BLUE REACTIVE DYESTUFF MIXTURE HAVING IMPROVED COMPATIBILITY

MELANGE DE COLORANTS REACTIFS BLEUS PRESENTANT UNE COMPATIBILITE AMELIOREE

English Abstract

Blue reactive dyestuff mixture having improved
compatibility
A b s t r a c t
Mixtures based on a triphendioxazine dyestuff of the
formula (I.1) or (I.2)
(I.1)
(1.2)
<IMG>
Le A 28 728 - Foreign Countries

and an anthraquinone dyestuff which, in the form of the
free acid, has the formula (II)
<IMG> (II)
in which the substituents have the meaning given in the
description, show improved compatibility with other
dyestuffs.
Le A 28 728 - Foreign Countries

Claims

Patent Claims
1. Reactive dyestuff mixture containing at least one
triphendioxazine reactive dyestuff, and at least one
anthraquinone reactive dyestuff characterised in
that the triphendioxazine dyestuff, in the form of
the free acid, has the formula (I.1) or (I.2)
(I.1)
<IMG>
(I.2)
in which
Le A 28 728- US - 11 -

R1, R2 are H or a substituent customary in tri-
phendioxazine dyestuffs,
R3 is H, substituted or unsubstituted C1-C4-
alkyl,
Hal is Cl, F,
X1-X3 are, independently of one another, NR3, O,
S,
Y1,Y2 are, independently of one another, alkyl-
ene, in particular C2-C6-alkylene, which may
be substituted or interrupted in the
alkylene chain by hetero atoms,
Z is -CH=CH2 or -CH2-CH2-W in which
W denotes radical which can be eliminated
with the formation of the group -CH=CH2,
each L is, independently of the other, a water-
solubilising group,
it being possible for the rings A to contain, if
desired, further customary substituents, and in that
the anthraquinone reactive dyestuff has the
following formula (II)
Le A 28 728 - 12 -

<IMG>
(II)
2. Reactive dyestuff mixture according to Claim 1,
characterised in that the compound (I) has the
following formula
<IMG>
in which the substituents have the meaning given in
Claim 1.
3. Reactive dyestuff mixture according to Claim 1,
characterised in that the compound I has the follow-
ing formula (Ia)
<IMG> (Ia)
Le A 28 728 - 13 -

in which
R1, R2 and Y have the abovementioned meaning and
Z denotes -CH2-CH2-OSO3H or -CH=CH2.
4. Reactive dyestuff mixture according to Claim 1,
characterised in that the dyestuff (I) has the
following formula (Ib)
<IMG> (Ib)
in which
Y is C2-C4-alkylene.
5. Reactive dyestuff mixture according to Claim 1,
characterised in that the dyestuff I has the follow-
ing formula (Ic) or (Ie)
<IMG> (Ic)
Le A 28 728 - 14 -

<IMG> (Ie)
6. Reactive dyestuff mixture according to
Claim 1 , characterised in that 10 to
90% by weight of dyestuff I and 90 to 10% by weight
of dyestuff II are present, relative to the mixture
of dyestuffs I and II.
7. Reactive dyestuff mixture according to
Claim 1 , characterised in that the
dyestuff mixture contains 1 to 50 parts of an
inorganic salt, 1 to 5 parts by weight of an
inorganic buffer, 0.5 to 10 parts of an organic
anionic dispersant and 0.5 to 5 parts of a
dustproofing agent per 100 parts by weight of
reactive dyestuff mixture.
Le A 28 728 - 15 -

8. Reactive dyestuff mixture according to
Claim 1 , characterised in that it is
present as a liquid brand.
9. Process for the dyeing of cellulose fibres and fibre
blends containing cellulose fibres, characterised in
that a reactive dyestuff mixture according to
Claim 1 is used.
Le A 28 728 - 16 -

Description

2081639
The invention relates to a blue reactive dyestuff mixture
of two blue reactive dyestuffs of the same hue which, in
the dyeing of cellulose fibres or cellulose fibre blends,
has an improved compatibility behaviour compared with the
individual components.
Reactive dyestuffs are used in the form of their indivi-
dual components or in the form of combinations with other
dyestuffs of different hues, the fixation yield of a
eomponent in the combination being expected to give the
same fixation yield as the dyeing of the individual com-
ponents by themselve~ given an identical total dyestuff
content of the dye liquor. The triphendioxazine dyestuffs
described in DE-A-3,439,756 are very useful dyestuffs.
~owever, when combined with the red and yellow reactive
dyestuffs necessary for producing fashionable shade~ they
show in some cases a reduced yield, 80 that a dichromatic
dyeing may exhibit a shift towards the shade of the
combination dyestuff and the blue portion in trichromatic
dyeings may be reduced.
The object of the invention is to improve the u~e of such
dyestuffs in combinations.
~he pre~ent invention relates to a mixture of a triphen-
dioxazine reactive dyestuff, an anthraquinone reactive
dyestuff and, if desired, further dyestuffs, charac-
terised in that the triphendioxazine dye~tuff, ~n the
Le A 28 728 - 1 -

2081639
form of the free acid, has the formula (I.1) or (I.2)
L-Y~-XI ~ x~-r~-L (I.1)
j Z-25 R2
.'~
C l S03H
X2J~N0~x2 (I.2)
2 SO3H Cl 1 2
13 X3
N~lN N~N
Ha 1 1~N~ ~Y~Ha I
tS03H) 1-~ tS03H) 1-3
in which
S Rl, R2 are H or a ~ubstituent, in particular Cl or Br,
X1-X3 are, independently of one another, NR3, O, S,
R3 is H, substituted or unsubstituted Cl-C~-alkyl,
Le A 28 728 - 2 -

- 208~639
yl, y2 are, independently of one another, alkylene, in
particular C2-C6-alkylene, which may be substi-
tuted or interrupted in the alkylene chain by
hetero atom~,
Z i3 -CH-CH2 or -CH2-CH2-W in which
W denotes a radical which can be eliminated
with the formation of the group -CH=CH2, for
example -OSO3H, -SSO3H or -OPO3H2, -O-acyl, in
particular -O-Cl-C4-alkylcarbonyl,
it being possible for the rings A to contain,
if desired, further customary ~ubstituents,
each L i8, independently of. the other, a water-
solubilising group, in particular sulpho,
carboxyl and sulphato,
Hal is F, Cl
and the anthraquinone reactive dye~tuff, .in the form of
the free acid has the formula (II)
O NH2
03H (II)
O Nlt--Q
S02CH2CH2-O-sOIH
Preferred compounds I.l have the formula
~e A 28 728 - 3 -

203163~
Rl S2 Z
H03SO-Yl-xl ~
~ ~ X1-Y1-0503H
Z-02S R2
in which the substituents have the meaning given.
Particular preference i~ given to:
R1 52-Z
Ho350_y1_ ~ ~ ~Ia)
~ H-Y1-0503H
Z-02S R2
in which
R1, R2 and y1 have the abovementioned meaning and
Z denotes -CH2-CH2-OSO3H or -CH=CH2,
in particular
Cl
1 1 502-CH2-CH2-OS03H
H03SO-Y -H ~ ~
~ -Y1-0503H
~0350-CH2-cH2-o2s C 1
(Ib)
Le A 28 728 - 4 -

2081~3~
in which
yl is C2-C4-alkylene.
A very particularly preferred dyestuff has the following
formula (Ic)
Cl
502-CH2-cH2-0so3H
H03SO-CH2-CH2 HN ~ ~
~ ~NH-CH2-CH2-OSO~H
H03SO-CH2-C~2-02s
Cl
(Ic)
Further preferred compounds have the formula (Id)
R1 52 Y
_y1-NH (Id)
HN-Y3-N~ o~ f =
f =o S2-Z R2 Y2 cooM
Y4-COOM
in which
Rl, R2 are Cl
y~ y2~ y3~ y4 are, independently of one another, an
alkylene group having 2 to 6 C atoms,
in particular of the formula (Ie)
Le A 28 728 - 5 -

20~163~
l 02H
12~4
- C-O
H03SO-~ H2-CH2
NH
Cl
2H4 (1~)
12H4 Cl 12
NH CH2-C~2-S3H
C - o
2H4
C02H
Preferred compounds I.2 have the following formulae:
Le A 28 728 - 6 -

208163~
~3r'
~ ~ k
~ I
S~
U
N
~ X
X U
Z
3: ~ O ~
N N
U U
0~
O ~ 0~ U~
ot~
Le A 28 728 - 7 -

2081~39
In a preferred embodiment of the invention 10 to 90% by
weight of I and 90 to 10% by weight of II, in particular
30 to 70 parts of dyestuff I and 70 to 30 parts of
dyestuf II, are present, relative to the mixture of
dyestuff~ I and II.
The mixture according to the invention of dyestuffs I and
II surprisingly produce~ an exhaust and fixation curve
which are very sLmilar to those of the two individual
components and thus result~ in a type of tinctorial
behaviour which is very clo~e to that of the two
individual dyestuffs. ~owever, the mixture according to
the invention when combined with a third dyestuff is
distinctly less degre~3ive than the dyestuff of the
formula tI) and produces the same fixation yield as
without admixing of foreign dyestuffs.
For explanation, see Fig. 1:
where the fixation curve (fixation time in minutes versus
amount of dyestuff fixed on the fibre in per cent of
final fixation) i9 plotted. Curve Ic shows the course of
fixation for dyestuff Ic by itself, curve II the course
of fixation for dyestuff II by itself and the solid line
the course of fixation of a 50:50 mixture of Ic and II.
The shape of the curve show~ that the colouristic beha-
viour of the individual dyestuffs becomes similar in the
mixture, re~ulting in a new dyestuff having a uniform new
fixation curve.
Le A 28 728 - 8 -

2 ~ 3 ~
~he claimed dyestuff mixture is suitable in particular
for the dyeing of cellulose fibres and blend~ thereof by
any dyeing process for dyestuff I. A preferred
application consists in dyeing at 60C by the following
S dyeing scheme:
Time (min.) Temperature (C~ Measure
0 30C
30C addition of sodium
bicarbonate
30C addition of NaCl or
Na2SO4 / 20-60 g/l
30C addition of ~odium
carbonate, 10-20 g/l
45-75 heating to 60C ~tanding at 60C
The dyestuff mixture can contain customary additives;
preferably, it contains 1 to 50 parts of an inorganic
salt, 1 to 5 parts by weight of an inorganic buffer, 0.5
to 10 parts of an organic anionic disper~ant and 0.5 to
5 parts of a dustproofing agent per 100 parts by weight
of reactive dyestuff mixture.
~ample 1
100 parts of a knitted cotton fabric are treated at 30C
with 1000 parts of an aqueous dye liquor containing, in
dissolved form:
2 parts of the reactive dyestuff mixture of 1 part of the
Le A 28 728 - 9 -

208~639
dyestuff Ic, 1 part of the dye~tuff III of the formula
S03H CH3
~ ' ~ H2-S03H
NH ~OH
CI~ ~H3
F~
and 1 part of the dyestuff II
1/2 part of sodium bicarbonate
50 parts of sodium chloride and
15 part~ of sodium carbonate.
After uniform distribution of the dyestuff on the fibre
material at 30C over a period of 45 minute~, the liquor
i8 heated to 60C over a period of 30 minutes, and dyeing
0 iB continued for another 30 minutes while vigorously
agitating the material in the liquor. The liquor ia then
di~charged, and the dyed material i8 rinsed twice at 50C
and once at 80C.
The bath ia then filled with fresh liquor, heated to
98C, and the material i~ treated at thi~ temperature for
15 minutes. After cooling, a clear green dyeing having
good fastness properties is obtained.
Le A 28 728 - 10 -