Note: Descriptions are shown in the official language in which they were submitted.
This invention relates to a process for the dyeing of synthetic
fibres.
Many variants of processes for the dyeing of synthetic fibres
under high temperature ~HT) conditions according to exhaustion processes with
developing blac~ dyestuffs on the basis of the diazo and oxydation technique
are well known. The very long dyeing time ~4 1/2 hours) is criticized as a
great disadvantage of all conventional methods.
According to the present invention, there is provided a process
for the dyeing of textile materials made from synthetic fibres or from mixtures
which contain such synthetic fibres, in the form of wound bodies, with water-
insoluble developing black dyestuffs based on the diazo and oxidation dyeing
technique according to the exhaust method at temperatures in the range of
rom 105 to 135C, in which process the wound bodies contained ln a pressure-
tight dyeing vessel are heated as well as de-aerated before the actual dyeing
operation, and subsequently contacted with the dyeing liquor which has been
separately heated to about dyeing temperature in a pressure-tight batch
vessel, placed under a relative excess pressure of from ~.9 to 9.81 bars and
then transferred in its total amount from said batch vessel into said dyeing
vessel, after both vessels have attained a temperature of 105 to 135 C,
whereupon the dyeing operation is continued by circulation of the dyeing
liquor alternately from the inside to the outside and from the outside to the
inside through the wound material, and developing of the dyestuffs is carried
out under the above-mentioned pressure and temperature conditions according
to the same principle, the improvement of which comprises: exposing the
wound bodies to an atmosphere of steam at about dyeing temperature prior to
contact with the dyeing liquor in order to preheat and de-aerate said
textile materials; and transferring the dyeing liquor within a time of 3 to
60 ~econds by means of said relative excess pressure and towards the pressure
of ~he air-free atmosphere of the steam into the dyeing vessel, simultaneously
from both the inside and the outside of said wound bodies, thereby entirely
condensing the steam in said vessel and filling it completely by the trans-
ferred liquor.
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1~53857
The principle of the present invention consists in that a
dyebath is prepared in a HT-vessel under the selected pressure and
temperature conditions and is passed from there by means of pressure
(pressurized steam, compressed air, pump pressure) into another autoclave
filled with steam and containing the wound bodies of syn~hetic fibres,
for example wound filaments or balls of piece goods on dyeing beams.
This is effected by pressing the bath simultaneously from the outside
and from the inside into the wound bodies through correspondingly sized
tubes, pumps and a distributor valve. This permits uniform distribution
of the dyeing liquor in the goods to be dyed within an extremely short
time, even with texturized synthetic filaments, without deformation of
the wound bodies and filaments. In general, periods of less than 60
seconds, in most cases even less than 30 seconds, are requirèd. This
rapid "shooting in" of the dyebath is achieved by a high pressure from
the side of the vessel which contains the dyebath (pressure difference of
5 to 10 atmospheres gauge). The vessel in which the dyeing operation
takes place is previously deareated by pressurized steam and at the same
time the goods are pre-heated. The textile material may be dry or pre-
washed, which process can be carried out in the dyeing vessel itself.
The dyeing vessel is pressure-tight, well isolated and provided with a
heat exchanger of high capacity in order to hold the dyeing temperature
constant. The bath itself is heated to about
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135C in ths bath vessel and the~ pres~ed into the dyeing ~essel
which is filled with steam. Within this proce~s the dyeing
~es~el may be filled completely al90 with c`losed val~e, provided
that the corresponding differential pressure has built up,
since the previously present steam condenses ~ith increasing
pre!3su.re .
A modification of the proce~s of the invention consists
in connecting the dyeing vessel filled with pressurized steam
to a condensation apparatus which may be closed. This, too,
enables the formation of a relative pressure difference which
makes it possible to completely fill the dyeing vessel with
the dyebath with closed de-aeration ~alve. It is also possi~le
to produce a rel~tive under-pressure in the dy~ing vessel
after the deaeration with steam, by a partial ~acuum from 2
vacuum line *hat can be closed. Hence there are several methods
possible for producing the necessary pressure gradient. Complete
evacuation of the dyeing vessel, however, is not necessary.
When the dyeing liquor is in the dyeing vessel, i.e.
when "shooting-in" is completed, the liquor i~ pumped with a
circulation pump alternately from in~ide to the outside and
from the outside to the inside through the ~round material,
whereby the circulation pump may start during the filling phaseO
The selected dyeing temperature is maintained during this time.
Final fixatiGn of the dyestuff generally takes place within
a short time. Under these temperature conditions it is of
ad~antase to operate with a sufficiently high output of the
pump. An output of more than 60 l/kg gi~es a good dyeing result.
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The fact that the total dyeing liquor is introduced with
high ~peed into the dyeing vessel and onto and into the more
or less dry material in the form of ~ound bodies distinguishes
it from the hitherto applied high temperature dyeing processe~
which with all their ~ariants ha~e largely been discussed in
literature. Thus, according to the invèntion, not just a part
of the dyeing liquor or a concentration dyastuff dispersion is
introduced into *he dyeing ~esse.L, but the total dyeing liquor
i8 pressed into it suddenly. It was not foreseeable that under
10 the-~e conditions level dyeings would be obtained, since
dispersion diazo black dyestuffs have a high abso~ptive power
at the~e temperature~v
In additi~n it was not expected that the dyestuff dispersions
would be suitabla for the penctration into wound bodies at such
high temperature~, pressure differences and possible turb~lence~.
It i8 furthermore surprising that the dyestuff dispersions
remain stable under these complicated apparati~e conditions
and do not tend to agglomerations.
An essential advantage in the process of the invention
resides in the fact that the absorptiv0 power of the dispersiol1
diazo black dyes*uffs i8 fully utilized at the high temperatures
used.
As dyestuff~ there may be used the u~ual commercial
- brands in the form of liquid preparations. Such dyestuffs are
described in the Colo~r Index, 2nd edition (1971) ~nder the
- - class desi$nation 'tAzoic Dyes".
For carrying out the process claimed synthetic fibres in
any stage of processing which may be dyed according to the HT-
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~ 57 HOE 74/F o63
dyeing method are ~uitable. However, the process is preferably
used for texturized threads of polyester and threads and
fibres of triacetate.
In the dyeing no other addition~ are nece sary except
di~persing agents and the chemic,al products for adjusting the
pH-value and to diazotize or purify the fibre material. The
constancy of the pH-value 6 of the dyebath permit~ i
reproducibility of the dyeings which is achieved by known
suitable buffer ~ystems. The material to be treated may be dry
- 10 or wet.
For a level dyeing it is important *hat the circulation
of the bath is not interrupted when switching over, which,`
as i8 known, may be achieved by a four-way co~nection o~
valve control.
The followins Example~ illustrate the invention.
:
Example 1
Wound bodies of linear texturized polyester filAments
were introduced into the dyeing vessel suitable for hi~h
temperatùre dyeing; this ~essel was deaerated with saturated
steam having 2 kp/cm and preheated with the goods. At the
same time the total quantityyof bath required for the dyeing was
prepared in a batch vessel; the quantity of bath amounted to
10 time~ the weight of ghe goods and contained, referred to
the weight of the dry goods, a mixture dispersed in water of
the componentY -
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1~5385 7 HOE 74/F o63
3.6 % of Disperse Black 1, C.I.No. 11365,
2.1 % of Azoic Coupling Comp. 20, C.I.No. 37530,
1 g/l of a condensation product of cresol and
formaldehyde and
1 g/l of a slightly adjusted buffer on the basis of
polymer phosphates and a 60% acetic acid (to pH 6).
An air pres~ure of 5.-5 kg/cm2 ~as then adjusted above
the level of the bath.
The bath under pressur~e wa~ then heated to 135C. By
opening a locXing valve in a suitable distributor line, the
heated bath was allowed to enter into the wound bodies fro~
the in~ide as well as from the outside within 7 to 10 seconds.
After the beginning of the circulation of the bath a mixed
temperature of about 125 C adjusted. With alternating circulation
f the bath, the bath temperature was raised to 135 C and
the good~ were dyed for 20 minutes at this temperature.
Then the dyeing apparatus was emptied by mean~ of high
temperature (~T) discharge.
In the meantime an a~eous bath was prepared in the
pressure ~ess~l with
2 cm3/l of sodium hydroxide solution`38 Bé (32.5 %),
0.5 g/l of the reaction product of 1 mol of nonyl
phenol with
mols of ethylene oxide
and heated to 90C. The bath was introduced into the dyeing
vessel fro~ the inside as well as from the outside by
applying pres~ure with compressed air. A mixed temperature of
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about 100 C adjusted. With alterna*ing circulation of the
bath and a tempera*ure of 100C the goods were treated for
10 minutes. By continuous overflow rinsing the temperature
was reduced to 60C and then the treating bath was allowed
to flow off. Then the material was steamed for 5 minutes at a
pressure of the saturated ~team of 1.5 kg/cm . In the meantim~
an aqueous bath was prepared in l;he press~re ~essel with
6 cm3 of acetic acid (60 ~) as wall as
4 g/l of sodium nitrite
at 110 C and after superpo~ing compressed air, introduced
into the dyeing ~essel under the Xnown conditions, A mixed
temperature of 1~0 C was adjusted and the material W&S t~ated
for 15 minutes at 110C with alternating circulation of the
bath. After completing as usual a level and very fast black
dyeing was obtained.
Example 2
Wound bodies of polyester filaments and cotton in a
mixture ratio of 65:35 were introduced into a dyeing ~essel
according to Example 1 and pre~iously steamed. The further
treatment to dye the material was ef~ected, as de4cribed in
Example 1, but with a mixture dispersed in water of the
components (from the weight of the material)
2.35 % of Disperse Black 1, C.I.No. 11365 and
1.4 % of Azoic Coupling Comp. 20, C.I.No. 37530,
- until the intermediate purification was finished. ~y
continuous o~erflow rinsing the bath temperature was reduced
to 30 C and the bath was subsequently allowed to discharge.
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The subsequent cro~-dyeing of the cotton portion wa3
effected with an aqueous bath containing (from the weight of
the material)
. o.6 ~ of ~he dye~tuff Sol.Vat Orange 1, C.I.No. 59106,
1 g/l of calcinated soda and
10 g/l of calcinated sodium sulfate
during 20 minutes at a temperature of 30 C. Then the dyebath
was discharged.
In the meantime a bath had been prepared in the pressure
-10 vessel which contained on an aqueous base
6 cm3~1 of acetic acid (60 %) as well as
4 g/l of sodium nitrite
and which, after superposing compressed air, wa~ heated to
135C. By opening a block~ng valve in a ~uitable distributor
line the bath was introduced into the dyeing ves~el with the
material from the inside as wèll as from the outside and
after starting the pump for the circulation of the bath a
mixed temperature of 85 C was adjusted. With an alternating
circulation of th~ bath the temperature of treatment was
increased to 110C and the material ~-as treated for 15 minutes.
After ~ompleting as usual an even dyeing was obtained,
whereby the polye~ter fibre had a black color and the portion
of cstton a yellow color.
~
Wound bodies of polyester filaments and cotton in a
mixture ratio of 50:50 were introduced according to Example 1
,
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_ l~S3857 HOE 74/F 063
into a dyeing ve~sel and previously dyed. The further treatment
for dyeing the goods wa3 effected, as de~cribed in Example 1,
but with (from the weight Or the material)
the dispersed mixture o~ dyestuff components in analogy to
Example 2,
until the high temperature ~taga wa~ finished when dyeing
the polyester portion. The dyebath was subsequen~ly discharged
under high temperature conditions (HT-.outlet).
In the meantime a bath ~as prepared in the pres~ure ~essel,
- 10 which contained in the aqueou~ medium
7 % of the dyestuff Vat Black 9, C.I.No. 65230
and which was heated to 65C. After introducing compres-~ed air
into the batch the bath was transferred from the inside and
from the outside into the dyeing ~essel containing the textile
15 material and after starting the pump for the circulation of
the bath a mixed temperature of 80C was adjusted. With an
alternating circulation of the bath
40 cm3/l of sodium hydroxide so~ution 38Bé (32.S %) and
10 g~l of sodium dithionite (as a solution in water)
20 wsre addad after 20 minute~ over the open circulation and the . -
material was dyed for ~0 minutes at 80 C. By cold continubu~ .
rinsing the pH-value of the textile material was ad3usted to
pH 8 and then the rinsing bath was allowed to discharge. ~ :
The textile material was ~ubsequently steamed for 5 minutes
25 at 120C. .:
The diazotation bath prepared in the meantime and heated
to 110C containing in water
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- 1053857 HOE 74/F o63
8 cm3/1 of acetic acid (60 ~)
~ g/l of sodium nitrite,
was snperposed in the pressure vessel with compressed air of
5.5 kp/cm and introduced in*o the dyeing ~essel from the
inside and from the out~ide by opening a distributor line.
After starting the circulation of the bath a mixed temperature
of 110C adjusted and the textile material was treated for
15 minutes with alternating bath circulation.
After completing as u~ual an even fast black dyeing was
obtained on both fibre portions.
Example 4
Looped materials of triace*ate fibres were introduced in
- a wound-up state into a HT beam dyeing appar~tus for piece
goods. This vessel was $hen dearearated by saturated steam
- of 0.~ kp/cm2 and pre-heated with the material. Simultaneously,
the whole amount of the bath necessary for dyeing wa~ prepared
in a batch vessel necessary for the dyeing; the quantit~ of
bath amounted to 10 times the weight of the goods and
contained, referred to the weight of the dry good~, a mixture
disperYed in water of the components
3.0 ~ of Disperse Black 1, C.I.No. 11365,
1.75 % of Azoic Coupling Comp. 20, C.I.No. 37530,
1 g/l of the condensation product of cresol/formaldehyde
and
- 1 g~l of *he bRffer mentioned in Example 1, on the basis
of polymer phosphates and 60 ~ acetic acid (to pH 6).
A pressure of compressed air of 5.5 kp/cm was adju~ted.
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` 1053857 HOE 74~F o63
The bath preparation under pressure was heated to 110 C.
By opening a lockin~ valve in a suitable di~tributor line
the heated bath wa~ allowed to enter within 7 to 10 seconds
into the ~ound bodie-~ from the inside as well as from the
outside. After beginning the bath circulation a mixed
temperature of 110C wa~ adjusted. With alternating bath
circulation the material was treated for 30 minute~. Then
the dyeing liquor was cooled to 85 C. The matenal was then
rinsed continuously at 60 C during 10 minutes.
For an intermediate purification
2 cm3/l of sodium hydroxide solution 38Bé (32.5 %) and
0.5 g/l of the reaction product of one mol of nonyl
phenol and
10 mols of ethylene oxide
were added to thi~ aqueous bath over the open circ~lation
and the textile material was treated for 10 minutes at 70C.
It wa~ followed by a rinsing process at 60C. Then the
material was diazotized during 15 minutes at 60 C with an
aqueous bath containing 2.5 cm3/l of sulfuric acid (96 ~) and
- 2 g/l of sodium nitrite.
The additives were introduced o~er the open circulation.
After completing as usual an even black dyeing was obtained.
Example 5
Wound bodies of linear texturized polyester filaments
were introduced ac~ording to Example 1 into a dyeing Yessel
and pre~iously -~teamed. The further treatment for dyeing the
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- ~ 10538S~ OE 74/F o6 3
textile material was effected, as described in Exa~ple 1,
but with a mixture dispersed-in wa*er of the component~:
3.0 % of Solvent 8rown, 3, C.I.No. 11360
1.75 ~ of Azoic Coupling Comp. 20, C.I.No. 37530
1 cm3/l of ~odium hydroxide ~olution 38Bé (32.5 %)
1 g~l of the condensation product of cresol/formaldehyde
and
g!l of qodium monochloracetate.
After impregnation the material was subjected to
ip intermediate purification and diazotation a~ described in
Example 1.
An even black dyeing was obtainedO
.
Example 6
Wound bodie~ of polyester fibres and cotton in a mixture
ratio of 65:35 were introduced according to Example 1 into
a dyeins ~e~el and previously steamed. The further treatment
for dyeing the textile material was effected, as described in
- Example 1, but with a mixture dispersed in water of the
components (from the weisht of the material)
2.1 ~ of Disperse Black 1, G.I.No. 11365 and
1,2 ~ of Azoic Coupling Comp. 20, C.I.No. 37530,
until the HT-s~age wa~ completed when dyeing the polyester
~ portion. The dyebath ~as discharged under high-temperature
conditions (~IT-outlet).
- In the meantime a bath was prepared in the pres~ure
ve~sel which contained on an aqueou~ base
6 % of a dyestuff Sol. Sulphur Black, C.I.No. 53186 and
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11353~35i7 HOE 74/~ 063
5 g/l of calcinated ~odium carbonate.
After pressing compres~ed air onto the bath preparation
~nd heating to 115C, the bath was transferred from the inside
and the outside into the dyeing ~ressel containing the textile
material. After starting the circulation of the bath a mixed
temperature of 110C was adjusteld. With alternating bath
circulation
12 cm3/l of sodium hydrogen sulfide ~olution (21 ~) and
3 cm3/l of ammonium polysulfide solution (15 ~)
were added after 10 minutes over the open circulation, then,
in the same way
20 g/l of ~odium sulfate were added.
With alternating bath c2rculation the material was d~ed
for 30 minutes at 95C. Then the material was rinsed continuously
for 10 minutes. After dischargins the rinsing bath the
dyestuff was oxyd~ed during 10 minutes at 40C with an
aqueouq bath containing 1 cm3/1 of hydrogen peroxide (35 %),
the oxydation bath was discharged, the dyeing was rin~ed
fon a short time and the textile material was steamed for
5 minutes at 120C.
The diazotation bath prepared in the meantime in the
pressure ~essel and heated to 110C, containing on an aqueous
ba~e
o cm3/l of acetic acid (60 %) and
4 g/l of sodium nitrite 2
- was superposed with compressed air of 5.5 kp/cm , and by
opening a distributor line, introduced into the dyeing vessel
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1~ S 3~ HOE 74/F o63
from the inside as well as from the outside. After starting
the bath circulation a mixed temperature of i10C appeared
and the textile ma*erial was treated for 15 minutes with
alternating bath circulation.
After completing as usual a even black dyeing was
obtained on bot~ fibre portions
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