IMPROVE- " MENTS IN THE MANUFACTURE AND APPLICATION OF COLORING MATTERS
Year: 1883

page_text: LETTERS PATENT to Charles Denton Abel of N° 28 Southampton Buildings
Chancery Lane in the County of Middlesex for an Invention of IMPROVE-
"
MENTS IN THE MANUFACTURE AND APPLICATION OF COLORING MATTERS
"
communicated to him from Abroad by the Farbwerke vormals Meister Lucius
and Brüning of Hoechst-am-Main in the Empire of Germany, a Company
carrying on business as Chemical Manufacturers
PROVISIONAL SPECIFICATION left by the said Charles Denton Abel at the
Office of the Commissioners of Patents on the 17th December 1883.
"
CHARLES DENTON ABEL of N° 28 Southampton Buildings Chancery Lane in the
County of Middlesex IMPROVEMENTS IN THE MANUFACTURE AND APPLICATION
OF COLORING MATTERS [communicated to him from Abroad by the Farbwerke
vormals Meister Lucius and Brüning of Hoechst-am-Main in the Empire of
Germany, a Company carrying on business as Chemical Manufacturers]
This invention relates to the conversion of the coloring matters belonging to
the well known series of azo-coloring matters, whether soluble or insoluble in
water, into new compounds soluble in water, by combining such azo-coloring
matters with the bisulphites of the alkalies or other bases.
In carrying out this invention, any azo coloring matter, in the form of a powder
or of a paste, is dissolved or suspended in a suitable solvent, which may be water
in the case of sulphonated azo colors that are soluble in water, or may be spirits of
wine in the case of azo-colors that are insoluble in water but are soluble in spirits.
To this is added a solution of the bisulphite of an alkali, such as soda, ammonia
or potash or of another base, the bisulphite of which is soluble in the solvent
employed. The mixture may be left standing for a time, but preferably it is
heated on a water bath. and the bisulphite combines with the azo coloring matter,
forming bisulphite compounds which we term "azo-S-colors," soluble in water. In
most cases, the conversion is complete, but when it is not so, the azo-S-color can
be separated from the unconverted azo coloring matter by taking advantage of
their different degrees of solubility in water and spirits. The azo-S-colors are
easily obtained in crystalline form by cooling their hot aqueous or alcoholic solutions,
or by adding common salt to these solutions.
The crystals of azo-S-colors vary in color from yellow to red, but all of them give
with water yellow solutions with more or less of a red tint. When an azo-S-color
is steamed or boiled for some time with water, or heated with a solution of a

page_text: nitrite, or when it is treated with an alkaline agent, the bisulphite compound is
decomposed and the original azo-coloring matter from which it had been prepared,
or its salt, is precipitated.
The azo-S-colors are not changed however by the addition in the cold of metallic
salts used as mordants or by acetic and tartaric acid. This property is of great
value in applying the azo-S-colors in dyeing and printing, either with a mordant, to
form a lake, or without such a mordant.
In order to develop the color on a textile fabric, the fabric is impregnated with
the azo-S-color in solution or as a paste with or without an alumina, iron or
chromium mordant, and the impregnated fabric is then exposed to the action of
steam or of an alkaline agent or of a nitrite, as may be most suitable for the
particular fabric. By this treatment, the unstable yellow shade, imparted to the
fabric by the azo-S-color, is converted into the stable tint of the original azo-
coloring matter from which the azo-S-color had been prepared, or to the
corresponding salt or lake.
The following are examples of the preparation of azo-S-colors and of their
analisation in In
By diazotizing alpha-naphthylamine and combining the product with a molecular
quantity of beta naphthol, according to the method taught by Griess and well
known to chemists, a claret azo-coloring matter is obtained which is insoluble in
water but soluble in spirits of wine. To about 14 lbs of this substance in fine
powder or paste are added about 1 cwt. of spirits of wine with, say, 28 lbs of a
concentrated solution of ammonium or sodium bisulphite. The mixture in a closed
vessel or a vessel provided with a cooler, is kept at a temperature from 70 to
100 degrees centigrade for about 7 hours, and then an equal volume of hot water
being added, the whole is heated to boiling and filtered while hot. Upon the filter
is found some of the original claret azo-coloring matter employed, which has
escaped the re-action, and from the hot filtrate, there separate, on cooling, red
crystals of the new Azo-S-color. These crystals are removed and the liquid, still
containing azo-S-color, is treated as follows:-
The alcohol is nearly all distilled off, and the residual liquor saturated with
common salt, when the remainder of the azo-S-color is obtained in the shape of
very small crystals. The unchanged portion of the original azo-coloring matter
left on the filter is, by subjecting it to the same treatment as above described,
converted into azo-S-color.
The azo-S-color obtained as before described as a powder or paste is soluble in
water, giving a yellow color. When an alkali is added to this solution, or when
it is boiled by itself, or with a solution of a nitrite, it is decomposed, and the claret
azo-coloring matter from which it had been prepared is precipitated. When a
textile fabric is steeped in a solution of the azo-S-color, it is dyed yellow. By
exposing the textile fabric so dyed to the action of steam or of an alkaline agent
or of a hot solution of a nitrite, the yellow color is changed into claret, and the
textile fabric has thus a fast claret tint imparted to it.

page_text: shape of a powder or of a paste, say, 14 lbs are added to, say, 1 cwt. of spirits of
wine along with, say, 28 lbs of a concentrated solution of ammonium or sodium
bisulphite. The mixture is now kept at a temperature of from 70 to 100 degrees
centigrade in a closed vessel or in a vessel with a reversed cooler for say two hours,
stirring all the time, after which treatment the whole of the scarlet azo-coloring
matter is found converted into its orange colored bisulphite compound. The alcohol
is now distilled off, and the residual crystalline paste is allowed to cool. The
crystals are separated from the suspending liquid by filtration, and now represent
the azo-S-color ready for use, either in the shape of a powder, or of a paste, or in
solution.
The Azo-S-color thus obtained is termed "Azoarin B S." It is soluble in hot
water, producing a yellow color. When an alkali is added to this yellow solution,
or when it is boiled with a nitrite, the azo-S-color, termed Azoarin B S, is
decomposed, and the violet colored salt of the scarlet azo-coloring matter from
which it had been prepared is precipitated. When the yellow solution aforesaid is
boiled by itself for some time, the original scarlet azo-coloring matter as such is
precipitated. When a textile fabric is steeped in the yellow solution of the
aforesaid azo-S-color termed Azoarin B S, it is dyed yellow, which shade is
converted into scarlet or violet when treated with steam or with an alkaline agent
or with a nitrite. By impregnating a textile fabric with a paste of the Azoarin B S,
along with an alumina, iron or chromium mordant, it assumes a yellow color.
When the fabric so impregnated is now exposed to the action of steam, the alumina,
iron or chromium oxide lake of the original azo coloring matter is formed upon the
fabric, which will now have the fast color appertaining to the particular lake or
Jelena immuted
In substantially the same manner as that in which the claret azo-coloring matters
described in example 2 are prepared, according to the method taught by Griess and
well known by Chemists, an orange azo-coloring matter, known in commerce
under the name of Orange 2, is obtained by diazotizing sulphanilic acid and
combining the product with Beta-Naphthol. This azo-coloring matter is soluble
in water, forming a reddish brown solution which dyes textile fabrics of an orange
color. Of this substance, in the shape of a powder or of a paste, are taken, say,
14 lbs and thereunto are added, say, 28 lbs of water along with, say, 56 lbs of a
solution of sodium bisulphite, containing about 20 per cent of sulphurous acid.
The whole is raised to a temperature of about 90 to 100 degrees centigrade for
half an hour. After this treatment, the color of the solution is found to have
changed from reddish brown to yellow. The solution is mixed with common salt
and allowed to cool, by which the new azo-S-coloring matter is separated in the
shape of yellow crystals, which are separated from the liquid by filtration. The
azo-S-color so obtained is easily soluble in water with a yellow color. Textile
fabrics steeped in such a solution are dyed yellow. By boiling the azo-S-color
with water, or with a solution of a nitrite, or by treating it with an alkaline
agent, it is decomposed, and the original orange azo-coloring matter or its salt is
formed.
In the above, three typical azo coloring matters and their conversion into their
bisulphite compounds, termed "Azo-S-colors," are described, and the methods are
stated by which these azo-S-colors are made use of in dyeing and printing.
By adopting one of the three methods according to requirement, any azo-coloring
matter capable of forming a bisulphite compound, on being treated with the
bisulphite of an alkali or other base, may be converted into what has been termed
an Azo-S-color suitable for dyeing or printing, substantially in the manner set
forth.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Charles Denton Abel in the Patent Office on the 10th June 1884.
CHARLES DENTON ABEL of N° 28 Southampton Buildings Chancery Lane in the
County of Middlesex "IMPROVEMENTS IN THE MANUFACTURE AND APPLICATION
OF COLORING, MATTERS A communication to me from Abroad by the Farbwerke
vormals Meister Lucius and Brüning of Hoechst-am-Main in the Empire of
Germany, a Company carrying on business as Chemical Manufacturers
"
This invention relates to the conversion of the coloring matters belonging to
the well known series of azo-coloring matters, whether soluble or insoluble in
water, into new compounds soluble in water, by combining such azo coloring
matters with the bisulphites of the alkalies or other bases.
In carrying out this invention, any azo-coloring matter, in the form of a powder
or of a paste, is dissolved or suspended in a suitable solvent, which may be water
in the case of sulphonated azo-colours, that are soluble in water, or may be spirits
of wine, in the case of azo-colors that are insoluble in water, but are soluble in
spirits. To this is added a solution of the bisulphite of an alkali, such as soda,
ammonia or potash or of another base, the bisulphite of which is soluble in the
solvent employed. The mixture may be left standing for a time, but preferably it
is heated on a water or oil bath, and the bisulphite combines with the azo-colouring-
matter, forming bisulphite compounds, which are termed "Azo-S-colors," soluble in
water. In most cases the conversion is complete, but when it is not so, the azo-
S-color can be separated from the unconverted azo coloring matter by taking
advantage of their different degrees of solubility in water and spirits. The azo-
S-colors are easily obtained in crystalline form by cooling their hot aqueous or
alcoholic solutions, or by adding common salt to these solutions.
The crystals of the azo-S-colors vary in color from yellow to red, but all of them
give with water yellow solutions with more or less of a red tint. When an azo-
S-color is steamed or boiled for some time with water, or heated with a solution of
a nitrite, or when it is treated with an alkaline Agent, the bisulphite compound is
decomposed and the original azo-coloring matter from which it had been prepared,
or its salt, is precipitated.
The azo-S-colors are not changed however by the addition in the cold of neutral
metallic salts used as mordants or by acetic and tartaric acid. This property is of
great value in applying the azo-S-colors in dyeing and printing, either with a
mordant when the azo-coloring matter is capable of forming a lake, or without
such & mordant when it possesses no such property.
In order to develop the color in or on a textile fabric, the fabric is impregnated
with the azo-S-color in solution or as a paste, with or without an alumina, iron or
chromium mordant, and the impregnated fabric is then exposed to the action of
heat or of steam or of an alkaline agent, or of a nitrite as may be most suitable for
the particular fabric. By this treatment, the unstable yellow shade imparted to
the fabric by the azo-S-color, is converted into the stable tint of the original
azo-coloring matter, from which the azo-S-color had been prepared, or to the
corresponding salt or lake.
The following are examples of the preparation of azo-S-colors and of their
application in dyeing and printing.
EXAMPLE I
By diazotising alpha-naphthylamine and combining the product with a molecular
quantity of beta-naphthol, according to the method taught by Griess, and well
known to chemists, a claret azo-coloring matter is obtained, which is insoluble in
water but soluble in spirits of wine. To about 14 lbs. of this substance in fine
powder or paste are added about 1 cwt. of spirits of wine, with, say, 28 lbs of a
concentrated solution of ammonium or sodium bisulpbite. The mixture in a closed
vessel or a vessel provided with a reversed cooler, is kept at a temperature of about
100 degrees Centigrade for about 7 hours, and then an equal volume of hot water

page_text: being added, the whole is heated to boiling, and filtered while hot. Upon the
filter is found some of the original claret azo-coloring matter employed, which has
escaped the reaction, and from the hot filtrate, there separate on cooling, red
crystals of the new Azo-S-color. These crystals are removed and the liquid, still
containing azo-S-color, is treated as follows:-
The alcohol is nearly all distilled off, and the residual liquor saturated with
common salt, when the remainder of the azo-S-color is obtained in the shape of
very small crystals. The unchanged portion of the original azo-coloring matter
left on the filter is, by subjecting it to the same treatment as above described,
converted into azo-S-color.
The azo-S-color obtained as before described as a powder or paste is soluble in
water, giving a yellow color. When an alkali is added to this solution or when it
is boiled by itself, or with a solution of a nitrite it is decomposed, and the claret
azo-coloring matter from which it had been prepared, is precipitated. When a
textile fabric is steeped in a solution of the azo-S-color, it is dyed yellow.
By exposing the textile fabric so dyed to the action of steam or of an alkaline
agent or of a hot solution of a nitrite, the yellow color is changed into claret and
the textile fabric has thus a fast claret tint imparted to it.
EXAMPLE II.
In substantially the same way as that in which the claret azo-coloring matter
described in Example I is prepared, according to the method taught by Griess, and
well known to Chemists, a scarlet azo-coloring matter is obtained by diazotising
dichlorortho-amidophenol, and combining the product with ethylbetanaphthol.
This azo-coloring matter is insoluble in water, but soluble in spirits of wine. It
possesses the property of forming violet salts with alkaline bases, and different
colored lakes with alumina, iron and chromium oxides. Of this substance in the
shape of a powder or of a paste, say 14 lbs are added to say 1 cwt. of spirits of
wine along with, say, 28 lbs of a concentrated solution of ammonium or sodium
bisulphite. The mixture is now kept at a temperature of about 100 degrees
centigrade in a closed vessel, or in a vessel with a reversed cooler for say two hours,
stirring all the time, after which treatment, the whole of the scarlet azo-coloring
matter is found converted into its orange colored bisulphite compound. The
alcohol is now distilled off and the residual crystalline paste is allowed to cool.
The crystals are separated from the suspending liquid by filtration, and now
represent the azo-S-color ready for use, either in the shape of a powder, or of a
paste, or in solution.
The azo-S color thus obtained is termed "Azoarin B S." It is soluble in hot
water, producing a yellow color. When an alkali is added to this yellow solution
or when it is boiled with a nitrite, the azo-S-color, termed "Azoarin B S," is
decomposed, and the violet colored salt of the scarlet azo-coloring matter from
which it had been prepared, is precipitated. When the yellow solution aforesaid
is boiled by itself for some time, the original scarlet azo-coloring matter, as such,
is precipitated. When a textile fabric is steeped in the yellow solution of the
aforesaid azo-S-color, termed azoarin B. S, it is dyed yellow, which shade is
converted into scarlet or violet when treated with steam or with an alkaline agent
or with a nitrite. By impregnating a textile fabric with a paste of the
Azoarin B. S, along with an alumina, iron or chromium mordant, it assumes a
yellow color. When the fabric so impregnated is now exposed to the action of
steam, the alumina, iron or chromium oxide lake of the original azo coloring matter
so formed upon the fabric, which will now have the fast color appertaining to the
particular lake or lakes imparted to it.

page_text: "
are prepared, according to the method taught by Griess and well known by
Chemists, an orange azo-coloring-matter, known in commerce under the name of
'Orange 2" is obtained by diazotising sulphanilic acid and combining the product
with Beta Naphthol. This azo-coloring matter is soluble in water, forming a
reddish brown solution which dyes textile fabrics of an orange color. Of this
substance in the shape of a powder or of a paste, are taken, say, 14 lbs, and thereunto
are added, say, 28 lbs of water along with say, 56 lbs of a solution of sodium
bisulphite, containing about 20 per cent of sulphurous acid. The whole is raised
to a temperature of about 100 degrees Centigrade for half an hour. After this
treatment the color of the solution is found to have changed from reddish brown
to yellow. The solution is mixed with common salt and allowed to cool, by which
the new Azo-S-coloring matter is separated in the shape of yellow crystals, which
are separated from the liquid by filtration. The azo-S-color so obtained easily
soluble in water with a yellow color. Textile fabrics steeped in such a solution
are dyed yellow. By boiling the azo-S-color with water, or with a solution of a
nitrite, or by treating it with an alkaline agent, it is decomposed, and the original
orange azo-coloring matter or its salt is formed. In the above three typical azo-
coloring matters and their conversion into their bisulphite compounds, termed
'Azo-S-colors," are described and the methods are stated by which these
Azo-S-colors are made use of in dyeing and printing.
"
By adopting one of the three methods according to the requirement any
azo-coloring matter being capable of forming a bisulphite compound on being
treated with the bisulphite of an alkali or other base, may be converted into what
has been termed an azo S color suitable for dyeing or printing, substantially in
the manner set forth.
เ
Having thus described the nature of this invention and in what manner the
same is to be performed, as communicated to me by my foreign correspondents,
. I claim:-
First, The manufacture of Azo-S-coloring matters, that is to say, Azo coloring
matters converted into bisulphite compounds, substantially as herein described.
Second. The within described processes for the conversion of any coloring
matter belonging to the well known series of azo-coloring matters, being capable
of forming a bisulphite compound, into what is termed an azo-S color, soluble in
water, by reacting on such azo-coloring matter with the solution of the bisulphite
of an alkali or other base in the presence of water or of alcohol or of any other
solvent medium which can supply their place.
Third. The within described processes for developing azo-coloring matters in or
upon textile fabrics, by impregnating such fabrics with azo-S-colors and then
exposing the fabric so impregnated to the action of heat, preferably of steam, or
to the action of an alkaline or basic agent or to the action of the solution of a
nitrite.
Fourth. The within described processes for developing the lake of an azo-
coloring matter in or upon a textile fabric, by impregnating the said fabric with
azo-S-colors capable of forming lakes together with such salts of aluminium, iron
or chromium, as are used as mordants, and then exposing the fabric so impregnated
to the action of steam or of any other known agent which causes the Azo-S-color
to decompose.
In Witness whereof I the said Charles Denton Abel have hereunto set my
hand and seal this tenth day of June in the year of our Lord One thousand eight
hundred and eighty-four