The Manufacture and Production of New Black Substantive Azo-dyes.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Black Substantive
Azo-dyes.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, 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 German Empire) to be as follows:-
This invention consists in the manufacture and production of a new class of black
substantive azo colouring-matters suitable for dyeing cotton without the aid of a
mordant.
These new colouring-matters are derived from 1.8-amido-naphthol-4- or 5-mono-
sulphoacid. They are obtained from the said acids by the suitable combination of
two tetrazo residues therewith. The said tetrazo residues may be regarded as tetrazo
compounds, of which one diazo group is already combined with a component whilst
the second diazo group remains and is eventually combined with the amido-naphthol-
sulphoacid. Not all such azo dyes which can be obtained by the combination of such
tetrazo residues with the said amido-naphthol-sulphoacids are valuable black sub-
stantive colouring-matters in accordance with this invention. In order to obtain the
new valuable colouring-matters according to this invention the tetrazo residues must
be suitably chosen and their combination with the amido-naphthol-sulphoacid
effected in a certain definite manner, all as hereinafter explained. My foreign
correspondents have discovered that if the combination of suitably chosen tetrazo
residues be so effected that a tetrazo residue containing a basic group, or basic
groups, attaches itself to the part of the amido-naphthol-sulphoacid residue which
contains the aido group, and further a tetrazo residue which contains a hydroxyl
group, or hydroxyl groups, attaches itself to the part of the amido-naphthol-
sulphoacid residue which contains the hydroxyl, then the particular black
colouring-matters of excellent quality in accordance with this invention are
obtained.
These new colouring-matters therefore possess the following general formula: -

page_text: OH
In this the tetrazo residue containing the basic groups is obtained from para-
phenylene-diamine-azo-meta-phenylene-diamine, and the tetrazo residue containing 5
the acid groups is obtained from para-phenylene-diamine-azo-salicylic acid.
This colouring-matter yields, on cotton, excellent black shades, whilst the isomeric
colouring-matter that can be obtained containing the tetrazo residues arranged in
the reverse manner to that herein defined yields, when using the same quantity of
colouring-matter, only dark-green shades on cotton.
Other members of this new class of colouring-matters are obtained if, for instance,
para-phenylene-diamine-azo-meta-toluylene-diamine be used as the source of the
tetrazo residue containing the amido groups, instead of para-phenylene-diamine-
azo-meta-phenylene-diamine. Also on the other hand, benzidine azo-phenol,
benzidine-azo-salicylic acid, para phenylene-diamine-azo-phenol, or para-phenylene-
diamine-azo-resorcinol are instances of bodies that can be used instead of the para-
phenylene-diamine-azo-salicylic acid as the source of the tetrazo residues containing
the acid groups.
The following example will serve to further illustrate the nature of the invention,
but it is not restricted to this example. The parts are by weight :-
EXAMPLE.
-
Diazotise two hundred and twenty-eight (228) parts of para-phenylene-diamine-
azo-meta-phenylene-diamine in the well-known way, using sixty nine (69) parts of.
sodium nitrite and three hundred and eighty (380) parts of hydrochloric acid (con-
taining about 30 per cent. HCl). Take such a quantity of water that about two 2
thousand (2,000) parts of diazo solution are obtained. Run this into a suspension of
two hundred and forty (240) parts of 1.8-amido-naphthol-4-sulpho acid in sixteen
thousand (16,000) parts of water and four thousand (4,000) part of ice. After a short
time add two thousand (2,000) parts of sodium acetate solution, containing ten per cent.
sodium acetate. Stir for about five or six hours. A test portion on paper should no 3
longer shew a yellow liquid that turns blue-violet with soda. When this is the case
the production of the intermediate product may be regarded as finished. In this way
the combination of the tetrazo residue containing the basic groups in the part of the
amido-naphthol-sulpho acid molecule containing the amido group is effected.
Next add to the liquid eight thousand (8,000) parts of a solution of carbonate of 3
soda (containing 10 per cent. Na, CO) and to the liquid so obtained add a diazo
solution obtained in the well known way from two hundred and eighty (280) parts of
paraphenylene diamine-azo-salicylic acid (mono-sodium salt) four hundred and
twenty (420) parts of hydrochloric acid (containing 30 per cent. HCI) and sixty nine (69)
parts of sodium nitrite. Stir for twelve hours. The formation of the coloring matter 4
will then be finished. Warm up to about from 75 to 80 degrees Centigrade, and
stir in eight thousand (8,000) parts of common salt. The coloring matter is
precipitated. Filter press and dry.

page_text: The Manufacture and Production of New Black Substantive
Azo-dyes.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin & Soda Fabrik of Ludwig-
shafen-on-Rhine, in the German Empire) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:-
This invention consists in the manufacture and production of a new class of black
substantive azo colouring matters suitable for dyeing cotton without the aid of a
mordant.
These new colouring matters are derived from 1-8 amido-naphthol-4-, or. 5-mono
sulpho acid. They are obtained from the said acids by the suitable combination of
two tetrazo residues therewith. The said tetrazo residues may be regarded as tetrazo
compounds, of which one diazo group is already combined with a component, whilst
the second diazo group remains, and is eventually combined with the amido-naphthol
sulpho acid. Not all such azo dyes as can be obtained by the combination of such
tetrazo residues with the said amido-naphthol sulpho acids are valuable black sub-
stantive colouring matters in accordance with this invention. In order to obtain the
new valuable colouring matters according to this invention the tetrazo residues must
be suitably chosen, and their combination with the amido naphthol-sulpho acid
effected in a certain definite manner, all as hereinafter explained. My foreign
correspondents have discovered that if the combination of suitably chosen tetrazo
residues be so effected that a tetrazo residue containing a basic group, or basic
groups, attaches itself to the part of the amido naphthol-sulpho acid residue which
contains the amido group, and further a tetrazo residue which contains a hydroxyl
group, or hydroxyl groups, attaches itself to the part of the amido-naphthol sulpho-
acid residue which contains the hydroxyl, then the particular black colouring matters
of excellent quality in accordance with this invention are obtained.
These new colouring matters therefore possess the following general formula :-

page_text: In this the tetrazo residue containing the basic groups is obtained from para-
phenylene-diamine-azo-meta phenylene-diamine, and the tetrazo residue containing
the acid groups is obtained from para-phenylene-diamine azo salicylic acid..
This colouring matter yields, on cotton, excellent black shades whilst the isomeric
colouring matter that can be obtained containing the tetrazo residues, arranged in
the reverse manner to that herein defined, yields when using the same quantity of
colouring matter, only dark-green shades on cotton.
Other members of this new class of colouring matters are obtained if, for instance,
para-phenylene-diamine azo-meta-toluylene-diamine be used as the source of the
tetrazo residue containing the amido groups, instead of para-phenylene-diamine-azo-
meta-phenylene-diamine. Also, on the other hand, benzidine-azo-phenol, benzidine-
azo-salicylic acid, para-phenylene-diamine-azo-phenol, and para-phenylene-diamine-
azo-resorcinol, are instances of bodies that can be used, instead of the para-phenylene-
diamine-azo salicylic acid, as the source of the tetrazo residues containing the acid
groups.
The following example will serve to further illustrate the nature of the inven-
tion but it is not restricted to this example The parts are by weight
Diazotise two hundred and twenty eight parts of para-phenylene-diamine-azo-meta-
phenylene-diamine in the well known way, using sixty nine parts of sodium nitrite
and three hundred and eighty parts of hydrochloric acid (containing about thirty per
cent. HC). Take such a quantity of water that about two thousand parts of diazo
solution are obtained. Run this into a suspension of two hundred and forty parts
of 18 amido-naphthol 4-sulphoacid in sixteen thousand parts of water and four
thousand parts of ice. After a short time add two thousand parts of sodium acetate
solution containing ten per cent. sodium acetate. Stir for about five, or six hours.
When a test portion on paper no longer shews a yellow liquid that turns blue-violet
with soda, the production of the intermediate product may be regarded as finished.
In this way the combination of the tetrazo residue containing the basic groups in
the part of the amido-naphthol-sulphoacid molecule containing the amido group is
effected.
Next add to the liquid eight thousand parts of a solution of carbonate of soda
(containing ten per cent. Na, CO₂) and to the liquid so obtained add a diazo solution
obtained in the well known way from two hundred and eighty parts of para-phenylene-
diamine-azo-salicylic acid (mono sodium salt), four hundred and twenty parts of
hydrochloric acid (containing thirty per cent. HCI) and sixty nine parts of sodium
nitrite. Stir for twelve hours. The formation of the colouring matter will then be
finished. Warın up to about from seventy five to eighty degrees Centigrade and stir
in eight thousand parts of common salt. The colouring matter is precipitated.
Filter press and dry.

page_text: 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. The process for the manufacture of new black substantive azo dyes from 1.8
amido naphthol 4 or 5 mono-sulphoacid which consists in combining one of the said
amido-naphthol-mono-sulphoacids with a tetrazo residue containing a basic group,
or basic groups in such a way that it becomes attached to the part of the amido-
naphthol-sulphoacid residue which contains the amido group; and also with a tetrazo
residue containing a hydroxyl group, or hydroxyl groups, in such a way that it becomes
attached to the part of the amido-naphthol-sulpho acid residue which contains the
hydroxyl group, all substantially as hereinbefore described.
2. The manufacture of new black substantive azo dyes substantially as described
in the foregoing Example.
3. As new articles of manufacture the new group of black substantive azo dyes such
as can be obtained substantially as hereinbefore described.
Dated the 12th day of June 1900.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.