Improvements in the Production of Fast Colours on the Fibre for Printing and Dyeing Purposes.
Year: 1892

page_text: Date of Application, 24th Mar., 1892
Complete Specification Left, 24th Dec., 1892-Accepted, 4th Mar., 1893
PROVISIONAL SPECIFICATION.
Improvements in the Production of Fast Colours on the Fibre for
Printing and Dyeing Purposes.
I, 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
communicated to me from abroad by the Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of Germany) to be as follows:-
In order to produce by printing, colours fast to washing and soaping different
methods are employed. Usually the colouring matters mixed with a thickening
and a mordant are printed and the material is then steamed employing for example
as mordants tannin for the basic aniline dye stuffs and metallic salts for the colouring
matters derived from hydroxyketones. When the material after printing is steamed
a combination of the dye-stuff with the mordant used is produced which possesses a
sufficient resistance to washing and soaping. Another process which has been in
use only a few years consists in producing fast azo colours on fibre by causing the
material to pass through an alkaline solution of a phenol, most advantageously
betanaphthol, and subsequently printing it with a diazo compound which is dissolved
in water and mixed with a suitable thickening. This method is defective as it has
been found to be very difficult to obtain so called uniform colours by means of such
a process.
The preparation of the mixtures of diazo compounds is very minute and the diazo
compounds themselves are easily decomposed.
A combination of the said two methods has not however been hitherto made known
or used.
My foreign correspondents have now found that certain azo dye-stuffs containing
a free amido group, after having been printed on the fibre with the aid of mordants,
can directly be diazotised by subjecting the fibre so printed to treatment with acidu-
lated watery solutions of sodium nitrite and then can be combined with phenols,
amines, amido phenols, sulpho or carboxylic acids thereof. A great variety of
shades is produced in this manner the lakes fixed on the fibre not being
decomposed.
The following is given in order to illustrate how this valuable printing process
may be carried out. An amido azo compound which contains besides the free amido
group, such a group (as for example a carboxylic group or hydroxyl groups in ortho
or peri position) as will allow of the formation of so called lakes by employing
chromium or alumina salts as mordants, is printed together with a suitable mordant
and the necessary thickening. After steaming, malting and soaping the cloth is
brought without having been dried, into a much diluted aqueous solution of sodium
nitrite moderately acidulated.
My foreign correspondents have found that on employing a weakly acid bath of
sodium nitrite the metallic lake is not decomposed. On carefully agitating the
printed cloth the diazotation is complete in about a quarter of an hour and the end
of the reaction can be recognised by the change in colour as the diazo products
which likewise remain fixed on the fibre usually possess a colour other than that of
the original lakes. When the diazotation is completed the cloth is carefully washed
in cold water, and placed in a moderately alkaline solution of a phenol or in a neutral
or weakly acid solution of an amine, and agitated therein until the intensity of the
colour ceases to increase. The cloth after removal from the bath is washed and
soaped.
The great variety of the shades thus obtainable and their great fastness against
washing and soaping cannot be easily obtained by other processes hitherto known,

page_text: COOH,
62 parts, of an acetic acid starch tragacanth thickening and 8 parts of a solution
of acetate of chrome at 20 degrees Baumé is printed and the material after steaming
malting soaping and washing is placed at first in a bath of sodium uitrite moderately
acidulated and then in an aqueous solution of the hydrochlorate of ethyl-beta
naphthylamine. After about one hour the temperature of the bath is raised to from
about 30 to 40 degrees centigrade. The original orange red colour of the printed
material is changed into a deep bluish-black which is extremely fast against
washing.

page_text: By replacing ethyl-beta-naphthylamine of the preceding example by phenol, cresol
or resorcine a brown colour is obtained, with alpha naphthol a deep brownish-violet,
with beta naphthol a deep violet, with alphanaphthylamine a brown, with ethyl-
alpha naphthylamine a brownish-black with beta naphthylamine a reddish-brown,
with amido naphthols a violet-brown, with amidonaphthol ethers a violet-black and
with dihydroxynaphthalenes from violet to bluish-black shades are produced.
When instead of phenols, amines, or amido-phenols the sulpho acids thereof are
employed similar shades are obtained; for example, with alpha naphthol alpha-
monosulpho acid a violet-brown and with 1.8 dihydroxynaphthalene-alpha-mono-
sulpho acid a greenish-black with a bluish tinge is obtained. Of course the last
named compounds likewise can be employed in place of beta-naphthol of the
the preceding first example. By subsequently allowing the material to pass through
a moderately alkaline bath of betanaphthol a deep bluish-green results.
PRODUCTION OF A CLARET RED WITH WHITE FIGURES ON
COTTON-FIBRE.
The cotton fabric is padded with a suitable chromium mordant (for example with
chromium bisulphite) and after discharging the figures desired by means of citric
acid or lemon juice is dyed by employing a neutral or moderately acid solution of
paraphenylene-diamine-azo-meta-cresotinic acid. After washing the cloth is placed
(and allowed to remain for some time) in a weakly acid bath of sodium nitrite. It
is then taken out and rinsed and afterwards is well turned in a moderately alkaline
solution of beta-naphthol the brownish-red colour of the diazo compound being
changed into a beautiful claret-red. When the production of the dye-stuff is
completed the cloth is taken out of the bath washed and soaped.
Of course instead of white figures coloured figures can also be discharged in the
cloth mordanted with chromium salts.
In the processes for printing and dyeing hereinbefore described all amido azo-
dye stuffs that contain au amido-group and owing to their carboxylic group or
hydroxylic groups can form so called lakes when metallic salts are employed as
mordants can be used with similar results. By diazotising the lakes on the fibre
and combining the resulting diazo products with amines, phenols, or amido-phenols.
or sulpho or carboxylic acids thereof a great variety of shades is obtained.
My foreign correspondents have employed hitherto with good results especially
those colouring-matters which are obtained by combining the diazo-derivatives of
amido-benzoic acids, amido-hydroxy benzoic acids amido-cresol-carbonic acids,
amido-anisic-acid, amido-dihydroxy-benzoic acid, amido-phthalic acid and the
sulpho acids thereof with alphanaphthylamine amidonaphthol amido-naphtholether,
amido naphthoxy acetic acid, amido naphthol mono sulpho acid G, amido-naphthol-
monosulpho acid R; amido naphthol-mono-sulpho acid B, (which is described in
the German Patent No. 58352 dated 3rd July 1890); 1.8 amido naphthol-beta-di-
sulpho acid; alphanaphthylamine-ortho-mono-sulpho acid (described in the German
Patent No. 56563 dated 21st January 1890) and the alphanaphthylamine beta-
monosulpho acids (y-ß and 8) obtained by Clève, amido-naphtholether-beta-mono-
sulpho-acids and amido-naphthoxy-acetic-sulpho acids. Instead of the simple

page_text: dye-stuffs so produced those which result by combining the diazo compounds of these
simple azo-colouring-matters with amines or sulpho acids thereof can also be
employed with good results.
After diazotizing these two series of colouring matters on the fibre the resulting
diazo products which likewise remain fixed on the fibre can be combined with every
of the known dye stuff components; amines, phenols or amido-phenols, substitution
or other derivatives especially sulpho or carboxylic acids thereof.
Dated this 24th day of March 1900
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.
COMPLETE SPECIFICATION.
Improvements in the Production of Fast Colours on the Fibre for
Printing and Dyeing Purposes.
I, 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
communicated to me from abroad by 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 :-
In order to produce colours which will withstand washing and soaping by
printing, different methods are employed. Usually the colouring matters are
mixed with a thickening material and a mordant and printed on the fabric which is
then steamed, tannin for example being used as mordant for basic aniline dye-stuffs
and metallic salts for the colouring matters derived from hydroxyketones. When
the fabric thus printed is steamed, a combination of the dye-stuff with the mordant
used is produced which sufficiently withstands washing and soaping. Another
process which has been in use only a few years consists in producing fast azo colours
on fabrics by causing them to pass through an alkaline solution of a phenol, (beta-
naphtol being usually most advantageously employed) and subsequently printing
with a diazo compound dissolved in water and mixed with a suitable thickening
material. This method is defective it having been found very difficult to obtain
uniform colours by means of such a process and the preparation of the diazo
compounds is in some cases a somewhat troublesome operation and they are easily
decomposed.
A combination of the said two methods has not however been hitherto made
known or used.
My foreign correspondents have now found that certain azo dye-stuff's containing
a free amido group, printed on fabrics with the aid of mordants can be directly
diazotised by subjecting the fabric so printed to treatment with acidulated solutions
in water of sodium nitrite and can then be combined with phenols, amines, amido-
phenols, or sulpho or carboxylic acids thereof. In this manner, a great variety of
shades is produced, the lakes fixed on the fibre not being decomposed.
The following is given, in order to show how this valuable printing process may
be carried out. An amido azo compound containing, besides the free amido group,
a group (as for example a carboxylic group or hydroxyl groups in ortho or peri
position) which will allow of the formation of so-called lakes by means of chromium
salts employed as mordants, is printed on the fabric together with a suitable mordant
and the necessary thickening material. After treating the printed fabric in the
usual manner it is immersed either before or after drying in a highly diluted
moderately acidulated, aqueous solution of sodium nitrite the point being that my
foreign correspondents have found that if a weakly acid bath of sodium nitrite be
used the metallic lake is not decomposed. On carefully agitating the printed
fabric the diazotisation is complete in a short time the end of the action being
recognised by the change in colour, as the diazoproducts which remain fixed on the

page_text: fibre usually possess a colour other than that of the original lakes. When the
diazotisation is complete, the fabric is treated in the usual manner and placed in a
moderately alkaline solution of a phenol, or in a neutral or weakly acid solution of
an amine, and is kept therein until the intensity of the colour ceases to increase.
After removal from the bath the fabric is treated in the known manner.
The great variety of shades thus obtainable and their great fastness when the
fabric is washed and soaped cannot be easily secured by other processes hitherto
known.
My foreign correspondents have further found that the above described process
can also be very advantageously employed for dyeing purposes by taking the fibrous
material such as cloth or yarn mordanted with metallic salts (for example with
chromium salts) and dyeing it with the above mentioned or analogous amido-azo
colouring-matters, by immersing it in a moderately acid bath of sodium nitrite
and then in a suitable bath of any dye-stuff component as hereinbefore described.
In this manner also patterns or figures can be produced on the goods, if the
latter be first padded with an alkaline or acetic acid chromium solution, discharged
with citric acid or lemon juice, in order to produce the desired patterns, and then
dyed with a suitable amidoazo colouring matter. The discharged places remain
white, whilst the other parts of the fabric assume the colour of the chromium lake
which is formed. After rinsing the goods are placed in a moderately acid bath of
sodium nitrite, in order to produce the diazo compound of the chromium lake, and
thereupon after washing are introduced into an acetic acid, neutral or moderately
alkaline solution of the known dye-stuff components. When the coupling is
finished the goods are washed and dried.
The following examples are given in order to illustrate these processes in printing
and dyeing. The parts are by weight.
PRODUCTION OF A CLARET-RED.
The fabric is printed with a colour prepared by mixing a solution of 20 parts,
of paraamido-benzene azosalicylic acid (described in the Journal of the Chemical
Society 1885 pages 657-658) in 300 parts of water with 620 parts of an acetic
acid starch tragacanth thickening material and 60 parts, of a chromium acetate
solution at 20 degrees Baumé. After steaming for one hour without pressure the
fabric is passed through a chalk bath treated with malt (that is to say treated at
a temperature below 60 degrees centigrade with an extract of malt, in order to
convert the starch, which remains on the fibre together with the dye after printing,
into soluble substances) soaped for say 20 minutes at 40 degrees centigrade and
washed with cold water. The wet fabric is then introduced into a very dilute
solution of sodium nitrite in water which is weakly acidulated. The original
yellow colour of the chromium lake changes into the brownish-black of the resulting
diazo product. After about half an hour the fabric is washed with cold water and
is then allowed to pass through an aqueous solution of 20 parts, of the sodium salt
of betanaphthol. When the brown, colour of the diazo compound has been
changed into the claret-red of the new azo dye-stuff formed in this reaction, the
fabric is removed from the naphthol bath, rinsed with water and soaped at
about 40 degrees centigrade.
Similar shades are produced, if analogous amidoazo dye-stuffs be used in place
of the amido-benzene-azosalicylic acid of the preceding example.
A
1
PRODUCTION OF A BLUISH-BLACK.
C
1
2

page_text: 62 parts of an acetic acid starch tragacanth thickening material and 8 parts, of
a solution of acetate of chromium at 20 degrees Baumé is printed on the fabric and
after steaming, treating with malt, soaping, and washing, this is introduced first into
a moderately acidulated bath of sodium nitrite and then into an aqueous solution of
the hydrochloride of ethylbetanaphthylamine. The original orange-red colour of
the printed fabric is changed into a deep bluish-black which is extremely fast on
washing.
By replacing the ethylbetanaphthylamine of the preceding example by phenol,
cresol or resorcinol, a brown colour is obtained, alphanaphthol affording a deep
brownish violet, beta naphthol a deep violet, alphanaphthylamine a brown, ethyl-
alphanaphthylamine a brownish-black, beta-naphthylamine a reddish-brown,
amidc-naphthols a violet-brown, amidonaphthol ethers a violet-black, and di-
hydroxynaphthalenes from violet to bluish-black shades. When instead of
phenols, amines, or amidophenols the sulpho acids thereof are employed, similar
shades are obtained; for example, alphanaphtholalphamonosulpho acid affords a
violet-brown and 1-8-dihydroxynaphthalençalphamonosulpho acid a black.
last named compounds can also be employed in place of the betanaphthol of the
preceding first example.
The
is printed on the fabric and the fixed chrome lake is diazotised as described in the
preceding first example. By subsequently allowing the fabric to pass through a
moderately alkaline bath of betanaphthol a deep bluish-green is obtained.
PRODUCTION OF A CLARET-RED WITH WHITE FIGURES ON
COTTON-FIBRE.
The cotton fabric is padded with a suitable chromium mordant (for example with
chromium bisulphite) and the desired patterns or figures having been produced
by discharging by means of citric acid or lemon juice it is dyed by means of a
neutral or moderately acid solution of paraphenylenediamineazometacresotinic acid.
After it has been washed the fabric is placed and allowed to remain for some time,
in a slightly acid bath of sodium nitrite. It is then taken out and rinsed and is
afterwards well turned in a moderately alkaline solution of betanaphthol whereby
the brownish-red colour of the diazo compound is changed into a beautiful claret-
red. When the production of the dye-stuff is completed, the fabric is taken out of
the bath, and treated in the usual manner.
Of course, instead of white figures coloured figures can also be produced by
properly discharging the mordanted fabric.
In the processes for printing and dyeing herein before described all amidoazo dye-
stuffs can be used with similar results which contain further diazotisable amido
groups and which in virtue of their carboxylic or hydroxylic groups can form so
called lakes, when metallic salts are employed as mordants. By diazotising the
lakes on the fibre and combining the resulting diazo products with amines, phenols,
or amido-phenols, or sulpho or carboxylic acids thereof a great variety of shades is
obtained.
My foreign correspondents have hitherto employed with good results those
colouring matters especially which are obtained by combining the diazo derivatives
of amidobenzoic acids, amidohydroxy benzoic acids, amidocresolcarboxy acids,
amidoanisic acid, amidophthalic acid, and the sulpho acids thereof with amido-

page_text: naphtolmonosulpho acid G, 1.8-amidonaphthobetadisulpho acid alphanaphthyl-
amineorthomonosulpho acid (described in the German Patent No. 56563 dated
21st January 1890) the alphanaphthylamine betainonosulpho acids (beta and delta)
obtained by Clève and the amido-naphtholether-betamonosulpho acids.
My
The above examples are given, in order to illustrate the method of producing
fast colours on fabrics by means of the amidoazo products above referred to.
foreign correspondents do not limit themselves to the above proportions, which can
be greatly varied and all methods employed in dyeing and printing for analogous
purposes can be made use of without the nature of this invention being altered by
such modifications.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is.
1. In the production of colours on the fibre the employment of amidoazoproducts
which are capable of forming so called lakes in the presence of metallic salts which
can be further diazotised when fixed on the fibre.
2. The process of producing fast colours on the fibre which consists either in
printing on the fabric the amidoazoproducts (defined in the foregoing first claim)
together with a chromium salt or mordant and a suitable thickening material or in
dyeing the fibre mordanted with a chromium salt or mordant (after or without
discharging patterns or figures) with the amidoazoproducts above referred to and
subsequently treating the fibre thus printed or dyed with moderately acid solutions
of sodium nitrite and then with solutions prepared from the known dye-stuff
components (viz., phenols, amines amidophenols, amidophenolethers, or the sulpho or
carboxylic acids thereof; and rendered slightly alkaline or acid according to the
nature of the components employed.
3. Cotton fibres or textures printed or dyed in the manner hereinbefore described
or by any other process producing a like result.
Dated this 21st day of December 1809
B. WILLCOX,