Improvements in the Manufacture of Disazo and Trisazo Colours or Dyes.
Year: 1896

page_text: Date of Application, oth Feb., 1896
Complete Specification Left, 2nd Nov., 1896-Accepted, 2nd Jan.. 1897
oth Feb., 1896
Complete Specification Left, 2nd Nov., 1896-Accepted. 2nd Jan.. 1897
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Disazo and Trisazo Colours or
Dyes.
I, THOMAS RICHARD SHILLITO of 89 Chancery Lane, London, W.C.,
Engineer and Patent Agent, do hereby declare the nature of this invention, a
communication to me from abroad by Messieurs John Rudolph Geigy & Co., of
Basle, Switzerland, Colour Manufacturers, to be as follows:-
This invention relates to the production of a new series of disazo and trisazo
colours dyeing unmordanted cotton by aid of alkylated B₁ a amidonaphtol
ẞ, sulpho acids especially of the mono and diaethylated and the mono and
dimethylated sulpho acid. The colouring matters obtained from them are to be
divided into three classes, that is to say:-
1. Symmetrical disazo dye stuffs.
2. Mixed disazo dye stuffs.
3. Trisazo dye stuffs.
The following are the p-diamines which the communicators have used for their
production Benzidine, diamidophenyltolyle, tolidine, aethoxybenzidine, diamido
diphenolaether, p-diamidodiphenylamine, p-phenylen-diamine, a₁ a, naphtylen-
diamine a a naphtylendiamine ẞ sulpho acid. The three last mentioned
substances are, in the usual manner, first diazotised in form of their acetyle
compounds, then combined, saponified, subsequently diazotised and combined.
The following is an explanation of the colouring matters belonging to the
above mentioned classes with some examples of their production.
1. Symmetrical disazo dye stuffs:-If two molecules of the above named
alkylated B₁ a, amidonaphtol ẞ, sulpho acids are combined with one molecule
of a tetrazo compound, colouring matters are formed dyeing unmordanted cotton
in reddish to blueish grey shades, for instance, 18.4 kilos. of benzidine are diazotised
in the well known manner and combined in an alkaline solution with 50-6 kilos. of
monomethyl B a amido naphtol ẞ sulpho acid. The colouring matter is
produced in the form of a black precipitate and is filtered off and dried.
2. Mixed disazo dye stuffs :-These are produced by combination of the above
mentioned p-diamines with one molecule of an alkylated B₁ a amidonaphtol
ẞ, sulpho acid and with one molecule of another compound, for instance, salicylic
acid, cresotinic acid, m-toluylenediamine sulpho acid, a, a, naphtol sulpho
acid, a naphtol B, a disulpho acid, a₁ a amidonaphtol a, sulpho acid, B. a,
amido naphtol 3. sulpho acid, a₁ a amido naphtol BB, disulpho acid,
a a dioxynaphtalene a sulpho acid, dioxynaphtoë sulpho acid (of the
German Patent No. 67,000), B₁ a amido naphtol B, sulpho acid, amido-
naphtol disulpho acid (of the German Patent No. 53,023) or with another
alkylated B, a, amidonaphtol B, sulpho acid different from the first used. The
shades produced by these mixed disazo dye stuffs vary from brown to violet,
greyish blue, grey and black, for example 19.8 kilos. of tolidine are diazotised in
the usual manner, then combined with a solution containing 30 kilos. of carbonate
of sodium and 14 kilos. of salicylic acid. The intermediary compound which is
formed is after some hours added to an alkaline solution of 26-7 kilos. of dimethyl

page_text: Ba amido naphtol ẞ, sulpho acid. The colouring matter is then filtered off and
dried. It dyes unmordanted cotton dark brown shades.
For another example, a solution of 21.4 kilos. of dianisidine diazotised in the
usual manner is alkalised by the addition of 30 kilos. of carbonate of sodium, then
a solution of 32 kilos. of a₁ a amido naphtol 3, 6, disulpho acid is added. The
intermediary compound is introduced into an alkaline solution of 26-7 kilos. of
monoaethyl Ba, amidonaphtol ẞ, sulpho acid. The colouring matter is then
separated by the addition of common salt, filtered off and dried. It dyes
unmordanted cotton greyish blue to blackish blue.
3. Trisazo dye stuffs:-In the production of these, some colours of the second
claes may be further diazotised and combined with resorcine or metadiamines.
For this purpose the mixed disazo dye stuffs which contain one molecule of an
alkylated Ba, amido naphtol 33 sulpho acid besides one molecule of the non-
alkylated sulpho acid or of one molecule of the amidonaphtol disulpho acid of the
German Patent No. 53023, or of B, a, amidonaphtol ẞ, sulpho acid, are particularly
useful. The commercial value of these trisazo dye stuff's consists in the grey to
deep black shades, produced by them on unmordanted cotton, for instance,
75-6 kilos. of the mixed disazo colour obtained from one molecule of tetrazo-
diphenyl, one molecule of monomethyl B, a, amidonaphtol ẞ, sulpho acid, and one
molecule of the non-alkylated ẞ, a, amidonaphtol ẞ, sulpho acid, are in form of a
paste introduced into 1000 litres of cold water, then 35 kilos. of hydrochloric acid
of 21 Bé. are added, and diazotised with 7 kilos. of nitrite of sodium. The diazo
compound, the formation of which is finished after reposing several hours, is then
poured into a solution of 11 kilos. of resorcine in about 300 litres of water
containing 30 kilos. of carbonate of sodium. The colouring matter which forms a
black precipitate is filtered off, pressed and dried. It dyes unmordanted cotton in
silver grey to deep black shades.
Dated this 6th day of February 1896.
THOMAS R. SHILLITO,
89 Chancery Lane, London, W.C.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Disazo and Trisazo Colours or
Dyes.
I, THOMAS RICHARD SHILLITO of 89 Chancery Lane, London, W.C.,
Engineer and Patent Agent, do hereby declare the nature of this invention, a
communication to me from abroad by Messieurs John Rudolph Geigy & Co., of
Basle, Switzerland, Colour Manufacturers, and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement :-
This invention relates to the production of a new series of disazo and trisazo
colours, dyeing unmordanted cotton by the aid of alkylated B, a, amidonaphtol
B, sulpho acids especially of the mono and dimethylated, the mono and diaethylated
sulpho acid and the methylaethyl sulpho acid. The colouring matters obtained
from them are to be divided into three classes, that is to say :-

page_text: for their production :-Benzidine,. diamidophenyltolyle, tolidine, aethoxybenzidine,
diamidodiphenolaether, p-diamidodiphenylamine, p-phenylendiamine, a₁ a naph-
tylendiamine, a₁ a naphtylendiamine ẞ, sulpho acid. The three last mentioned
substances are, in the usual mauner, first diazotised in form of their acetyle
compounds, then combined, saponified, subsequently diazotised and combined.
In the following is an explanation of the colouring matters belonging to the
above mentioned classes with some examples of their production :-
I. Symmetrical disazo dyestuffs:-If two molecules of the above named
alkylated B, a, amidonaphtol sulpho acids are combined with one molecule of a
tetrazo compound, colouring matters are formed dyeing unmordanted cotton in
reddish to blueish grey shades, for instance, 184 kilos. of benzidine are diazotised
in the well known manner and combined in an alkaline solution with 50-6 kilos. of
monomethyl B, as amidonaphtol ẞ, sulpho acid. The colouring matter is produced
in form of a black precipitate and is filtered off and dried.
II. Mixed disazo dye stuffs:-These are produced by combination of the above
mentioned p-diamines with one molecule of an alkylated B₁ a amidonaphtol
B sulpho acid and with one molecule of another compound as for instance,
salicylic acid, crešotinic acid, m-phenylendiamine, m-toluylendiamine, m-toluylen-
diamine sulpho acid, a₁ a, naphtolsulpho acid, a naphtol ẞ, a disulpho acid,
01 a amidonaphtol a, sulpho acid, B₁ as amidonaphtol B sulpho acid,
a a amidonaphtol B B disulpho acid, as a dioxynaphtolene a sulpho
acid, dioxynaphtoaic sulpho acid of the German Patent No. 67000, B₁ a amido-
naphtol sulpho acid, amidonaphtol disulpho acid of the Gerinan Patent
No. 53023, or lastly with another alkylated B₁ a amidonaphtol sulpho acid,
different from the first used.
The shades produced by these mixed disazo dye stuffs vary from brown to violet,
greyish blue, grey and black.
EXAMPLES.
1.) 19-8 kilos. of tolidine are diazotised in the usual manner, then combined with
a solution containing 30 kilos. of carbonate of sodium and 14 kilos. of salicylic
acid; the intermediary compound which is formed is after some hours added to an
alkaline solution of 26-7 kilos. of dimethyl B₁ a amidonaphtol B, sulpho acid,
then the colouring matter is filtered off and dried. It dyes unmordanted cotton in
dark brown shades.
2.) The solution of 21.4 kilos. of dianisidine, diazotised in the usual manner, is
alkalised by addition of 30 kilos. of carbonate of sodium, then a solution of
32 kilos. of a, a, amidonaphtol B, B disulpho acid is added; the intermediary
compound is introduced into an alkaline solution of 26-7 kilos. of monoaethyl
Ba amidonaphtol ẞ sulpho acid, then the colouring matter separated by
addition of common salt, filtered off and dried. It dyes unmordanted cotton
greyish blue to black blue.
III. Trisazo dye stuffs :-For their production some colours of the second class
can further be diazotised and combined with resorcine or metadiamines. For this
purpose the mixed disazo dye stuffs which contain one molecule of an alkylated
Bia, amidonaphtol ẞs sulpho acid besides one molecule of the non alkylated sulpho
acid or one molecule of the amidonaphtol disulpho acid of the German Patent
No. 53023 or one molecule of B₁ a, amidonaphtol ẞ, sulpho acid are particularly
useful. The commercial value of these trisazo dye stuffs consists in the grey to
deep black shades which are produced by them on unmordanted cotton, for
instance, 75-6 kilos. of the mixed disazo colour obtained from one molecule of
tetrazodiphenyl, 1 molecule of monomethyl B, a amidonaphtol ẞ, sulpho acid and
1 molecule of the non alkylated ẞ₁ a amidonaphtol ẞ, sulpho acid are in the form
of a paste introduced into 1000 litres of cold water, then 35 kilos. of hydrochloric
acid of 21° Beaumé added and diazotised with 7 kilos. of nitrite of sodium. The
diazo compound, the formation of which is finished after reposing for several hours
is then poured into a solution of 11 kilos. of resorcine in about 300 litres of water

page_text: containing 30 kilos. of carbonate of sodium. The colouring matter which forms a
black precipitate, is filtered off, pressed and dried. It dyes unmordanted cotton
in silver grey to deep black shades.
Having now particularly described and ascertained the nature of said invention,
as communicated to me by my foreign correspondents, and in what manner the
same is to be performed, I declare that what I claim is:-
1. The production of symmetrical disazo dye stuffs from one molecule of the
following p-diamines :-Benzidine, diamidophenyltolyl, tolidine, diamidoethoxydi-
phenyl, diamidodiphenolaether, p-diamidodiphenylamine p-phenylendiamine, a, a
naphtylendiamine, a₁ a, naphtylendiamine sulpho acid and two molecules of
monomethyl, monoaethyl, dimethyl, diaethyl, or methylaethyl ẞ, a, amidonaphtol
B, sulpho acid, substantially as described.
2. The production of mixed disazo colours from one molecule of the above cited
p-diamines with one molecule of the above mentioned alkylated ẞ a amidonaphtol
B, sulpho acids and with one molecule of the following substances:-Salicylic acid,
cresotinic acid, m-phenylendiamine, m-toluylendiamine, m-toluylenediamine sulpho
acid, a, a, naphtol sulpho acid, a, naphtol B, a disulpho acid, a, a, amidonaphtol
as sulpho acid, B₁ a, amidonaphtol ß, sulpho acid, a, a, amidonaphtol B, B, disulpho
acid, a, a dioxynaphtalene a sulpho acid, dioxynaphtoaic sulpho acid of the
German Patent No. 67000, B₁ a amidonaphtol B, sulpho acid, amidonaphtol
disulpho acid of the German Patent No. 53023, or with one molecule of another
alkylated B₁ a amidonaphtol ẞ, sulpho acid, different from the first used,
substantially as described.
3. The production of trisazo dye stuffs by combination of the diazo compounds of
those mixed disazo colours of Claim 2 which contain one molecule of an alkylated
B, a, amidonaphtol ẞ, sulpho acid above mentioned together with one molecule of
B, a amidonaphtol B, sulpho acid or one molecule of ẞ, a, amidonaphtol ẞ, sulpho
acid or one molecule of amidonaphtol disulpho acid of the German Patent
No. 53023 with resorcine, metaphenylendiamine or metatoluylendiamine, sub-
stantially as described.
Dated this 2nd day of November 1896.
THOMAS R. SHILLITO,
89 Chancery Lane, London, W.C.