Improvements in the Production of Azo Colours upon Fibres.
Year: 1890

page_text: Date of Application, 2nd June, 1890
Complete Specification Left, 4th Mar., 1891-Accepted, 4th Apr., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Production of Azo Colours upon Fibres.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Farbenfabriken vormals Friedrich Bayer &
Co., of Elberfeld, in the Empire of Germany,) to be as follows:-
According to this invention black azo colours are produced upon the fibre
by taking cotton or fibre previously dyed with colouring matters obtained
from the tetrazo combinations of benzidine, tolidine, dianisidine, diamido-stilbene.
and amido-naphthol-sulpho-acid-G and subjecting it to successive treatments with
weak acid solutions of sodium nitrite and alkaline or acetic acid baths of plienols,
amines, amido-phenols, or their sulpho or carbon acids.
Azo colours are obtainable from the tetrazo compounds of benzidine, tolidine,
dianisidine and diamido stilbene on the one hand and on the other hand from those
amido naphthol-sulpho-acids obtained by melting beta-naphthylamine-sulpho-acid-G
with caustic soda. These colouring matters dye unmordanted cotton a black colour
tinged with red and possess the property of forming on the fibre, under the action
of sodium nitrite, diazo combinations which can be further combined with phenols,
amines, amido-phenols or their sulpho or carbon acids to form intense blue or black
azo colouring matters.
The process for the production of these colouring matters consists in taking the
fibres say in the form of skeins or hanks dyed with the dye obtained from tetrazo-.
diphenyl and amido-naphthol-sulpho-acid-G for example (combined in an alkaline
solution) and plunging them in the first place into a cold and slightly acidulated
nitrite bath. The fibres are at first blue tinged with red, and acquire after a short
time a greenish blue shade which is peculiar to the diazo combination of the
colouring matter.
On being placed, after careful rinsing, in a cold alkaline bath of beta-naphthol
they change to a deep blue-black colour. The depth of this colour is much greater
than that of the original colour, the shade is of a considerably bluer tinge and the
fastness to alkali and acid is almost absolute.
The following table gives the shades of colour obtained with the colouring matter
produced from tetrazo-diphenyl and amido-naphthol-sulpho-acid-G. Similar tones
of colour are obtained by substituting diamido-stilbene in the place of the benzidine
contained in this colouring matter greener tones result with the employment of
tolidine or dianisidine.
The coupling of the phenols and amido phenols is performed in an alkaline*
solution and that of the amines in an acetic acid solution.
Colouring matters from tetrazo-diphenyl and amido-naphthol-sulpho-acid-G
diazotised and combined with the substances specified in the first column.
Phenol
Resorcin
Salicylic acid
m phenylene diamine
Alpha naphthol.
|Alpha, alpha, naphthol mono-sulpho-acid (Piria)
greenish blue
blue black
dull green
green blue
dull gray green
reddish blue
blue
green black
blue black
green black
violet black
blue black

page_text: Alpha, alpha, naphthol-mono-sulpho-acid (Clève-
Laurent)
Alpha, alpha,
kopf)
naphthol-mono-sulpho-acid(Schöll-
Alpha naphthol-disulpho-acid (Schöllkopf')
Alpha naphthol-disulpho-acid (German Patent
No. 45776)
Alpha naphthol-disulpho-acid (German Patent
38281) -
Beta naphthol
Beta naphthol alpha mono sulpho acid (Bayer)
Beta, beta, naphthol mono sulpho acid (Schaeffer)
Beta, beta, naphthol mono sulpho acid F
Beta naphthol disulpho acid K-
blue
blu
blue
blu
reddish blue
redd
blue
blu
blue
blu
green blue
blu
reddish blue
red
blue
blu
green blue
blu
Beta naphthol disulpho acid G
green blue
blu
reddish blue
redd
Beta naphthol disulpho acid F
green blue
blu
Alpha naphthol carbon acid
green blue
blu
Alpha naphthol carbon sulpho acid
reddish blue
viol
Beta naphthol carbon acid
greenish blue
blu
Beta naphthol carbon acid (melting point 216
degrees Centigrade)
greenish blue
blu
Beta naphthol carbon sulpho acid from the naph-
thol carbon acid melting at 216 degrees Centi-
grade
greenish blue
blu
Alpha, alpha, dioxynaphthaline
blue
blu
Alpha, beta, dioxynaphthaline (beta naphtho
hydro quinone)
reddish blue
redd
Beta dioxynaphthaline (from Bayer's acid)
reddish blue
redd
Beta, beta, dioxynaphthaline
blue
blu
Dioxynaphthaline mono sulpho acid (Schöllkopf)
reddish blue
viol
Dioxynaphthaline disulpho acid (Schöllkopf)
reddish blue
viol
Dioxynaphthaline mono sulpho acid R
greenish blue
blu
Dioxynaphthaline mono sulpho acid G
greenish blue
blu
Dioxynaphthaline mono sulpho acid F
greenish blue
blu
Dioxynaphthaline disulpho acid (from naphthol
trisulpho acid)
Alpha naphthylamine
Alpha naphthionic acid
greenish blue
blu
dull red blue
-
reddish blue
]
Alpha naphthylamine mono sulpho acid (Clève
Laurent)
reddish blue
Alpha naphthylamine mono sulpho acid (Schöll-
kopf)
Beta naphthylamine -
blue
blu
reddish blue
redd
Beta naphthionic acid (Brönner)
reddish blue
redd
Beta naphthylamine mono sulpho acid F
Ethyl beta naphthylamine mono sulpho acid F
green blue
blu
reddish bluc
redd
Beta naphthylamine disulpho acid R
reddish blue
redd
Beta naphthylamine disulpho acid G
reddish blue
redd
Beta naphthylamine disulpho acid F
blue
Beta, beta, amido naphthol
blue
Alpha, beta, amido naphthol ether
Amido naphthol mono sulpho acid G
reddish blue
redd
greenish blue
blu
Amido naphthol mono sulpho acid (from sulphu-
rated Dahl's beta naphthylamine mono sulpho
acid)
reddish blue
viole

page_text: Some of these colouring matters yet contain
diazotised on the fibre and combined with pho
following are given as examples
Colouring matters obtained with the aid of meta-
phenylene-diamine diazotised and coupled with
the following substances namely
m phenylene diamine
Beta naphthol
-
-
In like manner the colouring matter obtained
with alpha naphthylamine treated with alpha,
alpha, naphthol mono sulpho acid
Beta naphthol
-
The colouring matter obtained with alpha, beta,
amido naphthol ether further treated with beta
naphthol
The colouring matter obtained with amido naph-
thol sulpho acid G with amido naphthol
sulpho acid G.
COMPLETE SPECIFICATION.
Improvements in the Production of Azo Colours upon Fibres.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Farbenfabriken vormals Friedrich
Bayer & Co., of Elberfeld, in the Empire of Germany), and in what manner the same
is to be performed, to be particularly described and ascertained in and by the following
statement
According to this invention black azo colours are produced upon the fibre by
taking cotton previously dyed with colouring matters obtained from the tetrazo
compounds of benzidine, tolidine, dianisidine, diamido-stilbene and amido-naphthol-
sulpho-acid-G and subjecting it to successive treatments with weak acid solutions
of sodium-nitrite and alkaline or acetic acid baths of phenols, amines, amido-
phenols, or their sulpho- or carboxy-acids.
Azo colours are obtainable from one molecular proportion of the tetrazo com-
pounds of benzidine, tolidine, dianisidine, and diamido-stilbene on the one hand,
and on the other hand from two molecular proportions of the amido-naphthol-
sulpho-acid-Gobtained by melting beta-naphthylamine disulpho acid G with
caustic soda, or from one molecular proportion of the above mentioned tetrazo
compounds on the one hand and on the other hand from one molecular proportion of
the amido-naphthol-sulpho-acid-G and one molecular proportion of a phenol,
naphthol, dihydroxy-naphthalene or their sulpho or carboxy-acids. These colouring
matters dye unmordanted cotton a violet to blue-black colour and possess the
property of forming on the fibre, under the action of sodium-nitrite, diazo com-
pounds which can be further combined with phenols, amines, amido-phenols or their
sulpho- or carboxy-acids to form intense blue or blue-black colouring matters.
The process for the production of these colouring matters on the fibre consists in

page_text: taking the cotton say in the form of skeins or hanks dyed with the above mentioned
dyes obtained from the tetrazo compounds and one or two molecular proportions of
amido-naphthol-sulpho-acid-G (combined in an alkaline solution) and plunging
them in the first place into a cold and slightly acidulated nitrite bath. The fibres
are at first blue tinged with red and after a short time turn to a greenish-blue
shade which is peculiar to the diazo compound of the colouring matter.
On being placed after careful rinsing in a cold alkaline bath of beta naphthol
they change to a deep blue-black colour. The depth of this colour is much greater
than that of the original colour, the shade is of a considerably bluer tinge and the
fastness against the action of alkalies and acids is almost absolute.
The table hereinafter set out gives the shades of colour obtained with the
colouring matter produced from one molecular proportion of tetrazo-diphenyl and
Similar tones of
two molecular proportions of amido-naphthol-sulpho-acid-G.
colour are obtained by substituting diamido-stilbene for the benzidine. Greener
tones result from the employment of tolidine or dianisidine. In place of the
colouring matters formed by reacting with one molecular proportion of a tetrazo
compound upon two molecular proportions of amido-naphthol-sulpho-acid-G in an
alkaline solution the so-called mixed azo colouring matters may be employed which
are produced by the re-action of one molecular proportion of a tetrazo compound
first upon one molecular proportion of amido-naphthol-sulpho-acid-G and tlien on
another molecular proportion of a phenol, naphthol, dihydroxynaphtalene or their
sulpho or carboxy-acids, or first on phenols etc. and then on amido-naphthol-sulpho-
acid-G.
The coupling of the phenols and amido-phenols is performed in an alkaline
solution and that of the aniines in an acetic acid solution. In the second column of
the following table are the weaker shades, and in the third column the stronger
shades of the colouring matter resulting from the use of one molecular proportion
of tetrazodiphenyl and two molecular proportions of amido-naphthol-sulpho-acid-G
diazotised and combined with the substances specified in the first column.
Phenol
Resorcin
Salicylic acid
-
m-phenylene-diamine
Alpha-naphthol
greenish blue
dull green
green-blue
blue-black
green-black
blue-black
dull grey-green
green-black
reddish bluc
violet-black
Alpha, alpha, naphthol-mono-sulpho-acid (Piria)
Alpha, alpha, naphthol-mono-sulpho-acid (Clève
Laurent)
blue
blue-black
blue-
blue-black
Alpha alpha, naphthol-mono-sulpho-acid (Schöll-
No. 45776)
kopf)
Alpha-naphthol-disulpho-acid (Schöllkopf)
Alpha-naphthol-disulpho-acid (German Patent
-
blue
blue-black
reddish blue
reddish black
blue
blue-black
Alpha-naphthol-disulpho-acid
(German Patent
No. 38281)
blue
blue-black
Beta-naphthol
green-blue
blue-black
Beta-naphthol-alpha-mono-sulpho-acid (Bayer)
Beta, beta, naphthol-mono-sulpho-acid (Schaeffer)
Beta, beta, naphthol-mono-sulpho-acid-F
Beta-naphthol-disulpho-acid-R
Beta-naphthol-disulpho-acid-G
Beta-naphthol-disul pho-acid-F
Alpha-naphthol-carboxy-acid
Alpha-naphthol-carboxy-sulpho-acid-
Beta-naphthol-carboxy-acid
green-blue
green-blue
reddish blue
green-blue
green-blue
reddish bluc
reddish black
blue-black
blue-black
violet-black
greenish blue
blue-black
reddish blue
red-black
blue
blue-black
blue-black
blue-black

page_text: Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed; 1 declare that what I
claim is :-
The process for producing violet to blue-black or black azo colours on the fibre
consisting in treating the fibre previously dyed with the above mentioned colouring.
matters obtained from one molecular proportion of the tetrazo compounds of
benzidine, tolidine, dianisidine, diamido-stilbene, and one or two molecular propor-
tions of amido-naphthol-sulpho-acid-G in an alkaline solution and subjecting the
dyed fibre to successive treatments with weak acid.solutions of alkaline-nitrite and
alkaline or acetic acid solutions of phenols, naphthols,, dihydroxyphenols,
dihydroxynaphthalenes, amines, diamines, amido-phenols amido-naphthols or their
sulpho- or carboxy-acids as above described.
Dated this 4th day of March 1891.
J. H. JOHNSON & Co.