Improvements in the Manufacture of Azo Colouring Matters for Dyeing and Printing.
Year: 1890

page_text: Date of Application, 3rd Feb., 1890
Complete Specification Left, 18th Nov., 1890-Accepted, 20th Dec., 1890
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Azo Colouring Matters for
Dyeing and Printing.
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 invention has
been communicated to me from abroad by Farbenfabriken vormals Friedrich Bayer
and Company of Elberfeld in the Empire of Germany to be as follows:-
In the Provisional Specification accompanying my application for a Patent
No. 8299 dated the 18th day of May 1889 a class of azo colouring matters is described
which presents the valuable property, due to the presence of the carboxyl group, of
being suitable for dyeing as well as for printing purposes.
These products are obtained partly by the action of the diazo compounds of the amido
carbon acids, amido benzoic acids, and amido oxy benzoic acids mentioned in the
aforesaid Provisional Specification as well as of the amido para oxy benzoic acids,
amido salicylic acids and amido cresotinic acids, amido phthalic acids, amido sulpho
benzoic acids, amido sulpho salicylic acids, amido sulpho cresol carbon acids and amido
anisic acid upon dyestuff components or by the action of the diazo compounds of
amido naphthaline azo carbon acid dyestuffs upon suitable amides phenols or their
sulpho and carbon acids.
My foreign correspondents have now discovered by way of a further improvement
in this branch of manufacture that a new group of mordant dyeing colouring matters
is obtained when the alpha naphthylamine is replaced by its ether, the alpha amido
beta naphthol ether.
The combination of the alpha amido beta naphthol ether with the several diazo
compounds of the amido carbon acid proceeds with somewhat greater difficulty than
that of the alpha naphthylamine.
The coupling is effected in an acetic acid solution and the temperature is raised to
about 50 degrees Centigrade.
The further diazotizing of the amido azo colouring matter formed takes place as
described in my said former Specification that is to say the filtered amido azo com-
pound is dissolved in alkali, mixed with the calculated quantity of nitrite and
acidulated. The diazotising completed after standing for a few hours.
The coupling of the new diazo compound formed must be performed with the
materials in a very concentrated condition and amido phthalic acids, amido sulpho
salicylic acids and amido sulpho benzoic acids in particular are found on account of
their greater solubility to give better results than the amido salicylic acids and amido
benzoic acids.
The properties of the new colouring matters agree in a general way with those of
the corresponding products obtained from alpha naphthylamine described in the said
Provisional Specification No. 8299 of 1889.
As a carbon acid colouring matter they possess the property of mordant dyeing and
are capable of being used for printing but are especially suited for dyeing wool that
has been previously mordanted or prepared with a chromium salt or in case the
colouring matter possesses sufficient solubility they may be also employed for the
direct dyeing of wool in an acid bath or with common salt.
The colours thus produced are very fast. The shades obtained have a greener
tinge than the corresponding dyes obtained with alpha naphthylamine colouring
matter.
With secondary amines and amido naphthol ethers for example a greenish blue is
obtained.
Tl murhthalina lubid lead to blue vialet onlours

page_text: Phenol, salicylic acid and the like produce brown and beta naphthol greenish blue.
Naphthol sulpho acids yield greenish blue in the same way as dioxynaphthaline and
sulpho acids and the like.
The following is given as an example of the manufacture of the new colouring
matter according to this invention.
PRODUCTION OF THE COLOURING MATTER OBTAINED FROM AMIDO SULPHO SALICYLIC
ACID ALPHA AMIDO BETA NAPHTHOL ETHER BETA NAPHTHOL.
The diazo compound of the amido sulpho salicylic acid going with 5 kilos. of nitrite
is mixed with a hydrochloric acid solution of 12 kilos. of alpha amido beta naphthol
ether.
On the addition of acetate of soda the coupling proceeds slowly and may be
accelerated by heat.
After beating for several hours to about 50 degrees Centigrade the materials are
filtered off, the colouring matter obtained is dissolved in alkali and mixed with a
solution of five kilos. of nitrite.
After acidulation the diazotising proceeds slowly whilst continually stirring.
The black deposit which forms at first gradually assumes a red colour and after
standing for several hours the diazotising is completed.
The diazo compound formed is filtered off and caused to run into an alkaline
solution of about 12 kilos. of beta naphthol. The colouring matter which is immediately
formed dyes a beautiful greenish blue.
Datel this Thind dose at th
1000
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Azo Colouring Matters for
Dyeing and Printing.
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 com-
municated 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 the Specification of Letters Patent No. 8299 dated the 18th day of May 1889 a
class of azo colouring matters is described which colouring matters present the valuable
property owing to the presence of the carboxyl group of being suitable for dyeing as
well as for printing purposes.
These products are obtained by the action of the diazo compounds of the amido-
carboxy acids e.g. the amido-benzoic acids, amido-hydroxy-benzoic acids, amido-para-
hydroxybenzoic acids, amido-salicylic acids and amido-cresotinic acids, amido-phthalic
acids, amido-sulpho-benzoic acids, amido-sulpho-salicylic-acids, amido-sulpho-cresol
carboxy acids and amido-anisic acid upon dyestuff components or by the action of the
diazo compounds of the combination of the above mentioned carboxy acids with alpha
naphthylamine upon suitable amines, phenols, or their sulpho or carboxy acids.
My foreign correspondents have now discovered a further improvement in this branch
of manufacture riz. :-that a new group of mordant dyeing colouring matters is obtained
when alpha-naphthylamine is replaced by alpha-amido-beta-naphthol ethers 1:2 (for
instance methyl or ethyl-ether).
The combination of the alpha-amido-beta naphthol-ethers 1:2 with the several
diazo compounds of the amido carboxy acids proceeds with somewhat greater difficulty
than that of alpha-naphthylamine.
The coupling is effected in an acetic acid solution and the temperature is raised to
about 50 degrees Centigrade.
The further diazotising of the amido azo colouring matter formed is effected as

page_text: described in the said former Specification that is to say the filtered amido-azo com-
pound is dissolved in alkali, mixed with the calculated quantity of nitrite of soda
and the solution acidulated. The diazotising is completed after standing for some
hours.
The coupling of the new diazo compound must be performed with the phenols,
naphthols or their sulpho, or carboxy acids in a very concentrated condition. The
amido phthalic acids, amido sulpho-salicylic-acids and amido-sulpho benzoic acids in
particular give on account of the greater solubility of their diazo compound better
results than the amido-salicylic acids and amido-benzoic acids.
The properties of the new colouring matters agree in a general way with those of
the corresponding products obtained from alpha-naphthylamine described in the said
Specification of Patent No. 8299 of 1889.
As colouring matters derived from carboxy acids they possess the property of dyeing
mordants, they are capable of being used for printing purposes but especially dye
wool which has been previously mordanted or prepared with a chromium salt or in
case the colouring matter possesses sufficient solubility they may also be employed for
the direct dyeing of wool in an acid bath or with common salt.
The colours thus produced are very fast against the action of air and light. The
shades obtained have a greener tinge than have the corresponding dyes obtained with
alpha naphthylamine.
The amido-naphthalene-sulpho acids afford blue-violet colours. Phenol and salicylic
acid produce brown. Beta-naphthol produces greenish-blue, naphthol sulpho acids
and di-hydroxy naphthalenes and their sulpho acids also produce greenish blue.
The following is given as an example of the manufacture of the new colouring
matter according to this invention.
PRODUCTION OF THE COLOURING MATTER OBTAINED FROM AMIDO-SULPHO-SALICYLIC
ACID ALPHA-AMIDO-BETA NAPHTHOL-ETHERS 1:2 + BETA-NAPHTHOL.
The quantity of diazo compound of amido sulpho salicylic acid produced by means
of 5 kilos. of nitrite is mixed with a hydrochloric acid solution of 12 kilos. of alpha-
amido-beta-naphthol ethers 1:2. On the addition of acetate of soda the coupling
proceeds slowly and may be accelerated by heat.
After heating for several hours to about 50 degrees Centigrade the materials are
filtered off, the colouring matter obtained is dissolved in alkali and mixed with a
solution of five kilos. of nitrite.
After acidulation the diazotising proceeds slowly and it is necessary to stir
continually.
The black deposit which forms at first gradually assumes a red colour and after
standing for several hours the diazotising is completed.
The diazo compound thus formed is filtered off and run into an alkaline solution of
about 14 kilos. of beta naphthol. The colouring matter which is immediately formed
dyes a beautiful greenish blue.
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 as this invention is :-
1st. The process for the manufacture of azo colouring matters for dyeing or printing
by substituting; in the process according to the Specification of Letters Patent
No. 8299 and claimed under claim 1c; alpha-amido-beta-naphthol ethers 1:2 for
alpha naphthylamine.
2nd. As new articles of manufacture the new dyestuffs herein before described.
Dated this 18th day of November 1800
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.