A Process for Dyeing Fast Tannin Antimony Lakes of Polyazo Dyestuffs and Basic Safranine Azo Dyestuffs on the Vegetable Fibre.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
A Process for Dyeing Fast Tannin Antimony Lakes of Polyazo
Dyestuffs and Basic Safranine Azo Dyestuffs on the Vegetable
Fibre.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the County
of London, Chartered Patent Agent, do hereby declare the nature of this invention
(as communicated to me from abroad by The Farbwerke vormals Meister Lucius and
Brüning of Hoechst a/Main, in the Empire of Germany, Chemical Manufacturers) to
be as follows:-
It is well known fact that the fixing of basic dyestuffs on materials made of
vegetable fibres demands the troublesome three baths system namely first mordanting
in the tannic bath, then fixing in a bath containing a salt of antimony and finally
dyeing.
The inconvenience of this method-a bundle of yarn for instance requiring on the
average five hours work, besides immersion over night in the tannin mordant-and
the heavy costs connected therewith, increased by the expense of maintaining a large
plant of vats, were the cause that the application of fast basic dyestuffs was neglected
for many purposes and that the less fast, but simpler and consequently cheaper,
directly acting dyestuffs were employed.
My foreign correspondents have succeeded in finding a new method suitable for
the purposes of cotton dyeing and applicable to a large group of basic dyestuffs,
particularly basic polyazo dyestuffs, having as component aromatic amido ammonium
bases or amido-benzylamine or their derivatives and such basic monoazo dyestuffs,
deriving from diazo safranines.
This method constitutes a great technical progress by its simplicity and easy
working on the one hand and by the fastness of the tints thus obtained on the other.
hand.
They have, in fact, discovered that the said basic azo dyestuffs may be directly
fixed on the vegetable fibre without mordant, if the fibre be treated in neutral or
slightly acid baths, preferably with an addition of neutral salts such as common
or Glauber's salt, together with the solution of the dyestuffs at a warm temperature or
still better at the boil and that the dyed colours may be transformed on the fibre by
a subsequent treatment with solutions of tannins and antimony salts or mixtures of
both in the dye fluids themselves or in a second bath, into their very fast tannin
antimony lakes.
This transformation not only takes place if the fibre dyed with the basic colouring
matter be treated in one or two separate baths, first with tannin and then with
antimony solutions, but it also takes place in the same bath, if the dyeing be done
in presence of an antimony salt followed by treatment with tannin; it is likewise the
case in the same or in a second bath, if the subsequent treatment is carried out with
mixtures of tannin and antimony salt solutions, containing for the most. part insoluble
tannate of antimony.

page_text: It is remarkable that in this latter case the best results as regards even dyeing
and fastness are obtained.
The affinity to the fibre is evidently so great; that the tannate of antimony of the
bath not only does not withdraw the colouring matters but, on the contrary is itself
withdrawn from the bath by the dyestuffs in the fibre which are not yet fast, thus
forming the fast tannin antimony dyestuff lake on the fibre. This formation of lakes
on the fibre is not only easier according to this new method than by the old one, as
one or at the most two baths only are necessary instead of three and which can both
be further used for boiling, but this formation of lakes is also more complete than
that by the old method, producing much faster and more evenly dyed tints, an
importance not to be underrated in the cases of firm twisted yarns, threads and close
tissues.
or
When using alkaline water of factories sufficient acetic, sulphuric or hydrochloric
&c. acids must be added to the dye fluid so as to avoid formation of the badly acting
dye bases. This new method is found to be applicable to all such strong basic
disazo-dyestuffs, as contain as first component a diazotisable ammonium base (m- and
p-amidophenyltrialkylammonium p-methyl-o-amidophenyltrialkylammonium)
amidobenzylamine or its alkylderivatives (p- and o-amidobenzyl-dialkylamine,
amidobenzyltrialkylammonium) in middle position a further diazotisable amine (a-
naphthylamine, amidonaphtholethyl-and-methylether, p-xylidine, symmetrical m-
xylidine, m-toluidine, m-chloraniline, o-anisidine, o-phenetidine, o-amido-p-cresol-
alkylether, p-chloro-m-toluidine etc.), in final position a not sulphonated amine or
phenol capable of being combined (phenol, a and B-naphthol, amidonaphthols,
dialkyl-m-amidophenols and naphthols, m-phenylene- and toluylene-diamine,
chrysoïdine, pyrazolone) as well as such basic disazo-dyestuffs resulting from the
action of amidoazo bodies upon 2.7 oxynaphthaline-trialkylammonium, and finally
such monoazo-dyestuffs as result from the action of diazosafranines (also alkylated)
upon a and ẞ-naphthol, dioxynaphthaline, phenol, dimethyl- and diethyl-aniline,
dimethyl y diethyl-m-amidophenol, amidonaphthols, alkylamidonaphthols, a-naph-
thylamine, toluylene diamine and phenylenediamine.
The new method, which is limited to a group of strong basic azo-dyestuffs, is
based upon the fact hitherto unknown and now discovered by my correspondents that
the affinity of these dyestuffs to the vegetable fibre is greater than the inclination
to form tannin-antimony lakes. Just the reverse is the case with most of the basic
dyestuffs hitherto introduced in the dyeing industry; their affinity to the vegetable
fibre is so weak, that even when applied to the fibre by means of padding they are
extracted from the fibre by a subsequent treatment of tannin applicable in the case
of silk, instead of adhering to it.
:
The new method has opened a new field for the practical fixing on the fibre of a
large group of fast basic dyestuffs, involving a very important technical progress with
regard to the to the saving of steam, wages and a mortisation of the plant; the length
of time (2-2 hours as a rule suffice for one lot) and the better dyeing obtained as
well as greater fastness compared to the process of previously mordanting hitherto
employed.
This great technical improvement is applicable to all modifications of the inethod,
even when working according to the separate baths system, as the using again of the
dye and mordant fluids also permits a further application of the heat therein
contained in contrast to the 3 baths system and all other advantages above mentioned
assert themselves in the fullest degree.
The following illustrates the mode of working :—

page_text: in-toluidine by further diazotising and combining with B-naphthol. The cotton is
worked at the boil for one hour, then taken out; 800 grammes of tannin and 1 kilo.
of acetic acid are added, the cotton is again introduced, boiled for another half hour,
while it is well worked then slung and dried..
2) DARK BLUE ON 20 KILOS. COTTON YARN.
The well boiled yarn in a hot bath of about 500 litres and prepared with 5 kilos. of
common salt, 200 grammes of the dyestuff fron diazosafranine and B-naphthol and
200 grammes of the dyestuff from diazosafranine and m-toluylenediamine, is worked
for 1 hour at the boil. The yarn is taken out and wrung and introduced into the
second boiling bith, prepared with 500 litres of water, 1 kilo. of acetic acid, the
decoction of 5 kilos. of sumac in leaves and 400 grammes of tartar emetic (or
the equivalent quantity of oxalate of antimony or antimony salt).
The yarn is
boiled and well worked in this bath for hour, then taken out, washed and dried. A
dark indigo-like very fast navy blue results. Both baths may serve again for the
next lots.
3) GREEN ON 20 KILOS. COTTON SATEEN.
The well boiled sateen is dyed in about of an hour on a jigger in about 200 litres
of water with 4 kilos. of common salt, 400 grammes of the dyestuff from
diazodiethylsafranine or dimethylaniline and 100 grammes of the disazodyestuff from
m-amidotrimethylphenylammonium, o-chloro-m-toluidine and methylphenyl-
pyrazolone, to which are then added 1 kilo. of acetic acid and the solution of
800 grammes of tannin and 400 grammes of tartar-emetic and boiled for another
of an hour.
T
1
1005
ABEL & IMRAY,
Agents for the Applicant.
A Process for Dyeing Fast Tannin Antimony Lakes of Polyazo
Dyestuffs and Basic Safranine Azo Dyestuffs on the Vegetable
Fibre.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (which has been communicated to me from abroad by The Farbwerke
vormals Meister Lucius and Brüning, of Hoechst a/ Main, in the Empire of Germany,
Chemical Manufacturers) and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement:-
It is a well known fact that the fixing of basic dyestuffs on materials made of
vegetable fibres demands the troublesome three baths system namely first mordanting
in the tannic bath, then fixing in a bath containing a salt of antimony and finally
dyeing.
The inconvenience of this method-a bundle of yarn for instance requiring on on
the average five hours work, besides immersion over night in the tannin mordant-
and the heavy cost connected therewith, increased by the expense of maintaining
a large plant of vats, were the cause that the application of fast basic dyestuffs
was neglected for many purposes and that the less fast, but simpler and consequently
cheaper, directly dyeing dyestuffs were employed.

page_text: My foreign correspondents have succeeded in finding a new method suitable for
the purposes of cotton dyeing and applicable to a large group of basic dyestuffs,
particularly basic polyazo dyestuffs, having as component aromatic amido ammonium
bases or amido-benzylamine or their derivatives and such basic monoazo dyestuffs,
deriving from diazo safranines.
This method constitutes a great technical progress by its simplicity and
easy working on the one hand and by the fastness of the tints thus obtained on the
other hand.
They have, in fact, discovered that the said basic azo dyestuffs may be directly
fixed on the vegetable fibre without mordant, if the fibre be treated in neutral or
slightly acid baths, preferably with an addition of neutral salts such as common
or Glauber's salt, together with the solution of the dyestuffs at a warm temperature or
still better at the boil and that the dyed colours may be transformed on the fibre
by a subsequent treatment with solutions of tannins and antimony salts or mixtures
of both in the dye fluids themselves or in a second bath, into their very fast tannin
antimony lakes.
This transformation not only takes places if the fibre dyed with the basic colouring
matter be treated in one or two separate baths, first with tannin and then with
antimony solutions, but it also takes place in the same bath, if the dyeing be done
in presence of an antiinony salt followed by treatment with tannin; it is likewise the
case in the same or in a second bath, if the subsequent treatment is carried out
with mixtures of tannin and antimony salt solutions, containing for the most part
insoluble tannate of antimony.
It is remarkable that in this latter case the best results as regards even dyeing
and fastness are obtained.
The affinity to the fibre is evidently so great, that the tannate of antimony of the
bath not only does not withdraw the colouring matters but, on the contrary is itself
withdrawn from the bath by the dyestuffs in the fibre which are not yet fast, thus
forming the fast tannin antimony dyestuff lake on the fibre. This formation of lakes
on the fibre is not only easier according to this new method than by the old one, as
one or at the most two baths only are necessary instead of three and which can both
be further used, but this formation of lakes is also more complete than that by the
old method, producing much faster and more evenly dyed tints, an importance
not to be underrated in the cases of firm twisted yarns, threads and close tissues.
When using alkaline water sufficient acetic, sulphuric or hydrochloric &c. acids
must be added to the dye fluid so as to avoid formation of the badly dyeing dye
bases.
My correspondents have also found that light and medium shades may be dyed
without the addition of any salts; and also that the dyeing of all shades may safely be
executed at a temperature considerably under boiling point.
This new method is found to be applicable to all such strong basic disazo-dyestuffs
as contain as first component a diazotisable ammonium. base (m- and p-amidophenyl-
trialkylammonium p-methyl-o-amidophenyltrialkylammonium) or amido-benzylamine
or its alkylderivatives (p- and o-amidobenzyl-dialkylamine, amidobenzyl-trialkyl-
ammonium) in middle position a further diazotisable amine (a-naphthylamine,
amidonaphtholethyl- and methylether, p-xylidine, symmetrical m-xylidine, m-
toluidine, m-chloraniline, o-anisidine, o-phenetidine, o-amido-p-cresol-alkylether,
p-chloro-m-toluidine etc.), in final position a not sulphonated amine or phenol
capable of being combined (phenol, a- and B-naphthol, anidonaphthols, dialkyl-m-
amdiophenols and naphthols, m-phenylene- and toluylene-diamine, chrysoïdine,
pyrazolone) as well as such basic disazo-dyestuffs resulting from the action of
amidoazo bodies upon 2.7 oxy-naphthaline-trialkylammonium, and finally such
monoazo dyestuffs as result from the action of diazosafranines (also alkylated) upon
a-and- B-naphthol, dioxy-naphthaline, phenol, dimethyl- and diethyl-aniline,
dimethyl y diethyl-m-amidophenol, amidonaphthols, alkylamidonaphthols, a-naph-
thylamine, toluylene diamine and phenylene diamine.
*The new method, which is limited to a group of strong basic azodyestuffs, is based

page_text: a) By first dyeing the basic polyazo- and safranineazo-dyestuffs in a bath with
salts favouring the attraction, such as common or Glauber's salt or also without the
addition of any salts; and simultaneous addition of antimony salts, and by
subsequently treating these fibres thus dyed in the same bath with tannins ;
b) By first dyeing the basic polyazo- and safranineazo-dyestuffs in a bath with salts
favouring the attraction, such as common or Glauber's salt, or without the addition
of any salts, and by subsequently treating the fibre thus dyed in the same or a
separate bath, either subsequently or simultaneously with tannins and antimony
salts, substantially as described.