Improvements in the Production of Blue, Bluish-black, or Greenish- black Poly-azo-dyes on Vegetable Fibre or on Silk.
Year: 1895

page_text: Date of Application, 5th July, 1895
Complete Specification Left, 20th Feb., 1896-Accepted, 28th Mar., 1896
PROVISIONAL SPECIFICATION.
Improvements in the Production of Blue, Bluish-black, or Greenish-
black Poly-azo-dyes on Vegetable Fibre or on Silk.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of London
Gentleman do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:-
on
In the Specification of Letters Patent No. 1002 of January 15th 1895 a process
is described by means of which certain azo-dyes derived from the 1. 1' amido-
naphthol-4-and-41-mono-sulpho acids can be used for the production
vegetable or animal fibre of fast black shades. For this purpose the goods to be
dyed are padded with a solution of the azo-dyes and then these are converted into
black disazo-dyes on the fibre by combination with a further proportion of diazo
or tetrazo compound. As azo dyes the mono-azo dyes of the scheme
from one molecule of a diazo-compound of a primary amine R' - NH, and one
molecule of the said 1. 1' amido-naphtol-sulpho acids as also dis-mono azo dyes
of the scheme
OH
N = N - C₁H NH₂
R
SO,H
OH
NNCH,NH2
SO,H
NH₂,
obtained from one molecule of a tetrazo-compound of a paradiamine R
NH,
for instance benzidine, and two molecules of the 1. 1' amido-naphthol-mono-sulpho
O acids can be used.
My foreign correspondents have now discovered that the black dyestuffs, in as
far as they are produced on the fibre by the aid of a tetrazo-compound, still have
the properties of diazo- or tetrazo-compounds and can be converted into new
black colouring matters by treating with naphthol and the like.
[Price Bd.]
3

page_text: SO₂H
which both can be regarded as intermediate products.
10
By these intermediate products the fibre is dyed blue, or bluish-green, to black
and very fast new reddish-blue, to blue, or greenish black, shades are obtained if
the said goods be introduced directly before soaping, into an alkaline beta-
naphthol bath, or into a solution of meta-phenylene-diamine containing sodium
acetate, or carbonate. Instead of beta-naphthol, or meta phenylene-diamine, 16
other phenols, amines, and the sulpho and carboxylic acids thereof can be
employed.
•
The following examples will serve to further illustrate the nature of the

page_text: departure from the nature of the invention. The parts are by weight.
EXAMPLE I.
PRODUCTION OF BLUE, BLUISH-BLACK, OR GREENISH-BLACK ON VEGETABLE
OR ANIMAL FIBRE (COTTON OR SILK).
Dissolve about twenty five (or more for deeper shades say from one hundred to
two hundred) parts of the dyestuff prepared from one molecule of the diazo
compound of para-dichlor-aniline and one molecule of 1. 11 amido naphthol
4 sulpho acid in an acid solution together with five (relatively twenty or forty).
parts of caustic soda in about ten thousand parts of water, pad the goods to be
dyed with this solution, wring out and dry. Subsequently pass the goods through
a one per cent. solution of tetrazo-diphenyl-acetate, the quantity of which is nearly
the same as that of the dyestuff supplied for padding the goods. The formation
of the dyestuff is practically finished when a test portion introduced into a soda
solution containing about three per cent. of soda at a temperature of sixty to
seventy degrees Centigrade, does not discharge with violet colour. Then wash
out and introduce the goods into twenty times the quantity of a solution of beta-
naphthol containing in one thousand parts about fifteen parts of beta-naphthol,
fifty parts of Turkey red oil, and three parts of caustic soda. The combination
takes place very quickly and is usually finished in a minute or two.
Its
termination can be easily recognized by the conversion of the colour from greenish-
blue, to red blue.
In this example the beta-naphtol can be substituted by an equivalent quantity
of the following compounds, given in the first column when the shades given in
the second column will be obtained.
alpha naphthol
1-naphthol 4 sulpho acid
2-naphthol 3 sulpho acid-
1. 1' dioxy-naphthaline
1.4¹ dioxy-naphthaline
2.2 dioxy naphthaline
-
1. 11 amido naphthol 4 sulpho acid
1. 1' amido naphthol 4' sulpho acid
1. 1¹ benzoyl-amido-naphtol-4- or 4¹ sulpho acid. -
5 diethyl-meta-amido-phenol
phenol
resorcine
beta oxy-naphthoic acid (F.P. 216° C.)
meta-phenylene-diamine
0 meta-toluylene-diamine
-
blue to bluish black
blue to black
blue violet to black
blue to brown black
blue to black
blue violet to black
blue to black
.
greenish blue to black
blue to bluish black
bluish green to black
green to greenish black
gray violet to black
-
bluish violet to bluish black
grayish black to brown black
grayish black to brown black

page_text: PRODUCTION OF BLUISH VIOLET TO BLUISH BLACK COLOURS ON VEGETABLE
FIBRE (COTTON).
Dye say about one hundred parts of cotton during one hour in a nearly boiling
bath containing:
One part (relatively two or three parts) of the dyestuff from one molecule of
tetrazo diphenyl and two molecules of 1. 11 amido naphthol 4' sulpho acid, five
parts of calcinated soda, fifteen parts of Glauber's salt and three thousand parts of
water.
Wash out with cold water (it is not necessary to dry in this case) then pass the
dyed goods through a two per cent. solution of tetrazo ditolyl acetate, the quantity
of which is nearly the same as that of the dyestuff employed for dyeing the goods.
Work the goods in this solution until the combination is finished.
In this process
the blue colour is converted into a greenish black. Wash again with cold water
and then develope with beta naphthol as described in Example I and bluish violet
to bluish black colours will be obtained.
Dated this 5th day of July 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Production of Blue, Bluish-black, or Greenish-
black Poly-azo-dyes on Vegetable Fibre or on Silk.
JAMES YATE JOHNSON of 47 Lincoln's Inn Fields, in the County of
London, Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin & Soda Fabrik
of Ludwigshafen-on-Rhine 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 the Specification of Letters Patent No. 1002 of January 15th 1895 granted
to me on a communication from my present foreign correspondents a process is
described by means of which certain azo dyes derived from the 1. 11 amido-naphthol
4-and-4-mono-sulpho acids can be used for the production of fast black shades on
vegetable fibre or on silk (I will hereinafter refer to them as "the fibre"). For
this purpose the goods to be dyed are padded with a solution of the azo dyes and
then these are converted into black dis-azo-dyes on the fibre by combination with a
further proportion of diazo or tetrazo compound. As azo dyes can be used the
mono-azo-dyes of the scheme

page_text: and one molecular proportion of the said 1. 1'-amido-naphthol-sulpho acids as also
dis-mono-azo dyes of the scheme
R
OH
N = N
CoH,{NH,
(SO,H
гон
\N = N – C₁₂H₁ NH,
SO,H
obtained from one molecular proportion of a tetrazo, compound of a paradiamine
Ru
NH,
\NH,
for instance benzidine and two molecular proportions of the 1. 1'-amido-
naphthol-mono-sulpho acids.
My foreign correspondents have discovered that the black dyestuffs, in as far as.
they are produced on the fibre by the aid of a tetrazo-compound still have the
properties of diazo or tetrazo compounds and can be converted into new black.
colouring matters by treating with naphthol and the like.
Thus the mono azo dyes

page_text: which both can be regarded as intermediate products.
By these intermediate products the fibre is dyed blue or bluish-green to black
and very fast reddish-blue to blue or greenish-black new dyes are obtained. on the
fibre if the said goods be treated directly before soaping with an alkaline beta-
naphthol solution or with a solution of meta phenylene diamine containing sodium
acetate or carbonate: Instead of beta naphthol or meta-phenylene diamine other
phenols, amines and the sulpho- and carboxylic-acids thereof, such as are in use for
combination with diazo bodies can be employed.
The following examples will serve to further illustrate the nature of the invention
but they are merely typical cases and can be varied greatly without departure from
the nature of the invention.
PRODUCTION OF BLUE, BLUISH-BLACK OR GREENISH-BLACK COLOUR ON
THE FIBRE.
Dissolve about twenty five (or more for deeper shades say from one hundred to
two hundred) parts of the dyestuff' prepared from one molecular proportion of the
diazo compound of para-dichlor-aniline and one molecular proportion of 1.1'-amido-
naphthol-4-sulpho-acid in an acid solution together with five (relatively for deeper
shades from twenty to forty) parts of caustic soda in about ten thousand parts of
water, pad the goods to be dyed with this solution, wring out and dry. Subsequently
pass the goods through a one per cent. solution of tetrazo-diphenyl-acetate; the
quantity of which is nearly the same as that of the dyestuff applied for padding
the goods. The formation of the dyestuff is practically finished when a test portion
of the material does not discharge with violet colour on treatment with a soda
solution containing about three per cent. of soda at a temperature of sixty to
seventy degrees Centigrade. Then wash out and introduce the goods into twenty
times the quantity of a solution of beta-naphthol containing in one thousand parts,
about fifteen parts of beta-naphthol, fifty parts of Turkey red oil and four parts of
caustic soda. The combination takes place very quickly and is usually finished in
a minute or two. Its termination can be easily recognised by the conversion of the
colour from greenish-blue to red-blue.
In this example the beta-naphthol can be substituted by an equivalent quantity of

page_text: the following compounds, given in the first column, and the following shades, given
in the second column, will be obtained:
In some cases it will be useful to pass the dyed goods through a solution of
copper-sulphate for this treatinent renders the dye faster against soaping and light.
•
EXAMPLE II.
PRODUCTION OF BLUISH-VIOLET TO BLUISH-BLACK COLOURS ON COTTON.
Dye say about one hundred parts of cotton during one hour in a nearly boiling
bath containing one part (relatively for darker shades from two to three parts) of
the dyestuff from one molecular proportion of tetrazo-diphenyl and two molecular
proportions of 1. 1' amido-naphthol-4-sulpho acid, five parts of calcined soda, fifteen
parts of Glauber salt and three thousand parts of water.
Wash out with cold water (it is not necessary to dry in this case) then pass the
dyed goods through a two per cent. solution of tetrazo-ditolyl-acetate, taking so
much that a quantity of tetrazo compound nearly equal to that of the dyestuff
employed for dyeing the goods is present. Work the goods in this solution until
the combination is finished. In this process the blue colour is converted

page_text: into a greenish-black. Wash again with cold water and then develop with beta-
naphthol as described in Example 1. Bluish-violet to bluish-black colours will be
obtained.
Having now particularly described and ascertained the nature of this inven-
tion aud in what manner the same is to be performed I declare that what I
claim is
1. In the production of poly-azo-dyes on the fibre, the combination of the inter-
mediate compounds herein defined with phenols or amines or their sulpho or
carboxylic acids substantially as herein before described.
2. In the production of poly-azo-dyes on the fibre, the combination of the inter-
mediate compounds herein defined with beta-naphthol, or meta-phenylene-diamine,
or the other components herein before mentioned.
3. The production of dark shades on the fibre substantially in the manners
herein before described in the examples.
4. As new manufactures the dyes produced on fibres or fibrous materials
substantially as herein before described.
Dated this 20th day of February 1896.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.