Improvements in the Manufacture and Production of Colouring Matters.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Colouring
Matters.
I, GEORGE WILLIAM JOHNSON, 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 Kalle & Co., of Biebrich-on-Rhine, in the German
Empire) to be as follows:--
My foreign correspondents have found that very valuable black colouring matters
are obtained by diazotising the amidoazo products obtained from a para-amido-
diphenylaminsulphonic or carboxylic acid and a₁ B3-or a, B-naphthylaminesulphonic
acid, and by combining these diazo products with an unsulphonated phenol (mainly
beta-naphthol or an unsulphonated amine (mainly alpha-naphthylamine). The
colouring matters thus obtained are suitable for dyeing as well as printing upon wool,
they produce black tints or shades of great fastness against washing, and are alkali-
and acid proof. These colouring matters are distinguished from all other black
secondary disazo colouring inatters by their very great intensity of colour. Speaking
generally, the products, with a phenol in the terminal position, are more suitable for
printing purposes than those with an amine in the terminal position. Sulphonated
terminal components give, in connection with the diazo compounds above referred to,
less valuable colouring matters.
The following examples will serve to further explain the nature of this invention
but it is not limited to the precise details given.
EXAMPLE I.
Colouring matter from para-amidodiphenylamine carboxylic acid, a₁-napthy-
lamine-6-sulphonic acid and ẞ-naphthol.
23-0 kilogr. of para-amidodiphenylamine carboxylic acid, obtained by the
condensation of 1.2.4 chlornitrobenzoic-acid (Cl.COOH.NO,: 1.2.4) with aniline
and the reduction of the condensation product obtained, are diazotised in water
with 300 kilogr. of hydrochloric acid and 70 kilogr. of nitrite. To the diazo-
solution is added a solution of
24-5 kilogr. of sodium a, B-naphthylamine sulphonate and
80 kilogr. of sodium carbonate and the product is stirred for about 12 hours.
12.0 kilogr. of caustic soda of 40° Bé. and.
7.0 kilogr. of nitrite are then added and acidified with
45.0 kilogr. of hydrochloric acid.
The formation of the violet-black coloured diazo intermediate product is completed
after stirring for a short time. To obtain the colouring matter, the diazo liquid is
allowed to run into an aqueous solution of
14.5 kilogr. of beta-naphthol.
4.0 kilogr. of caustic soda and
30-0 kilogr. of ignited sodium carbonate.
After stirring for some little time the

page_text: product is warmed and the colouring matter salted out filtered and pressed. The
If in this
colouring matter dyes wool a deep black with a beautiful violet lustre.
example the diamido diphenyl carboxylic acid employed is replaced by the product
which is obtained during the action of nitrochlor carboxylic acid upon toluidine a
colouring matter of precisely similar properties but with a slightly more blueish lustre
is obtained.
EXAMPLE II.
Colouring matter from para-amidodiphenylamine sulpho acid, a₁-naphthylamine-B
sulpho acid and 6 naphthol.
26-5 kilogr. of para-amidodiphenylamine-sulphonic acid are diazotised in water
with 180 kilogr. of hydrochloric acid and 70 kilogr. of nitrite. Into the diazo
solution a cooled aqueous solution of 245 kilogr. of sodium a₁ ß, naphthylamine
sulphonate and 3.0 kilogr. of ignited sodium carbonate is poured and the product
stirred for about 12 hours.
120 kilogr. of caustic soda of 40° Be. and 70 kilogr. of nitrite are then added and
the product acidified with 30-0 kilogr. of hydrochloric acid and stirred until the
diazotization is completed. The diazo compound which is readily soluble in water
forming a violet colour, is made to combine in the presence of an excess of sodium
carbonate with 14.5 kilogr. of beta-naphthol which has been dissolved in water by
means of a sufficient amount of caustic soda. The colouring matter dissolves with
difficulty in the product of the reaction. To isolate the product the liquid is heated
to about 80° Centigrade and filtered.
The colouring matter dyes wool a deep black. If the amidodiphenylamine
sulphonic acid is replaced by para-amido phenyl tolylamine-sulphonic acid there is
obtained, without any other modification of the process a colouring matter of precisely
similar properties but of a slightly more blueish shade.
Colouring matter from para-amidodiphenylamine sulphonic acid, α-naphthylamine-
B-sulpho acid and a-naphthylamine.
The diazo-azo compound obtained according to Example II. is poured into a
solution of 14.3 kilogr. of a-naphthylamine in 500.0 kilogr. of water and 12.0 kilogr.
of hydrochloric acid.
The product is stirred for several hours made alkaline with sodium carbonate
warmed and the colouring matter precipitated with salt. This colouring matter dyes
wool in an acid bath deep-violet-black. The dyes prove fast when washed or fulled.
The product from para-amido-phenyl-tolyl-amine sulphonic acid shews similar
properties but a somewhat bluer shade.
This 15th day of T₁l., 1900
Improvements in the Manufacture and Production of Colouring
Matters.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been 4
communicated to me from abroad by Kalle & Co., of Biebrich-on Rhine, in the

page_text: German Empire) and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement :-
My foreign correspondents have found that very valuable black colouring matters
are obtained by diazotising the amido azo products obtained from a para amido
diphenyl amine sulphonic or carboxylic acid and alpha, beta-or alpha, beta
-napththylamine sulphonic acid and by combining these diazo products with an
unsulphonated phenol (mainly beta naphthol) or an unsulphonated amine (mainly
alpha-naphthylamine). The colouring matters thus obtained are suitable for
dyeing as well as printing upon wool, they produce black tints or shades of great
fastness against washing, and are alkali and acid proof. These colouring matters
are distinguished from all other black secondary disazo colouring matters by
their very great intensity of colour. Speaking generally the products with a
phenol in the terminal position, are more suitable for printing purposes than
those with an amine in the terminal position. Sulphonated terminal components
give in connection with the diazo compounds above referred to, less valuable colouring
matters.
The following examples will serve to further explain the nature of this invention
and the way in which it can be carried out but it is not limited to the precise details
given.
EXAMPLE I.
Colouring matter from para-amido diphenylamine carboxylic acid, alpba₁-naphthyl-
amine-beta, sulphonic acid and beta-naphthol.
23.0 kilogr. of para-amido diphenylamine carboxylic acid obtained by the con-
densation of 1.2.4. chlornitro benzoic acid (Cl. COOH.NO: 1.2.4) with aniline and
the reduction of the condensation product obtained are diazotised in water with
300 kilogr. of hydrochloric acid and 7.0 kilogr. of nitrite. To the diazo-solution is
added a solution of 245 kilogr. of sodium alpha, beta-naphthylamine sulphonate
and 8.0 kilogr. of sodium carbonate and the product is stirred for about 12 hours.
120 kilogr. of caustic soda of 40 degrees Beaumé and 7.0 kilogrammes of nitrite
are then added and the mixture is acidified with 450 kilogr. of hydrochloric acid.
The formation of the violet-black coloured diazo intermediate product is completed
after stirring for a short time. To obtain the colouring matter the diazo liquid is
allowed to run into an aqueous solution of 14.5 kilogr. of beta-naphthol, 4.0 kilogr.
of caustic soda and 300 kilogr. of ignited sodium carbonate. After stirring for some
little time the product is warmed and the colouring matter salted out filtered and
pressed.
The colouring matter dyes wool a deep black with a beautiful violet lustre. If in
this example the diamidodiphenyl carboxylic acid, employed is replaced by the
product which is obtained during the action of nitrochlor benzoic acid upon toluidine
à colouring matter of precisely similar properties but with a slightly more blueish
lustre is obtained.
EXAMPLE II.
Colouring matter from para-amido-diphenylamine-sulpho acid, alpha-naphthyl-
amine-beta-sulphoacid and beta-naphthol.
26-5 kilogr. of para-amidodiphenylaminesulphonic acid are diazotised in water
with 180 kilogr. of hydrochloric acid and 7.0 kilogr. of nitrite. Into the diazo-
solution a cooled aqueous solution of 24-5 kilogr. of sodium alpha, beta, naphthyl-
amine sulphonate and 3.0 kilogrammes of ignited sodium carbonate is poured and
the product stirred for about 12 hours. 120 kilogrammes of caustic soda of 40°
Beaumé and 7.0 kilogrammes of nitrite are then added and the product acidified
with 300 kilogrammes of hydrochloric acid and stirred until the diazotisation is
completed.
The diazo compound which is readily soluble in water, forming a violet colour, is
made to combine, in the presence of an excess of sodium carbonate with 14.5 kilo-
grammes of beta-naphthol, which has been dissolved in water by means of a sufficient

page_text: amount of caustic soda. The colouring matter dissolves with difficulty in the reaction
liquid. To isolate the product the liquid is heated to about 80° Centigrade and
filtered.
The colouring matter dyes wool a deep black. If the amido-diphenylamine-
sulphonicacid is replaced by para-amido-phenyl-tolylamine-sulphonic acid, there is
obtained, without any other modification of the process, a colouring matter of
precisely similar properties but of a slightly more blueish shade.
EXAMPLE III.
Colouring matter from para-amidodiphenylaminesulphonic acid, alpha,-naphthyl-
amine-beta-sulphoacid and alpha-naphthylamine.
The diazoazo compound obtained according to Example II. is poured into a solution
of 14.3 kilogrammes of alpha-naphthylamine in 5000 kilogrammes of water and
120 kilogrammes of hydrochloric acid.
The product is stirred for several hours, made alkaline with sodium carbonate,
warmed, and the colouring matter precipitated with salt. This colouring matter dyes
wool in an acid bath deep violet-black. The dyes prove fast when washed or fulled.
The product from para-amido-phenyltolylaminesulphonic acid shews similar properties
but has a somewhat bluer shade.
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 manufacture of secondary disazo colouring matters by combining diazotized
para-amido-diphenylamine-sulphonic or -carboxylic acid with alpha, beta-or alpha,
beta, naphthylamine-sulphonic acid, rediazotizing the so obtained amidoazoproduct,
and combining it finally with beta-naphthol or alpha-naphthylamine, all substantially
as herein before described.
2. As new articles of manufacture the new secondary disazo colouring matters such
as can be obtained, substantially as herein before described.
Dated this 17th day of April 1900.
TAUNCON
e
IT TAAV
47, Lincoln's Inn Fields, London, W.C., Agents.