The Production of Colours on Fibres.
Year: 1893

page_text: Date of Application, 16th June, 1893
Complete Specification Left, 16th Mar., 1894-Accepted, 12th May, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, Vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Production of Colours on 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 Letters Patent
No. 22641, dated 28th December 1891, and No. 11395, dated 17th June 1892, that
the substantive so called symmetrical or mixed disazo dye-stuffs which result by
combining the tetrazo salts of "benzidine or its analogues with certain amido-
naphthalene derivatives, when fixed on the fibre, can further be diazotised and
coupled (likewise on the fibre) with phenols, amines, amidophenols, amido-
phenolethers, sulpho or carboxylic acids thereof,-dye stuffs being thus formed
which yield a great variety of shades. Particularly those symmetrical or mixed
dye stuffs have been employed in the said process, which are produced from Clève's
alphanaphthyl amine beta-mono-sulpho acids (beta or delta), amidonaphthols,
amidonaphtholethers, amidonaphtholethersulpho acids, amido naphthoxy acetic acid,
or amidonaphthoxyacetic sulpho acid, viz., by coupling them with the tetrazo salts
of diamines or substituted diamines.
In addition thereto, my foreign correspondents have described in the Specification
of application for Letters Patent No. 15439 dated 27th August 1892, that shades
of greater intensity and fastness can be produced by replacing in the above
mentioned two processes, the colouring matters from tetrazo compounds and the
said components, by the corresponding polyazo dye stuffs (so called tris- or tetrakis
azo dye stuffs), which contain, as "middle components," one or two molecular
proportions of the following "naphthylamine derivatives," viz., alpha naphthyl-
amine, alphanaphthylamine-beta-mono-sulpho acid (a, ẞ, or a Bs), amidonaphthol
amidonaphtholmono- or disulpho acid, alpha amido beta naphthol ether, alpha amido
beta-naphtholether-beta monosulpho acid, alpha amido-beta-naphtholether-delta-
mono sulpho acid, alpha-amido-beta naphthoxy-acetic acid, alpha amido beta
naphthoxy-acetic sulpho acid, and which contain as "last components," either two
molecular proportions of amidonaphtholsulpho acid alpha-naphthylamine-ortho-
monosulpho-acid, alpha-naphthylamine-beta-mono sulpho acid (Clève's ẞ or & acid),
amido-naphthol-ether sulpho acid, amidonaphthol, amido naphtholether, amido-
naphthoxy acetic acid, amidonaphthoxyacetic sulpho acid, or one molecular
proportion of these products, and one molecular proportion of another dye stuff
component.
According to the researches of my foreign correspondents, the colouring matters
from amidonaphtholmonosulpho acid G, or 18 amidonaphthol-beta-disulpho acid,
likewise can be employed for the said purposes, as described in the Specifications
of Letters Patent No. 8530, dated 2nd June 1890, and No. 9636, dated
6th June 1891.
My foreign correspondents have now found that the tetrazo- or diazo compounds
obtained by diazotising, on fibre, the colouring matters mentioned in the Specifica-
tions above referred to (in place of coupling them with phenols, amines, or the
like), can be treated in hot moderately acid or alkaline baths, in order to obtain
extremely fast brown, brownish black, or black shades.
The process taking place during this reaction, consists in that azoxy compounds or

page_text: analogous products are probably formed in this way on fibre, as, according to the
investigations of my foreign correspondents, the same result can be obtained, if the
aforesaid disazo, trisazo, or tetrakis azo dyestuffs, when fixed on fibre (without being
diazotised), are directly subjected to a treatment in gently oxidising baths, for
instance, such as that prepared from chloride of lime.
The process for producing on fibre shades in the manner hereinbefore referred
to, in general, consists in first dyeing cotton with the disazo, trisazo, or tetrakis
azo dye stuffs, obtainable from "benzidine or its analogues," and the above named
"middle components" or "last components," and described in the Specifications of
Letters Patent No. 8530, 96361, 22641º¹, & 11395%, and in the Specification of
application for Letters Patent No. 15439%, further placing the thus thus dyed cotton
in acidulated baths of sodium nitrite, and subsequently treating it (after rinsing) in
hot acid or alkaline baths, or in subjecting the dyed goods to a treatment in gently
oxidising baths.
The following dye-stuffs especially can be employed with good result in the above
new processes for producing fast dyes on fibre, viz. : the colouring matters obtainable
from one molecular proportion of the tetrazo compound of "benzidine or its
analogues or homologues," and two molecular proportions of Clève's alphanaphthyl-
amine betamonosulpho acid (beta or delta), alpha-amido betanaphtholetherbeta-
monosulpho acid, alp'.a amido-beta-naphtholether-delta-monosulpho acid, or from
one molecular proportion of a tetrazo compound, and one molecular proportion of
Clève's alphanaphthylamine beta mono sulpho acid (beta or delta), alpha amido-
beta-naphtholether-beta-monosulpho acid, or alphaamido beta naphtholether delta-
mono sulpho acid, and one molecular proportion of a phenol, an amine, amido-phenol,
or a sulpho or carboxylic acid thereof, or the corresponding polyazo dyestuffs which
contain, as "middle components," one or two molecular proportions of alpha-
naphthylamine, or another of the aforesaid "naphthylamine derivatives."
By the expression "benzidine, its analogues or homologues," my foreign corre-
spondents mean, for instance, the following diamines, viz., benzidine, tolidine,
diamidophenyltolyl, diamidophenolether, diamidoalkyloxydiphenyl, diamidoalkyl-
oxyphenyltolyl, diamidoazobenzene, diamido azotoluene, diamidoazoxylene, diamido-
azoxybenzene, diamido azoxy toluene, diamido stilbene, diamidofluorene, diamido-
naphthalene, diamido carbazol, diamido diphenylene oxide, diamidoditoluylene
oxide, paraphenylene diamine, paratoluylene diamine, benzidine sulphone, tolidine
sulphone, diamidophenyltolylsulphone, diamidodiphenoxy acetic acid, diamido
diphenylene ketoxime, m.p.-diamido-phenylbenzimidazol, amidobenzeneazoalpha-
naphthylamine, amidotoluene azoalpha naphthylamine, amidoxyleneazoalpha-
naphthylamine, amido benzene azoparaxylidine, amidotoluene azo paraxylidine,
amidoxylene azo para xylide, amido benzene azo meta (or ortho) amido para-
cresolether, amidotoluene azo meta (or ortho) amido paracresolether, amidoxylene
azo meta (or ortho) amido paracresolether, amido benzene azo beta ethoxy alpha-
naphthylamine, amido toluene azobetaethoxy alpha naphthylamine, amidoxyiene
azo beta ethoxy alpha naphthylamine, sulpho or carboxylic acids thereof.
Of course, in order to produce the dyestuff's, which can be employed in the
processes above referred to, other diamines or sulpho acids thereof, which are
changed into teti azo compounds, either directly or by means of the mono acetylised
derivatives thereof, can likewise be employed. In place of the mono-acetylised.
diamines, the corresponding mononitro amines also can be employed, in which case
the nitro group of the resulting intermediate products is to be reduced at the
appropriate time by means of suitable reducing agents, whilst in the employment
of mono acety lised diamines, the acetyl group is to be displaced at the same time.
In carrying out these new processes in the manners hereinbefore defined, from
brown to brownish black and black shades in general result, which are extremely
fast against washing.
. In order to illustrate these new processes, the following example is given, which,
however, is merely to be regarded as typical, as the invention is not restricted
thereto.

page_text: 100 parts (by weight) of cotton are dyed in the known manner with 3 parts of
the colouring matter from one inolecular proportion of tetrazoditolylchloride, and
two molecular proportions of Clève's alphanaphthylamine beta-mono-sulpho acid
beta (a Bs), viz., by dyeing in a bath prepared by dissolving the said dye stuff,
20 parts of sodium sulphate, and 5 parts of sodium carbonate, in a sufficient
quantity of water. After rinsing, the material is placed in a moderately acid bath
of sodium nitrite, and agitated therein for, say, about half an hour. The original
bluish black colour is turned thereby into violet brown, and after rinsing again, the
material is placed in a hot bath containing 5 per cent. of sodium carbonate, and
agitated therein during half an hour at about 50 degrees centigrade.
The shades thus produced possess a cutch-brown colour, and are distinguished
for their intensity and fastness against the action of washing.
The same shade results if the material dyed as described in the foregoing
example with the dye stuff from tolidine and Clève's alphanaphthylamine-beta-
mono sulpho acid (beta) is placed in a gently oxidising bath (for instance, such as
that prepared from chloride of lime), and treated therein for some time.
The process proceeds in an analogous if, in place of the dye stuff above mentioned,
other of the aforesaid simple or mixed disazo, trisazo, or tetrakis azo coloring
matters are employed, shades being thus produced which are in general from brown
or brownish black to black, and possess great fastness against washing. The bath
above used, containing sodium carbonate, may further be replaced by such hot
baths as contain ammonia, or by hot acid baths, such, for instance, as contain
sulphuric acid. In the latter case, care must be taken that the sulphuric acid
adherent to the treated goods is entirely removed by rinsing.
The chemical reactions taking place during the operations herein before defined,
seem to consist in that azoxy products or the like are formed, whilst in the
employment of baths prepared with the aid of ammonia, diazo amido compounds
probably are produced.
Dated this 16th day of June 1893.
NEWTON & SON,
Agents. for the Applicant.
COMPLETE SPECIFICATION.
The Production of Colours on 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 described in the Specifications of Letters
Patent No. 226414, dated 28 December 1891 and No. 11395 dated 17th June 1892,
the manner in which the so-called symmetrical or mixed substantive disazo dye
stuffs formed by combining the tetrazo salts of "benzidine or its analogues" with
certain amidonaphthalene derivatives, fixed on fibres, can be further diazotised, and
coupled (also while on the fibre) with phenols, amines, amidophenols, or amido-
phenolethers, sulphonic or carboxylic acids thereof, dye stuff's being thus formed
which exhibit a great variety of shades. Particularly those symmetrical or mixed
azo dyestuffs have been used in the said processes, which are derived from Clève's
alphanaphthylamine beta-monosulphonic acids (beta or delta), amidonaphthols,

page_text: amidonaphtholethers, amidonaphtholethersulphonic acids, amidonaphthoxyacetic
acid, or amidonaphthoxyacetic sulphonic acid.
Moreover, my foreign correspondents have described in the Specification of
Letters Patent No. 15439, dated 27th August 1892, the manner in which dyes
of still greater intensity, which generally produce black shades, can be formed on
the fibre, by using in the above mentioned two processes, instead of the colouring
matters from tetrazo compounds and the said components, the corresponding
polyazo dyestuffs (so-called tris or teti akis azo dye stuffs) containing, as "middle
components," either one or two molecular proportions of the following “naphthyl-
amine derivatives," viz., alphanaphthylamine, alphanaphthylaminebetamono-
sulphonic acid (a₁ ß, or a B.), amidonaphthol, amidonaphtholmono- or disulphonic
acid, alpha-amido-beta-naphtholether, alpha amido-beta-naphtholether-beta-mono-
sulphonic acid, alpha-amido-beta naphtholether-delta-monosulphonic acid, alpha-
amido-beta-naphthoxy-acetic acid, alpha-amido-beta-naphthoxyaceticsulphonic acid;
and, as "last components either two molecular proportions of amidonaphthol-
sulphonic acid, alpha-naphthylamine-ortho-monosulphonic acid, alpha-naphthyl-
amine beta monosulphonic acid (Clève's ẞ or 8 acid), amidonaphtholethersulphonic
acid, amidonaphthol, amidonaphtholether, amidonaphthoxy acetic acid, amido-
naphthoxyaceticsulphonic acid, or one molecular proportion of these products and
one molecular proportion of another dyestuff component.
1:
"
The colouring matters derived from amidonaphtholmonosulphonic acid G, or
8-amidonaphthol-beta-disulphonic acid, can also be used for the said purposes,
as described in the Specifications of Letters Patent No. 8530, dated 2nd June 1890,
and No. 9636, dated 6th June 1891.
My foreign correspondents have now found, that instead of coupling the tetrazo
or diazo compounds obtained by diazotising the colouring matters mentioned in
the Specifications above referred to, while on the fibre, with phenols, amines, or
the like, they may be treated in hot moderately acid or alkaline baths, and may
thus be made to afford new shades, chiefly browns, some of which are of great
fastness.
The change taking place during this treatment probably involves the formation
of azoxy compounds or analogous products on the fibre, as it appears that the
same result can be obtained, if the aforesaid disazo, trisazo, or tetrakisazo
dyestuffs fixed on fibres are directly subjected, without being diazotised, to a
treatment in mild oxidising baths, for instance, a. bath prepared from chloride
of lime.
29
"
The general process for producing such shades on fibres in the manner herein-
before referred to, consists in first dyeing, for instance, cotton with the disazo,
trisazo, or tetrakis azo dye-stuffs obtainable from "benzidine or its analogues,'
and the above named "middle components or "last components," and defined in
the Specifications of Letters Patent Nos. 8530, 9636º¹, 226411, 11395°, and
15439; then introducing the cotton thus dyed into acidulated baths of sodium
nitrite, and subsequently treating it (after rinsing) in hot acid, or alkaline
baths, or in subjecting the dyed undiazotised goods to a treatment in mild oxidising
baths.
The said process can also be carried out on woollen or silky fibres or
materials, using such of the dye stuffs herein before defined as are capable of dyeing
wool or silk.
The following dye stuffs especially can be used with advantage in the above
processes for producing dyes on fibres, viz. :-the coloring matters obtainable from
one molecular proportion of the tetrazo compound of "benzidine or its analogues
or homologues," and two molecular proportions of Clève's alpha naphthylamine
betamonosulphonic acid (beta or delta), alpha amido betanaphtholether beta mono-
sulphonic acid, alpha amidobetanaphtholetherdeltamonosulphonic acid, or from one
molecular proportion of a tetrazo compound and one molecular proportion of
Clève's alphanaphthylaminebetamonosulphonic acid (beta or delta), alpha amido-
betauaphtholetherbetamonosulphonic acid, or alphaamidobetanaphtholetherdelta-

page_text: monosulphonic acid, and one molecular proportion of a phenol, amine, amido--
phenol, or a sulphonic or carboxylic acid thereof, or the corresponding polyazo
dyestuffs containing, as "middle components," one or two molecular proportions of
alpha naphthylamine or another of the aforesaid "naphthylamine derivatives."
By the expression "benzidine, its analogues or homologues," my foreign corre-
spondents mean, for instance, the following diamines, viz. :-benzidine, tolidine,
diamidophenyltolyl, diamidophenolether, diamidoalkyloxydiphenyl, diamido
alkyloxyphenyltolyl, diamido azo benzene, diamidoazotoluene, diamidoazoxylene,
diamidoazoxybenzene, diamidoazoxytoluene, diamidostilbene, diamidofluorene,
diamidonaphthalene, diamidocarbazol, diamidodiphenylene oxide, diamidodi-
toluylene oxide, paraphenylene diamine, paratoluylene diamine, benzidine sulphone,.
tolidine sulphone, diamidophenyltolylsulphone, diamidodiphenoxyacetic acid,
diamidodiphenylene ketoxime, m-p-diamidophenylbenzimidazol, amidobenzeneazo-
alphanaphthylamine, amidotolueneazoalphanaphthylamine, amidoxyleneazoalpha--
naphthylamine, amidobenzene azoparaxylidine, amidotolueneazoparaxylidine,
amidoxy leneazoparaxylidine, amidobenzeneazometa (or ortho) amidoparacresol-.
ether, amidotoluene azo meta (or ortho) amidoparacresolether, amidoxyleneazo-
meta (or ortho) amidoparacresolether, amidobenzeneazobetaethoxyalphanaphthyl-
amine, amidotoluenea zobetaethoxyalphanaphthylamine, amidoxyleneazobetaethoxy-.
alphanaphthylamine, sulphonic or carboxylic acids thereof.
The dye-stuffs derived from other diamines, or sulphonic acids thereof, which
can be changed into tetrazo compounds, either directly, or by means of the mono-
acetylated derivatives thereof, can, as a matter of course, also be used.
In pro-
ducing such dye-stuffs fit for the said purposes, the corresponding mononitramines
can also be used in place of the monoacetylated diamines, in which case the
nitro group of the resulting intermediate products is to be reduced at the
appropriate time by means of suitable reducing agents, whilst, on using mono-
acetylated diamines, the acetyl group has, at the same time, to be displaced.
On carrying out these dyeing processes in the manners hereinbefore defined,
brown shades are chiefly produced, some of which are very fast, and withstand
washing.
In order to illustrate these processes, the following example is given, which,
however, is merely to be regarded as typical, as the invention is not restricted

page_text: EXAMPLE.
PRODUCTION OF A CUTCH BROWN ON THE FIBRE WITH THE AID OF A MILD
OXIDISING BATH.
100 parts of cotton are dyed in the usual manner by means of 3 parts of the
coloring matter from one molecular proportion of tolidine and two molecular
proportions of Clève's a naphthylamine ẞ, monosulphonic acid. The material
having been rinsed, is introduced into a very dilute solution of chloride of lime
(Baumé), and agitated therein during about 5 minutes, at from about 30 to 40
degrees centigrade, until there is no further increase in the intensity of the
resulting cutch brown shade. Care must be taken that the material does not
remain too long in the said bath of chloride of lime, as otherwise the brown shade
thus produced would be destroyed. The material is finally rinsed and dried.
The process is carried out in an analogous manner if, in place of the dye-stuff
above mentioned, another of the aforesaid simple or mixed disazo, trisazo, or
tetrakis azo coloring matters is employed, shades being thus produced which, as a
rule, are brown, and withstand washing. Instead of a bath containing sodium
carbonate, a hot bath containing ammonia, or a hot acid bath containing, for
example, sulphuric acid, can be used. In the latter case, care must be taken that
the sulphuric acid adherent to the goods is entirely removed by rinsing.
Thus, for instance, a cutch brown is obtained, if silk previously dyed with the
dye-stuff from one molecular proportion of tetrazoditolylchloride and two molecular
proportions of Clève's alpbanaphthylamine beta monosulphonic acid (ai ßa) is first
immersed in an acidulated bath of sodium nitrite, and then in a hot bath containing
sulphuric acid.
The chemical actions taking place during the operations hereinbefore defined, viz.,
on treating the dyed diazotised material in acid or alkaline baths, seem to involve
the formation of azoxy products or the like, whilst on using baths containing
ammonia diazoamido compounds are probably produced.
Having now particularly described and ascertained the nature of the said 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. The production of dyes on fibres by first dyeing cotton, woollen, or silk fibres,
or materials, with the coloring matters used in the processes described in the
Specifications of Letters Patent Nos. 8530⁰⁰, 9636º¹, 22641491 113959,
and 15439, subsequently placing the dyed fibres or materials in acidulated baths
of sodium nitrite, and then treating them in hot acid or alkaline baths.
2. The process for producing dyes on the fibre, which process consists in first
dyeing cotton, woollen, or silk fibres or materials with the coloring matters used in
the processes described in the Specifications of Letters Patent Nos. 85300, 96361,
226411, 11395", and 15439", and subsequently treating the fibres or materials
thus dyed, in mild oxidising baths.
3. As new products of manufacture, the fibres or materials dyed by the processes
herein before defined or by any other process affording the same result.
NEWTON & SON,
Agents for the Applicant.