Note: Descriptions are shown in the official language in which they were submitted.
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The present invention relates to the pad--dyeing or
pri.nting of textile material macle from natural or synthetic
polyamide fibers.or mixtures thereof wi.th other fibers with
reactive dyestuffs which in comme~^cial constitution are
present in a form incapable of reacti.ng by itself with the .
fiber substance, and which from an aqueous medium are
otherwise induced to fixation on the fiber in the case of
exhaust dyeing accordincJ to known processes (i) either
directly in their non-reactive form under acidic conditions
o~ (ii) be converted ~o their reactive form by the
influence of alkaline agents durin~ the dyeing operation
prior to being fixed uncler subsequently adjusted acidic
conditions. The invention comprises furthermore special
formulations of such reactive dyes suitable for application
in the novel procoss.
Dyeing with so-called reaetive dyes is, as principally
eellulose fibers are concerned, already known for a certain
ime and has fully proved its wor-th in the practice because
of the clear and dull shades and the fas-tnesses so obtainable.
Such coloring agen-ts are of organic origin and listed i.n
Colour Index, 3rd edition 1971, under the generic term
"Reactive Dyes". Dyestuffs of said species belony to the
series of azo-, anthraquinone- or phthalocyanine compounds
which may be present in the form of metal cornplexes and
which cont:ain at least one group capable of reacting with
the fiber. In sorne.cases, however, such a group reacting
with the fiber is not present a priori but formed by
suitable operati.orls only in the dyeing process from a
precursor thereo A current example of this latter type
are reactive dyes on the basis of esters of mono- or poly-
valent, inorganic or organic acids which can easily be
s~lit Or~, especially of sulfuri.c acid esters, ~ith
B-hydroxyethylsulfone compounds (Ester dyestuffs), from
which in the course of the dyeing process by the influence
of alkaline agents the fiber-reactive vinylsulfone form
~VS form) of the dyestuff i.s formed.
For coloring cellulose textiles of all ~inds, reclc~i.ve
dyes arc? applied accordillc3 to texti1.e pri.nting processes as
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~8~i~57
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well as exhaust or continuous dyeing processes. In the
industrial practice these dyestuffs are usually fixed on
the fiber prevailing Erom an aqueous medium and prlmarily
in the presence of al}aline agents. Suitable fixation
alkali5are those which cause the conversion from the
commercial form of the Ester dyestuffs to the VS form reac-
ting with the polyhydroxy fiher, either at room temperature
or with the ai.d of heating, depending on the reactivity
degree of the dyestuffs. In the exhaust processes, as a
ruleJsodium hydroxide solution, sodium carbonate ox tri-
sodium phosphate are used for said purpose, while in
pad-dyeing water glass and sodium bicarbonate are suitable
as well as sodium hydroxide solution and sodium carbonate.
Fixation of the reactive dyes in the exhaust process
occurs immediately after their absorption by the fiber at
temperatures of up to the boiling point of the dyeing bath,
while in pad-dyeing after the application of the dyestuff
a separate operation including dwelling, steaming or dry
heat treatment is required for the saicl proceeding.
Disadvantageous for the pad-dyeing processes is the reduced
stability of the reactive dyes in the alkaline range. Under
these conditions, for example, from ~S dyestuffs due to
hydrolysis B-hydroxyethylsulfone dyestuffs are forrned which
canno-t react with the fiber. AlthoucJh this undesirable
behavlor can be overcome by a two-bath trea-tment rnethod
accorc1j.ncJ to which first the non-reactive Ester dyestuff
is applied without alkalis, and then the required amount
of alkali is supplied in a second paddlng operation, as
the COnSeqUenCQ for such a tactical round3 bout way,
3Q ho~ever, the disaclvantage of an intermediate drying must
be paid.
When printing with reactive dye~, the reduced s-tability
of these dyes in an alkaljne medium can be avoided by
mixillcJ to the printing pastes so-called alkali donors which
se-t free the alkali in the fixation process at elevated
temperature.C; only. Such alkali donor., are for examl?le
sodium bicarbonate, sodium tricllloroacetic acLd or dicyano-
diam i.de .
For the dyeing of wool and polyamide fibers, commercialreactive dyestuffs of the above type are used either in their
form non-reacting with -the fiber, :in an acidic medium and under
high temperature (HT) conditions (German Patent No. 2,834,997,
German Auslegeschrift No. 2,847,913 and German Offenlegungsschrift
No. 2,933,343), or they are converted first to -their fiber-
reactive form in the course of the dyeing process and then applied
in this latter form in an acidic medium (TED process, see
Technischer Rat aus Hoechst, Textil No. 73). However, applic-
ability oE these two operation modes remained as yet be limitedto the exhaust dyeing only. On the other hand, a continuous
process for the pad-dyeing or printing of wool and polyamide
fibers with reactive dyes which ls feasible in the industrial
practice does not exist until now.
It has now been found that reactive dyestuffs which in
cornmercial constitution are present in a form non-reactive by
itself with the fiber substance give a good color yield on
dyeing or printing of natural or synthetic polyamide fibers when
the said dyestuffs are pretreated (before dyeing or prin-ting) in
an aqueous medium in such a manner that they are converted to
their fiber-reactive form, and then chemically stabilized in this
latter form. Pad-dyeing or printing with these dyestuff
formulations is then carried ou-t exclusively from an aqueous,
neutral to acidic medium according to the opera-tional procedures
us-ual for these application types.
Accordingly, in a process for the pad-dyeing or printing
of textile material made from natural or synthetic polyamide
fibers or mix-tures thereof with other fibers, using a reactive
dyestuff whi.ch in commercial cons-titu-tion is present in a form
incapable of reacting on its own with the fiber substance and
containing reactive groups being derived from esters of mono- or
polyvalent, inorganic or organic acids easily split off, with a
~-hydroxyethylsulfone compound, the present invention provides
the improvement which comprises converting the reactive dyestuff
before application, in an aqueous medium by treatment with an
alkaline agent from the non-fiber-reactive to the fiber-reactive
vinylsu:Lfone form and chemically stabilizing i-t in this converted
form by adjusting to a neutral to acidic pH range by adding acid
to the alkaline dyestuff solution, and subsequently applying -the
dyestuff formulation -thus obtained to the fiber material from an
aqueous, neutral to acidic medium by pad-dyeing or printing, and
fixing the dyestufE on the fiber.
By the example of the sulfuric acid esters o:E ~-
hydroxyethylsulfone dyestuffs (sul:Eatoethylsulfone dyestuffs),
that is, the most impor-tant and most widely used
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co~nercia] form of thi.s type of reactive dyes, the formu-
lations prepared in accordance with the inventiorl anc3 tne
coxrespondinq dyeing processes for texti.les containing or
consisting of polyamide fihers are explained in detail as
follows:
For carrying out the process oE the inven-tion the Ester
dyestuffs are first dissolved in wa~er. Suhsequently, an
al~aline agent is added t-o t}le concentrated dyestuff
solv.tion so ob;:ained or a dyestuff solution diluted pre-
viously to the intended concentrat~Aon, in order to splitthe ester grouping withi.n the su].fatoethylsulfone radical
and to convert +the latter one to the directly fiber-reactive
vinylsulfone radical. This is carri.ed out at a temperature
of from room temperature to boilinq temperature, preferably
.15 25 to 60C, and in the alkaline range, preferably at a pH
of above 10. As alkaline agents, aqueous solutions of
alkali. metal hydroxides and/or sa].ts having an alk.aline
reaction in water, such as sodium carbonate, sodium
hydroxide solution, water glass, trisodium phosphate etc.
may be used. Depending on th~ temperature, the chemical
nature of the alkaline agent and the amount thereof, the
treatment period for dyes-tuff conversion to the VS form
is ~rorn 10 seconds.to 10 minutes. SubsecJuently, the alkaline
liquor so handled is aci.di.fied and adjust.e~ to a pH of frorn
7 to abov.t 3, preferably 6.5 to 5, for chelrlical stabili.7a--
tion of the VS form formed. AcidifLcation is ensure~ by
addition of a mineral acid, for example hydrochloric, sul-
furic or phosphoric acid, or an organic acid, for e~ample
formic or acetic acid, to the alkaline dyestuff soluti.on.
If adjustecl to the intended dyestuff concenkration already
prior to the treatment wi-th alkalis the dyestuff formulatlon
so prepared can be di.rectly used for the padding of the
textile material. Padding is preferably carri.ed OUt at room
temperature.
For reasors of a ra~ional opera-tion mode, prepor1deran-t-
ly such soluti.ons of the Es+er dyestuff obtained in a
concentr;lted form are treated ~i.ch the alkc.llirle aqr.-`nt, and
after acldificatiorl only diluted ~7ith wate.r ko the int.ended
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concen-t?ation for t:he dyelncJ or pac~ding bath or the pr:inti~
paste. It; is xecommended to check the pH after dilution onee
more and to correct it if necessary. It is, however, no-t
required to prepare the concentrated dyestuf formulations
immediately before dyeiny, padding or printiny; they can be
made for stock and are stable to storage for a prolonged
time in the form of 'lliquid dyestuffs" or printing pastes.
By evaporation, optionally to dryness, the concentration of
sueh a dyestuff formulation can be increased accordinc~ to
the requirements of the practice.
For use in continuous processes where lic~uor concen-
tration and liquor volume have to be maintained constant by
steady feeding-up addition, production of the spontaneously
reaetive VS form from the Ester dyestufE ~y treatment with
alkalis in accordanee with the invention can also be per-
formed automatieally by simply dosing and mixincJ the commer~
eial dyestuff solution and the alkaline agent, while, how-
ever, taking into consideration a certain residence time.
Subsecluently, by means of a seeond dosaye device aeidifi--
cation of the dyeing medium diree-tly introdueed into the
applieation opera-tion can be reali~ed, in dependenee on a
predeterrrined, weakly acidic pH.
In view of a simplifi.ed applieability, it has proved
to he advantageous that in the liquid formulations of the
invention the solubility in water of the vinylsulfo11e
dyes1:uffs, which hefore had been presel1t already in the
form of dissolved sulfatoethylsulfone dyestuffs, is greater
than in the case where pulverulent ~inylsu]fone dyest1lffs
are directly used for preparing such a so]ution. This is of
practieal importance in the case of formulations where due
to a high concentration and poor solubility crysta]lized
dyestuff has settled on storage, and this precipitate mus-t
b~ redi.sso]ved on dilution.
In the special dyeincJ and printi~lc~ tec~miq~es described as
follows in order to il]ustrate the utllization, the dye-
stuff formulat:ions obtained in accorclance wi-th the inverl'_io
are used ln the acldic range at a pII of prefera~bly from
5 to 6.5. In an acid:Lc mediur~l, the hydrolys1s ra-te is
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relatively lo~., sc that less hydroly7.ed dyestuff is formed;
thus avoiding the formation of a large arnoun-t of inactive
hydroxyethylsulfone dyestuff from the vinylsulforIe form,
whi.ch cannot react any more with the f:iber and is -therefore
lost.
When pad-dyeing or printing natural or synthetic poly
amide fibers of their mixtures with other fibers, the reac-
tive dye formulations obtained are applied to the flber in
the acidic pH range. The dyestuff is fixed subsequently hy
dwelling, steaming or dry heat treatment. Preferably, such
a heat fixation directly after padding or printin~ is
effected upon the rnoist goods. ~lternatively, the padded
or printed flber material. can be subjected to an inter-
mediate drying at a teMperature a.round 100~C after the
application step of the dyestuff.
The dry heat treatment is carried out within 30 seconds
to 10 minutes, preferably 2 to 5 minu-tes, at a temperature
of from 120 to 240C, preferably 150 to 200C. Steaming
or high tempera-ture steaming is c~rried ou-t within 30
seconds to 30 minut:es at 100 to 240C. Preferred is high
temperature steaming, for example for 5 minutes at 180C.
A saturated stearn atmosphere is not absolu-tely required.
Good results are for example obtainecI wherI the moisture in
the steami.ng apparal:us is about 90 % of the satura-tion
amount present at the corresponding temperature.
As compar~d to known operation modes for the dyeing
of wool and polyamlde fibers with reactive dyes, the novel
process has the follow:incJ advantages:
~ Wool and polyamide fibers can ~e dyed conti.nuously
according to a pad-dyeing process.
- Due to the fact that in accordance with the inventio
nearly no inactive BA-hydroxyethylsulforle dyestuff is formed~
there are srna].l dyestuff losses only.
- Moreover, due to the improved clyestlIff utili~.atlon, ]ess
waste water pollution occurs.
-- Mi.xed fabr:i.cs can be dyed in one single bathO For e~ample,
these speciGl reacti.ve dyestuff formulatioIls can be used
together w~ h di.sperse dyes ln an acld:ic I~at;h for. the
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dyeing of mixt-lre~s of polyester fibers and wool. Furtherl~loj-e,
mixed fabrics of natural or synthetic polyamide fihers and
cellulose fibers can jointly be treated with these reactive
dyc formulations; both fiber types being dyed sim~lltaneous~y
in this case.
As in -the krlo~ll processes, the clyestuEf yield of the
process of the invelltion can be improved by increasirlg the
dyestuff substantivity, for example by addition o electro--
lytes.
The following Examples illustrate the inventionO Tlle
p~rcenta~es are by weight unless otherwise stated, and
relative to the weight of the dry goods in the case of
textile n~aterial.
E X A M P L E
50 g of the reactive dyes-tuff of the formula
CH3
02S~N = N - C -- C - CH3
1 2 HO-C N
OS03Na ~3
~5 S03Na
are dissolved in 50 cm3 of hot water, and dilu-tecl wi-th cold
water to 1 liter. 20 cmJ of sodium hydroxide so~ution
(32.5 ~ strength) are added to this dyestuff solution, and
after 1 minute of dwelling the formulation ls neutralized
hy means of acetic acid, and adjus-t~d to pH ~.5. Jsillg the
liquor so obtained, fabrics of
a) wool,
b~ polyamide 6 fibers, and
c) polyarnide 6,6 fibers
are padded. Subscquently, -the padded fabrics are trea-'.ed in
all cases for dyestuff fixation as follows
(I~ for one part ~7;-th hot air for 3 min-l-tes at 180~C, and
fo~ the o~her part
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(II) hy steaming for 5 minutes at 130C, the steam amourt
being 95 ~ of t:he saturation amount possible at this
temL~erature.
Subsequel1tly, the dyei.ngs are rinsed with hot and cold water,
and soaped at 70C for 10 ml.nutes in an aqueous bath
containing 1 g/l of a nonionic detergent. Yellow dyeincJs
are obtained in all cases. Similar results i.n the corres-
pondiny shades are obtained when accordi.ng to the operation
mode of the above Example the dyestuffs indicated in the
following Examples S to 9 are used:
E X A M P L E 2
_ _ .
Reactive dyestuff of the formula
/ Cu\
SO3~1 /
-N = N - ~ N = N- ~
SO3H SO2-CH2-CEI2-OSO3EI
E X ~ M P L E 3
_
Dyestuff Reactive Orange 16, C.I~-No. 17757.
E X ~ M P L E 4
Dyestuff Reactive Blue 19, C.I.-No. 61200.
E X A M P IJ E 5
DyestuEf Reactive B1.ack 5, C~ No. 20205.
F. X A M_ L E 6
30 g of the dyestuff of Exarnple 3 are formulated as
described in Examp].e 1. Two mixed fabr~~cs of polyamide/
cotton and polyamide/spun rayon, respcctively, are padded
with this liquor, and subsequen-tly for dyestuff fixation
steamed for 6 minuces at 130C (90 % moisture in the
steamina apparatus~. ~he dyeinys are then rinsed with hot
and colcl water, and soaped at 60C in an aqueous bath
containing 1 g/l of a norlionic detergent. Orange dyeings
are obtained; in each case both fi.ber compone~lts of the
mi~ecl fa~rics are dyed in i.dentical shades.
~ 10 - HO~ n
E X A ~I P L ~ 7
_. __ _ _ _ _
- ~l0 g of the reactive dyesturf of the formula
CH3CO~HN OI-I
~ ~-N = N- ~ -CO-NH~
HO3S- -~SO H ~-~
SO2-CH2-CH2~OSO3H
are dissol~ed in 200 cm3 of hot water. Af-ter cooling,
10 cm3 of a 32.5 % sodium hydroxide solution are added to
the d~estuff solution, the batch is allowed to dwell for
1 minute, and is then neutralized with the aid of acetic
acid, and adjusted to plI 6.5.
The dyestuff formulation so prepared is then nlade up
to 1 kg of print.ing paste by adding water and a usual
thic~ener, and 50 g/kg of urea are added to the printing
paste. A T~ool fabric is subseqllently printed with this
paste, and the dyestuff is fixed by steaming for 5 minutes
at 130C (98 ~ rnoisture in the steaming apparatus). Subse-
quently, the textile material is rinsed with hot and cold
water, and soaped at boiling ternperature for 15 rninutcs at
60C in an aqueous liquor Contai.rlincJ 1 g/l of a nonionic
detergent. A rcd print on the fabric is ob-tained.
E X ~ M P L E
50 g of the dyestuEf Reactive Blue 19,.C.~.-No. 61200
~re formula~ted as described in Example 1. 40 g of the
dyestuff Disperse Yellow 64, C~ o. 47023 and 2 g of a
cor~.ercial wetting agent- are added to this dyestuff liquor.
A mixed fabric of polyester/~700l ~mixincJ ratio 55/45)
i5 padded with -this padding liquor. Thereafter, -the fabric
is steamed for 4 minutes at 150C ~95 % of moisture in the
steamin(~ apparatus) for f.ixation of the two dye~tuffs.
Subsequently, the goods so dyed are rinsed with hot and colcl
water/ and soaped for 10 rninutes a-t 70C in an aqueous bath
containing ~ c3/l of a nc-,nionic deter(3ent. A bicolor dyeing
is ohtained on the r.~ ed fabric; the polyester fi.ber port:i.on
~ein(~ dyed yelloT.A7 and the woo:l portion b~-:i.ncJ uycd h1ue~
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E X A ~ P L F, 9
50 g of the dyest~ff as used in Example 3 are formul-
atecl as descrihed in Example 1. After havirl~ adde~ to the
batch 10 g of sodium acetate and 2 g of a commercial
wetting agent, a fab.ric of wool is padded wi.th the paclding
liquor so prepared, and wound up. After a dwelling time of
12 hours at room temperature for dyes-tuff fixation, the
dyed fabric is rinsed with cold and ho-t water arld subse-
quently soapecl for 10 minutès at 60C i.n an aqueous ba-th
containing 2 g/l of a nonionic detergent. An orange dyeing
10 i.s obtained.
