Improvements in or connected with the Dyeing and Printing of Animal and Vegetable Fibres.
Year: 1889

page_text: Date of Application, 6th Mar., 1889
Complete Specification Left. 9th Dec, 1889-Accepted, 11th Jan., 1890
PROVISIONAL SPECIFICATION.
Improvements in or connected with the Dyeing and Printing of
Animal and Vegetable Fibres.
1. BENJAMIN WILLCOX; of 47 Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention which has been com-
municated to me from abroad by the Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany to be as follows:-
This invention relates to an improved process for fixing colouring matter such
as the azo dye stuffs which possess the property of directly dyeing unmordanted
cotton in an alkaline bath and which are known in the trade as substantive
colouring matters on or in the animal or vegetable fibres to which they are applied
in the processes of dyeing and printing.
In dyeing wool and silk and in printing processes for example it is found that
these dye stuffs cannot be fixed on the fibre so to be fast enough for certain
purposes.
My foreign correspondents have now discovered a dyeing and printing process or
a process to be employed in connection with dyeing and printing whereby these
disadvantages are for the greater part removed and the direct acting dyes or sub-
stantive colouring matters are more permanently fixed on vegetable fibre or on
animal fibre and are thus enabled to be more generally employed than heretofore.
The said substantive cotton colouring matters possess the property of forming with
the salts of the earthy and of the heavy metals, lakes which in part are very
permanent. By boiling in a solution of a metallic salt goods which have been
dyed or printed in the usual way the metal becomes fixed by the colouring matter
in the form of a fixed lake. The results obtained naturally vary according to the
nature of the solution and colouring matter employed.
In all cases a lake is formed which is faster than the original colouring matter
and which is fast to hot water and to fulling or milling. In certain cases the
metallic salts also have the effect of changing the shade or colour of the dye, salts of
iron
and nickel generally makes it redder. Others such as
zine, for example make it duller and nickel-generally-ina
A remarkable result is obtained when salts of copper are employed with colouring
matters of diamido diphenyl ether. These salts form with the colouring matter lakes
With the reddish bluc which is
which presents little similarity to the original shade.
obtained by means of benzo azurine and of benzo azurine 3G in particular there
results a beautiful fast greenish blue, azo violet changes to red blue.
This peculiarity is observed in the case of the diamido diphenyl ether, other
colouring matters such as those obtained from benzidine do not act in the same
way.
Zinc is found to be best suited for wool and silk dyeing as it has no influence
whatever on the colour and forms lakes which perfectly resist the action of boiling
water and fulling or milling. The zinc is employed in the form of sulphate of zinc
or white vitriol.
Woollen goods dyed in the usual way with delta purpurine for example are boiled
for a few minutes with a quantity of white vitriol corresponding to the dye employed.
The zinc is then completely taken up from the bath, the wool so treated is now
perfectly fast to fulling or milling and can be acted on with boiling water without
suffering in the least.
With the direct dyeing colouring matters the metals do not form on cotton goods
in a general way such resistant lakes as in the case of animal fibres nevertheless com-
binations are formed which enable the process to be employed with considerable
advantage in practice.

page_text: The lakes formed with sulphate of copper and nickel are considerably faster to soap
and stand hot soaping at 10 degrees centigrade whilst dyes not so prepared are known
to suffer even with cold soaping. In particular cotton yarns and fabrics dyed with
blue colouring matter derived from diamido diphenol ether such as benzo azurine and
azo violet especially the benzo azurine 3 G are not only rendered faster to soap by
boiling with blue vitriol but also change their shade very essentially and lose the
peculiar and disagreeable property which they otherwise possess of turning red when
exposed to heat.
The improved process can be employed in printing in the same way as in dyeing.
In this case a large variety of combinations can be employed according as the goods
printed by the ordinary methods of printing are treated with the boiling solution of
the metallic salt before or after the steaming or dyed and soured or mordanted goods
are boiled with a metallic salt solution.
Goods which have been boiled with benzo azurine and sulphate of copper or
blue vitriol cannot afterwards be mordanted or acted on in the usual way with salts
of tin.
My foreign correspondents have further discovered that the dyestuffs which
result from the action of the tetrazo combinations of para diamine such for example
as benzidine diamido-phenyl-tolyl, tolidine, diamido diphenol ether diamodo carbazole
diamido stilbene and the like, para phenylene diamine or naphthylene diamine and
their urea derivatives upon two molecules of salicylic acid or the isomers and
homologues thereof such as cresotic acid or of resorcylic acid and oxy naphthoic
acid form with salts of chromium a fast lake. Like results are obtained with the
dyestuffs resulting from the action of the tetrazo combinations in the first place
upon one molecule of the above mentioned acids (phenol or carbo acids) for the
production of what are termed intermediate products and in the second place upon
one molecule of an amine or amide and phenol or the sulpho or carbo acids
thereof nevertheless containing no sulpho group such for example as aniline, meta
phenylene diamine, alpha and beta naphthylamine, phenol, resorcin, alpha or beta
naphthol oxy naphthalin, dioxy naphthalin and the homologues thereof and the
like. These dyestuffs form with salts of chromium a lake that is perfectly fast to
soap and when this property is utilised in dyeing and printing operations the dye
on wool is perfectly fast to fulling or milling and on cotton is perfectly fast to soaping.
The said dyestuffs are preferably employed for printing in the form of a neutral
paste with the addition of a chromium salt or cotton or wool dyed or printed with
the dyestuff is caused to pass through a solution of a chromium salt or is mordanted
with chromium before undergoing the drying process.
The process consists in a general way in adding acetate of chromium or any
other salt of chromium suitable for printing purposes to prepared printing paste
and steaming. When the colour is then cleared or brightened the chrome combination
of the excess dyestuff washes completely under and this lake is incapable of being
taken up by bleaching or decolorising agents.
The following may be taken as an example eighty parts by weight of the neutral
thickening or paste, from five to fifteen parts (according to the shade to be obtained)
one of the above mentioned dyestuffs which is preferably employed in the form of
a 10 per cent. paste and from about ten to twenty parts of acetate of chromium
of about 130 degrees Baumé are put together; the product is strongly steamed and
strongly cleared.
In order to dye cotton with this yellow red to red brown direct dyeing
azo dyestuff so as to be fast to fulling the cotton is prepared in the first place
with a chrome mordant and then dyed in the known manner or it is first dyed
and then passed through a solution of acetate of chromium. The fact that the
dyestuff obtained according to this process can be employed with great advantage
is to be ascribed to the presence and position of the hydroxyl and carboxyl groups
appertaining to all these dyestuffs. These two groups being in the ortho position
relatively to one another the dyestuffs are endowed with the capacity of forming
chrome lacs.

page_text: To dye wool with these dyestuffs the wool is preferably mordanted in the first
place with any chromium combination in the known manner and then dyed with
a weak acid or neutral bath. By boiling with chromium salts the same valuable
property is imparted to the above mentioned dyestuffs which are applied in the
known manner.
By causing the intermediate products which are obtained by the combination of
one molecule of the tetrazo compounds with one molecule of an oxy carbo acid
such as salicylic or cresotic acids to act upon the sulpho or carbo acids of the
phenols or amides dyestuffs are formed as is understood presenting peculiarities
resembling those of the unsulphurised products but are somewhat more readily
soluble. They do not in general yield chrome lakes which are so fast to soap
although the fastness is greatly increased. Some that is to say all those which
contain together with the carbo acid the beta naphthol disulpho acid R or the beta
naphthylamine disulpho acid R. show notwithstanding the presence of two sulpho
groups the remarkable and interesting peculiarity of forming when treated as
hereinbefore described lakes which are absolutely fast to soup and are thereby
enabled to be employed in the production of very useful yellow to red blue and
orange dyes which are fast to steam and fulling.
Wind this 4th day at Mauch 1000
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in or connected with the Dyeing and Printing of
Animal and Vegetable Fibres.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this Invention (which has been com-
municated to me from abroad by The Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
This Invention relates to an improved process for fixing colouring matter such as
the azo dyestuffs which possess the property of directly dyeing unmordanted cotton_
in an alkaline bath and which are known in the trade as substantive colouring
matters,
on or in the animal or vegetable fibres to which they are applied in the processes of
dyeing and printing.
In dyeing wool, silk and cotton for example it is found that these dyestuffs
cannot be fixed on the fibre so as to be fast enough for certain purposes.
My foreign correspondents have now discovered a dyeing and printing process or
a process to be employed in connection with dyeing and printing whereby these dis-
advantages are for the greater part removed and the direct acting dyes or substantive
colouring matters are more permanently fixed on vegetable or animal fibre and can
therefore be more generally employed than heretofore.
The said substantive colouring matters possess the property of forming with
the salts of the earthy and of the heavy metals lakes which in part are very
permanent.
By boiling in a solution of a metallic salt goods which have been dyed or printed
in the usual way the metal becomes fixed by the colouring matter in the form of a
fixed lake. The results obtained naturally vary according to the nature of the metallic
salt and colouring matter employed.
the metallic
Salts of iron
Others such
In all cases a lake is formed which is faster than the original colouring matter and
which is fast to hot water and to fulling or milling. In certain cases
salts also have the effect of changing the shade or colour of the dye.
for example make it duller and those of nickel generally make it redder.
as those of zinc for example, have no effect whatever on the colour.

page_text: A remarkable result is obtained when salts of copper are employed with azo-
colouring matters of diamido-diphenol-ether. These salts form with the colouring
matter lakes which present little similarity to the original shade.
With the reddish-blue which is obtained by means of benzo-azurine 3 G in
particular there results a beautiful fast greenish-blue. Azo violet changes to red
blue.
This peculiarity is observed in the case of the diamido-diphenol-ether. Other
colouring matters such as those obtained from benzidine do not act in the same
way.
Zinc is found to be best suited for use in dyeing wool and silk as it has no
influence whatever on the colour and forms lakes which perfectly resist the action of
boiling water and better resist fulling, or milling than do the original colours. The
zinc can be employed in the form of sulphate of zine or white vitriol.
Woollen goods dyed in the usual way, with deltapurpurine for example, are
boiled for a few minutes with a quantity of white vitriol corresponding to the dye
employed.
The zinc is then completely taken up from the bath, the wool so treated is now
faster to fulling or milling and can be acted on with boiling water without suffering
in the least.
With the direct dyeing colouring matters the metals do not forin on cotton goods
in a general way such resistant lakes as in the case of animal fibres, nevertheless
combinations are formed which enable the process to be employed with considerable
advantage in practice.
The lakes formed with sulphate of copper and nickel are considerably faster to soap
and stand hot soaping at 40 degrees Centigrade whilst dyes not so prepared are known
to suffer even with cold soaping.
In particular cotton yarns and fabrics dyed with blue colouring matter derived
from diamido-diphenol-ether such as benzo-azurine and azo violet, especially the
benzo-azurine 3 G are not only rendered faster to soap by boiling with blue vitriol,
but also change their shade very essentially and lose the peculiar and disagreeable
property which they otherwise possess of turning red when exposed to heat. The
improved process can be employed in printing in the same way as in dyeing. In
this case a variety of combinations can be employed according as the goods printed
by the ordinary methods of printing are treated with the boiling solution of the
metallic salt before or after the steaming or dyed and discharged goods are boiled
with a metallic salt solution.
Goods which have been dyed with benzo-azurine and then boiled with sulphate of
copper or blue vitriol cannot afterwards be discharged or acted on in the usual way
with salts of tin.
My foreign correspondents have further discovered that the dyestuffs which
result from the action of the tetrazo combinations of diamines such for example
as benzidine diamidophenyltolyl, tolidine, diamido-diphenol-ether, diamido-carbazol,
diamido-stilbene, diamido-mono-alkyloxyldiphenyl, diamido-mono-alkyloxylphenyl-
tolyl, diamido-oxybenzol, diamidoazooxybenzol, diamido tolane, diamidodiphenylene-
oxide para phenylenediamine or naphthylene diamine and their urea derivatives
upon two molecules of salicylic acid or the isomers and homologues thereof such
as cresolcarbonic acids, form with salts of chromium a fast lake. Like results
are obtained with the dyestuffs resulting from the action of the tetrazo combinations
in the first place upon one molecule of the above mentioned acids (phenol or
carbo acids) for the production of what are termed intermediate products and in 5
the second place upon one molecule of an amine and phenol or the sulpho or carbo
acids thereof such for example as meta phenylene diamine alpha and beta naphthy-
lamine, phenol, cresol, resorcin, alpha or beta naphthol dioxynaphthaline and the
sulpho and carbo acids thereof. These dyestuffs form with salts of chromium a
lake that is perfectly fast to soap and when this property is utilised in dyeing 5
and printing operations the dye on wool is perfectly fast to fulling or milling and
on cotton is very fast to soaping.

page_text: The said dyestuffs are preferably employed for printing in the form of a neutral
paste with the addition of a chromium salt or cotton or wool dyed or printed with
the dyestuff is caused to pass through a solution of a chromium salt or is mordanted
with chromium before undergoing the dyeing process. The process consists in a
general way in adding acetate of chromium or any other salt of chromium suitable
for printing purposes to prepared printing paste and steaming.
The following may be taken as an example-Eighty parts by weight of the
neutral thickening or paste, from five to fifteen parts (according to the shade to be
obtained) of one of the above mentioned dyestuffs which is preferably employed in
the form of a 10 per cent. paste and from about ten to twenty parts of acetate of
chromium of about 13 degrees Baumé are put together, the product is strongly steamed
and strongly cleared.
In order to dye cotton with this yellow-red to red-brown direct dyeing azo dyestuff
so as to be fast to fulling the cotton is prepared in the first place with a chrome
mordant and then dyed in the known manner or it is first dyed and then passed
through a solution of acetate of chromium. The fact that the dyestuff obtained
according to this process can be employed with great advantage is to be ascribed to
the presence and position of the hydroxyl and carboxyl groups appertaining to all
these dyestuffs. These two groups being in the ortho position relatively to one
another the dyestuffs are endowed with the capacity of forming chrome lakes.
To dye wool with these dyestuffs the wool is preferably mordanted in the first place
with any chromium combination in the known manner and then dyed with a weak
acid or neutral bath. By boiling with chromium salts the same valuable property
is imparted to the above mentioned dyestuffs which are applied in the known
manner.
By causing the intermediate products which are obtained by the combination of
one molecule of the tetrazo compounds with one molecule of salicylic or ortho or
meta oxy cresol carbonic acids to act upon the sulpho or carbo acids of the phenols or
amines dyestuffs are formed as is understood presenting peculiarities resembling those
of the unsulphurised products but are somewhat more readily soluble. They do not
in general yield chrome lakes which are so fast to soap although the fastness is greatly
increased.
= =>
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The process of boiling animal fibres dyed or printed with any substantive cotton
colouring matters such as those herein before mentioned, with a solution of zinc salts
especially white vitriol.
2. The process for dyeing and printing with substantive cotton colouring matters
by boiling animal and vegetable fibres (which are dyed or printed with such colouring
matters) with a solution of copper salts and especially with blue vitriol.
3. The process for dyeing and printing with those substantive cotton colouring
matters which result from the combination of the tetrazo compounds of the diamines
such as those hereinbefore named with
(a) Two molecules of salicylic acid or cresol-carboxylic acid or with
One molecule of salicylic acid or cresol carboxylic acid, and then with another
molecule of any amine, phenol or their sulpho or carbo acids, the said process
consisting in printing the dyestuff in neutral thickening in the presence of a