16 -
~L081876
175 to 220C and takes as a rule 10 to 200 seconds,
preferably 20 to 100 seconds. Particularly good results
are obt~ined with 10 to 60 seconds.
The procedure according to the invention is preferably
S carried out in such a manner that the deposit of constituent
(a) relative to the treated fibre material, obta;ned by
suitable dilution of the fireproofing composition with
water, is 1 to 12 per cent by weight, depending on the
nature of the fibre material and on the weight per unit
area thereof.
The polyes~er and polyamide fibre materials to which
is imparted according to the invention a fireproof finish,
can be in any desired stage of processing, i.e. they can
be treated in the form of staple or continuous filaments,
or in the form of fabrics or knitwear, dyed or undyed, or
in the form of textiles that have been further processed.
Preferably, however, the material to be treated is textile
fibre material.
The fireproofing composition containing the constituent
(a) can be applied to the fibre material by conventional
methods, e.g. by rinsing, printing or, preferably, by
absorption onto the material, or especially by padding.
. ~ .
,
:
.~ : . ... .
~081876
The materials to which the fireproof finish is
preferably imparted are polyester fibre materials. They
are preferably those derived from terephthalic acid, e.g.
poly(ethylene glycol terephthalate) or poly(l,4-cyclo-
hexylenedimethyleneterephthalate). Polyester fibres towhich an effective fireproof finish can be imparted
according to the invention are described, e.g.S in the
US Patent Specifications Nos. 2,465,319 or 2,901~446.
Suitable polyamide fibres are, e.g., those made frorn
poly-2-caprolactam, polyhexylmethylenediamine-adipate or
poly- W-aminoundecanoic acid.
There are obtained according to the invention on
polyester fibre materials and on polyamide fibre materials
permanent fireproofing effects which are retained even
after several washings or dry cleanin~s. The finishes
obtained have moreover the advantage that the handle of the
fireproofed fibre materials is not found to be oily in the way
that it often is when they are treated with known compositions.
Furthermore, the proneness of the fabrics to become soiled
in ~he dry state and in the wet state is not increased.
The fastness to light and to rubbing of dyeings is scarcely
affected.
- 18 -
.
- , , , - . : ~
~081876
A particular advantage of the process according to
the invention is that better fireproofing effects are
obtained with deposited amounts that are smaller than
those required in the case of known processes.
As a result of the present fireproof finishing, the
textile-mechanical properties of the treated fibre
materials are moreover not disadvantageously affected.
By virtue of the small amount deposited, there is -
furthermore scarcely any impairment of, in particular,
the good handle properties of the fabrics treated. The
same applies with regard to the low flexural stifness and
to the high resistance to tearing of the finished fibre
materials. Even printed fabrics can be treated according to
the invention without the quality of the printing in any
way becoming impaired.
The present fireproofing compositions can also be used
simultaneously with dyestuffs or with optical brighteners,
so that dyeing or brightening and fireproofing can be
performed in one process.
Good results are obtained even with the use of small
amounts of dispersing agent, e.g. 0.1 to 3 per cent by
weight relative to the liquor, so that subsequent washing
can, if required, be dispensed with.
- 19 -
- - . - - , - - , - ..
: , , .: ~ ' . -
- , ,
1~8~876
.: :
Percentage values in the following Manu~acturing
Instructions and in the Examples are percentages by weight.
Manufacturing.Instructions for dispe~:sions and emulsions
A. 90 g of the bromine compound of the formula (32) and
18 g of a condensation product from naphthalenesulphonic
acid and formaldehyde (as the dispersing agent) are stirred
with 192 g of water and 200 g of glass balls (diameter 1 mm)
to give a fine dispersion which has a particle size of
1 to 3 ~ and which, after separation of the glass balls,
L0 is ready. for use.
With the stirri.ng of 90 g of the bromine compound of
the formula (32) with 210 g of water and 200 g of glass .
balls without a dispersing agent being present, there is
obtained a frothy suspension which is not read~ for use,
the particle size of which is over 100 ~. -
B. The procedure as described in the Lnstruction A
is carried out with the exception that 1.8 g of dispersing
agent and 208.2 g of water are used. The resulting fine
dispersion with a particle size of 1 to 3 ~ is ready for
use after removal of the glass balls.
C. The procedure as described in the Instruction A
is carried out with the use, however, of 90 g of the bromine
- 20 - .
,, : . . . . .
-
i08i876
compound of the formula (33). After removal o~ the glass
balls, the resulting fine dispersion having a particle
size of 1 to 3 ~ is ready for use.
D. The procedure as described in the Instruction A
S is carried out with the use of, however, 90 g of the
bromine compound of the formula (35). After separation of
the glass balls, the resulting dispersion with a particle
size of 1 to 3 ~ is ready for use.
- E. The procedure as described in the Instruction A
is carried out with the use of, however, 90 g of the
bromine compound of the formula (29). After removal of
the glass balls, the resulting fine dispersion with a
particle size of 1 to 3 ~ is ready for use.
F. 90 g of the bromine compound of the formula (27) and
22.5 g of the ammonium salt of an adduct from nonylphenol
and 2 moles of ethylene oxide as emulsifier are stirred
together with 187.5 g of water, using a high-speed stirrer,
to give a fine and stable emulsion which is ready for use
and which has a particle size of 1 to 20JU.
G. The procedure as described in the Instruction F
is carried out except that in this case there is used 90-g
of the bromine compound of the formula (28). The resulting
- 21 -
... ...
- . . ,. ~ - : -
. . .
. ;~ .
- ' ~ '. '
' ~' " - ' - ,
iO81876
fine and stable emulsion has a particle size of 1 to 20
and is ready for use.
H. 90 g of the compound of the formula (30) and
22.5 g of the ammonium s:alt of an adduct from nonyl phenol
and 2 moles of ethylene oxide as dispersing agent are
stirred with 187.5 g of water and 200 g of glass balls
(diameter 1 ~n) to give a fine dispersion which has a
particle size of L to 20,u and which, after separation of ..
the glass balls, is ready for use.
I. The procedure is carried out as described in
the Instruction H but with 90 g of the bromine compound
of the formul.a (31). After separation of the glass balls,
the resulting fine dispersion with a particle size of 1 to
20 ~ is ready for use.
J. 90 g of the bromine compound of the formula (27) and 9 g
of a lignin sulphonate as emulsifier are stirred together
with 201 g of water by means of a high speed stirrer to
obtain a fine stable emulsion ready for use with a particle
size of 1 to 20~u.
K. The procedure is carried out as described in . .
the Instruction J but with 90 g of the bromine compound of -
the formula (28). The resulting fine, stable and ready-for- .
use dispersion has a particle size of 1 to 20 ~. :.
- 22 -
.
. .
~0818q6
L. 90 g of the bromine compound of the formula (30)
and 9 g of a lignin sulphonate as dispersing agent are
stirred together with 201 g of water and 200 g of glass
balls (diameter 1 mm) to form a fine dispersion which
has a particle size of 1 to 20 ~u and which is ready for
use after separation of the glass balls.
M. 90 g of the bromine compound of the formula (27)
and 9 g of the ammonium salt of a sulphonated adduct from
nonylphenol and 2 moles of ethylene oxide as emulsifier
are stirred together with 201 g of water, by means of a
high-speed stirrer, to give a fine, stable and ready-for-use
emulsion having a particle size of 1 to 20Ju.
N. The procedure is carried out as described in
the Instruction M but with 90 g of the bromine compound
of the formula (28). The stable emulsion obtained has a
particle size of 1 to 20 ,u and is ready for use.
0. 90 g of the bromine compound of the formula (31)
and 9 g of the ammonium salt of a sulphonated adduct from
nonylphenol and 2 moles of ethylene oxide as dispersing
agent are stirred together with 200 g of glass balls
(diameter 1 mm) to give a fine dispersion which has a
particle size of 1 to 20 ~u and which is ready for use after
removal of the glass balls.
.
.
.
108~87G
P. 90 g of the bromine compound of the formula (28)
and 9 g of an adduct, cross-linked with 1% of 1,6-
hexamethylenediisocyanate, from hydroabietyl alcohol and
200 moles of ethylene oxide as emulsifier are stirred
.together with 201 g of water, by means of a high-speed
stirrer, to obtain a fine, stable and ready-for-use
emulsion having a particle size of 1 to 20 ~. -
Q. The procedure is carried out as described in
the Instruction P but with 90 g of the bromine compound
of the formula (28). The fine, stable and ready-for-use
emulsion obtained has a particle size of 1 to 20 ~.
.R. 90 g of the bromine compound of the formula (31)
and 9 g of an adduct, cross-linked with 1% of 1,6-
hexamethylenediisocyanate, from hydroabietyl alcohol and
200 moles of ethylene oxide as dispersing agent are stirred
with 201 g of water and 200 g of glass balls (diameter 1 mm)
to obtain a fine dispersion which has a particle size of -~
l to 20 ~ and which, after removal of the glass balls, is
ready for use.
S. 90 g of the bromine compound of the formula (27),
6.75 g of an adduct from hydrogenated castor oil and 200
moles of ethylene oxide, as well as 4.5 g of an adduct from
- 24 -
''' ' .
.. . . .
. ~ ~08~876
sorbitol-triolea~e and 20 moLes of ethylene oxide as
emulsifier, and 199 g of water are stirred together with
a high-speed stirrer to produce a fine, stable and
ready-for-use emulsion having a particle siz,e of 1 to 20 ~.
T. 90 g of the bromine compound of the formula (283,
9 g of a sulphonated adduct from stearyl al.cohol and lS
moles of ethylene oxide, as well as 9 g of a lignin
sulphonate as emulsifier, and 192 g of water are stirred
together by means of a high-speed stirrer to obtain a
fine, stable and ready-for-use emulsion having a particle
size of 1 to 20 ~.
U. 90 g of the bromine compound of the formula (31),
9 g of a sulphonated adduct from stearyl alcohol and 15
moles of ethylene oxide, as well as 9 g of a lignin
sulphonate as dispersing agent, are stirred together with
192 g of water and 200 g of glass balls (diameter 1 mm)
to give a fine dispersion which has a particle size of
1 to 20 ~u and which is ready for use after separation of
the glass balls.
V. The procedure is carried out as described in
the Instruction U but with 90 g of the bromine compound of
the formula (34). The resulting fine dispersion having a
particle size of 1 to 20~u is ready for use after removal
- 25 -
.. . . .
:. - . . ~ . . .
, . . . .
- . ~ . .
.
", . ' '`. . ' '. '- ''.' . ' ' . :.:
-
1~81876
of the glass balls.
W. 90 g of the bromine compound o~ the formula (36)
and 4.5 g of a condensation product from naphthalene-
sulphonic acid and formaldehyde as dispersing agent are
stirred together with 205.5 g of water and 200 g of glass
balls (diametex 1 mm) to obtain a fine dispersion which
has a mean particle size of 1 ~, and which is ready for
use after separation of the glass balls.
X. The procedure is carried out as described in
the Instruction W but with 45 g of the bromine compound
of the formula (36) and 45 g of the bromine compound of
the formula (37). The resulting fine dispersion has a
particle size of 1 to 4 Ju and is ready for use after
separation of the glass balls.
.
- 26 -
?
.
., : . . . : - .
- . . .
... . . . . .. .
.
~ , ' ~ . .. ' . ' ' - '
.'~" .,, , .-, ', . ' ,, " ,; .. ' , .. ' , ' ' ' ~ .. '.' : '. . '" ,. ' , ' ' : ' '
1081876
Example 1
Polyester fabrics having a weight per unit area of
162 g/m are padded with the aqueous liquors according to
the following Table I, dried for 30 minutes at about
80~C, and subsequently subjected to the thermosol
treatment for 20 or 60 seconds at 200C. The liquor
uptake is 60~/o~
The degree of'thermosolation'indicates the amount of
product present on the fibre material after the thermosol
treatment (relative to the amount originally taken up).
The fabric is subsequently washed for 5 minutes at
60C in a liquor containing per litre 4 g of anhydrous
sodium carbonate and 1 g of a condensation product from
l mole of p-nonylphenol and 9 moles of ethylene oxide. The
material is afterwards rinsed and dried.
The individual fabrics are then tested with respect
to their handle properties.
The degree of fixing indicates the amount of product
present on the fibre material after subsequent washing
(relative to the amount taken up after the thermosol
treatment).
The fabrics are subsequently washed 20 and 40 times
- 27 -
'' .
... . .. :: . ,. - . - , , : .......... - , . . . .. :.
... .... .-,. , ... , : . . -- . . . .
- 10818~6
.
for 45 minutes at 60C,in a domestic washing machine, in
a liquor containing per litre 4 g of a household
detergent (SNV 198 861 - wash).
The individual fabric samples are then tested for ,:
their fireproofness (Vertical Test DIN 53 906, ignition
time 3 seconds).
The results are given in the foilowing Table I.
- 2~ -
, ~.. , , . , . .. . . .. . ~ . . . . . .. .
-` ~081876
~ TABLE I
Treatment Treated Un-
rea-
_ . _
treatment conditions
liquor No. 1 1 2 2 3 3
dispersion according to
Instruction A A D D E E
% of bromine compound in
dispersion 30 30 30 30 30 30
g/dispersion/kg of liquor 555 555 555 555 555 555
thermosol treatment time
(sec.) 20 60 20 60 20 60
_ _ _
deposit and degree of fixin~ .
% deposit after drying 13,8 13,7 10,1 10,0 12,0 12,
% deposit after thermosol
treatment 11,2 13,2 8,9 6,9 11,0 9,
% deposit after subsequent
washlng 8,3 10,5 3,9 3,2 7,8 6,1
% degree of thermosolation 81 96 88 69 92 78
~ degree of fixing without
thermosol treatment 74 80 44 46 71 64
degree of fixing with
thermosol treatment 60 77 39 32 65 50 .
_
handle*) after subsequent 1 1 1/2 1/2 1 1 0
washing
.
fireproofness
~fter subsequent washing
burning time sec. 0 3 6 4 1 1
tear lenght cm 7 7,5 8,5 7,5 9,5 6,5 c
after 20 machine washes ~
burning time sec. 0 0 0 0 0 0 m
tear length cm 7 7,5 8 7,5 6,5 7,5
after 40 machine washes
burning time sec. 3 1 0 0 0 0
tear length cm 7 7,5 8 6,5 7,5 8 _ _
column No. - 1 2 3 4 5 6 1 7
Handle rating 0 unchanged
1 slightly stiffer than 0
2 somewhat stiffer than 0
3 stiff
4 very stiff
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.:: . . . ... . .. .
,. . .... . . .. ~ :: . .: . :
::.- : : .: : :
-.~ o8~,~,76
Example 2
The procedure is carried ou~ as given in Example 1 -
except that the polyester fabrics are padded with the
liquors of the following Table II, in which the results
are summarised.
- 30 -
.
1081876
TABLE II
Treatment Treated Un-
trea-
_ _ ted
treatment conditions
liquor No. 1 1 2 2
dispersion according to Instruction A A C C
% bromine compound in dispersion 30 30 30 30
g/dispersion/kg of liquor ~55 555 555555
thermosol treatment time (sec.) 20 60 20 60
deposit and degree of fixin~ .
% deposit after drying 16,8 16,6 14,3 14,1
% deposit after thermosol .
treatment 16t3 15,9 14 13,7
% deposit after subsequent washing 16,0 12,4 11,5 11,2
% degree of thermosolation 97 96 98 97
degree of fixing without
thermosol treatment 98 78 82 82
% degree of fixing with thermosol
treatment 95 75 80 79
fireproofness
after subsequent wasching
burning time sec. 2 2 2 5
tear length cm 7~5 7 8,5 8 burns
after 20 machine washes
burning time sec. Q 0 1 0 burn
tear length cm 6,5 7 7,5 7,5
after 40 machine washes
burning time sec. 1 2 0 0 burn
tear length cm _ _ 7,5 8 _
~column No. 1 _ 3 4 S
.
.
- 31 - I
:
. . ~ . ,: ., : : - ,, . . . : . . :
. ~ : .
1C)81876
Example 3
Polyamide fabrics having a weight per unit area of
177 g/cm are padded with the aqueous liquors according
to the following Table III; they are dried for 30 minutes :.
at about 80C and subsequently subjected to a thermosol
treatment for 20 or 60 seconds at 200C.
The liquor uptake is 80 - 110% depending on the liquor.
The remainillg conditions are as given in Example 1.
The results are given in the following Table III.
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. , . , . : - . .
-, . .
., . .: :~ ,
~08:1876
TABLE III
Treatment Treated ~re~-
l _ _ ~treatment conditions
liquor No. 1 l 2 2 3
dispersion according to
instruction B B ~ A D
% bromine compound in
dispersion 30 30 30 30 30
g/dispersion/kg liquor 555 555 555 555 555
thermosol treatment time
~sec.) 20 60 20 60 20
. . ...
deposit and degree of fixing ~
% deposit after drying 14,8 14 r 0 17,3 17,9 13,9
% deposit after thermosol
treatment 13,7 12,0 17,0 17,0 11,7
% deposit after subsequent
washing 4,9 8,7 7,2 8,3 8,2
% degree of thermosolation 92 86 98 95 84
% degree of fi~ing without
thermosol treatment 36 73 42 49 70
% degree of fixing with
th~rmosol treatment 33 62 42 46 59
handle *3 after su~sequent
washing l/2 l/2 0 0 l 0
. ......................... _
fireproofness
after thermosol treatment
burning time sec. 0 l 2 2 2
tear length cm 8 7,5 7,57,5 9 burns
after subse~uent washing
burning time sec. 0 1 0 0 2 b
tear length cm 7,5 8 7 7 6,5 urns
after 1 machine wash
burning time sec. l l 4 4 2
tear lenght cm 7,5 8 6,56,5 7 burns
after 2 machine washes
burning time sec. 5 2 _ 4 1
tear length cm 7 7 _ 6,5 7 burns
column No. 1 2 3 4 - 5 6
*) Handle rating: see Table I
- 33 -
.
. . ,. . . : : .; ,: : . . , . . . : ..
, . . . . . . .. .
- : ... , .. . . .. .. ~ . .
: ,, ..... ;, , : ' . . ' ~ ~ ,: ' '
1081876
Example 4
The procedure is carried out as in Example 3 except
that the polyamlde fabrics are padded with the liquors
according to the following Table IV, in which the results
are summarised.
- 34 -
., .
,
. . . -
~081876
TABLE IV
Treatment Treated Untreated
treatment conditions
liquor No. 1
dispersion according to Instruction C C
% bromine compound in dispersion 30 30
g/dispersion/kg liquor 555 555
thermosol treatment time (sec.) 20 60
deposit and de~ree of fixin~
% deposit after drying 18,4 16~5
% deposit after thermosol treatment 18,2 15,7
% deposit after subsequent washing 10,5 6,9
% degree of thermosolation 99 95
% degree of fixing without thermosol
treatment 58 44
% degree of fixing with thermosol
treatment 57 42
fire~roofness
after thermosol treatment
burning time sec. 1 2 burns
tear length cm 8 8
after subsequent washing
burning time sec. 1 1 burns
tear length cm 8 7
after 1 machine wash
burning time sec. 1 1 burns
tear length cm 7 7
after 2 machine washes
burning time sec. 1 1
tear length cm 6,5 7 burns
column No. 1 2 3
!
- 35 -
.
' ~
- ~ ' . :
.. . . . .
81876
Example 5
Polyester fabrics having a welght per unit area of
200 g/m2 are padded with the liquor according to the
following Table V for 30 minutes at about 80C, and
subsequently subjected to a thermosol treatment for
20 seconds at 200C.
The procedure otherwise is as described in Example 1.
The results are summarised in the following Table V.
- 36 - .
.
.
.
81876
rABLE V
Treatment Treated Un- l
_ . _ trea-
treatment co_ditlons
liquor No. 1 2 3 4 5 6 7 8 9
dispersion accorting
to InstructionF G K M ~ P Q S W
% bromine compound
in dispersion30 30 30 30 3C 30 30 30 30
g/dispersion/kg
liquor416 416 416 416 416 416 416 416 538
% liquor uPtaken 80 80 80 80 8C 80 80 80 65
deposit and degree
~f fixing
~, deposit after
drying 11,4 9,9 10,7 9,0 9,6 10,6 11,7 15 8,9
% deposit after
thermosol treatment 10 8,6 9,5 8,0 8,4 9,3 10,4 14, 7,8
% deposit after
subsequent washing 8,9 6,7 7,0 6,9 6,3 6,0 6,4 12, 5,C
~, degree of thermo-
solation 88 87 89 89 88 88 89 95 88
% degree of fixing
without thermsol
treatment 89 78 74 86 75 65 62 90 64
% degree of fixing
with thermosol treat .,78 68 65 76 66 57 55 85 56
sequent washing ~/4 1 1 ll/4 1 llk llh llk ~/2 0
fireproofness
after thermosol treat.
burning time sec. 0 0 0 0 0 0 0 5 0 rn~
tear length cm 4,5 4,5 5 4,5 5 5 5,5 5,5 6,5 ~u _
after subsequent wash.
burning time sec. 0 0 0 0 0 0 0 6 0 ~ n~
tear length 5 5,5 5 5 6,5 4,5 5,5 5 7 ~ur _
after 20 machine wash.
burning time sec. 0 0 0 0 0 0 hurnc
tear length cm 4,5 4,5 4 4,5 4,5 5 5 5 7 _
column No. 1 2 3 4 5 6 7 8 _ 10
*) Handle rating: see Table I
- 37 -
- . . . : - : :: ' ' .
.. ~ . ,.
~ . . ~,. -
.. . .: . . .
81876
Example 6
The procedure is carried out as in Example 5 except that
the polyester fabrics are padcled with the liquors according
to the following Table VI, in which the results are
summarised.
- 38 -
- :
, ` :
~ 81876
TABLE VI
. .. _ _ _ _ . _ _ _ ___ _ _ . _ __
I _ Gntreated
Treatment ¦ Treated
. ~
treatmeQt conditlons _ _._ _ _
liquor No. 1 2 3 4 5
dispersion according to I J 0 R U
Instruction , .
% bromine comyound in dispersior 30 30 30 30 30
g/ dispersion / kg liquor 416 4L6 416 416 371
% liquor uptake ~0 80 80 80 90
deposit and cLe~ree of fixin~ __ _ __ _ _ _ ___. _ __ l ~:
% deposit after drying 10,9 13,6 lO,S 11,~ 13,3
% deposit after thermosol treat 10,~. 12,4 10,3 11,0 11,0 ¦~
% deposit after subsequent wash 7,4 1055 7,5 8,8 8,8
% degree of thermosolation 95 91 98 97 83 ~ :
% degree of fixing without 71 85 71 80 80 ,::
thermosol treatment
% degree of fixing with 68 77 71 77 66
. thermosol treatment .
--- , ,.. -~ . _ _ .._ _ _
_ _ _
fireproofness
after thermosol treatment
burning time sec. 9 0 2 2 _
tear length cm. 7 5,5 6,5 5 _ burns j
after subsequent washing
burning time sec. 0 7 0 2 0
tear length cm. 5 7,5 6 6,5 6,5 burns
after 20 machine washes .
burning time sec. 2 0 0 1 0
tear length cm. 5 5 5 5,5 6,5 burns
column No. 1 2 3 4 5 7
. __ _ _ _ ..... ~ -
- 39 -
','''''.
.
. . .
.. : . . .. : ~ : . . : .
`-` 1081876
Exam~
The procedure is carried out as in Example 5 except
that the polyester fabrics are padded with the liquors
according to the following Table VII, in which the results
are summarised.
- 40 -
; .
.,.. . : , , -
, ~ ,
- . . -
. - - . : , , ~
..
` ` 11:~81876
TABLE VII
__ ___ _ ~ _~
Untreated
Treatment Treated
__ _ _ . _
Ir-3~ r ~o~d~-~o-~ _ _ _ _ __ ~ _
liquor No. 1 2 3
dispersion according to T V X
Instruction
% bromine compound in dispersion30 30 30
g/ dispersion / kg liquor 371 371 385
~/0 liquor uptake 90 90 65
_ _............................ ____ _ _ _.__ .:
% deposit after drying 11,6 10,3 4,6
_ __ _ .
handle*) after subsequent wash. 1 1 ~ 1 ~ 0
_
fireproofness
after subsequent washing
burning time sec. 6 ~25 burns
tear length cm. 6 ,5 ,
after 20 machine washes
burning time sec. 0 0 0 burns
tear length cm. 6 6,5 7
after 40 machine washes 0 0 0 burns
burning time sec. 5,5 6 7
tear length cm.
. __
column No. 1 2 3
*) Handle ratin~: see Table I
.
- 41 -
- . ~., .
',, . . : . : ' . , ' . ' .. ' :.. . ' : ,.. ' '. ~ ,
-`` 1081876
Example 8 . -
The procedure is carried out as in Example 5 except
that the polyester fabrics are padded with the l.iquors
according to the following Table VIII, in which the
results are summarised.
- 42 -
.
- .: . -
.
... ~ . :
-
1~8~876
TABLE VIII
.
Treatment Treated Untreated ~: .
___ ..
treatme t condit-ions _._ _ _ . _ -~:
liquor No. 1 2
dispersion according to H L
Instruction
% bromine compound in dispersion 30 30 .
g/ dispersion / kg liquor 416 416
% liquor uptake 80 ~0 .
_ __ . __ ~ __
% deposit after thermosol treat. 2,6 3,7
~ __~ ___
fireproofness
after thermosol trea~ment
burning time sec. 0 1 b
tear length cm. 5 5 urns
-after subsequent washing
burning time sec. 0 4
tear length cm. 4,5 5,5 burns
after 20 mach;ne washes . -
burning time sec. 0 0
tear length cm. 5,5 4,5 burns
___ . ___ . _ . . _
column No. 1 2 3
.. . __. ___ _ .. . _ __ _
.
.
- 43 -
.
.
. . . . : . .. . ., : ~ -; , : ., , , - , . . ..
, . - . . .
