Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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2 ~ ~ 2 ~
The invention relates to a single-bath two-step method
for dyeing polyester/cellulose fibre blends with disperse
and reactive dyestuffs in an Lmproved reactive dyestuff
yield.
A ~ingle-bath two-step method for dyeing
polyester/cellulose fibre blends with disperse and
reactive dye~tuff~ by the exhaust method is already ~nown
(A.K. Jain, R.M. Mittai and N.C. Mali, Amer. Dyest. Rep.
80 (1991)57).
In thi~ method, the polyester portion and the cellulo~e
fibre portion of the textile material are dyed from the
~ame bath, hence "single-bath", in succe~sion at
different pH value~, i.e. in two steps.
In the fir~t ~tep, dyeing of the polye~ter fibre portion
and, in the ~econd ~tep, dyeing of the cellulo~e fibre
portion are effected. In the fir~t ~tep, the bath has
been brought to an acid p~ and reache~ a te~perature of
120 to 140C, and, in the second ~tep, the bath ha~ been
cooled to 80 to 50C and ha~ been brought to an alkaline
p~. The duration of eaoh ~tep i~ 30 to 60 minute~.
: .
The amount of disper~e dyeatuff and reactive dye~tuff
required for dyeing and the amount of salt in the form of
~odium sulphate required for the ~econd step are added to
th- dyo b~th at the boglnning of th- ov-ral1 dy-ing
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process prior to heating. At the same time, acid, usually
acetic acid, is added in order to establish the desired
pH of the first step. The pH switch from acid to alkaline
for the second step is usually effected after cooling
from 120 to 130C to 80 to S0C has been completed.
In le~s common variants of the standard processl addition
of the reactive dyestuff and of the amount of salt
required to the bath may also be delayed until the second
step is carried out.
Dyeing polyester/cellulose fibre blends by the ~ingle-
bath two-step method has the advantage over the two-bath
method that ~horter dyeing times, i.e. shorter machine
occupation time~, are needed. Compared with the ~ingle-
bath single-step method, the single-bath two-step method
has the advantage of a larger selection of suitable
disperse dye~tuffs.
However, when the previou~ly known range of reactive
dyestuffs is used, the single-bath two-step method has
the disadvantage of insufficlent reactive dyestuff yield
since the rea¢tive dyestuff added in the single-bath two-
~tep method before fixation of the disper~e dyestuff
hydrolyzes in part in the temperature range of 120 to
140C necessary for fixing the disperse dyestuff, result-
ing in a significant reduction of the reactive dyestuff
yield.
The reduction in yield by treating a reactive dye3tuff in
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the weakly acid pH range under the conditions of
polyester dyeing is all the greater, the greater the
desired colour depth of the cellulose fibre portion,
i.e., the higher the effective reactive dyestuff con~
S centration established in the dye bath in the range of
120 to 130C.
In practice, this loss in yield is countered by increas-
ing the initial salt concentration of the dye bath.
However, this has the serious disadvantage that the
dispersion stability of the disperse dyestuffs used i~
the same bath i5 adversely affected, as a result of which
precipitations or unlevelness may occur or a rigorous
selection of suitable electrolyte-resistant disperse
dyestuffs becomes necessary, depriving the process of its
general applicability and economic attractiveness.
Moreover, increasing the salt used has the disadvantage
of higher cost ànd increased environmental pollution,
limiting the process which is already characterized by
reduced yields of fixation.
~0 The present invention relates to a mixture of reactive
dyestuffs and at least one di~perse dyestuff containing
at least one mono- or bifunctional monochlorotriazine or
trichloropyrimidine reac~ive dye~tuff and at lea~t one
mono-, bi- and/or trifunctional reactive dyestuff which
contains at least one monofluorotriazine, mono- or
difluoropyrimidine group and/or ~-sulphatoethylsulphonyl
or vinylsulphonyl group~
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Suitable reactive dyestuffs are any wat0r-soluble
reactive dyestuffs containing at least one sulpho group
and/or carboxyl group, for example tho~e from the azo,
copper azo, copper formazan, anthraquinone, phthalo-
cyanine, triphendioxazine series.
Surprisingly, it ha~ now been found that it is possible
to carry out a single-bath two-step process for dyeing
polyester/cellulose fibre blends which uses a reduced
amount of salt and gives an improved fixation yield of
reactive dyestuff. Accordingly, the invention also
provides a eingle-bath two-~tep dyeing proces~ for dyeing
polye~ter/cellulose fibre blend~, characterized in that
a mixture according to the invention i8 u8ed-
A further advantage i~ the on-tone exhau~tion of the
reactive dye~tuffs under the proce~s conditions according
to the invention, which en~ure~ a high degree of
reproducibility.
Preferably ~uitable reactive dye~tuff mixture~ are tho~e
con~isting of 40 to 60% by weight of a monochlorotriazine
or o a bi~(monochlorotriazine) dyestuff ant 60 to 40% by
weight of a reactive dye~tuff containing at least one
monofluorotriazine,monofluoropyrimidine,difluoropyr~ m~ - :
dln~ or ~ulphatoethyl~ulphonyl or vinyl~ulphonyl group.
The proce~s according to the invention i~ preferably
25 carried out by the following ~cheme: '~
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Time pH measured Temp. Measure(min) at 25C ~C)
.
0 6-8.2 20-60 Addition of buffer
6-8.2 20-60 Addition of ~,alt
6-8.2 40-60 Addition of reactive dye-
stuff
6-8.2 40-60 Let stand
6-8.2 40-60 Addition of dis,per~,e dye-
stuff
130 6-8.2 130 Heat
160 6-8.2 130 Let stand
170 6-8.2 80 Cool
200 6-8.2 80 Add fixing alkali
230 10.5-10.8 80 Let ~tand
240 10.5-10.8 80 Sampling
250 10.5-10.8 80 Discharge
270 10.5-10.8 30 Rinse
290 10.5-10.8 40 Rin~e
310 10.5-10.8 60 Rinse
315 10.5-10.8 60 Fill
320 10.5-10.8 60 Add detergent
330 10.5-10.8 80 Heat :
345 10.5-10.8 80 I,et ~tand -
:25 350 10.5-10.8 60 Di w harge
360 . 10.5-10.8 20 Rin~,e
3iO 10.5-10.8 20 Remove tyed material
The disperse dyestuffs to be used in accordance with the ::.
~' proae~s are preferably commercially available di~perse
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dyestuffs from the azo and anthraquinone series.
In a particularly preferred embodiment, a buffer is added
in the process according to the invention, in particular
prior to addition of the dyestuffs.
. .
Suitable buffers to be uæed in accordance with the
proces6 are the known inorganic buffer mixtures which
give an initial room temperature pH of 6.0 to 8.5,
preferably 7.5 to 8.0 in aqueou~ solution. Buffer~ which
have proved to be particularly suitable are isodium
carbonate or potas~ium carbonate on their own and/or in
a mixture with disodium phosphate or dipota~sium
phosphate or mixtures of monosodium phosphate and di-
~odium phosphate or potassium phosphate, borax and/or
lithium carbonate. The room temperature p~ of the bath
can change during dyeing at 130C without impairing or
changing the course of the process. The amounts of buffer
to be u~ed are in general 0.5 to 3 g/l, preferably 1 to
2 g/l.
,
Suitable fixing alkalls are commercially available
alk~lio, such a~ sodium carbonate and/or sodium hydroxide
solutions. They can be added to the dye bath in solid or
liguid form, preferably in the form of dilute aqueous
solution~, the volume of the fixing alkali solution being
preferably 3 to 10% of the dye bath. The amount of fixing
alkali to be added depend~ on the amount of reactive
dyestuff u~ed.
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In general, amounts of alkali of S to 20, preferably 10
to 20, g/l of anhydrous sodium carbonate and/or 1 to
4 ccm/l of sodium hydroxide solution 38 se have proved
to ~e most favourable.
The salt to be u~ed in accordance with the proce~s can be
either sodium ~ulphate or sodium chloride, preferably
~odium sulphate.
~he use o~ sodium chloride as the electrolyte under high-
temperature dyeing conditions is taken into account by
the buffered dyeing pH of the first step of the process
which is set at a weakly alkaline value. The claimed
process thus makes it possible not only to improve the
fixation yields with a moderate use of salt but, if
de~ired, also to use sodium chloride instead of sodium
lS sulphate which is used in the customary single-bath
process of the prior art. The amount of salt to be used
depents on the depth of shade and the liquor length. In
the ca~e of light-coloured dyeings, it is 20 to 40 g/l
~nd, in the case of deep-coloured ones, it is 40 to
80 g/l. The process can be carried out in any
commercially available dyeing machine3 approved $or high-
temperature dyeing ~from 130 to 140C), such as are used
for dyeing polyester/cellulose fibre blends.
The process for dyeinq polyester/cellulose fibre blends
is particularly advantageously used in short-liquor and
ultrashort-liquor machines since in tho~e machi~ee the
presence of high salt concentrations tends to cause
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precipitation of the disperse dyestuff and makes it
difficult to wash off the unfixed hydrolysate.
Accordingly, the process according to the invention
achieves dyeings having an improved colour yield and
improved fastness properties specifically on the newly
developed dyeing machines with a significant saving of
water and salt.
Suitable polyester/cellulose fibre blends to be dyed for
the proce~ according to the invention are those con~ist-
ing of native cellulose, ~uch as, in particular, cottonand linen, and al30 those consi~ting of regenerated
cellulose fibres, such as filament vi~cose and staple
viscose. The blend ratio~ of the polye~ter/cellulo~e
fibre blend~ can vary between 10/90 and 90/10, and are in
general between 80/20 and 20/80, preferably between 70/30
and 30/70.
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~he following dyestuff~ and combination~ t.hereof are
particularly preferred:
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U~ S
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U~ ZU~ Z
x~ z o
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z~ ~ :~
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O-- z=
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Mono-, bi- or trifunctional reactive dyestuffs containing
at least one monofluorotriazine, mono- or difluoro- -
pyrimidine and/or sulphatoethylsulphonyl or vinyl-
sulphonyl group Rh
Rh 1
503H OH F
H035{~N - N~N = ~ N~N
HO35 NlN N~503H :~
H H .:~:
: . ' ':
Rh 2 S03H
N r h~N=~
F Cl H~N-CO-HN H03
Rh 3
N--~N
503NI- OH NHlN'lN~ O
~N~aN~
~J N~03S~S03N-
Rh 4
503H H0 NH2
' - ~N~N~3--so2cHz-cH2oso3H
HNH035~503H . .
N~CI
F~N~F
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Rh 5 `~ ~:
S03H ~ NHz S03H
= N ~ = N ~ Cl
H035 03H NH~
S03H ::~
Ho350CH2-cH2o2s~
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Rh 6 ClSo~cH2cH2oso3H
~ N ~ O ~ H~CH~)2-NH
HN-tCH~)2HN ~ ~N ~ CO
lo~ Cl (l~2)2
tCIH~)2 CH2cH2oso3H COOH
COOH
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Rh 7
Ho3soH4c2N~o~so2c2H4-oso3H
.. Ho350H4c2o2 ~ NHC2H4-0503H
Cl
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Rh 8
F ` ~
N1N 53H :
1N'1NH{~ ~ ~
NH . ~ :
Ho35J3~N~ `NH~S03H
N~ ~N "~",.;,.
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Rh 9 : ~
:
i ~' ItS03~2-3
~1 N--~_ 1 ~502^NH2]0~9
j ~ ;~ Oz N~;
0 ~ 8
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Disperse dyestuffs D
D 1
O~N ~ N=N ~ N~
CH4CH2CN ,.
~' :
D 2
H3C ~ N~N ~ C4H
CN NHSO2CH3
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D 3 ~ :
O~N ~ N~N ~ ~C~H4C~
C4HqOCONHC4H9 ~ .
CN
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D 4
HO O NH~
~ r
H2N O OH
D 5 :~
NH2 OH
GH3
OH O NH2 ;
CN
02N ~ N - N ~ ~C2Hs
CN NHCOCH3
D 7
Br OCH3
2~ ~ N - N ~ (CHzCH20COCH~)z
NO2 NHCOCH3
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D a
o o
~N-~CH~)3-OCH~
o NH
Unlesq stated otherwi~e, the amount~ given in the : :
examples which follow are parts by weight. .~
.: :
Example 1 . ~ ~:
100 parts of a polyester fibre/cotton knitwear con~i~ting :~ ;
of 40 part~ of polye~ter fibre and 60 part~ of cotton are
treated in a commercially avallable jet-dyeing machine . : :
(Eco Soft from ~hies, Coe~feld) with 900 part~ of a hot
squeou~ dye liquor at 60C containing
part~ of anhydrous ~odium ~ulphate
10 1 part of a ¢ommer¢ially available anionic . .
dispersant
2 part~ of ~odium bi¢arbonate
2.41 parts of a reactive dye~tuff m~xture of ...
part~ of Rh 1,
. 14.5 parts of Rl 1 and
25.5 part~ of Rl 2
0.15 part of the dyestuff D1 and
0.30 part o~ the dyo~tuf~ D2.
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The material is treated at this temperature for 10
minutes with vigorous circulation of the liquor and then
heated to 130c over a period of 60 minutes and dyed at
this temperature for 30 ml~utes. It i5 then cooled to
80C over a period of 10 minutes, and 100 parts of a
fixing solution containing 10 parts of ~odium carbonate
are then added over a period of 30 minutes. The material
i9 then treated at 80C for another 60 minutes, and the
liquor is then discharged. The dyed material is rinsed
twice with hot water at 60C and soaped at 80C with a
commercially available nonionic detergent for 15 minute~
and then rinsed.
This give~ a clear red dyeing having good fa~tnes~
propertieq.
Examle 2
100 part~ of a polyester/cotton knitwear con~i~ting of 40
part~ of polyester fibre and 60 parts of cotton are
treated in a commercially available jet-dyeing machine
(Rotostream from Thies, Coesfeld) with 900 parts of a hot
aqueou~ dye liquor at 60C containing
part~ of ~odium chloride
1 part of a commercially available anionic
disper~ant
2 part~ of a buffer mixture consisting of
25 parts of tri~odium phosphate
S parts of mono~odium pho~phate 2HlO
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S0 parts of anhydrous sodium monochloro~
acetate
1.30 parts of a reactive dyestuff mixture of
50 part~ of Rl 3 and :
50 part~ of Rh 2
3.10 parts of a reactive dye~tuff mixture of
50 part~ of Rl 4 and
50 parts of Rh 3
0.5 part of a reactive dye~tuff mixture of
50 parts of Rh 4 and
parts of Rh 5
1.35 parts of the dye~tuff D3 and
0.11 part of the dye~tuff D4.
The material i8 treated at this temperature for 10
minute~ with rigorous circulation of the liquor and then
heated to 130C over a period of 60 minutes and dyed at
this temperature for 30 minutes. It is then ~ooled to
80C over a period of 10 minutes, and sodium carbonate in
~olid form i~ then added in three portions of 5 parts
each at an interval of 15 minutes each, and the material
is dyed at this temperature for another 30 minutes.
The llquor is then disaharged, the dyed material is
rin~ed twice at 60C and twice at 80C and then soaped
twice at 80C in the presence of 2 parts of a
nonionic/anionic deterqent for 15 minutes. It i~ then
rinsed with cold water.
. . .
, ~ This giveq a bordeaux dyeing having good fastness
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properties.
Example 3
100 parts of a polyester/cotton blend yarn consisting of
50 parts of polyester fibre and 50 parts of cotton are
treated in a commercially available yaxn-dyeing machine
with 600 parts of a hot aqueous dye liquor at 40C
containing
S0 parts of sodium chloride
1 part of a commercially available anionic
dispersant
1 part of sodium hexametaphosphate
2 parts of sodium bicarbonate
1 part of m-nitrobenzenesulphonate
1.9 parts of a reactive dyestuff mixture of
30 parts of Rl 5 and
parts of Rh 6 and/or Rh 7
1.1 parts of the dyestuff D5.
The liquor is heated to 130C over a period of 90 minutes
and circulated at this temperature for 30 minutes. It is
then cooled to 80C, and 60 parts of an alkali solution
containing 5 parts of anhydrous qodium carbonate and 2
; parts of sodium hydroxide solution 38 Be in dissolved
form are metered in from the add tank over a period of 4S
minutes. The material is then dyed at 80C fox lS
minutes, and the liquor i8 discharged.
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The dyed material is rinsed twice at 60C and twice at
80C, and then soaped at 80C for 15 minute~ with the
additional use of 1 part of an anionic/nonionic detergent
and rinsed with cold water.
This gives a deep blue dyeing having good fa6tness
properties.
Exam~le 4
100 parts of a polyester/filament visco~e blend fabric
consi~ting of 50 parts of polyester fibre and 50 parts of
viscose fibre are treated in an ~T ~hort-liquor jet-
dyeing machine (Ringsoft from Thies, Coesfeld) with 750
parts of a hot aqueou~ dye liquor at 60C containing
parts of anhydrous sodium sulphate
1 part of a commercially available anionic
dispersant
1 part of m-nitrobenzenesulphonic acid
0.5 part of 60% strength acetic acid
1 part of borax
2.2 parts of a reactive dyestuff mixture of
55 parts of Rl 6 and
45 part~ of Rh 8
1.8 parts of the dyestuff D6.
The material is treated at this temperature for 10
m~nutes with vigorous circulation of the liquor and then
heated to 130C over a period of 70 minutes and dyed at
,
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this temperature for 30 minutes. It is then cooled to
80C over a period of 10 minutes, and 50 parts of an
alkaline fixing solution containing S parts of potash and
1 part of 40~ strength potassium hydroxide solution in
dissolved form are then metered in over a period of 60
minute~, and the material is then dyed at 80C for 60
minutes. The liquor is then discharged, rin~ed twice with
cold and twice with hot water (60C) and then soaped
twice at 80C for 15 minutes each with additional use of
1 part of an anionic/nonionic detergent and rinsed with
cold water.
This gives a blue dyeing having good fastness properties.
Exam~le 5
100 part~ of a polye~ter/cotton blend fabric consisting
of S0 parts of polyester fibre and 50 parts of cotton are
treated in an HT ~hort-liquor ~et-dyeing machine ~Airflow
from Then) with 420 parts of a hot dye liquor at 70C
containing
parts of ~odium ~ulphate
1 part of a commercially available anionic
dispersant
1 part of 60% ~trength acetic acid
3.8 part~ of a reactive tyestuff mixture of
50 parte of Rh 4 and
50 parte of Rh 5
2.4 parts of the dyestuff D7.
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The liquor is heated to 130C over a period of 60 minutes
and circulated at this temperature for 30 minutes. It is
then cooled to 60C, and 30 parts of a fixing solution
containing 4 parts of anhydrous sodium carbonate and 2
parts of ~odium hydroxide solution 38C (Be) are added
over a period of 60 minute~. The material is then dyed at
thi~ temperature for 15 minutes, ant the liguor is
discharged. The dyed material is rinsed twice at 60C and
twice at 80C and then soaped at 80C for 15 minutes with
the additional use of 1 part of a nonionic detergent and
rinsed twice with cold water.
This gives a navy dyeing having good fa~tness propertie~.
Exam~le 6
100 parts of a polyester/viscose/linen blend fabric
consi~ting of 30 parts of polye~ter fibre, 40 part~ of
visco~e fibre and 30 parts of linen are treated in a
commercially available HT overflow dyeing machine
equipped with additional pump and make-up vessel with
1150 parts of a hot, aqueou~ dye liquor at 60C contain-
ing
part~ of anhydrous sodium sulphate
1 part of a commercially available anionicdispersant
1 part of monosodium phosphatQ 2~20
0.5 part of trisodium phosphate
0.7 part of the dyestuff D8
Le A 29 371 - 24 -
2.8 parts of a reactive dyestuff mixture of
50 parts of Rh 9 and
50 parts of Rl 8
The liquor is heated to 135C over a period of 60 minutes
S and circulated at this temperature for 20 minutes. It is
then cooled to 60C, and 100 parts of a fixing solution
containing 10 parts of anhydrous sodium carbonate are
added. The liquor is then heated to 90C over a period of
30 minutes, and the material is dyed at thi~ temperature
for 60 minute~. It is then cooled to below 80C, and the
llquor is discharged. The dyed material i8 rinsed twice
at 60C and twice at 80C and then soaped at 90 to 95C
for 15 minutes with additional u~e of 1 part of a non-
ionic detergent. It is then rinsed with hot and cold
water.
This gives a clear turquoise blue dyeing having good
fastness properties.
,
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