Improvements in the Production of Black Azo Colours upon Fibres.
Year: 1892

page_text: Date of Application, 27th Aug., 1892
Complete Specification Left, 27th May, 1893-Accepted, 15th July, 1893
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
Improvements in the Production of Black Azo Colours upon Fibres.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have described in the Specifications of the Letters
Patent granted to Benjamin Willcox, No. 8530, dated 2nd June 1890, and No. 9636,
dated 6th June 1891, that the so-called substantive azo dye-stuffs derived from
amidonaphtholmonosulpho acid G, and 18-amidonaphthol betadisulpho acid
(resulting from naphthalenetrisulpho acid of the German Patent No. 38281, or
from the so called diamidonaphthalene alpha disulpho acid) can be diazotised upon
fibres, and that the diazo or tetrazo compounds thus produced, can be directly
combined with phenols, amines, amido phenols, sulpho or carboxylic acids thereof,
black colours being formed in this manner.
In the Specification of the application for Letters Patent in the name of the said
Benjamin Willcox, No. 22641A, dated 28th December 1891, the analogous
production of azo colours upon fibres is described. This process consists in further
diazotising on fibre the tetrazo dye-stuffs obtained from tetrazo compounds and
alpha-naphthylamine betamonosulpho acids, and coupling the diazo or tetrazo
products with phenols, amines, amidophenols, sulpho- or carboxylic acids thereof,
likewise on fibre.
The employment of tetrazo dye-stuffs derived from amidonaphtholether sulpho
acids, amido naphthols, amidonaphtholethers, amidonaphthoxyacetic acids, or amido
naphthoxyacetic sulpho acid, iz., their conversion into diazo or tetrazo derivatives,
and the combination of the latter with the known dye-stuff components, both processes
being effected on fibre, forms the object of the invention which my foreign
correspondents have described in the Specification of application for Letters Patent
No. 11395, dated 17th June 1892, in the name of B. Willcox.
Amongst the substantive dye-stuff's employed in the processes hereinbefore
described, the symmetrical products resulting by the combination of tetrazo
compounds of paradiamines with amido-naphthosulpho acids, amido naphtholether-
sulpho acids, alpha_naphthylaminebeta monosulpho acids, amidonaphthols, amido-
naphtholethers, amido naphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid,
and likewise the so-called mixed products obtained by combining one molecular
proportion of a tetrazo salt, one molecular proportion of a phenol, an amine, a sulpho
or carboxylic acid thereof, and one molecular proportion of amidonaphtholsulpho
acids, amidonaphtholethersulpho acids, alphanaphthylaminebetamonosulpho acid,
amidonaphthol, amidonaphtholether, amidonaphthoxyacetic acid, ог amido
naphthoxyacetic sulpho acid, can be used for producing azo dyes on fibre by means
of the said methods.
My foreign correspondents have now further found, that black dyes of still
greater intensity can be produced on fibre, by employing the azo colouring matters
which are obtained by the combination of tetrazo compounds of paradiamines, with
one or two molecular proportions of alphanaphtylamine, or certain naphthylamine

page_text: derivatives (middle components), by further diazotising the so-formed intermediate
products, and subsequently coupling with the following components:-amido-
naphtholsulpho acids, alpha naphthylamine betamonosuipho acids, amidonaphthol-
ether sulpho acids, amidonaphthols, amidonaphtholethers, amidonaphthoxyacetic, or
amido naphthoxyacetic sulpho acid (employing two molecules of these components),
or with one molecule of the last named components and one molecule of another
amine or phenol.
These colouring matters, which are termed trisazo dye stuffs, if one molecule of
a so called middle component be employed, and which are named tetrakisazo dye
stuffs, if two molecules of the said middle components be used, are in general
produced according to the process described in the Specification of Letters Patent
No. 16484 of 1887 granted to James Yate Johnson for an invention communicated
by my present correspondents.
My foreign correspondents employ the tetrazo compounds of the following
diamines, . benzidine, ortho tolidine, para diamido phenylorthotolyl, para-
diamido orthomonoalkylhydroxydiphenyl, paradiamido ortho mono alkylbydroxy-
phenyl ortho tolyl, paradiamido ortho diphenolether, paradiamido azo benzene,
paradiamido azo toluene, paradiamido azoxylene, and the corresponding three
diamido azoxy products, para amido benzene azo paratoluidine, para amido benzene
azo para xylene, amido benzene azo amidonaphthalene, and the hydroxyethers
thereof (alkylhydroxy-products), diamido naphthalene, diamidostilbene, diamido
fluorene, diamido carbazol, diamido diphenic acid, diamido diphenoxyacetic acid,
diamido diphenylene ketoxime, and analogues thereof, paradiamidophenylene
oxide, paradiamido toluylene oxide, paraphenylene diamine, toluylene diamine, and
analogous diamines, and sulpho products of all these diamines (including sulpho
acids, sulphones, and sulphone sulpho acids).
As "middle components," the following products can be used; alphanaphthyl-
amine, alpha naphthylamine beta monosulpho acid, alpha amidonaphtholether,
alpha amidonaphtholether sulpho acid, amidonaphthoxyacetic acid, or amido-
naphthoxyacetic sulpo acid, amidonaphthols, and amidonaphtholsulpho acids.
The combination of the tetrazo compounds of diamines with alphanaphthylamine,
alphanaphthylamine betamonosulpho acid, alpha amido naphtholether, alphaamido
naphtholether sulpho acid, amido naphthoxyacetic acid, and amido naphthoxyacetic
sulpho acid, more practically is effected in acid solution in presence of sodium
acetate, whilst the union with the amido naphthols and amido naphtholsulpho acids
takes place more profitably in alkaline solution.
One molecular proportion of the tetrazo salts of the aforesaid diamines can be
combined either with one or two molecular proportions of the above naphthylamine
derivatives. In the former case, one molecular proportion of nitrous acid is
necessary, whilst in the latter case two molecular proportions of nitrous acid must
be employed, in order to produce the corresponding tetrazo compounds. The
coupling of the latter with two molecular proportions of amidonaphthol monosulpho
acid G, 1.8-amidonaphtholbeta disulpho acid, or other amido naphtholsulpho
acids, most practically is effected in alkaline solution, whilst the alpha naphthyl-
amine beta monosulpho acids, amidonaphtholethers, amidonaphtholether sulpho
acids, amidonaphthoxyacetic acids, and amidonaphthoxyacetic sulpho acids, are
coupled more practically in acid solution. Amidonaphthols can be coupled either,
in alkaline or acid solution.
So-called "mixed dye stuff's" result by combining, one molecule of a tetrazo-
tised diamine with one or two molecular proportions of the above said middle
components, re-diazotising, and combining at first with one molecular proportion of
amido naphtholsulpho acid, or the other aforesaid components, and then, with one
molecular proportion of another phenol, amine, amido phenol, sulpho or carboxylic
acid thereof, or inversely, by coupling at first with one molecular proportion of a
phenol, an amine, amido-phenol, a sulpho or carboxylic acid thereof, 'and'

page_text: subsequently with one molecular proportion of amidonaphtholsulpho acid, or the
other components above enumerated.
The process for producing azo dye-stuffs on fibre, by dyeing cotton at first with
trisazo and tetrakisazo colouring matters obtained from one molecular proportion of
a tetrazo compound, one or two molecular proportions of alpha naphthylamine or
alpha amido naphtholether, and either two molecular proportions of 1.8 amido
naphtholbeta disulpho acid, or one molecular proportion of the latter acid, and one
molecular proportion of another dyestuff component, has been described by my
foreign correspondents in the Specification of the English Patent No. 9636, dated
6th June 1891, above referred to.
The general method for producing black shades on fibre by means of the
aforesaid azo colouring matters, is analogous to that described in the Specifications
of the before mentioned Letters Patent No. 853090 and No. 9636", and of the
applications for Letters Patent No. 22641A and 11395 above referred to.
In order to illustrate how to employ the above named azo colours and components,
the following examples are given :—
PRODUCTION OF A BLACK SHADE BY MEANS OF THE TRISAZO DYE STUFF
FROM 1 MOLECULE OF TETRAZO DITOLYLCHLORIDE, 1 MOLECULE OF
DELTA MONO SULPHO ACID, AND 2 MOLECULES
ALPHANAPHTHYLAMINE
OF 18-AMIDONAPHTHOLBETA DISULPHO ACID.
10 kilos. of cotton are dyed in the known manner with 0.8 kilos. of the colouring
matter resulting from the combination of one molecular proportion of tetrazo-
ditolylchloride, one molecular proportion of alphanaphthylamine delta monosulpho
acid, by further diazotising the so-formed tetrazo compound, and combining the
same with two molecular proportions of 18-amido naphthol beta disulpho acid.
The cotton (which has acquired a blue colour) is placed in a solution of 0.2 kilos.
of sodium nitrite in about 200 litres of cold water, acidulated with 0.6 kilos. of
hydrochloric acid (20 degrees Baumé), and well agitated therein. After from
about 10 to 15 minutes, the cotton is taken out, well rinsed, and placed in an
alkaline solution of 0.4 kilos. of the sodium salt of beta naphthol. The cotton
soon acquires a pure black colour.
In employing a solution of 0.4 kilos. of the sodium salt of alphanaphthol, or
05 kilos. of ethylbetanaphthyl amine hydrochlorate, in place of the sodium salt of
|betanaphthol, a black colour likewise is produced.
PRODUCTION OF A BLUISH BLACK BY MEANS OF THE DYE STUFF OBTAINED
BY COMBINING ONE MOLECULE OF TETRAZO DITOLYLCHLORIDE WITH
ONE MOLECULE OF ALPHANAPHTHYLAMINE, RE-DIAZOTISING, AND
COUPLING WITH TWO MOLECULES OF ALPHANAPHTHYLAMINEBETAMONO
SULPHO ACID (1.6).
Ten kilos. of cotton are dyed in the usual manner in an alkaline soap bath by
means of 0.8 kilos, of the last named dye-stuff'; placed, after rinsing well, in a
solution of 0.2 kilos. of sodium nitrite in 200 litres of cold water, acidulated by
means of 0-6 kilos. of hydrochloric acid (20 degrees Baumé), and well agitated
therein. When, after about 15 minutes, the diazotation is complete, the cotton is
rinsed well in cold water, and placed in a solution of 0.4 kilos. of the sodium salt
of betanaphthol. The cotton thus treated soon acquires a bluish-black color.
In the same manner, dark, and mostly pure black and fast shades, are produced

page_text: on fibre by employing the other aforesaid coloring matters, viz., by dyeing cotton
therewith, diazotising the tris- or tetrakisazo dyes fixed on fibre, and coupling
likewise on fibre with naphthols, amidonaphthalene derivatives, amidonaphthols, or
amidonaphtholethers, or, in general, with phenol, cresol, resorcinol, pyrocatechine,
dioxy-naphthalene, amido phenol, amido phenolether, or other amines of the benzene
or naphthalene series, or with sulpho or carboxylic acids of these components.
The foregoing two examples are typical for the employment of all those coloring
matters (tris or tetrakisazo dye stuffs) which result by combining the tetrazo
compounds of the above-named diamines with one or two molecules of alpha-
naphthylamine, alphanaphthylamine betamonosulpho acid, amidonaphtholether,
amidonaphtholether sulpho acid, amidonaphthol, amidonaphthosulpho acid, amido-
naphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, or with one molecule of
these components and one molecule of another dye stuff component; by further
diazotising the so-formed intermediate products, and coupling with one or two
molecules of amidonaphtholsulpho acid, alphanaphthylaminebetamonosulpho acid,
amidonaphtholethersulpho acid, amidonaphthol, amidonaphtholether, amido-
naphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, or with one molecule of
the last named components, and subsequently with one molecule of another dye
stuff component.
If two components are coupled in middle position, or in last
place, either the same products, or two different ones, can be obtained for further
employment.
My foreign correspondents have further found that the dis-, tris, and tetrakisazo
dye stuffs derived from paraphenyline diamine, naphthylene diamine, and analogous
diamines, can be profitably employed in the processes described in the said Letters
Patent No. 81300 and No. 9636, and in the said applications for Letters Patent
No. 22641A and 11395º.
These azo colors can be produced with the aid of diazotised monoacetyl para-
phenylene diamine, monoacetyl naphthylene diamine, in the following ways:-
+66
a) By combining said diazo products with alphanaphthylamine, alphanaphthyl-
aminebetamono sulpho acid, alphaamidonaphtholether, alpha amido naphthol ether
sulpho acid, amidonaphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, amido-
naphthol, amidonaphthol sulpho acid, which components may be briefly termed
components A ; by further diazotising the so-formed intermediate products, and
coupling with the so-called "components B," viz., amido naphtholsulpho acid, alpha
naphthylaminebetamonosulpho acid, amidonaphtholethersulpho acid, amidonaphthol,
amidonaphtholether, amidonaphthoxyacetic acid, amidonaphthoxyacetic sulpho
acid, and subsequently splitting off the acetyl group.
6) By combining said diazo products with one of the "components A;" further
diazotising, coupling with the same "component A," or another amido product,
rediazotising, combining with the "components B," and finally splitting off the
acetyl group.
c) By combining said diazo compounds with one of the "components A,"
separating the acetyl group, further diazotising, and coupling with two molecules
of the "components B," or with one molecule of the " components B," and one
molecule of another dye-stuff component.
d) By combining said diazo products with phenols, sulpho or carboxylic acids
thereof, splitting off the acetyl group, rediazotising, and coupling with one molecule
of the "components B."
"components B."
e) By coupling said diazo derivatives with phenols, sulpho or carboxylic acids
thereof, separating the acetyl group, rediazotising, combining with one molecule
of one of the
components A," further diazotising, and coupling with the
These dye stuff's enumerated under a to e, and derived from paraphenylene-
diamine, can be obtained in an analogous manner from paranitro-aniline; however,
the nitro group of the intermediate products thus obtained is to be reduced by

page_text: means of ammonia sulphide, or other moderate reducing agent, when, in the
corresponding products from diazomonoacetylparaphenylene diamine, the acetyl
group is separated.
By dyeing cotton with these paraphenylene diamine colors obtained from mono-
acetylparaphenylene diamine, or paranitraniline, diazotising the dis, tris, or tetra-
kisazo colors on fibre, and combining with phenols, amines, amidophenols, sulpho or
carboxylic acids thereof, in general, brownish black, bluish-black, violet black or
greenish black shades result, which are distinguishable by their great "fastness to
the action of washing and soaping.
"
The employment of these dye stuffs derived from paraphenylene diamine is
described in the following example.
PRODUCTION OF A BLUISH-BLACK BY MEANS OF THE COLORING MATTER
OBTAINED BY COUPLING DIAZOTISED MONO-ACETYLPARAPHENYLENE
DIAMINE WITH ONE MOLECULE ALPHANAPHTHYLAMINEBETAMONOSULPHO
ACID (17), REDIAZOTISING TILE SO-FORMED AMIDO AZO PRODUCT,
COUPLING WITH ALPHA AMIDOBETANAPHTHOLETHER BETAMONO SULPHO
ACID, AND SPLITTING OFF THE ACETYL GROUP.
Ten kilos. of cotton are dyed by treating for, say, one hour, in a boiling bath
prepared from 0-6 to 0.8 kilos. of the last named dye stuff, with the addition of
sodium sulphate, and soap, or common salt. After rinsing, it is placed in the
manner described in the foregoing first example, at first in a bath of nitrous acid,
then in a bath containing the sodium salt of betanaphthol.
In this manner, a
beautiful bluish black color is produced on fibre.
If the betanaphthol be replaced by phenol, cresol, resorcinol, alphanaphthol, or
naphtholsulpho acids, a violet black results, whilst dihydroxynaphthalenes,
dihydroxynaphthalenesulpho acids, ethylbetanaphthylamine, and amido naphthol-
ether, in general yield shades more green, and darker.
In an analogous manner, the other dis-, tris, and tetrakisazo dye staffs, derived
from paraphenylene diamine, and those derived from naphthylene diamine and
analogous diamines, are diazotised on fibre, and combined with phenols, amines,
amido phenols, amidophenolethers, sulpho or carboxylic acids thereof.
The combination of the diazo or tetrazo compounds on fibre with phenols,
naphthols, and the like, is in general effected in alkaline solution, whilst the
coupling with amines is in general carried out in acid solution Amido phenols and
dihydroxynaphthalenes and sulpho acids thereof, can be combined either in alkaline
solution or in acid solution, in presence of sodium acetate.
Dated this 97th day of August 1892
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Black Azo Colours upon Fibres.
1, HENRY EDWARD NEWTON, of The Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention 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 stated in the Specifications of the Letters
Patent granted to Benjamin Willcox, No. 8530, dated 2nd June 1890, and No. 9636,

page_text: dated 6th June, 1891, that certain substantive azo dye-stuffs derived from amido-
naphtholono sulpho acid, G, or 18-amidonaphthol betadisulpho, acid (which
latter acid is obtainable from naphthalene trisulpho acid of the German Patent
No. 38281, or from the so-called diamidonaphthalene alpha disulpho acid), can be
diazotised upon fibres, and that the diazo- or tetrazo compounds thus produced can
be directly combined with phenols, amines, amidophenols, sulpho or. carboxylic
acids thereof, black colours being formed in this manner.
In the Specification of the Letters Patent granted to the said Benjamin Willcox,
No. 22641A, dated 28th December 1891, an analogous production of azo colours
upon fibres is described. This process consists in further diazotising the symmetrical
or mixed tetrazo dye-stuffs obtained from tetrazo compounds and Cleve's alpha
naphthylamine-beta-monosulpho acids (beta or delta), while on the fibre, and
coupling the diazo or tetrazo products with phenols, amines, amidophenols, amido-
phenolethers of the benzene or, naphthalene series, or sulpho or carboxylic acids
thereof, likewise while on the fibre.
The employment of tetrazo dye-stuffs derived from amidonaphtholether sulpho
acids, amidonaphthols, amidonaphtholethers, amido naphthoxyacetic acids, or
amidonaphthoxyacetic sulpho acids, viz., their conversion into diazo or tetrazo
derivatives, and the combination of the latter with the known dye-stuff components
(both processes being effected on the fibre), forms the object of the invention which
my foreign correspondents have described in the Specification of application for
Letters Patent No. 11395, dated 17th June 1892, in the name of Benjamin
Willcox.
Amongst the substantive dye-stuffs employed in the processes hereinbefore
described, the symmetrical products resulting from the combination of tetrazo
compounds of paradiamines, with amidonaphthol sulpho acids, amidonaphtholether-
sulpho acids, alpha naphthylamine beta monosulpho acids, amidonaphthols, amido-
naphtholethers, amidonaphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid,
and likewise the so-called mixed products obtained by combining one molecular
proportion of a tetrazo salt, one molecular proportion of a phenol, an amine, a
sulpho or carboxylic acid thereof, and one molecular proportion of an amido-
naphtholsulpho acid, an amidonaphtholethersulpho acid, alpha naphthylamine beta
monosulpho acid, amidonaphthol, amidonaphtholether, amidonaphthoxyacetic or
amidonaphthoxyaceticsulpho acid, can be used in producing azo dyes on the fibre,
by means of the said methods.
My foreign correspondents have now further found, that dyes of still greater
intensity and yielding, in general, black shades, can be produced on the fibre by
employing the azo colouring-matters which are obtained by the combination of
tetrazo compounds of para-diamines with one or two molecular proportions of alpha
naphthylamine, or certain naphthylamine derivatives ("middle components"),
excluding those of the resulting combinations which are not true amido-azo
products, and are not further diazotisable, by diazotising the intermediate products
so formed, and subsequently coupling them with the following components: amido-
naphtholsulpho acid, alpha naphthylamine-beta-monosulpho acids (excluding
Clève's gamma acid), amidonaphtholether sulpho acids, amidonaphthols, amido-
naphtholethers, amidonaphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid
(employing two molecules of these components, either the same or two different
ones), or with one molecule of the last named components and one molecule of
another dye-stuff component.
These colouring-matters, which are termed "trisakis-azo dye-stuffs," if one
molecule of a so-called "middle component" be employed, and which are named
"tetrakisazo dye-stuffs," if two molecules of the said "middle components" be
used, are in general produced according to the process described in the Specification
of Letters Patent No. 16484 of 1887, granted to James Yate Johnson, for an
invention communicated by my present correspondents.
My foreign correspondents employ the tetrazo-compounds of the following

page_text: diamines, viz., benzidine, ortho tolidine. para diamidophenylorthotolyl, para-diamido
ortho monoalkylhydroxydiphenyl, para diamido ortho mono alkylhydroxy phenyl-
orthotolyl, paradiamido orthodiphenolether, paradiamido azo benzene, paradiamido-
azotoluene, paradiamido azoxylene, and the corresponding three diamidoazoxy
products, para-amido benzene-azo-paratoluidine, para amido benzene-azo-para-
xylidine, amido benzene azo amido naphthalene, and the hydroxyethers thereof
(alkylhydroxy products), diamidonaphthalene, diamidostilbene, diamido fluorene,
diamidocarbazol, diamidodiphenic acid, diamido-diphenoxyacetic acid, diamido-
diphenylene ketoxime, and analogues thereof, paradiamidodiphenylene oxide,
paradiamidoditoluylene oxide, para phenylene diamine, toluylene diamine, and
analogous diamines and sulpho products of all these diamines (including sulpho
acids, sulphones, and sulphone sulpho acids).
As "middle components," the following products can be used :-alpha naphthyl-
amine, alphanaphthylamine beta monosulpho acids (excluding Clève's alpha-
naphthylamine betamono sulpho acid gamma), alpha amido naphtholether sulpho
acid, amidonaphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid, amido-
naphthols, and amidonaphtholsulpho acids.
Of course, my foreign correspondents exclude those of the said "middle com-
ponents" which, when combined with the tetrazo compounds of diamines, do not
yield true amidoazo products, which are diazotisable.
The combination of the tetrazo compounds of diamines with alpha naphthylamine,
alpha naphthylamine-beta-monosulpho acid, alpha amidonaphtholether, alpha amido
naphtholether sulpho acid, amido naphthoxy acetic acid, or amido naphthoxyacetic
sulpho acid, more practically is effected in acid solution in presence of sodium
acetate, whilst the union with the amido naphthols, or amidonaphthol sulpho acids,
is more profitably effected in alkaline solution.
One molecular proportion of the tetrazo salts of the aforesaid diamines can be
combined either with one or two molecular proportions (employing, in the latter
case, either one or two different compounds) of the above naphthylamine derivatives
("middle components"). In the former case, one molecular proportion of nitrous
acid is necessary, whilst in the latter case two molecular proportions of nitrous acid
must be employed, in order to produce the corresponding products containing free
diazo groups. The coupling of the latter products with two molecular proportions
of amidonaphthol monosulpho acid G, 1:8-amido naphthol beta disulpho acid, or
other amido naphthol sulpho acids, is most practically effected in alkaline solution,
whilst the alphanaphthylamine beta mono sulpho acids, amido naphtholethers,
amido naphtholethersulpho acids, amido naphthoxyacetic acids, and amido
naphthoxyacetic sulpho acids, are coupled preferably in acid solution. Amido-
naphthols can be coupled either in alkaline or acid solution.
So-called "mixed dye stuffs," which can be employed in this process, result on.
combining one molecular proportion of a tetrazotised diamine with one or two.
molecular proportions (employing, in the latter case, either one or two different
compounds) of the above said middle components, rediazotising, and combining at
first with one molecular proportion of amidonaphtholsulpho acid, or one of the,
other aforesaid components, and then with one molecular proportion of another dye
stuff component, such as a phenol, amine, diamine, amido phenol, amidophenolether
of the benzene or naphthalene series, a sulpho or carboxylic acid thereof, or,
inversely, by coupling at first with one molecular proportion of a phenol an amine,
diamine, amidophenol, amidophenolether, a sulpho or carboxylic acid thereof, and,
subsequently with oue molecular proportion of amido naphtholsulpho acid, or of the
other components above enumerated.
The process for producing azo dye stuffs on the fibre, by dyeing cotton at first
with trisazo and tetrakis azo colouring matters, obtained from one molecular
proportion of a tetrazo compound, one or two molecular proportions of alpha
naphthylamine, or alpha amidonaphtholether, and either two molecular proportions

page_text: of 1:8 amidonaphthol beta disulpho acid or one molecular proportion of the latter
acid, and one molecular proportion of another dye stuff component, has been
described by my foreign correspondents in the Specification of the English Patent
No. 9636, dated 6th June 1891, above referred to. The employment of these dye
stuffs is disclaimed hereby.
The general method for producing, on the fibre, dyes which in general yield black
shades, by means of the above defined azo colouring matters (trisakis- or tetrakis
azo dye stuffs), is analogous to that described in the Specifications of the before-
mentioned Letters Patent, No. 8530° and No. 9636" and No. 22641 A", and of the
application for Letters Patent No. 113952 above referred to.
In order to illustrate how to employ the above named azo colours and components,
the following examples are given:
PRODUCTION OF A BLACK SHADE BY MEANS OF THE
TRISAKISAZO DYE-
STUFF FROM 1 MOLECULE OF TETRAZO DITOLYLCHLORIDE, 1 MOLECULE 1
NE DELTA MONOSULING ROID, AND 2 MOLBOULES
OF 1:8 AMIDONAPHTHOL-BETA-DISULPHO ACID.
10 kilos. of cotton are dyed in the known manner with 0-8 kilos. of the colouring
matter having the formula :—
OF 1:8 AMIDONAPHTHOL-BETA-DISULPHO ACID.
10 kilos. of cotton are dyed in the known manner with 0-8 kilos. of the colouring
matter having the formula:
NH,
CH
SO, Na
OH
CH-N-N-C₁₂H, N=N-C₁H,
10
SO,Na
SO,Na
NH₂
OH
CH, N=N-C₁H¸
SO, Na
CH,
SO, Na,
which dye stuff is formed by combining one molecular proportion of tetrazo ditolyl-
chloride, with one molecular proportion of alpha naphthylamine delta mono sulpho
acid, further diazotising the intermediate product (containing one free diazo group)
so formed, and coupling the resulting product (containing two free diazo groups)
with two molecular proportions of 1:8 amidonaphthol-beta-disulpho acid. The
cotton (which has acquired a blue colour). is placed in a solution of 0.2 kilos. of
sodium nitrite in about 200 litres of cold water, acidulated with 0.6 kilos. of hydro-
chloric acid (20 degrees Baumé), and well agitated therein. After from about
10 to 15 minutes, the cotton is taken out, well rinsed, and placed in an alkaline
solution of 0.4 kilos. of the sodium salt of beta naphthol. The cotton soon acquires
a pure black colour.
By employing a solution of 0.4 kilos. of the sodium salt of alphanaphthol, or
05 kilos. of ethyl beta naphthylaminehydrochloride, in place of the sodium salt of
beta naphthol, a black colour is also produced.

page_text: PRODUCTION OF A BLUISH-BLACK BY MEANS OF THE DYE STUFF OBTAINED
BY COMBINING ONE MOLECULE OF TETRAZO DITOLYLCHLORIDE WITH
ONE MOLECULE OF ALPHA NAPHTHYLAMINE, REDIAZOTISING, AND
COUPLING WITH 2 MOLECULES OF ALPHA
MONOSULPHO ACID (1:6).
NAPHTHYLAMINE
BETA-
10 kilos. of cotton are dyed in the usual manner in an alkaline soap bath by
means of 0.8 kilos. of the above-named dye-stuff having the formula:
The cotton thus dyed is well rinsed, and is then introduced into a solution of
0-2 kilos. of sodium nitrite in 200 litres of cold water acidulated by means of
0-6 kilos. of hydrochloric acid (20 degrees Baumé), and well agitated therein.
After about 15 minutes, when the diazotisation is complete, the cotton is well rinsed
in cold water, and is then placed in a solution of 0.4 kilos. of the sodium salt of
beta naphthol. The cotton thus treated soon acquires a bluish-black colour.
In the same manner, dark, and mostly pure black, and fast shades, are produced
on fibre, by employing the other aforesaid colouring-matters, viz., by dyeing cotton
therewith, diazotising the trisakis or tetrakis azo dyes fixed on the fibre, and
coupling them likewise while on the fibre, with naphthols, amidonaphthalene
derivatives, amidonaphthols or amidonaphtholethers, or in general with phenol,
cresol, resorcinal pyrocatechol, dihydroxynaphthalene, amidophenol, amidophenol-
ether, or other amines or hydroxy compounds of the benzene or naphthalene series,
or with sulpho or carboxylic acids of these components.
The foregoing two examples are typical of the method to be followed in the case
of all the colouring-matters (trisakis or tetrakis azo dye-stuffs) which are formed
by combining the tetrazo compounds of the above-named diamines, with one or two
molecules of alpha naphthylamine, alpha naphthylamine beta nono sulpho acids
(excluding however Clève's alpha naphthylamine-beta-mono sulpho acid gamma),
amidonaphtholether, amidonaphtholether sulpho acid, amidonaphthol, amidonaphthol
sulpho acid, amidonaphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, or with
one molecule of these components; and one molecule of another dye-stuff component,
by further diazotising the so-formed intermediate products, and coupling them with
one or two molecules of amidonaphthol sulpho acid, alpha naphthylamine-beta-mono
sulpho acid, amidonaphtholethersulpho acid, amidonaphthol, amidonaphthiolether,
amido naphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, or with one mole-
cule of the last named components, and subsequently with one molecule of another
dye-stuff component.

page_text: If two components are introduced, either the intermediate or the final operation,
either one or two different compounds can be employed.
My foreign correspondents have further found, that the dis-, tris-, and tetrakis
azo dye-stuffs derived from para phenylene diamine, naphthylene diamine, and
analogous diamines, can be profitably employed in the processes described in the
said Letters Patent No. 853000 and No. 9636." and No. 22641A, and in the
Specification of application for Letters Patent No. 11395 0.
My foreign correspondents mean by the expression "analogous diamines," for
instance, toluylene diamine, including also the sulpho derivatives of para phenylene
diamine, toluylene diamine, naphthylene diamine, and the like. These azo colours
(dis-, tris-, or tetrakis azo dye-stuffs) can be produced with the aid of diazotised
monoacetyl para phenylene diamine, monoacetylnaphthylene diamine, etc., in the
following ways:-
a.) By combining the said diazo products with alphanaphthylamine, alpha-
naphthylamine beta monosulpho acids (excluding Clève's alpha naphthylamine beta-
monosulpho acid gamma), alpha amidonaphtholether, alpha amidonaphtholether-
sulpho acid, amidonaphthoxyacetic acid, amidonaphthoxyaceticsulpho acid, amido-
naphthol, amidonaphtholsipho acid,-which components may be briefly termed
components A,"-by further diazotising the so-formed intermediate products, and
coupling them with the so called "components B," viz., amidonaphtholsulpho acid,
alpha naphthylamine beta monosulpho.acid, amidonaphtholethersulpho acid, amido-
naphthol, amidonaphtholether, amidonaphthoxyacetic acid, amidonaphthoxyacetic-
sulpho acid, and subsequently displacing the acetyl group.
66
6.) By combining the said diazo products with one of the " components A,"
further diazotising, coupling with the same component A," or another amido
product, which, when combined with diazo products, yields true diazotisable
amidoazo products, rediazotising, combining with the "components B," and finally
displacing the acetyl group.
c.) By combining the said diazo compounds with one of the "components A,"
displacing the acetyl group, further diazotising, and coupling with two molecules of
the "components B," or with one molecule of the "
components B" and one
molecule of another dye-stuff component.
d.) By combining the said diazo products with phenols, sulpho or carboxylic
acids thereof, displacing the acetyl group, rediazotising, and coupling with one
molecule of the " * components B."
e.) By coupling the said diazo derivatives with phenols, sulpho or carboxylic
acids thereof, displacing the acetyl group, rediazotising, combining with one
molecule of one of the "components A," further diazotising, and coupling with the
components B."
The dye-stuff's enumerated under a to e, and derived from the aforesaid diamines,
can be obtained in an analogous manner from the corresponding nitroamines, in
which case the nitro group of the resulting intermediate products is to be reduced
at the appropriate time by means of ammonia sulphide, or other moderate reducing
agent.
In an analogous manner, the colouring-matters derived from sulpho acids of the
said diamines can be obtained, if the corresponding mononitroamidosulpho acids
are employed.
By dyeing cotton with the colouring-matters obtained from monoacetylised
diamines, or mononitroamido compounds, diazotising the dis-, tris-, or tetrakisazo
colours on the fibre, and combining with phenols, amines, amidophenols, sulpho or
carboxylic acids thereof, brownish-black, bluish-black, violet-black, or greenish-
black shades in general result, which are distinguished for their great
"fastness
"when washed and soaped.
"
The employment of the dye-stuffs derived from paraphenylene diamine is described
in the following example :-

page_text: THIRD EXAMPLE.
PHENYLENE
PRODUCTION OF A BLUISH-BLACK BY MEANS OF THE COLOURING-MATTER
OBTAINED BY COUPLING DIAZOTISED MONOACETYLPARA
DIAMINE, WITH ONE MOLECULE OF ALPHA NAPHTHYLAMINE-BETA-
MONOSULPHO ACID (1:7), REDIAZOTISING THE SO-FORMED AMIDOAZO
PRODUCT, COUPLING WITH ALPHA AMIDO-BETA-NAPHTHOLETHER-BETA-
MONOSULPHO ACID, AND SPLITTING OFF THE ACETYL GROUP.
10 kilos. of cotton are dyed by boiling during, say, one hour, in a bath prepared
by dissolving from 0-6 to 0.8 kilos. of the above-named dye-stuff, together with
sodium sulphate, and soap, or common salt.
The dye-stuff employed possesses the following composition viz. :—
After rinsing the dyed material, it is introduced, in the manner described in the
foregoing first example, at first into a bath of nitrous acid, then into a bath
containing the sodium salt of beta naphthol. In this manner, a beautiful bluish-
black colour is produced on the fibre.
If, instead of beta naphthol, phenol, cresol, resorcinol, alphanaphthol, or naphthol-
sulpho acids, are used, a violet-black results, whilst dihydroxynaphthalenes,
dihydroxynaphthalenesulpho acids, ethylbetanaphthylamine, and amidonaphthol-
ether, in general yield shades which are more green and darker.
In an analogous manner, the other dis-, tris-, and tetrakisazo dye-stuffs derived
from para phenylene diamine, and those derived from naphthylene diamine and
analogous diamines, are diazotised on the fibre, and combined with phenols, amines,
amidophenols, amidophenolethers, sulpho or carboxylic acids thereof.
The combination of the diazo or tetrazo compounds on fibre with phenols,
naphthols, and the like, is in general effected in alkaline solution, whilst the
coupling with amines is in general carried out in acid solution. Amidophenols and
dihydroxynaphthalenes, and sulpho acids thereof, can be combined either in alkaline
solution or in acid solution, in presence of sodium acetate.
Of course, my foreign correspondents exclude from use, those of the dye-stuffs
hereinhefore defined which are insoluble in water.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
1. In the production of dyes on fibre, the employment of the colouring matters
hereinbefore defined.
2. The process of producing dyes on fibre, which process consists first in dyeing
cotton fibres, fabrics, or materials with the colouring-matters hereinbefore defined,
in further diazotising these colouring-matters on the fibre, and coupling the resulting
diazo- or tetrazo products, also whilst on the fibre, with amines, diamines, phenols,
amidophenols, amidophenolethers of the benzene or naphthalene series, sulpho or
carboxylic acids thereof, effecting the latter two processes (viz. diazotising and

page_text: combination) by treating cotton, previously dyed, first in a moderately acidulated
bath of sodium nitrite, and then in a moderately acid or alkaline bath of an amine,
diamine, phenol, amidophenol,, amidophenolether of the benzene or naphthalené
series, or a sulpho or carboxylic acid thereof.
3. Cotton fibres or textures dyed in the manner hereinbefore described, or by
any other process producing a like result.
Dated 05th 1002
NEWTON & SON,
Agents for the Applicant.