Improvements in the Production of Azo Colours on Fibre.
Year: 1892

page_text: Date of Application, 17th June, 1892
Complete Specification Left, 10th Apr., 1893-Accepted, 13th May, 1893
PROVISIONAL SPECIFICATION.
Improvements in the Production of Azo Colours on Fibre.
1, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which has been com-
municated to me from abroad by The Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany to be as follows:-
In the Provisional Specification of my application for Letters Patent No. 226414
dated 28th December 1891 a process for producing azo dyes on fibre is described
which consists in treating with moderately acid solutions of sodium nitrite and
alkaline or acetic acid solutions of phenols, amines, amidophenols sulpho or
carboxylic acids thereof cotton that has been dyed with the colouring-matters
resulting by the combination of one molecular proportion of a tetrazo salt with
either two molecular proportions of Clève's alphanaphthylamine betamonosulpho
acids or alphanaphthylamine-orthomono-sulpho acid or with one molecular pro-
portion of the aforesaid alphanaphthylamine sulpho acids and one molecular
proportion of a phenol, an amine, amidophenol or a sulpho or carboxylic acid
thereof.
My foreign correspondents have now found that similar results are obtained by
employing instead of Clève's alphanaphthylamine betamonosulpho acids or alpha-
naphthylamine orthomonosulpho acid amidonaphthol ether sulpho acids which are
obtained by alkylating naphthol sulpho acids, nitrating the resulting alkylhydroxy-
naphthalene sulpho acids and reducing the so formed nitroalkylhydroxynaphthalene
sulpho acids.
When the amidoalkylhydroxynaphthalene sulpho acids (so called amido-
naphtholether sulpho acids) are replaced by amidonaphthols, amidonaphtholethers
amidonaphthoxylacetic acids or amidonaphthoxylacetic sulpho acids the process
may be effected in an analogous manner the said amidonaphthols and amidonaphthol-
ethers being most adapted for the combination with tetrazo compounds which
contain sulpho groups (such as benzidinemonosulpho or disulpho acid diamidostilbene
disulpho acid and the like).
By the combination of the aforesaid amido products viz., amidonaphtholether
sulpho acids amido naphthols amidonaphtholethers amidonaphthoxylacetic acids, or
amidonaphthoxylacetic sulpho acids with tetrazo salts of diamines or sulpho acids
thereof simple (symmetrical) or mixed tetrazo dyes are formed according to
whether one molecular proportion of a tetrazo salt is combined with two molecular
proportions of the above mentioned amido compounds or with one molecular
proportion thereof and a second molecular proportion of an amine, a phenol an
amidophenol, amidophenol ether of the benzene and naphthalene series or a sulpho
or carboxylic acid of these latter products. Of the diamines my foreign
correspondents have employed the following products: benzidine, methylbenzidine,
tolidine, monoalkyl hydroxybenzidine, monoalkylhydroxymethylbenzidine, dialkyl-
hydroxybenzidine, diamidodiphenylene oxide, diamido ditoluylene oxide, diamido-
carbazol, diamidodiphenic acid, diamidodiphenoxylacetic acid, diamidodiphenylene,
ketoxime, diamidofluorene, diamidonaphthalene, diamidostilbene, paraphenylene-
diamine, toluylene diamine, para phenylene diamidoazo alpha naphthylamine and
analogous compounds, diamido azo benzene, diamido azo toluene, diamido azoxylene,
diamidoazoxybenzene, diamido azoxytoluene, diamidoazoxyxylene or the sulphones,
sulpho derivatives or sulphone sulpho products thereof.
As my foreign correspondents have found the process of producing azo colours
on fibre as described in my aforesaid Specification is not limited to the employment
of the diamines mentioned therein but all the diamines herein before mentioned and

page_text: the sulpho products thereof likewise can be employed in the process of that
Specification as the simple and mixed tetrazo dyes resulting by the combination
of the tetrazo salts of the other diamines with Clève's alphanaphthylamine
betamonosulpho acids or alphanaphthylamine orthomonosulpho acids when fixed
on fibre can further be diazotised and combined with the known dyestuff
components.
In order to illustrate the process the following example is given.
A suitable dyeing-bath is prepared by dissolving 0.5 kilos. of the dye-stuff
obtained from one molecular proportion of tetrazo diphenyle chloride and two
molecular proportions of alphaamido beta naphtholethylether beta monosulpho acid
(the latter acid resulting by subsequently ethylising, nitrating and reducing beta
naphthol beta monosulpho acid 2.6) in about 125 liters of water and adding 0.5 kilos.
of common salt. 5 kilos. of unmordanted cotton are dyed by immersion for say
one hour in the boiling bath above described. After rinsing the cotton (which has
acquired a bluish-violet colour) is placed in a solution of 0.15 kilos. of sodium
nitrite in 250 liters of cold water acidulated with hydrochloric acid and well
agitated therein for say half an hour. When the diazotising is finished the cotton
is rinsed with cold water and then is placed in an alkaline solution of 0.4 kilos. of
the sodium salt of betanaphthol. The combination of the betanaphthol employed
with the diazo compound of the dye-stuff fixed on fibre is after a short time complete
and the cotton acquires a greenish-blue colour of great purity and of a perfect
fastness against washing.
In the preceding example the dye-stuff from tetrazodiphenyle chloride and two
molecular proportions of alpha amido betanaphtholether betamonosulpho acid can
be replaced by the analogous symmetrical or simple colouring matters from the
other tetrazo salts and the dye-stuffs resulting by the combination of the tetrazo
salts of the diamines or sulpho derivatives thereof hereinbefore mentioned with two
molecular proportions of another amidonaphtholether sulpho acid or amido-
naphthoxylacetic acid or amidonaphthoxylacetic sulpho acid may be employed
shades being thus obtained which in general are green.
In the same manner the mixed tetrazo dyestuffs can be employed which result
from one molecular proportion of the tetrazo salts of the diamines herein before
enumerated one molecular proportion of amidonaphtholether sulpho acids, amido-
naphthoxylacetic acids or amidonaphthoxylacetic sulpho acids and one molecular
proportion of an amine, a phenol an amidophenol, amidophenolether of the benzene
and naphthalene series or of a sulpho or carboxylic acid of the latter components
including the amidonaphthoxylacetic acids and amidonaphthoxylacetic sulpho
acids.
The simple and mixed tetrazo dye stuffs resulting from amidonaphthols and amido-
naphtholethers especially in combination with the tetrazo salts of diamines con-
taining sulpho groups may also be employed in this process with a similar result.
My foreign correspondents have also found that the diazo derivatives of the said
simple (symmetrical) and mixed colouring-matters can also be combined on fibre
with other phenols or with amines, amidophenols, amidophenolethers of the benzene
and naphthalene series with sulpho or carboxylic acids thereof with amido-
naphthoxylacetic acid or amidonaphthoxylaceticsulpho acid the amines dehydroxy-
naphthalenes and sulpho acids thereof being preferably allowed to react in
moderately acetic acid solution and in the presence of sodium acetate.
In the second column of the following table are the shades which are obtained in
dyeing unmordanted cotton with the colouring matters obtained from the tetrazo,
salts specified in the first column with two molecular proportions of alpha amido-
betanaphtholethyletherbetamonosulpho acid (OCH, SO₂H = 2 : 6) diazotising
the dye-stuffs on fibre and coupling these diazoderivatives likewise on fibre with
beta naphthol.
1
1

page_text: Orthotetrazoditolyle
Tetrazomonomethoxydiphenyle
Tetrazomonomethoxyphenyltolyle
Orthotetrazodiphenoldimethylether
Tetrazostilbene
Tetrazostilbenedisulpho acid
-
->
-
greenish blue
greenish-blue
greenish-blue
bluish-green
blue with a greenish-hue
blue with a greenish hue
The following table contains in the second column the different shades which
result in dyeing unmordanted cotton with the colouring matters obtained by the
combination of the tetrazo salts specified in the first column with two molecular
proportions of alpha amido beta naphtholether deltamonosulpho-acid (OC,H.:
SO,H=27), rediazotising the dyestuffs on fibre and coupling the formed diazo
products with beta naphthol likewise on fibre.
-
Tetrazodiphenyle
Tetrazophenyltolyle
Orthotetrazoditolyle
Tetrazomouomethoxydiphenyle
-
-
-
bluish with a greenish hue
bluish with a greenish hue
greenish-blue
-
greenish-blue
Tetrazomonomethoxyphenyltolyle -
-
greenish-blue
Orthotetrazodiphenoldimethylether
-
bluish-green
greenish-blue
greenish-blue
Tetrazostilbene
Tetrazostilbene disulpho acid
Similar shades are obtained by first fixing on fibre the mixed tetrazo dye-stuffs
from equal molecular proportions of a tetrazo salt, alpha amido beta naphtholether
beta monosulpho acid and alpha amido betanaphtholether delta monosulpho acid
which are both herein before specified rediazotising the tetrazo dye on fibre and
coupling the diazo product with heta naphthol likewise on the fibre.
Of the series of the other mixed dye-stuffs those which result for example, from
one molecular proportion of orthotetrazo diphenoldimethylether one molecular
proportion of alpha amidobetanaphtholethyletherbetamonosulpho acid and one
molecular proportion of the compounds specified in the first column of the following
table yield after diazotising on fibre by coupling the diazo or tetrazo products so
formed with betanaphthol, shades which are enumerated in the following second
column:
beta-
Phenol, kresol, resorcinol, pyrogallol phenol-
sulpho acids, kresolsulpho acids resorcinol-
sulpho acids, salicylic acids, ortho- meta and
cresotinic acid symmetrical dihydroxy-
benzoic acid (OH:OH:COOH = 1: 3:5).
Alpha or beta naphthol, alphanaphtholmono-
sulpho acids (1:4, 15, 1:8),
naphtholalphasulpho acids, betanaphthol-
betasulpho acid, betanaphtholgammasulpho
acid, betanaphthol delta sulpho acid, alpha-
naphthol delta disulpho acid, alphanaphthol-
-disulpho acid, alphanaphtholdisulpho acid
described in the German Patent No. 38281
betanaphthol disulpho acid R, G and F,
alpha hydroxynaphthoic acid, betahydroxy-
naphthoic acid.
Dihydroxynaphthalenes (1:2, 1: 5, 18, 2:6,
2:7, 1:6 2:8), 1-8-dihydroxynaphthalene
alpha monosulpho acid, 18-dihydroxynaph-
thalene alpha disulpho acid, 1-8-dihydroxy-
naphthalene beta disulpho acid dihydroxy-
naphthalene monosulpho acid R. G and F.
blue.
blue or greenish-blue.
greenish-blue.

page_text: Anilin, toluidine, xylidin
Metaphenylenediamine toluylendiamine and
sulpho acids thereof.
Alphanaphthylamine, alpha naphthylamine
ortho monosulpho acid, Clève's alpha naph-
thylamine beta monosulpho acids, (y B
and 8) ethylbeta naphthylamine delta mono-
sulpho acid phenyl- and tolylbetanaphthyl-
amine monosulpho acids.
Amidonaphthol (1:8, 1:5, 2:7) alpha amido-
betanaphtholether gamma amidonaphthol-
sulpho acid 1-8-amidonaphtholsulpho acids.
violet or blue.
brown.
bluish violet or greenish-blue.
black with a greenish hue.
Of course not only the products specified in the first column of the preceding
table can be used for the production of such tetrazo dyes as are diazotable on the
fibre and may be combined with ẞ-naphthol or the like, but all chemical compounds
known as dyestuff components can be employed for producing colouring-matters
which when subjected to the process hereinbefore described (riz. diazotation on the
fibre and combination with suitable dyestuff components) likewise yield valuable
results.
Shades similar to those specified in the second column of the preceding table are
obtained in replacing the alpha amidonaphtholethylether beta monosulpho acid by
the isomeric alphaamidonaphtholethylether deltamonosulpho acid viz. by coupling
equal molecular proportions of the latter one of the products enumerated in the
first column of the preceding table and a tetrazo salt rediazotising these tetrazo
dyes on fibre and combining the diazo or tetrazo compounds, so formed with beta
naphthol or the like.
The simple and mixed colouring matters which are obtained by means of the
tetrazo salts of the other diamines or sulpho derivatives thereof may also be
employed in the above process (viz. diazotised and then combined on fibre with
beta naphthol) shades being produced which in general are more reddish starting
from diamines not containing alkylhydroxy groups.
When amidonaphthoxyacetic acid and amidonaphthoxyaceticsulpho acid are
employed for the production of simple or mixed tetrazo dyestuffs and the latter
according to this process are diazotised and combined on fibre with suitable dye-
stuff components in general similar shades are produced whilst in the employment
of the simple and mixed tetrazo dye-stuffs obtained from amidonaphthols or amido-
naphtholethers by the combination with such tetrazo compounds as contain sulpho
groups from bluish-black to greenish-black and pure black are obtained.
Dated this 17th day of June 1892.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.
COMPLETE SPECIFICATION.
Improvements in the Production of Azo Colours on Fibre.
I BENJAMIN WILLCOX of 47 Lincolns 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 Farbenfabriken vorm. 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:-
In the Specification of the Letters Patent No. 226414 dated 28th December 1891
a process for producing azo dyes on fibre is described which consists in treating
cotton with moderately acid solutions of sodium nitrite and alkaline or acid

page_text: solutions of phenols, amines, amidophenols, amidophenolethers, supno or carboxylic
acids thereof such cotton having been previously dyed with the colouring-matters
resulting from the combination of one molecular proportion of a tetrazo salt with
either two molecular proportions of Clève's alphanaphthylaminebetamonosulpho
acids (beta or delta) or with one molecular proportion of the aforesaid alpha-
naphthylamine betamonosulpho acids (beta or delta) and one molecular proportion
of a phenol, an amine, amidophenol or a sulpho or carboxylic acid thereof.
My foreign correspondents have now found that similar results are obtained by
employing instead of Clève's alphanaphthylaminebetamonosulpho acids amido-
naphtholether sulpho acids which can be obtained for instance by alkylating
naphtholsulpho acids, nitrating the resulting alkylhydroxynaphthalene sulpho
acids and reducing the nitroalkylhydroxynaphthalene sulpho acids so formed.
When instead of the amidoalkylhydroxynaphthalene sulpho acids (so called
amidonaphthol ether-sulpho-acids) amidonaphthols, amidonaphtholethers, amido-
naphthoxyacetic acids or amidonaphthoxyaceticsulpho acids are used, the
process may be effected in an analogous manner, the said amidonaphthols and
amidonaphtholethers being most adapted for the combination with tetrazo com-
pounds which contain sulpho groups (such as beuzidinemonosulpho- or disulpho
acid, diamidostilbenedisulpho-acid and the like).
Necessarily my foreign correspondents exclude those combinations of the tetrazo
compounds with the said products (viz. amidonaphtholethersulpho acid, amido-
naphthol, amidonaphtholether, amidonaphthoxyacetic acid or amidonaphthoxy acid
sulpho acid) which are not amidoazo products further diazotable.
By the combination of the aforesaid amido products viz. amidonaphtholether
sulpho acids, amidonaphthols, amidonaphtholethers, amidonaphthoxyacetic acids or
amidonaphthoxyacetic sulpho acids with tetrazo salts of diamines or sulpho acids
thereof "symmetrical" or "mixed" tetrazo dye stuffs are formed. By the
expression "symmetrical tetrazo dye-stuffs" my foreign correspondents mean those
colouring-matters which can be produced by the combination of one molecular
proportion of a tetrazo salt with two molecular proportions of the above mentioned
amido compounds, whilst by the expression "mixed tetrazo dye-stuffs" those
colouring-matters are termed, which can be obtained by combining one molecular
proportion of a tetrazo salt with molecular proportions of each of two of the said.
products (viz. amidonaphtholethersulpho acids, amidonaphthols, amidonaphthol-
ethers, amidonaphthoxyacetic acids or amidonaphthoxy acetic sulpho acids) or by
combining one molecular proportion of the tetrazo salt of a diamine or substituted
diamine with one molecular proportion of one of the said products (viz. :-amido-
naphtholether sulpho acid, amidonaphthol, amidonaphthofether, amidonaphthoxy-
acetic acid or amidonaphthoxyacetic sulpho acid) and one molecular proportion of
an amine, a phenol, amidophenol, amidophenolether of the benzene or naphthalene
series, a sulpho or carboxylic acid thereof, or inversely by coupling a tetrazo salt
first with an amine, a phenol, amidophenol, amidophenolether, or a sulpho or
carboxylic acid thereof and then with amidonaphtholether-sulpho acid, amido-
naphthol, amidonaphtholether, amidonaphthoxyacetic acid or amidonaphthoxy-
acetic sulpho acid. My foreign correspondents have employed the following
diamines-benzidine, methylbenzidine, tolidine, monoalkylbydroxybenzidine,
monoalkylhydroxymethylbenzidine, dialkylhydroxybenzidine, diamidodiphenylene
oxide, diamidoditoluylene oxide, diamidocarbazol, diamidodiphenic acid, diamido-
diphenoxyacetic acid, diamidodiphenylene ketoxime, diamidofluorene, diamido-
naphthalene, diamidostilbene, paraphenylenediamine, toluylenediamine, para-
phenylenediamineazoalphanaphthylamine and analogous compounds, diamidoazobene,
diamidoazotoluene, diamidoazoxylene, diamidoazoxybenzene, diamidoazoxytoluene,
diamidoazoxyxylene or the sulphones, sulpho derivatives or sulphone sulpho
products thereof.
The above defined "symmetrical” and “mixed” colouring-matters, when fixed on
the fibre, can be directly diazotised and then combined with the known dye-stuff
components. The dye-stuff's thus produced on the fibre contain either three or

page_text: four azo groups (-N-N-) and will therefore, for the sake of brevity be called
"trisazo colouring-matters" or tetrakis azo colouring-matters.”
In order to illustrate the process, the following example is given :-
A suitable dyeing bath is prepared by dissolving 0-5 kilos. of the symmetrical
dye-stuff obtained from one molecular proportion of tetrazodiphenyl chloride and
two molecular proportions of alphaamidobetanaphtholethyletherbetamonosulpho acid
(the latter acid being formed by ethylating nitrating and reducing betanaphtholbeta
monosulpho acid 2:6) in about 125 litres of water and adding 0-5 kilos. of common
salt. 5 kilos. of unmordanted cotton are dyed by immersion during say one hour in
the boiling bath above described. After rinsing the cotton (which has acquired
a bluish violet colour) is placed in a solution of 0.15 kilos. of sodium nitrite in
250 litres of cold water acidulated with hydrochloric acid and well agitated therein
for say half an hour. When the diazotising is finished, the cotton is rinsed with
cold water and is then introduced into an alkaline solution of 0.4 kilos. of the
sodium salt of betanaphthol. The combination of the betanaphthol employed with
the diazo compound of the dye-stuff fixed on fibre is complete after a short time,
the cotton acquiring a greenish-blue colour of great purity and which withstands
washing.
In the preceding example instead of the symmetrical tetrazo dye-stuff from one
molecular proportion of the said tetrazo diphenyl chloride aud two molecular
proportions of the said alpha amidobetanaphtholether betamonosulpho acid the
analogous symmetrical colouring-matters from the other tetrazo salts, and the dye-
stuffs formed by the combination of the tetrazo salts of the diamines or sulpho
derivatives thereof hereinbefore mentioned with two molecular proportions of
another amidonaphtholether sulpho acid or amidonaphthoxyacetic acid or amido-
naphthoxyacetic sulpho acid may be employed, fast shades being thus obtained
which in general are green.
In the same manner the mixed tetrazo dye-stuffs can be employed which are
formed from one molecular proportion of the tetrazo salts of the diamines berein-
before enumerated, one molecular proportion of amidonaphtholethersulpho acid,
amidonaphthoxylacetic acid or amidonaphthoxylaceticsulpho acid and one
molecular proportion of an amine, a phenol, an amidophenol, amidophenolether of
the benzene and naphthalene series or of a sulpho or carboxylic acid of the
latter components (including the amidonaphthoxyacetic acids and amido
naphthoxyacetic sulpho acids).
The simple and mixed tetrazo dye-stuffs formed from amidonaphthols and amido-
naphtholethers, especially those formed from the tetrazo compounds containing
sulpho groups may also be employed in this process with a similar result.
My foreign correspondents have also found that the diazo derivatives of the said
symmetrical and mixed colouring-matters can also be combined, on fibre, with other
phenols, or with amines, amidophenols, amidophenolethers of the benzene and
naphthalene series, with sulpho or carboxylic acids thereof, with amidonaphthoxy-
acetic acid or amidonaphthoxyaceticsulpho acid; amines, certain dihydroxy-
naphthalenes and sulpho acids thereof being preferably allowed to interact in
moderately acetic acid solution and in the presence of sodium acetate.
In the second column of the following table the shades are noted which are
obtained on dyeing unmordanted cotton with the symmetrical tetrazo colouring-
matters obtained from the tetrazo salts specified in the first column and two
molecular proportions of alphaamidobetanaphtholethylether betamonosulpho acid
(OC,H, SO,H2: 6), diazotising the dye-stuffs on the fibre and then coupling
these diazo derivatives also while on the fibre with betanaphthol.
:
Tetrazodiphenyl
Tetrazophenyltolyl
Orthotetrazoditolyl
Tetrazomonomethoxydiphenyl
blue with a greenish-hue
blue with a greenish-hue
greenish-blue
greenish-blue

page_text: Orthotetrazodiphenoldimethylether
Tetrazostilbene -
Tetrazostilbene disulpho acid
bluish-green
blue with a greenish-hue
blue with a greenish-hue
The following table contains in the second column the different shades which
result on dyeing unmordanted cotton with the symmetrical colouring-matters
obtained by the combination of the tetrazo salts specified in the first column with
two molecular proportions of alpha amidobetanaphtholether deltamonosulpho acid
(OC,H, SO,H=2: 7), rediazotising the dye-stuffs on the fibre and coupling the
formed diazo products with betanaphthol, likewise on the fibre.
Tetrazodiphenyl
Tetrazophenyltolyl
Orthotetrazoditolyl
Tetrazomonomethoxydiphenyl
Tetrazomonomethoxyphenyltolyl
Orthotetrazodiphenoldimethylether
Tetrazostilbene
Tetrazostilbenedisulpho acid
-
bluish with a greenish-hue
bluish with a greenish-hue
greenish-blue
-
greenish-blue
greenish-blue
bluish-green
-
greenish-blue
greenish-blue
acid
Similar shades are obtained by first fixing on the fibre the mixed tetrazo dye-
stuffs from equal molecular proportions of a tetrazo salt, alphaamidobetanaphthol-
ether betamonosulpho acid and alphaamidobetanaphtholetherdeltamonosulpho
(which are both hereinbefore specified) rediazotising the tetrazo dye on the fibre
and coupling the diazo product with betanaphthol, likewise on the fibre.
Of the other series of mixed dye-stuffs those which are formed for example, from
one molecular proportion of orthotetrazodiphenoldimethylether, one molecular
proportion of alphaamidobetanaphtholethylether betamonosulpho acid and one
molecular proportion of the compounds specified in the first column of the following
table when diazotised on the fibre and the resulting diazo or tetrazo products are
coupled with betanaphthol yield shades which are enumerated in the following
second column :-
Phenol, kresol, resorcinol, pyrogallol, phenol- 1
sulpho acids, kresolsulpho acids, resorcinol- |
sulpho acids, salicylic acids, ortho-, meta-
and para-cresotinic acid, symmetrical
dihydroxybenzoic acid (OH OH:
COOH = 1: 3:5).
==
Alpha or betanapthol, alphanaphtholmono-
sulpho acids (1: 4, 15, 1: 8), beta-
naphtholalphasulpho acid, betanaphthol-
betasulpho acid, betanaphtholgammasulpho
acid, betanaphtholdeltasulpho acid, alpha-
blue.
naphtholdeltadisulpho acid, alphanaphthol > blue or greenish blue.
epsilon disulpho acid, alphanaphthol-
disulpho acid described in the German
Patent No. 38281, betanaphtholdisulpho
acid R, G and F, alphahydroxynaphthoic
acid, betahydroxynaphthoic acid.
Dihydroxynaphthalenes (1:2, 1:5, 1 : 8,2 : 6,
2:7, 16, 2:8), 1: 8-dihydroxynaphtha-
lene alphamonosulpho acid, 1 : 8-dihydroxy-
naphthalenealphadisulpho acid, 1 : 8-di-
hydroxynaphthalene betadisulpho acid, di-
hydroxynaphthalenen onosulpho acid R, G
and F.
greenish-blue.

page_text: delta) etnyioеtanaphthy
Чегатопо
sulpho acid, phenyl and tolylbetanaphthyl-
aminemonosulpho acids.
Amidonaphthol (1: 8, 1: 5, 2 : 7), alphaamido-
betanaphtholether, gamma amido naphthol-
sulpho acid, 1:8 amidonaphtholsulpho
acids.
black with a greenish hue.
Not only can the products specified in the first column of the preceding table be
used for the production of such mixed tetrazo dyes as are diazotisable on the fibre
and may be combined with B-naphthol or the like, but necessarily all compounds
known as dye-stuff components can be employed for producing colouring-matters
which when subjected to the process herein before described (viz. :-diazotisation
on the fibre and combination with suitable dye-stuff compoñents) likewise yield
valuable results.
Shades similar to those specified in the second column of the preceding table are
obtained, if instead of the alphaamidonaphtholethyletherbetamonosulpho acid the
isomeric alphaamidonaphtholethyletherdeltamonosulpho acid be used viz. :- by
coupling equal molecular proportions of the latter, one of the products enumerated
in the first column of the preceding table, and a tetrazo salt, rediazotising these
tetrazo dyes on the fibre and combining the diazo or tetrazo compounds, so formed
with betanaphthol or the like.
The symmetrical and mixed colouring-matters which are obtained by means of
the tetrazo salts of the other diamines, or sulpho derivatives thereof, may also be
employed in the above process (viz.: diazotised and then combined on the fibre with
betanaphthol) shades being produced which in general are more reddish, starting
from diamines which do not contain alkylhydroxy groups.
When amidonaphthoxy acetic acid and amidonaphthoxy acetic sulpho acid are
employed for the production of symmetrical or mixed tetrazo dye-stuffs and the
latter in accordance with this process are diazotised and combined on the fibre with
suitable dye-stuff components, in general similar shades are produced; whilst by
employing the symmetrical and mixed tetrazo dye-stuffs obtained from amido-
naphthols or amidonaphtholethers by combination with such tetrazo compounds as
contain sulpho groups from bluish-black to greenish-black and pure black are
obtained.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The process of producing trisazo- or tetrakisazo colouring-matters on the fibre
by means of the following colouring-matters viz.: the symmetrical tetrazo dye-stuffs
which result from the combination of one molecular proportion of a tetrazo salt of
a diamine or substituted diamine with two molecular proportions of an amido-
naphtholether sulpho acid, amidonaphthoxyacetic acid or amidonaphthoxyacetic
sulpho acid or the mixed tetrazo dye-stuffs resulting either from the combination of
a tetrazo salt with molecular proportions of each of two of the following products
viz.: amidonaphtholethersulpho acid, amidonaphthoxyacetic acid, amidonaphthoxy-
acetic sulpho acid or by the combination of one molecular proportion of a tetrazo
salt with one molecular proportion of an amidonaphtholethersulpho acid, amido-
naphthoxyacetic acid or amidonaphthoxyacetic sulpho acid and with one molecular

page_text: proportion of the known dye-stuff components (an amine, phenol, amidophenol,
amidophenolether of the benzene or naphthalene series, or a sulpho or carboxylic
acid thereof) or inversely first with one molecular proportion of these last named dye
stuff components and then with one molecular proportion of an amidonaphtholether-
sulpho acid, amidonaphthoxyacetic acid or amidonaphthoxy acetic sulpho acid
(excluding however the combinations which are not further diazotisable amidoazo
products,) which process consists first in dyeing cotton fibre or fabrics or materials
with the symmetrical or mixed colouring-matters above defined, further diazotising
these colouring-matters on the fibre and coupling the resulting diazo or tetrazo
products, also whilst on the fibre, with amines, phenols, amidophenols, amidophenol-
ethers of the benzene or naphthalene series, sulpho or carboxylic acids thereof,.
effecting the latter two processes (viz.: diazotisation and combination) by treating
cotton fibres, fabrics or materials which are previously dyed in the aforesaid
manner first in a moderately acidulated bath of sodium nitrite and then in moderately
acid or alkaline baths of amines, phenols, amidophenols, amidophenolethers of the
benzene or naphthalene series or a sulpho or carboxylic acid thereof.
2. The production of trisazo or tetrakisazo colouring-matters by first dyeing
cotton fibres, fabrics or materials with the symmetrical or mixed tetrazo dye-stuffs
resulting from the combination of tetrazo salts of diamines containing sulpho groups
either with amidonaphthol or amidonaphtholether, or with amidonaphthol or amido-
naphtholether and another dye-stuff component (excluding however those com-
binations which are not further diazotisable amidoazo products,) and by subsequently
treating the thus dyed cotton fibres, fabrics or materials first in moderately
acidulated baths of sodium nitrite and then in moderately acid or alkaline baths of
amines, phenols, amidophenols, amidophenolethers of the benzene or naphthalene
series or a sulpho or carboxylic acid of these components.
3. Cotton fibres or textures dyed in the manner hereinbefore described or by any
other process producing a like result.
M
1 1000
B. WILLCOX..