The Manufacture or Production of Colouring Matters and Processes for Dyeing and Printing therewith.
Year: 1893

page_text: Date of Application, 18th May, 1893
Complete Specification Left, 19th Feb., 1894-Accepted, 24th Mar., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Colouring Matters and Processes
for Dyeing and Printing therewith.
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 found that the intermediate products resulting
from the combination of one molecular proportion of the tetrazo compounds of
"benzidine and analogues thereof," with one molecular proportion of an amine, a
diamine, phenol, amidophenol, amidophenolether of the benzine or naphthalene
series, or a sulpho or carboxylic acid of these components, particularly with one
molecular proportion of a naphthylamine sulpho acid, naphtholsulpho acid, amido-
naphthol sulpho acid, or dihydroxy naphthalene sulpho acid, can further be combined
with one molecular proportion of such "amido compounds of the benzene series," as
either directly yield amido azo products, when combined with diazo compounds
(employing, for instance, watery solutions of the salts of the said amido compounds),
or yield (when combined with diazo derivatives) diazo amido compounds, which
can be converted into amido azo products in a suitable manner.
The following substances, for instance, belong to the aforesaid "amido com-
pounds of the benzene series," viz., aniline, toluidine, xylidine, amidophenolether,
amidocresolether, metaphenylene diamine, toluylene diamine, or similar amines
or diamines. or derivatives thereof, especially sulpho or carboxylic acids thereof.
Red, reddish-violet, or violet dye stuffs, suitable for dyeing unmordanted cotton
in chief, are obtained by means of the process herein before defined.
My foreign correspondents mean by the above expression "benzidine and
analogues thereof," the following products, e.g., benzidine, tolidine, diamido-
phenyltolyl, diamido phenolether, diamido-alkyloxydiphenyl, diamido-alkyloxy-
phenyltolyl, diamido azo benzene, diamido azo toluene, diamido azo xylene,
diamido azoxybenzene, diamido azoxytoluene, diamidostilbene, diamido fluorene,
diamidonaphthalene, diamido-carbazol, diamido-diphenylene oxide, diamido-
ditoluylene oxide, para phenylene diamine, paratoluylene diamine, benzidine
sulphone, tolidine sulphone, diamido phenyltolyl sulphone, diamido phenoxy acetic
acid, diamido diphenylene ketoxine, m-p-diamido phenylbenzimidazol, amidobenzene
azoalphanaphthylamine, amido toluene azo alpha naphthylamine, amido xylene azo
alpha naphthylamine, amido benzene azo para xylidine, amido toluene azo para
xylidine, amido xylene azo para xylidine, amido benzene azo meta amido para
cresol alkylether, amido toluene azo metaamido para cresol alkylether, amido
xyleneazometa amidoparacresol alkylether, amidobenzene azo ortho amido para
cresolalkyl ether, amidotolueneazoorthoamidopara cresolalkylether, amidoxylene-
azoorthoamidoparacresolalkylether, amidobenzeneazobetaalkyloxyalphanaphthyl-
amine, amidotolueneazobetaalkyloxyalphanaphthylamine, amidoxyleneazobeta-
alkyloxyalphanaphthylamine, or sulpho or carboxylic acids thereof. Similar
diamines or derivatives thereof, which can be converted into tetrazo compounds
either directly or by means of the corresponding mono acetylised products, likewise
can be employed in the above process. In place of the mono acetylised diamines
and sulpho derivatives thereof, the corresponding mononitro amines, and sulpho
derivatives thereof, also can be used. The mononitroazo products obtained in the

page_text: latter case, must then be reduced, carrying out this reaction at the same time
when, in the employment of the monoacetylised diamines, the acetyl group is
separated.
The coloring matters resulting according to the above process by means of the
components herein before defined, further possess the valuable property of being
diazotisable (when fixed on the fibre), and yield shades which withstand washing,
and are chiefly from red, violet, to blue, when the diazo or tetrazo salts produced
on the fibre are coupled with amines, diamines, phenols, amidophenols, amido-
phenolethers, sulpho or carboxylic acids thereof.
The process for producing these dye-stuffs in general consists either in combining
one molecular proportion of a tetrazotised diamine at first with one molecular
proportion of a naphthylamine sulpho acid naphtholsulpho acid, amidonaphthol-
sulpho acid, dihydroxynaphthalene sulpho acid (or generally with one molecular
proportion of an amine, a diamine, phenol, amidophenol, amidophenolether of the
benzene or naphthalene series, a sulpho or carboxylic acid thereof), and coupling
the intermediate products thus formed with one molecular proportion of one of the
aforementioned "amido compounds of the benzene series." Or the process can be
effected inversely, viz., by combining a tetrazo compound first with such an
"amido compound of the benzene series," and subsequently with one of the said
components viz., naphthylamine sulpho acids, naphthol sulpho acids, amido
naphthol sulpho acids, or dihydroxynaphthalene sulpho acids, or generally amines,
diamines, phenols, amidophenols, amidophenolethers of the benzene or naphthalene
series, sulpho or carboxylic acids thereof.
In order to illustrate the method of producing these new dyestuffs, the following
examples are given, the parts being hy weight
COLORING MATTER FROM BENZIDENE-a,-NAPHTHOL-a, α-DISULPHO ACID AND
ORTHO ANISIDINE.
18-4 parts of benzidine are converted in the well known manner into tetrazo
diphenylchloride by means of 14 parts of sodium nitrite. The resulting tetrazo
solution (when icy cold) is allowed to flow into a cold solution prepared by
dissolving 34-8 parts of the sodium salt of a₁ naphthol-a,-a-disulpho acid S, and
mixed with sodium acetate. The formation of the intermediate product immediately
begins, and is complete within a short time. After adding a solution prepared by
dissolving 13 parts of ortho anisidine in about 500 parts of water, the liquid mixture
is allowed to stand for about 24 hours. The mass is then heated at from 60 to
70 degrees centigrade, and when cold is acidulated by means of muriatic acid.
The dye stuff acid which separates, is filtered off, and converted in the known
manner into its sodium salt, which is the dye stuff itself. The latter forms, after
pressing and drying, a brownish black powder, and possesses the following
composition. riz.

page_text: $
SECOND EXAMPLE.
DYESTUFF FROM DIANISIDINE, PARAXYLIDINE, AND BETANAPHTHOLDISULPHO
ACID R.
24°4 parts of dianisidine are converted into the tetrazo compound by means of
14 parts of sodium nitrite. The tetrazo solution is mixed with a solution prepared
by dissolving 16 parts of paraxylidine hydrochloride in 500 parts of water, and
about 10 parts of sodium acetate are then added to the resulting mixture. When,
after some hours' standing, the formation of the intermediate product is complete,
the reaction mixture is introduced into a solution prepared by dissolving 35 parts
of the sodium salt of betanaphthol disulpho acid R in 1000 parts of water, with
the addition of sodium carbonate. The dyestuff separates after some time. It is
filtered off, pressed, and dried. Its composition corresponds with the formula :-
COLORING MATTER FROM DIANISIDINE BETANAPHTHOLDISULPHO ACID F AND
METAAMIDOPARACRESOLETHER.
34.8 parts of the sodium salt of beta naphtholdisulpho acid F are introduced into
the tetrazo solution obtained from 24.4 parts of dianisidine by means of 14 parts of
sodium nitrite, and about 10 parts of sodium acetate are then added, in order to
facilitate the formation of the intermediate product. When this latter stage is
arrived at, a solution prepared by dissolving 19 parts of metaamidoparacresolether
hydrochloride in 500 parts of water is added. When the coupling is complete, the
mixture is rendered alkaline. The dyestuff having the formula:

page_text: is then isolated in usual manner, viz., by filtering off, pressing, and drying. It
yields greyish-violet shades on unmordanted cotton.
"
Dyestuffs analogous or similar to those described in the foregoing examples result,
if either the diamines employed in these examples are replaced by the corresponding
quantities of other diamines, or if, in place of anisidine, paraxylidine, and meta
amido para cresolether, the equivalent quantities of other of the above "amido
compounds of the benzene series are employed, or if the a, naphthol a, a disulpho
acid S, betanaphtholdisulpho acid R and F, are replaced by other naphtholsulpho
acids, or by naphthylamine sulpho acids, amido naphtholsulpho acids, or dihydroxy-
naphthalene sulpho acids, or generally by amines, diamines, phenols, amidophenols,
amidophenolethers of the benzene or naphthalene series, sulpho or carboxylic
acids thereof.
My foreign correspondents have described in the above examples, certain distinct
methods of producing some of the coloring matters hereinbefore defined. Of
course they do not limit themselves to the particulars given therein, as the
production of these coloring matters can be effected by means of all those methods
which are employed for the manufacture of analogous or similar dye stuffs.
According to the investigations of my. foreign correspondents, the coloring
matters herein before defined are of special technical value, as they can, when
fixed on fibre (either in dyeing or in printing), be further diazotised, and coupled
(likewise on the fibre) with the so-called "developers,"-shades being thus produced
which are chiefly from reddish-violet and violet to blue, and withstand washing well.
My foreign correspondents mean by the expression "developers," the usual dye-
stuff components, viz.: amines, diamines, phenols, amidophenols, amidophenolethers
of the benzene or naphthalene series, sulpho or carboxylic acids thereof.
In order to illustrate this process of producing dyes on fibre, the following
example is given, the parts being by weight:
-
PRODUCTION OF A BLUISH-VIOLET BY MEANS OF THE DYE STUFF OBTAIN-
ABLE AS DESCRIBED IN THE ABOVE FIRST EXAMPLE.
100 parts of cotton are dyed in the usual manner in a bath containing 2.5 parts
of the said dye-stuff from equal molecular proportions of benzidine, alpha naphthol
disulpho acid S, and ortho anisidine. The dyed material is then placed in an
acidulated bath of sodium nitrite, and is well agitated therein for from to hour,
when cold. After being well rinsed, the material is introduced into a bath prepared
from the sodium salt of beta naphthol. The brownish color of the diazo compound
immediately is changed into bluish-violet. After some time, the goods are taken
out and washed.
The shades thus obtained effectually resist soaping and washing.
The dye-stuff resulting as described in the above second example, yields, when
fixed on fibre and treated in the manner herein before mentioned, viz., by diazotising
and coupling with the beta naphthol, fast reddish-blue shades, whilst the coloring
matter obtainable as described in the above third example, yields pure blue shades
in the same process.
Analogous shades in general, varying from reddish-violet to blue, and fast against
washing, result, if the dye stuff employed in the last example is replaced by other
of the coloring matters herein before defined, or if, on the other hand, the sodium
salt of beta naphthol, is replaced by suitable baths prepared from other phenols or
amines, diamines, amido phenols, amido phenol ethers of the benzene or naphthalene
series, sulpho or carboxylic acids thereof.
In order to employ the coloring matters hereinbefore defined for printing purposes,
it is only necessary to print them on the fibre in the well-known manner by means
of suitable thickening material, subsequently to treat the material thus printed in

page_text: acidulated baths of sodium nitrite, and then in suitable baths of so-called
"developers."
Duted thie 18th dow of Mo 1902
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Colouring Matters and Processes
for Dyeing and Printing therewith.
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 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 the intermediate products formed
by the combination of one molecular proportion of the tetrazo derivatives of
benzidine and analogues thereof," with one molecular proportion of a naphthyl-
amine sulphonic acid, naphtholsulphonic acid, amidonaphtholsulphonic acid, or
dihydroxynaphthalene sulphonic acid, can be converted into so-called mixed dye-
stuffs yielding shades on unmordanted cotton, chiefly varying from red and
reddish-violet to violet, the said mixed dyestuffs being obtained by combining such
intermediate products with one molecular proportion of such "amido compounds
of the benzene series," as either directly yield amidoazo compounds, when they are
coupled with diazo derivatives (using, for instance, solutions of the salts of the
said amido compounds), or which, when combined with diazo derivatives, yield diazo
amido compounds, which can be converted into amido azo compounds in the well-
known manner.
The following substances, for instance, belong to the aforesaid "amido compounds
of the benzene series," viz., aniline, orthotoluidine, paraxylidine, orthamido-
phenolether, metamidophenolether, orthamidoparacresolether, or metamidopara-
cresolether.
My foreign correspondents mean by the above expression, "benzidine and
analogues thereof," the following products, e.g., benzidine, tolidine, diamido-
phenyltolyl, diamido diphenolether, diamidoalkyloxydiphenyl, diamidoalkyloxy-
phenyltolyl, diamido azo benzene, diamidoazotoluene, diamidoazoxylene, diamido-
azoxybenzene, diamidoazoxytoluene, diamidostilbene, diamidofluorene, diamido-
naphthalene, diamidocarbazol diamidodiphenylene oxide, diamidoditoluylene oxide,
paraphenylenediamine, paratoluylene diamine, benzidine sulphone, tolidine sulphone,
diamido phenyltolylsulphone, diamidodiphenoxy-acetic acid, diamido diphenylene-
ketoxine, diamidophenyl benzimidazol, amido benzene-azo-alpha naphthylamine,
amido toluene azo alpha naphthylamine, amidoxylene azo alpha naphthylamine,
amidobenzene azo paraxylidine, amidotoluene-azo-para-xylidine, amidoxylene-azo-
para-xylidine, amidobenzene-azo-metamido-para-cresolalkylether, amidotoluene azo-
metamido-para-cresolalkylether, amidoxylene-azo-metamido para-cresolalkylether,
amido benzene-azo-ortho-amido-para-cresolalkylether, amido toluene-azo-ortho-
amido-para cresolalkylether, amidoxylene-azo-ortho-amido-para-cresolalkylether,
amido benzene-azo-beta-alkyloxy-alpha-naphthylamine, amido toluene-azo-beta-
alkyloxy-alpha naphthylamine, amidoxylene-azo-beta-alkyloxy-alpha-naphthyl-
amine, or sulphonic or carboxylic acids thereof. Similar diamines, or derivatives
thereof, which can be converted into tetrazo derivatives, either directly, or by
means of the corresponding monacetylated products, can also be used in the above
process. In place of the monoacetylated diamines and sulphonic derivatives thereof,
the corresponding mononitramines, and sulphonic derivatives thereof, can also be
used, in which case the intermediate mononitrazo products, which are first formed,

page_text: are to be reduced,-this reduction being effected when the monoacetylated diamines
are used at the same time that the acetyl group is separated.
The colouring matters prepared according to the above process by means of the
components herein before defined, possess the valuable property of being diazotisable
when fixed on the fibre, and when diazo or tetrazo salts derived from the dye stuffs
herein before defined, are produced on the fibre, and are coupled with amines,
diamines, phenols, amido phenols amido phenolethers, sulphonic or carboxylic acids
thereof, shades are obtained chiefly varying from red, through violet, to blue, which
withstand washing.
The process for producing these dye-stuffs in general consists either in combining
one molecular proportion of a tetrazotised diamine at first with one molecular
proportion of a naphthylamine sulphonic acid, naphtholsulphonic acid, amido
naphtholsulphonic acid, or dihydroxynaphthalene sulphonic acid, and coupling the
intermediate products thus formed with one molecular proportion of one of the
aforementioned "amido compounds of the benzene series." Or the process can be
effected inversely viz. :-by combining a tetrazo derivative first with such an "amido
compound of the benzene series," and subsequently with one of the said components,
riz., naphthylamine sulphonic acids, naphthol sulphonic acids, amido naphthol-
sulphonic acids, or dihydroxynaphthalene sulphonic acids.
In order to illustrate the method of producing the dye stuffs hereinbefore defined,
the following examples are given, the parts being by weight.
.COLOURING-MATTER FROM BENZIDINE, ALPHA1
NAPHTHOL-ALPHA ALPHA
DISULPHONIC ACID AND ORTHANISIDINE.
.
18.4 parts of benzidine are converted, in the well known manner, into tetrazo
diphenylchloride, by means of 14 parts of sodium nitrite. The resulting tetrazo
solution (when icy-cold) is allowed to flow into a cold solution of 34-8 parts of the
sodium salt of alpha, naphthol alpha, alpha, disulphonic acid S, mixed with sodium
acetate. The formation of the intermediate product immediately begins, and is
complete within a short time. After adding a solution prepared by dissolving
12.3 parts of orthanisidine (orthamido phenolmethylether) in about 500 parts of
water, the liquid mixture is allowed to stand for about 24 hours. The mass is then
heated to from 60 to 70 degrees centigrade, and when cold, is acidulated by means
of muriatic acid. The dye-stuff acid which separates is filtered off, and converted,
in the known manner, into its sodium salt, which constitutes the dye-stuff. After
pressing and drying, the product is a brownish-black powder the composition of
which is represented by the formula :-

page_text: DYE STUFF FROM DIANISIDINE, PARAXYLIDINE, AND BETA NAPHTHOL-
DISULPHONIC ACID R.
244 parts of dianisidine are converted into the tetrazo derivative by means of
14 parts of sodium nitrite. The tetrazo solution is mixed with a solution of 16 parts
of paraxylidine hydrochloride in 500 parts of water, and about 10 parts of sodium
acetate are then added to the mixture. After several hours, when the formation of
the intermediate product is complete, the mixture is introduced into a solution of
34-8 parts of the sodium salt of beta naphtholdisulphonic acid R in 1000 parts
of water, to which also sodium carbonate has been added. The dye stuff separates
after an interval. It is filtered off, pressed, and dried. Its composition is repre-
sented by the following formula :—
COLORING MATTER FROM DIANISIDINE BETANAPHTHOLDISULPHONIC ACID F,
AND METAMIDOPARACRESOLETHYLETHER.
34.8 parts of the sodium salt of betanaphtholdisulphonic acid F are introduced
into a solution of the tetrazo derivative prepared from 24.4 parts of dianisidine by
means of 14 parts of sodium nitrite, and about 10 parts of sodium acetate are then
added, to facilitate the formation of the intermediate product. When the interaction
is effected, a solution of 18-8 parts of metamidoparacresolethylether hydrochloride,
in 500 parts of water, is added. When the coupling is complete, the mixture is
rendered alkaline. The dye stuff is represented by the formula :—

page_text: It is isolated in the usual manner, viz.; by filtering off, pressing, and drying, and
yields greyish-violet shades on unmordanted cotton.
Dye-stuffs analogous or similar to those described in the foregoing examples, are
obtained by using, instead of the diamines specified in these examples, the corre-
sponding quantities of other diamines, or by using, in place of anisidine, para xylidine,
and meta amido para cresolethylether, equivalent quantities of other of the above
"amido compounds of the benzene series," or by using, instead of alpha, naphthol
alpha, alpha disulphonic acid S., or betanaphtholdisulphonic acid R or F, other
naphtholsulphonic acids, naphthylamine sulphonic acids, amidonaphtholsulphonic
acids, or dihydroxynaphthalene sulphonic acids.
As a matter of course, my foreign correspondents do not claim those combinations
which have already been described or claimed.
My foreign correspondents have described in the above examples, certain distinct
methods of producing some of the coloring matters herein before defined, but they do
not limit themselves to the particulars given therein, as these coloring matters can
be produced by all methods employed in manufacturing analogous or similar
dye-stuffs.
The investigations of my foreign correspondents have shown that the coloring
matters hereinbefore defined are of special technical value, owing to the fact that
when fixed on fibres, either by dyeing or printing, they can be further diazotised,
and then coupled, while still on the fibre, with so-called " developers," shades
being thus produced varying chiefly from reddish-violet and violet, to blue, which
withstand washing well.
My foreign correspondents mean by the expression "developers," the usual
dye-stuff components, viz., amiues, diamines, phenols, amidophenols, amidophenol-
ethers of the benzene or naphthalene series, sulphonic or carboxylic or other
derivatives thereof.
In order to illustrate the process of thus producing dyes on fibres, the following
example is given, the parts being by weight
PRODUCTION OF A BLUISH-VIOLET BY MEANS OF THE DYE-STUFF OBTAIN-
ABLE AS DESCRIBED IN THE ABOVE FIRST EXAMPLE.
100 parts of cotton are dyed, in the usual manner, in a bath containing 2.5 parts
of the said dye-stuff from equal molecular proportions of benzidine, alphanaphthol-
disulpho acid S and orthanisidine. The dyed material is then placed in an
acidulated and cooled bath of sodium nitrite, and is well agitated therein during
from to an hour. After well rinsing the material, it is introduced into a bath
containing the sodium salt of betanaphthol. The brownish color of the diazo
compound is immediately changed into bluish-violet. After a time, the goods are
taken out and washed.
The shades thus obtained effectually resist soaping and washing.
The dye-stuff prepared as described in the above second example, when fixed on
fibres, and treated in the manner hereinbefore mentioned; i.e., when diazotised and
coupled with betanaphthol, yields fast reddish-blue shades, the coloring matter
obtainable as described in the above third example yielding pure blue shades.
Shades which in general vary from reddish violet to blue, which will withstand
washing, are produced in an analogous mauner by using, instead of the dye-stuff
specified in the last example, other of the coloring matters herein before defined, or
if, on the other hand, instead of the sodium salt of beta naphthol, suitable baths
prepared from other phenols, amines, diamines, amidophenols, amido phenolethers of
the benzene or naphthalene series, or sulphonic or carboxylic acids thereof, are used.
In using the coloring matters herein before defined for printing purposes, it is only
necessary to print them on the fibre in the well-known manner by means of suitable
thickening material, and to subsequently immerse the material thus printed into

page_text: "
acidulated baths of sodium nitrite, and then into suitable baths of the so-called
developers."
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 manufacture or production of mixed tetrazo dye stuffs, by coupling one
molecular proportion of the tetrazo compounds derived from benzidine, or analogues
thereof, either with one molecular proportion of a naphthylamine sulphonic acid,
naphthol sulphonic acid, amidonaphtholsulphonic acid, or dihydroxy naphthalene
sulphonic acid, and one molecular proportion of aniline, orthotoluidine, paraxylidine,
orthamidophenolether, metamidophenolether, orthamidoparacresolether, or met-
amidoparacresolether; or, inversely, first with one molecular proportion of aniline,
orthotoluidine, paraxylidine, orthamidophenol-ether, metamidophenol-ether, orth-
amidoparacresolet her, or metamido paracresolether, and subsequently with one
molecular proportion of a naphthylamine sulphonic acid, naphtholsulphonic acid,
amidonaphtholsulphonic acid, or dihydroxynaphthalenesulphonic acid (excluding,
however, those combinations which have already been described or claimed)..
2. The production of shades on the fibre, by first dyeing or printing the fibre or
material with one of the new dye-stuffs hereinbefore defined, then diazotising the
dyes thus fixed on the fibre, and finally combining the resulting diazo or tetrazo
derivatives, also while on the fibre, with one of the so-called developers (such as a
phenol, amine, amido phenol, amido phenol ether, diamine, or a sulphonic or
carboxylic or other derivative thereof), effecting the latter two operations (viz.,
diazotising and coupling) by immersing the dyed or printed fibre, or material, first
in moderately acidulated baths of sodium nitrite or the like, and subsequently in
suitable alkaline or acid baths of the so-called developers.
3. As new products of manufacture,.-
a) The new coloring matters produced by means of the process herein before
defined, or by any other means producing the same result;
b) The fibres or material dyed, printed, or treated in the manner hereinbefore
defined, or in any other way affording the same result.
Dated this 17th day of February 1804
NEWTON & SON,
Agents for the Applicant.