Note: Descriptions are shown in the official language in which they were submitted.
~lO~'7~3~J~j
German OEfenlegun~sschriEten Nos. 2,331,669, 2,357,447, 2,357,439,
~,357,476 and 2,409,727 relate to processes for dyeing textile materials of
natural or synthetic origin or mixtures thereof, in the form of wound bodies
or dyeing beams, with dyestuffs or components of developing dyestuf~s appro-
priate for the corresponding fiber type according to the exhaust method by
deaerating wi~hin a closed system a pressure tight dyeing vessel with the
~ncluded fiber material by means of a Elow of saturated steam or super-heated
steam and heating it to the dyeing temperature typical for the corresponding
dye, then pressing the total quantity of a dyebath, prepared ;n a separate
pressure-tight batch vessel and having the same temperature or a higher tem-
perature, into the textile goods by means of excess pressure within a short
period ~within 3 to 60 seconds) as well as simultaneously from the inside and
from the outside of the material package and terminating the dyeing operation
with alternating circulation of the bath. This dyeing principle described in
the literature as 'IRapidcolor Technique" has been used successfully and with
an obvious economy of time as compared to conventional methods in various dye-
ing plants.
Said rapid dyeing process depends, however, on certain technological
cond~tions such as output of the pump and dimension of the dyeing vessels. ~`
2a In order to obtain an optimum levelness of a dyeing even with extremely un-
favorable clear shades, pumps having an output of at least 60 l/kg minute
are necessary. The resulting relatively high hydraulic pressure requires,
however, a special manner of feeding of the dyeing vessel, i.e. simultaneously
from the inside through the wound-up bodies as from the outside to the inside,
in order to avoid an unfavorable deformation of the fibrous material, which
may be texturized. The circula~ion pump is already started during the filling
process and the dyebath is pumped alternately from the inside to the outside
and from the outside to the inside through the wound-up material during the
C, ~ ,.
. ~ - . , .
- ~: .
~urth~r dy~ing proc~ss. During thls operation th0 dyeing vessel is comple~e
ly filled with the d~ebath. Ihe owtput of the pump requlred in this case
consequently puts a limit to the si~e of the dyeing vesselJ owing to the ~act
that bounds are set for the construction of pumps for dimensional reasons,
according to disclosure in the journal Chemiefasern 24 (lg74), page 747.
As the total quantity of dyebath is shot into the treating vessel
at one time when operating with the Rapidcolor plant of known design, a
pressure-ti~ht batch vessel is required having at least the same size as the
dyeing autoclava. A higher technological expenditure than in conventional
dyeing plants thus is inevitable, but may be slightly reduced by connecting
several dyeing vessels with batch vessels having the corresponding size.
Besides the requirement of a special machine equipment in the
Rapidcolor process there are made high requirementsJ owing to the existing
pressure and temperature conditions, to the dyes appropriate or this method
as to the levelness of the dyeing and the stability of the individual dyestufs
and their formation natureJ thus the number of suitable dyes is limited.
When further developing the Rapidcolor Technique it has been found
that the a~oresaid restrictions concerning the practicability of the dyeing
method in question may be cleared away when during the feeding phase of the
2a liquor the dyeing vessel is only partially filledJ generally up to half of
its total ~ath volumeJ with the hot dyebath so that there is obtainedJ while
the dye~ath is continually circuiating with regard to the material package
from the inslde to the outside during the actual operationJ owing to the
smaller volume of the bath, a higher circulation of the bath as compared to
completely filled dyeing vessels.
By~the aforesaid provisions the Rapidcolor process is adapted to
dyeing plants provided with a conventional equipment of apparatuses and it
may be operated with smaller pressure-tight batch vessels for the liquor as
- 2 -
78~)~
~ell as with circulation pumps having ttle conventional output.
~ en takl~g into account the low~r level of illing of the dyeing
vessel there results in the process of the invention a goods-to-liquor ratio
in the range of from 1:4 to at most 1:10, preferably o~ 1:4 to 1:7 (as com-
pared to apparatuses working with a goods-to-liquor ratio of from 1:12 to
1:18). The goods-to-liquor ratio appropria~ely reduced enables operating
wlth an output of the pump of from 2Q to 50 l/kg minute, pre~erably of from
30 to 40 l/kg minute and attaining circulation rates of the liquor of from
6 to 10, preferably of 8 per minute.
It is quite understandable for an expert in the art thatJ when the
dyeing vessel is only filled partially, the dyebath may only circulate from
the inslde to the outside through the wound material. Despite of the uni-
lateral direction of flow during the actual dyeing there is in the process of
invention owing to the lower output of the pump no risk of a deformation of
the textile material, even at places where th~ wound material is not exposed
to the counter-pressure by the liquor from the outside. It was consequently
surprising and by no means to be expected that level dyeings may be obtained
with the process of the invention even when introducing a dyebath preheated
to high temperatures of from-llO to 145C only from the inside to the outside
through the ~ound material. This result may be achieved owing to the fact
~hat there is performed by means of the hydraulic pressure of the liquor flow-
ing from the batch vessel only filling of the interior tubes ~material sup-
port), whereas supplementary pressing of the hot dyebath otherwise causing
the deformation of the textile material is avoided by the fact that the resi-
dual quantity of liquor either may flow from the outside to the textile ma-
terlal and/or is filled up with suction by the circulation pump. The time
required for the process of filling is only extended to an insignificant ex-
tent by this process, surprisingly.
- 3 -
,,~
...
......... .. .
.. . . . : . , ,
'7~
According to the present invention, there i~ provided
a process for dyeing textile mate~ials ofnatural or synthetic
origin or of mixtures thereof, in the form of wound bodies or
dyeing beams, with dyestuf~s or components of developing dyestuffs
appropriate for the corresponding fiber type according to the ex-
haust method by deaerating ~ithin a closed system a pressure-
tig~t dyeing vessel with the included fiber material by means
of a flow of satura~ed steam or super-heated steam and heating it
to the dyeing ~emperature typical for the corresponding dye, then
pressing the total quantity of a dyebath, prepared in a separate
pressure-tight batch vessel and having the same temperature or a
higher temperature, in~o the textile goods by means of excess
pressure within a short period as well as simultaneously from
the inside and from ~he outside of the material package and ter-
minating the dyeing operation in usual manner which comprises
fillingJ during the feeding phase of the liquor, the dyeing vessel
~th t~e hot dye~ath only partially with regard to its total bath
volume so that there is obtained a higher circulation of the bath
as compared to completely filled dyeing vessels, while the bath ~ :
is continuously circulating with regard to the material package
from the inside to the outside during the actual dyeing operation,
owing to the lower volume of the bath.
: .,:'
,, :
'
- 3a -
(~ ,
'7~
The present inven~ion consequentl~ permits obtaining level dy~ings
even when using pumps having a lower output in comparison to conventional
pumps used in Rapidcolor Technique. An essential fact indispensable for the
levelness of the dyeing is that the pump is working continuously, i.e. that
there is no cavitation. This result is obtained by connecting a small tube
having the dimension of the pump pipe and being fixed at the bottom of the
dyeing vessel directly below the material support with the pump so that the
flow of liquor can not be interrupted at the suction side of the pump. The
condltions to be maintained permit using conventlonal circulation dyeing ap-
paratuses having the usual output of the pump and by modifying them slightlyfor the Rapidcolor dyeing modified according to the invention~ Thus the
requirements of the practice are complied with in so far as there are no ex-
cessive costs for tube systems and ventiles having the extraordinary dimen-
sicns owing to the reduced output o the circulation pumps and as the expendi-
ture of energy is thus more favorable. The dimension of the apparatuses
- therefore have no longer such narrow limits so that large-sized dyeing plants
of the type used according to the invention may henceforth be constructed.
According to a variant of the present invention based on the Rapid-
color principle ~preheating of material and dyeing vessel with steam) it is
20 now possible to introduce the dye to be used and/or the auxiliary directly
into the supply of the hot liquor during the filling phase by means of a pres-
sure valve. Thereby the addition of dyes and/or auxiliaries through said
feeding device may already be performed at temperatures in the range of from
40 to 95C, preferably of from 50 to 80C. By transferring such dyestuff pre-
paration into the hot water flowing into the dyeing vessel a notable cooling
of the dyebath with regard to the optimum dyeing temperature being, for ex-
ample in the case of polyester fibers, of from 120 to 145C, pre~erably of
from 130 to 140C, does not occur. The relatively low cooling effect due to
~ ~.. ,`.3
` '
: ' . :: ' . , . ' ' ,:
~0~'780~
the feedlng o~ dyestuf~ andtor auxlliaries preparations ls not really impor~
tant as the volume o~ the pTessure valve and thus of the corresponding batch
quantity of dyes or auxiliaries is in the range of from 5 to 30%, preferably
of from 8 to 20% of the total volume of the dyebath. This reduction of the
temperature o~ the entering liquor may be compensated for by increasing the
batch temperature of the latter adequatel~ With regard to the feeding tech-
nique by means of such supplementary devices even allowing the addition of
~ supplementary quantities into a closed pressure system refer to Chemlefasern
; 20 ~1970), page 3g8 to 401.
Considerable advantages with regard to the space requirement reside
in the fact that a substantially smaller pressure valve is only necessary
instead of a batch vessel having the same dimension as the dyeing vessel, when
use is made of the combined Rapidcolor feeding method.
The feeding technique moreover has the advantage that even auxili-
aries or reducing agents for a reductive after-treatment of the dyeings may
he introduced at any time by means of the pressure valve. More~ver, for
rapidly cleaning the whole dyemg aggregate blank dyebaths advantageously
` with assistance of suitable auxiliaries may be introduced through the pressure
valve at a temperature in the range of f~om 120 to 145C.
In connection with the present invention it has proved advantageous
to assure the water supply for the dyebaths by a central high temperature (Hr)
water reservoir.
Such an occasion is of special importance when the central high tem
perature water supply is large-sized enough that all dyeing apparatuses in- ~.
tended to be installed in a normal yarn dyeing plant may be rapidly fed with
~ater having a temperature of from 110 to 145aC from this reservoir.
~t ~as unexpected and extremely surprising for the expert in the
art that all measures described can be carried out simultaneously and that
., ~,
~,.;,....................................................... , ~'
.: . . ~ -
; ~.. , . . : . : : .: ~ . . : :
:.... .. - .. . . - .. : .: -:
~o~
troubleless le~el dyeinKs can nev~rthcless be obtaLned. The process of the
invention permits using even dyestuffs successullyJ ~he resistance to heat of
which, for example due to risk of reduction, is not optimwn.
The described process is generally carried out in aqueous medium;
it may, however, also be used without difficulty for dyeing from organic sol-
vents, ~hen taking into ~ccount the boiling point typical for each solvent
as well as the vapor pressure.
For polyester types, which are particularly dif~icult to dye level,
for example, polyes~er endless threads, the use of a correspondingly higher
quantity of levelling agents has proved advantageous. Among such products
there may be used, by way of example, dispersing agents based on oxethylates,
le~elling carriers based on emulsified diphenyl and linear, water-soluble
polyesters ~aving an average molecular weight of from 1000 to 5000, of
ar~atic, sulfonated dicarboxylic acids and diols. They are advantageously
~ntroduced into the circulation system of the bath by a pressure valve, op-
t~onally as supplementary quantity, generally in an amount of from 0.5 to
2.a% Ccalculated on the weight of the goods).
The use of from 1 to 4% ~based on the weight of the goods)~ prefer-
ably of from 1.5 to 2.5%, of an auxiliary consisting of from 85% by weight of
perchloroethylene and 15% by weight of an emulsifier mixture in the dyebath
has proved advantageous for the process of the invention.
The following examples illustrate the invention:
EXAMPLE 1:
:
~ ound bodies of linear texturized polyester threads were given into
a dyeing vessel suitable for high temperature dyeing; said vessel then was
deaerated by saturated steam of 2.25 kp/cm and so preheated with the goods.
At the same time the whole quantity of aqueous bath necessary for dyeing was
prepared in a pressure-tight batch vessel, which amounted to 6 times the weight
, ~ - 6 -
, ~ ,,. -:
:~: , . . . ., . . ~: ................ - -: `;
,; - . : ~
of the goods and contaLnedl calculated on the ~elght of the dry goods,
1.5% of the disperse d~e of the formula
CN NH-CO-CH3
021~ ~11=N ~--N
CN
1 cm3~1 of acetic acid (of 60%)
1 cm3/1 of a liquid dispersing agent based on
; cresol/formaldehyde condensates,
1 g~l o a bufer substance be mg adjusted to
give a weakly acld value, based on polymer
phosphates and
~.5 cm3/1 o~ a dispersing age~t based on oxethylates.
A pressure o 6 kp~cm2-was adjusted over the level o the bath b~
means o~ compressed air.
Now the batch being under eievated pressure was heated to 135C. ~ ;
B~ opening a blocking valve in an appropriate distributor line the heated ' ;~
bath was allowed to enter into th. dyeing vessel w~thin 7 to lO secondsj this ;.
; proceeding sscured penetrat~on o the dyebath into the wound body from ins~de
as well as from the outside. A~ter the beginning o the circulation o the
bath a mixed temperature of about l25C adjusted. With unilateral flow direc-
tion o the ~ath from the inside to the outside, the quantity o bath present
in the dyeing vessel was heated to 135C and the goods were dyed at said tem-
, perature for 3Q minutes. The dyed material then was subjected to a reductive
i a$ter~treatment ln us,~al manner and dried. A level blue dyeing was obtained.
i W~en using in the above Example instead of said disperse dye the
d~perse dye o the ormula
~ 7
3tj
C~13
NaN
O ~ N ~ OH
CH3
a level yellow dyeing was obtained.
BXAMPLE 2:
Wound bodies of linear texturized polyester threads were placed in
a dyeing vessel suitable for hlgh temperature dyeing. Said vessel was de-
aerated with saturated steam of 2 kp/cm2 and so preheated wlth the goods. The
quantit~ of aqueous bath necessary for dyeing was prepared at the same time in
a pressure-tight batch vessel; it amounted to 5 times the weight of the goods
and consistsd of ~calculated on the weight of dry goods):
1 cm3/1 of a dispersing agent based on cresol/formaldehyde
condensates,
2.5 g/l of sodium acetate,
2 cm3/1 of acetic acid (50%) and
0.5 cm3~1 of a dlspersing agent based on oxethylates.
No~ a pressure of 5.5 kp/cm was adJusted by compressed air over
the level of tha bath. Simultaneously, a quan~ity of bath having a tempera-
ture of 8QC and amounting to half the weight of the dry goods was introduced
into a pressure valve connected with the system circulation of the bath. This
quantit~ of liquour contained 0.5% o the disperse dye of the formula
CN
~ ~ CH2-C~I -CN
2Q ~2N ~ N a N - ~ N \ ~r-~
H2 2
- 8 -
.. : ~-.. ;... ... . - .. : ~
By opening a blocking valve in a suitable distributor pipe as well
as by opening the blocking valves of the pressure valve, the bath was fed into
the dyeing vessel, both from ~he pressure-tight batch vessel and from the pres-
sure valve, within a period of from 7 to 10 seconds while being mixed continu-
ously. This proceeding secured penetration of the dyebath into the wound
bodies from the inside as well as from the outside. AEter the beginning of
the circulation of the bath a mixe~ temperature of 120C adjusted. The dyeing
was terminated according to Example 1 wlth unila~eral circulation of the bath
from the inside to the outside.
A level red dyeing was obtained.
EXAMPLB 3:
Wound bodies of linear polyester endless threads were introduced
lnto a dyeing vessel suitable for high temperature dyeing. Said vessel was
deaerated by saturated steam of 2.25 kp/cm2 and 50 preheated with the goods.
~t the same tlme the total quantit~ of aqueous bath necessary for the dyeing
~as prepared in a pressure-tight batch vessel; it amounted to 6.5 times the
weight of the goods and contained, referred to a weight of ~he dry goods,
4% of the disperse dye of formula
N02 OC2H5 ~ ~
~ CH2-cH2~o-co-cH3
02N ~ ~ N=N ~ ~ - N
CH2-CH2-0-cO-cH
Br NH
CO '
CH3
1 c~3~1 o~ a llquid dispersing agent based on a cresol/
formaldehyde condensates,
1 gll of a buffer substance being adjusted to give a
~eakly acid value, based on polymer phosphates,
~ _g_ ~
1 cm3/l of acetic aci(l ~60%) atld
~.5 cm3/1 of a dispersing agent based on oxethylates.
Now a pressure of 6 kg~cm2 was adjusted by compressed air over the
level of the bath. The heating and the beginning dyeing process were per-
formed as in Example 1. 10 Minutes after having attained the final dyeing
temperature of 135C, 1% of a carrier based on diphenyl ~calculated on the
dry weight of the goods) and being emulsified in a quantity of water amounting
to half the weight of the goods, was added to the circulating dyebath at a
temperature of 80C by opening blocking valves conneeting a pressure valve
lQ with the main circulation system of the bath. The goods were then treated for
another 20 minutes and the dyeing was terminated in usual manner.
A level navy blue dyeing was obtained.
EXAMPLE 4:
The heating of the dyeing vessel and the textile material, as well
as the dyeing process were performed according to Example 1. 20 Minutes after
ha~ing attained the dyeing temperature, 1.5~ of an auxlliary based on per-
chloroethylene (calculated on the dry weight of the goods), emulsified in a
quantlty of water amounting to 10~ the quantity of bath in the dyeing vessel,
, were added to the circulating dyebath at a temperature of 95C by opening
blocking valves connecting a pressure valve with the main circulation system
o the bath. The goods were then treated for 10 minutes at the final dyeing
temperature. After having discharged the bath, the dyeing was rinsed with hot
water and dried.
A level blue dyeing was obtained.
EXAMPLE 5:
.
~ arn wound bodies made of linear polyester fibers and cellulosic
staple fibers in a mlxlng ratio o 67:33 were treated according to Example 2
and dyed.
.,
0
~` ,
,: , ' . : ',' ' ' ~ `: . ' '' ' - ' ~' '
1~8~ U~
A r~d dyeing of the por~ion of polyester fibers of the goods was ob-
tained. Dyeing of the por~ion of cellulose fibers could be carried out by
using suitable dyes, for example direct, r0active, vat dyes and others, by a
single-bath or two-bath process.
EXAMPLE 6:
~Yound bodies o crimped nylon were introduced into a dyeing vessel
suitable for high temperature dyeing. Said vessel was deaerated with saturated
steam of 1.5 kg~cm2 and the goods were so preheated.
Simultaneously, the quantity of aqueous bath required for dyeing was
prepared in a pressure-tight batch vessel in a goods-to-liquor ratio of 1:6,
referred to the weight of the goods; it contained, calculated on the weight of
the dry goods:
0.8% of the anionic dye Acid Blue 41 ~C.I. No. 62 130)~
2.5% of the reaction product of 1 mole of cyanuric
chloride with 3 moles of metanlIic acid,
0.5% of a mixture of 75% of the reaction product of 1 mole
of stearylamine with 10 moles of ethylene oxidej and -
25% of dodecyl sulfonic acid and
0.8% o~ acetic acid ~60%)
2Q No~, a pressure of 6 kg/cm2 uas adjusted in the pressure-tight batch
vessel 6y compressed alr over the level of the bath.
The bath being under pressure was then heated to 115C. The bath
~as thereafter pressed into the dyeing vessel from the batch vessel as in
Example 1, whereby a mixed temperature of 110C adjusted at the beginning of
the circulation of the bath. The ~emperature of the bath was increased to
115~C and the goods were dyed for 20 minutes at this temperature. The dyed
material was rinsed with hot and cold water in usual manner and dried.
A level blue dyeing was obtained.
. ........
. . - . - :. . . ............. : . , ........ - - . , :
~: . , - - . . . :,. , , . ~ . . . ~ ,
