Improvements in the Production of Fast Colors on Fibres by Means of Dyeing and Printing.
Year: 1892

page_text: Date of Application, 11th Nov., 1892
Complete Specification Left, 11th Aug., 1893-Accepted, 30th Sept., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
Improvements in the Production of Fast Colors on Fibres by Means
of Dyeing and Printing.
I, PHILIP ARTHUR 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 :-
In the Specification of Letters Patent No. 2213, dated 15th February 1886, it is
stated, that in the reaction of tetrazo compounds on amines, phenols, sulpho or
carboxylic acids thereof, even if an excess of the latter components be employed,
intermediate products are formed at first by the combination of one molecular
proportion of a tetrazo compound with one molecular proportion of one of the said
components. These intermediate products are formed very casily by allowing one
molecular proportion of a tetrazo salt to act on one molecular proportion of a
component, for instance, if a tetrazo compound be combined with alphanaphthyl-
amine in equimolecular proportions, products are obtained which contain a
diazotable amido group and a diazo group, and possess the general formula :—
-
-
`N = N – C₁H¸ – NH₂HCl.
(in which R signifies the radicles of diphenyle, phenyltolyle, ditolyle, benzene,
monoalkylhydroxydiphenyle, monoalkylhydroxyphenyltolyle, diphenoldialkylether,
diphenoxyacetic acid, naphthalene, fluorene, stilbene, carbazol, diphenylene oxide,
ditoluylene oxide, or analogous products, which form the base of the so called
tetrazo compounds).
The resulting products, which can be termed diazo-azo compounds, and will be
brought by my foreign correspondents in pasty form into commerce, dissolve in
cold water with a crimson red color, are stable at temperatures not rising above
60 degrees centigrade, but cannot be dried without being altered, and are decom-
posed on boiling with water, nitrogen being disengaged. They are further
decomposed at ordinary temperatures by alkalies, nitrogen likewise being
disengaged.
My foreign correspondents have now found, that the said intermediate products
have the interesting and valuable property of being fixed in acid watery solutions,
without the addition of mordants, on the vegetable fibres and on silk, not becoming
thus destitute of the valuable properties as diazo-azo compounds, and of being
converted into new dyes, if the fibre dyed or printed with the specified intermediate
products be subjected to a subsequent treatment with solutions of amines, phenols,
analogues and derivatives thereof.
Amongst the intermediate products, or diazo-azo compounds, for instance, the
following can be employed, viz.: those which result by the action of one molecular
proportion of alphanaphthylamine on one molecular proportion of a salt of tetrazodi-
phenyle, tetrazophenyltolyle, tetrazoditolyle, paratetrazo benzene, tetrazomono-
alkylhydroxydiphenyle, tetrazomonoalkylhydroxyphenyltolyle, tetrazodiphenoldi-
alkylether, tetrazodiphenoxyacetic acid, tetrazonaphthalene, tetrazofluorene,

page_text: tetrazostilbene, tetrazocarbazol, tetrazodiphenylene oxide, or tetrazoditoluylene
oxide.
Of course, intermediate products (diazo-azo compounds), obtained from alpha-
naphthylamine and other tetrazo salts, likewise can be employed in this process.
In place of alphanaphthylamine, analogous amines and the substitution derivatives
of all these amines can be used for preparing the said intermediate products. By
"analogous amines and substitution derivatives of all these amines" my foreign
correspondents understand, for example, paraxylidine, paracresidine (orthoamido-
paracresol and metaamidoparacresol), ethers of the last named amido cresols and
the like, betanaphthyamine, amidonaphthols, amidonaphtholsulpho acids, amido-
naphtholethers, amidonaphtholethersulpho acids, amidonaphthoxy acetic acid,
amidonaphthoxy acetic sulpho acid, alphanaphthylamine sulpho acids, betanaphthyl-
amine sulpho acids, and the like.
In order to illustrate this new method of producing dyes ou the fibre for dyeing
1
PRODUCTION OF A BROWNISH-RED.
10 kilos. by weight of cotton or silk are placed in a bath, which is heated to
40 degrees centigrade, and is prepared by dissolving in 100 litres of water, with
the addition of 8 litres of hydrochloric acid (20 degrees Baumé), half a kilo., by
weight, of a paste (20 per cent.) of the intermediate diazo azo product from one
molecular proportion of tetrazodiphenyl salt, and one molecular proportion of
alphanaphthylamine. The goods are stirred for from about 3 to 5 hours at from
30 to 40 degrees centigrade.
After this time, the bath is perfectly spent, and the fibre treated therein has
acquired a deep reddish-black color. It is noticeable that the presence of metals
must be carefully avoided during this process. After wringing well, the goods,
without rinsing, are introduced into a bath prepared by dissolving 01 kilo., by
weight, of betanaphthol and 2 kilos., by weight, of sodium carbonate, in 100 litres
of water. The fibre assumes, in a few minutes, a deep brownish red color, and the
resulting shades are perfectly fast against the action of light, air, and soaping,
whilst the fibre is not in the least affected.
If betanaphthol employed in the foregoing example be replaced, for instance, by
phenol, a brownish yellow results, whilst dihydroxynaphthalene yields a blackish
brown; with alphanaphthylamine, a brownish red; with betanaphthylamine, a clear
red is obtained; and speaking broadly, the different phenols, amines, or substitution
products thereof, yield different shades.
Of course, betanaphthol used in the above example, as so-called developing
material, can in general be replaced by phenols, amines, amido-phenols, amido-
phenolethers of the benzene or naphthalene series, and the sulpho or carboxylic
acids of these components.
Amines are most practically coupled in hydrochloric or acetic solutions, phenols
in alkaline solutions, dihydroxynaphthalenes in alkaline or acid solutions. If the
components be coupled in acid solutions, the goods must subsequently be treated
with watery solutions containing a little quantity of alkali.
My foreign correspondents have further found that the shades resulting in the
manner specified in the above example, can be changed into new ones possessing a
much greater intensity, riz. by subjecting the goods treated in the aforesaid
manner to a subsequent treatment in moderately acidulated baths of sodium nitrite,
and in baths containing phenols, amines, amidophenols, amidophenolethers, sulpho
or carboxylic derivatives thereof.
The following example is typical for the further diazotation of the dyes produced
on the fibre, as illustrated in the first example, and the combination of the thus
formed diazo or tetrazo compounds likewise on the fibre with the known dye stuff
components.
.

page_text: 10 kilos. by weight of cotton are stirred for some hours at from 30 to 40 degrees
centigrade, in a bath prepared by dissolving half a kilo. by weight of a paste
(20 per cent.) of the intermediate product from one molecular proportion of tetrazo
diphenylchloride, and one molecular proportion of alphanaphthylamine, in the
manner described in the above first example.
The fibre having assumed a deep reddish black shade, is then directly introduced
into a bath containing 100 litres of a solution of alphanaphthylamine hydrochlorate
(1 per cent.). After some minutes, the combination of the above diazo-azo product
with alphanaphthylamine is complete.
The goods thus dyed are placed in a moderately acidulated bath of sodium nitrite
(containing 01 kilo. by weight of sodium nitrite), and when the diazotation is
finished, in a weakly alkaline bath prepared by dissolving 3 kilos. by weight of the
sodium salt of the 18 dihydroxynaphthalenealphamonosulpho acid. The fibre
alinost instantly acquires a deep black color, and shews, after rinsing and drying, a
perfectly pure black shade, which is superior even to the shades produced by means
of aniline black.
In an analogous manner to that described in the last second example, the fibrous
materials treated with the aforesaid diazo azo compounds, or dyed by combining
these diazo azo products on the fibre with amines, phenols, and substitution products
thereof, are further treated in acidulated baths of sodium nitrite, and a bath of the
sodium salt of 1.8 dihydroxynaphthalenesulpho acid. Of course, in place of the
latter component, phenols, amines, amidophenols, amidophenolethers, sulpho or
carboxylic derivatives thereof, in general, can be used. If alphanaphthylamine be
employed as middle component, from bluish black to greenish black, and pure black
shades, are obtained, which are especially excellent by reason of their intensity and
fastness.
When the above specified diazo azo products are required to be used for printing
purposes, this result is best attained by employing a paste containing from 5 to
per cent. of the said diazo azo compounds, a suitable thickening, acetic acid, and
sodium acetate.
6
The printed material is, without drying, placed in the different baths prepared
by means of amines, phenols, amidophenols, amidophenolethers of the benzene or
naphthalene series, or sulpho or carboxylic derivatives thereof.
The latter method can be modified, viz., by printing on the fibre prepared with
developing materials (such as amines, phenols, and the like) the printing paste.
In this manner, similar shades are obtained, which likewise possess great fastness.
The dyes thus produced on the fibre, in printing, can further be diazotised, and
the resulting diazo or tetrazo compounds can be combined with amines, phenols,
amidophenols, amidophenolethers, sulpho or carboxylic derivatives thereof, in the
same manner as hereinbefore described.
The employment of the above specified diazo azo products for printing purposes,
is illustrated by the following aramula.
per cent.
The material is printed with a paste containing 50 parts by weight of a 20
paste of the diazo azo product from equimolecular proportions of tetrazo diphenyl
chloride and alphanaphthylamine, 325 parts by weight of water, 600 parts by
50 weight of acetic starch tragacanth thickening, and 25 parts by weight of sodium
acetate. The material thus-printed, is washed with precaution, then placed in a

page_text: bath of sodium nitrite, which is moderately acidulated, and after a short time in a
solution of alphanaphthylamine hydrochlorate.
It assumes a reddish black on the printed places.
According to the method illustrated by the last third example, the other above
specified diazo azo products are employed for printing purposes; alphanaphthyl-
amine employed as second component can be replaced by analogous amines, or
phenols, amidophenols, amidophenolėthers, sulpho or carboxylic derivatives thereof.
In this manner, likewise, very fast shades are obtained, which possess a great
variety, caused by the different components employed.
The methods illustrated by the above three examples are adapted for vegetable
fibres of every kind, and likewise for silk in raw, bleached, loose, spun, or woven
state, but they are not adapted for wool and kindred animal fibres.
Of course my foreign correspondents do not limit themselves to the methods
described in the above examples, but the methods mentioned therein can be varied,
and all those processes, employed in printing and dyeing for analogous purposes,
can likewise be used in practically carrying out this invention.
The nature of this invention of course is not altered by such variations, as the
present invention in general relates to the employment, hitherto unknown, of diazo
azo products resulting from the combination of equal molecular proportions of a
tetrazo salt and an amine or substituted amine for dyeing and printing purposes.
Dated this 11th day of November 1892.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Fast Colors on Fibres by Means
of Dyeing and Printing..
I, PHILIP ARTHUR 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 :-
In the Specification of Letters Patent No. 2213, dated 15th February 1886, it is
stated that, by the interaction of tetrazo compounds and amines, or phenols, sulpho
or carboxylic acids thereof, even if an excess of the latter be employed, intermediate
products are first produced by the combination of one molecular proportion of the
tetrazo compound with one molecular proportion of the said components. These
intermediate products are readily formed on allowing one molecular proportion of a
tetrazo salt to act on one molecular proportion of a dye stuff component. If a
tetrazo compound be combined, for instance, with alphanaphthylamine in equi-
molecular proportions, a product results containing a diazotisable amido group,
and a diazo group of the composition represented by the following general
formula
By the letter "R," my foreign correspondents mean, for instance, the radicles of
diphenyl, phenyltolyl, ditoly, benzene, monoalkylhydroxydiphenyl, monoalkyl-
hydroxyphenyltolyl, diphenoldialkylether, diphenoxyacetic acid, naphthalene,
fluorene, stilbene, carbazol, diphenylene oxide, ditoluylene oxide, or analogous
products, which form the bases of the so-called tetrazo compounds.
Having regard to their chemical composition, such intermediate products may be.
termed "Jinzo-azo-compounds." They are brought into commerce by my foreign

page_text: correspondents in the form of paste. They generally dissolve in cold water,
forming a crimson-red coloured liquid, and are stable at temperatures not exceeding
60 degrees centigrade. They cannot be dried without undergoing change, and are
decomposed when boiled with water, nitrogen being disengaged. They are also
decomposed at ordinary temperature by treatment with alkalies.
My foreign correspondents have now found that the said intermediate products
may be fixed on vegetable fibres and on silk by dyeing or printing, using, for this
purpose, merely an acid solution in water, no mordants being necessary, and
furthermore, that the valuable properties of diazo-azo compounds are retained by
the products thus fixed, so that if the fabric which has been dyed or printed with the
said intermediate products, be subjected to a subsequent treatment with solutions of
amines, phenols, analogues, or derivatives thereof, the corresponding dyes are
produced on the fibre.
Of the various diazo compounds which can be thus employed, may be mentioned,
for example, those which are formed from one molecular proportion of alpha-
naphthylamine, and one molecular proportion of a salt of tetrazodiphenyl,
tetrazophenyltolyl, tetrazoditolyl, paratetrazobenzene, tetrazomonoalkylhydroxy-
diphenyl, tetrazo mono alkylhydroxyphenyltolyl, tetrazo diphenoldialkyl ether,
tetrazodiphenoxyacetic acid, tetrazo naphthalene, tetrazofluorine, tetrazostilbene,
tetrazocarbazol, tetrazodiphenyleneoxide, or tetrazo ditoluylene oxide.
The intermediate products ("diazo-azo-compounds") obtained from alpha-
naphthylamine and other tetrazo salts, can equally well be employed.
Thus, in place of alphanaphthylamine, the amidonaphtholethers, which yield true
diazotable amidoazo compounds, when combined with diazo or tetrazo salts, can be
profitably used in preparing similar suitable diazo-azo-compounds.
The following example is given as an illustration of this new method of producing
dyes on fibre by means of such diazo-azo-compounds.
PRODUCTION OF A BROWNISH-KED.
10 kilos., by weight, of cotton (or silk) are placed in a bath heated to
40 degrees centigrade prepared by dissolving, in 100 litres of water, 8 litres of
muriatic acid (20 degrees Baumé), and half a kilo., by weight, of a 20 per cent.
paste of the diazo-azo-compound prepared from one molecular proportion of tetrazo
diphenyl, and one molecular proportion of alphanaphthylamine. The goods are
kept agitated in this bath, from about 3 to 5 hours, at from 30 to 40 degrees
centigrade.
!
The bath is exhausted at the end of this time, the fibre treated therein having
assumed a deep reddish-black colour. It is to be noted that the presence of metals.
must be carefully avoided during this process. After wringing the goods well
(without rinsing), they are introduced into a bath prepared by dissolving 0.1 kilo.
by weight of betanaphthol, and 2 kilos., by weight, of sodium carbonate, in
100 litres of water. After a few minutes, the fibre assumes a deep brownish-red
colour, shades being thus produced which withstand the action of light, air, and
soaping, the fibre not being injuriously affected.
If the betanaphthol employed in the foregoing example be replaced, for instance,
by phenol, a brownish yellow is obtained, while dihydroxynaphthalene yields a
blackish brown. On using alphanaphthylamine, a brownish-red results, betanaphthyl-
amine affording a clear red, different phenols, amines, or substitution products,
thereof, yielding, as a rule, different shades.
The betanaphthol used in the above example as so called "developer," can be
replaced by other phenols, or amines, amidophenols, amidophenolethers of the
benzene or naphthalene series, or sulpho or carboxylic acids thereof.
Amines are profitably coupled in solutions acidulated with either muriatic or
acetic acid, phenols are employed in alkaline solutions, and dihydroxynaphthalenes

page_text: are coupled either in alkaline or acid solutions. When acid solutions are used, the
goods must be subsequently treated with a weak alkaline solution, in order to
remove the adherent acid.
0
The researches of my foreign correspondents have further shewn, that the shades
obtained by operating in the manner illustrated by the above example, can be
changed into others of much greater intensity, by further subjecting the goods to a
treatment in moderately acidulated baths of sodium nitrite, and subsequently in
baths prepared by means of phenols, amines, amidophenols, or amidophenolethers,
of the benzene or naphthalene series, or sulpho or carboxylic derivatives thereof.
The following example is typical of the mode of diazotising the dyes produced:
on the fibre in the manner illustrated by the first example, and of combining the
resulting diazo- or tetrazo compounds, while on the fibre, with the known dye-stuff
components.
10 kilos., by weight, of cotton are kept stirred during several hours, at from
30 to 40 degrees centigrade, in a bath prepared by dissolving half a kilo., by weight,
of a paste containing 20 per cent. of the diazo-azo-compound prepared from one
molecular proportion of tetrazodiphenyl chloride and one molecular proportion of
alphanaphthylamine.
The fibre assumes a deep reddish black shade. It is next introduced into a bath
prepared by dissolving 1 kilo. by weight of alphanaphthylamine hydrochloride in
100 litres of water. The combination of the "diazo-azo-compound" with alpha
naphthylamine is completed within a few minutes. .
The goods thus dyed are introduced into a moderately acidulated bath of sodium
nitrite (containing 0.1 kilo., by weight, of sodium nitrite). When diazotised, the
material is introduced into a weakly alkaline bath prepared by dissolving 3 kilos.,
by weight, of the sodium salt of 1:8 dihydroxynaphthalene alphamonosulpho acid.
The fibre almost instantly assumes a deep black colour, which, after rinsing and
drying, is superior even to the shades produced by means of aniline black.
In a manner analogous to that described in the last second example, the fibrous
materials which have either been treated with the above-named "diazo-azo-
compounds," or dyed by further combining the "diazo-azo-compounds," while on
the fibre, with known dye stuff components, are first introduced into an acidulated
bath of sodium nitrite, and subsequently into a bath prepared from the sodium salt
of 1:8 dihydroxynaphthalene sulpho acid. The last mentioned component can be
replaced by phenols, amines, amidophenols, amidophenolethers of the benzene or
naphthalene series, or sulpho or carboxylic derivatives thereof. If alphanaphthyl-
amine be used as middle component, from bluish-black to greenish-black and pure
black shades are obtained, which are remarkable on account of their intensity and
fastness.
In using the above specified "diazo-azo-compounds" for printing purposes, the
best result is obtained by employing a printing paste containing from 5 to 6 per cent.
of any of the said "diazo-azo-compounds," a suitable thickening, acetic acid, and
sodium acetate. The undried printed material is introduced into the different baths
prepared by means of amines, phenols, amidophenols, amidophenolethers of the
benzene or naphthalene series, or sulpho or carboxylic derivatives thereof.
The latter method can also be modified, viz., by first printing the printing paste
on the fibre prepared with developing materials (such as amines, phenols, and the
like), similar shades being thus obtained, which are also of great fastness.
My foreign correspondents have ascertained that the dyes thus produced on fibre
by printing, can also be diazotised, and that the resulting diazo or tetrazo com-
pounds can be combined with amines, phenols, amidophenols, amidophenolethers of
the benzene or naphthalene series, or sulpho or carboxylic derivatives thereof, in
the same manner as herein before described.

page_text: PRODUCTION OF A REDDISH-BLACK.
The material is printed with a paste containing 50 parts, by weight, of a paste
(containing 20 per cent.) of the "diazo-azo-compound" from equimolecular pro-
portions of tetrazo diphenylchloride and alpha naphthylamine, 325 parts, by weight,
of water, 600 parts, by weight, of acetic-starch-tragacanth thickening, and 25 parts,
by weight, of sodium acetate. The material thus printed, having been carefully
washed, is introduced into a moderately acidulated bath of sodium nitrite, and after
a short interval, into a watery solution of alphanaphthylamine hydrochloride. It
assumes a reddish-black colour on the printed parts.
The other above specified "diazo-azo-compounds are employed for printing
purposes in a manner analogous to that illustrated by the last third example.
Instead of using alphanaphthylamine as second component, other amines, or
phenols, amidophenols, amidophenolethers of the benzene or naphthalene series,
sulpho or carboxylic derivatives thereof, may be used,-a great variety of very fast
shades being thus obtained.
"
The methods illustrated by the above three examples are adapted for use with
vegetable fibres of every kind, and also with silk in its raw, bleached, loose, spun,
or woven state, but they are not adapted for use with wool and kindred animal
fibres.
Naturally my foreign correspondents do not limit themselves to the methods
described in the above examples, as the directions given therein can be varied, and
all the processes employed in printing and dyeing for analogous purposes, can also
be used in practically carrying out the invention hereinbefore defined.
The nature of this invention is not altered by such variations, as the present
invention relates generally to the hitherto unknown employment of the "diazo-azo-
compounds," resulting from the combination of equal molecular proportions of a
tetrazo salt and alpha naphthylamine, or amidonaphtholether, for dyeing and
printing purposes.
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 use, in producing dyes on vegetable or silk fibres, of the diazo-azo-
compounds, or intermediate products formed from one molecular proportion of a
tetrazo salt and one molecular proportion of either alphanaphthylamine or such
amido naphtholethers as yield true diazotisable amido azo products, when combined
with tetrazo salts.
2. The production of fast colours on vegetable or silk fibres, the which process
consists either in dyeing or printing the unmordanted fibre or texture with the
above defined "diazo-azo-compounds," and subsequently treating the thus dyed or
printed material in suitable solutions of dye-stuff components.
3. The process of producing colours on vegetable or silk fibre by treating the
fibre or texture in suitable solutions of the above defined "diazo-azo-compounds,"
diazotising the latter on the fibre, and combining the resulting tetrazo compounds
with the known dye stuff components (employing either a single or two different
components).
4. The production of fast colours on vegetable or silk fibres, which process
consists in introducing the fibre into a suitable bath of a dye-stuff component, and
ubsequently printing the material so treated with the above defined "diazo-azo-
compounds.'
5. The conversion of the dyes produced on fibres by means of the processes

page_text: hereinbefore defined, into other dyes, by a subsequent treatment thereof in
acidulated solutions of sodium nitrite, and in baths prepared from the known dye
stuff components.
6. The vegetable or silky fibres or textures dyed or printed in the manner
NEWTON & SON,
Agents for the Applicant.