A Method for Dyeing Half Wool with Basic 'Azodyestuffs in an Acid Bath
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
"A Method for Dyeing Half Wool with Basic 'Azodyestuffs in an
Acid Bath."
I, OLIVER IMRAY, of No. 28. Southampton Buildings, Chancery Lane, in the County
of London, Chartered Patent Agent, do hereby declare the nature of this invention
(as communicated to me from abroad by The Farbwerke vormals Meister Lucius and
Brüning, of Hoechst a/Main, Germany, Chemical Manufacturers,) to be as follows:-
The simultaneous working of wool and cotton are of great importance in the
manufacture of spun and woven goods of all kinds. Dyers accordingly have endea-
voured to find suitable methods for the equal dyeing of those two fibres, that is to say,
to improve the present system.
These efforts, however have not been thoroughly successful, the present methods
being very deficient.
Two methods are now mostly employed in dyeing half wool. The one consists, in
first dying the wool with acid dyestuffs in an acid bath, secondly, in mordanting the
cotton in cold baths containing tannin, thirdly in fixing the absorbed tannin, by
passing the material through fixing baths, (mostly antimonial or ferruginous) and
finally in dyeing the cotton thus previously mordanted with basic dyestuffs in a fourth
bath to the desired shade.
This method is cumbersome and uncertain on account of its many operations
and the difficulty of producing in two dyefluids the shade desired on wool and
cotton.
When the coal-tar industry put on the market the tetrazo dyestuffs derived from
para-diamines, the second important method for dyeing half wool was found and
applied.
The said diaminedyestuffs possess, as is known, the property of dyeing wool as well
as cotton in neutral or weak alkaline baths.
By a proper choice of dyestuffs, an appropriate regulation of the temperature when
dyeing and the addition of quantities of more or less alkaline salts, it is possible to
produce the most varied shades on half wool in an acid bath. This method is popular
on account of its simplicity, but it has one great drawback, namely, that the quality
of the goods suffers enormously as the fibre of the wool boiled in neutral or mostly
alkaline baths loses its most valuable properties.
This disadvantage is so great, that in the case of many articles and after vain
efforts with this single bath method, half wool dyers have returned to the old and
more troublesome system.

page_text: My foreign correspondents have succeeded in finding a method for dyeing half
wool, combining the advantages of the single bath method with the complete preser-
vation of the properties of the valuable wool material, thus proving it to be an
essential technical progress in the half wool industry.
They have found, that such strongly basic disazo dyestuffs, resulting from the
linking of at least 3 aromatic residues and containing as a component an aromatic
ammonium base or amido-benzylamine or their derivatives, as also basic safranine azo
dyestuffs, are easily fixed on half wool in an acid bath, preferably in a sulphuric acid
bath, dyeing cotton and wool equally. The simple azo dyestuffs produced from an
aromatic ammonium base or amidobenzylamine or their derivatives, do not possess
this property which is first obtained by the joining of a second residue combined
with an azo group, yet the strongly basic character of the dyestuff must be retained,
as the presence of acid groups reduces the affinity of the fibre and sulpho groups
mostly neutralizing the same.
The following dyestuffs have been found suitable for the above purpose.
1) The disazo dyestuffs having as first component an ammonium base
(trialkyl-my p-amidophenylammonium, p-methyl-o-amidophenyl-trialkylammonium,
trialkyl-o-and-p-amidobenzylaminonium) or dialkyl-o-and p-amidobenzylamine, and
&S component in middle position a-naphthylamine, p-xylidine, symmetrical
m-xylidine, m-toluidine, m-chloraniline o-chloro-m-toluidine, o-anisidine, o-amido-
p-cresol methylether, a-amido-ẞ-naphtholether and as component in final position
dimethyl-and diethyl-m-amido-phenol, phenylene- and toluylenediamine, chrysoïdine,
resorcinol, B-naphthol, phenyl and tolyl-ẞ-naphthylamine amidonaphthols,
pyrazolones, besides
2) those secondary basic disazodyestuffs, which are obtained by the action of one
molecul each of two different diazocompounds (of which one must be the diazo-
compound of an ammonium base or of a dialkyl-benzylamine, the other for instance
may be acetyl-p-phenylenediamine, m- and p-nitraniline, a-naphthylamine, aniline
etc.) to 1 inolecule of double combining phenols, amido-phenols or diamine, such as
resorcinol, dialkyl-in-amidophenol, m-phenylenediamine.
3) These disazodyestuffs, obtained by the action of the diazocompound of an
amidoazobody upon 2.7 oxynaphthalinetrialkylammonium.
4) The basic safranineazodyestuffs obtained by the action of diazosafranines or
diazoalkylsafranines upon phenols, amidophenols, naphthols dioxynaphthalines,
ainidonapthols, amidouaphthol ethers, amines or diamines.
For the dyeing of half wool, the bath is filled with 2 per cent of sulphuric acid
relatively to the weight of the goods, with the carefully prépared solution of the
above mentioned dyestuff in the quantity suitable to the required shade, as well as
'with 5 to 20 per cent of Glauber's salt, the previously cleaned and wetted material
is introduced into the bath at 40° to 50° C., which is then brought to boiling, whilst
being correspondingly worked, the boiling to continue for 1 hour.
The material is slightly washed, in case of dark colours with argillaceous or Fuller's
earth and dressed in the usual manner.
Instead of sulphuric acid, hydrochloride of sulphate of sodium may be employed,
if the wool is intended to be much lighter than the cotton, then the sulphuric acid is
partly or wholly substituted by oxalic acid.
The fixing on the fibre is increased by additions of neutral salts, such as Glauber's
and cominon salt.
Other acids, as hydrochloric or acetic acid as well as acid salts, alum, tartar may
be used, giving similar yet not quite so good results as sulphuric acid. The
after-shading of wool and cotton may be done in the boiling bath with the said basic
azo dyestuffs and such other dyestuffs as do not give with the former any insoluble
precipitates.
This method permits a short, easy and sure working as well as the exact point of
the intended shades; the boiling in an acid bath preserves the natural feel, gloss
and solidity of the wool and improves thereby the half wool material to be dyed.

page_text: 40
"
" "
green B.
uyestun
thyl-aniline.
400
"
sulphuric acid at 60° Bé.
The previously dressed and wetted material is introduced at 50° C brought to boil
within hour and kept at this temperature for a further hour; then the steam is
stopped and the dyeing is continued till all the cotton, as is required with these
goods, takes a darker hue than the wool; thereupon the pieces are taken out, washed
slung, slightly dressed with gelatine, dried and pressed.
II. GRAY UPON 9 KILOS 1 PIECE 45 METRES HALF WOOL ZANELLA.
The bath is prepared with :-
45 grammies half wool yellow A.
27
"
"
"
50
9
"
"
وو
وو
red M.T.
dyestuff from
trimethyl-m-amido-phenyl-
ammonium y m-nitrobenzene azo resor-
cinol.
[dyestuff from trimethyl-m-amidophenyl-
1 ammonium + m-toluidine + ẞ-naphthol.
green B [dyestuff from diazo-diethyl safranine and
dimethyl aniline.
blue R
"
22
dyestuff from diazo-safranine + ẞ-naphthol.
900 grammes Glauber's salt and 180 grammes sulphuric acid. The previously
dressed material is introduced at 50° C, brought to boil within hour and kept at
this temperature till the cotton be sufficiently dyed, completing the dyeing process
by another half hour's boil.
III. BROWN UPON 9 KILOS 1 PIECE 45 METRES HALF WOOL ZANELLA.
The bath is prepared with :-
215 grammnes half wool brown A (dyestuff from trimethyl-m-amido phenyl-
ammonium a-naphthylamine y chrysoïdine.
flyestuff from diazo diethyl-safranine and di-
methyl-aniline.
67
39
"
"
green B
20
دو
"
"
13
"
"
9
"
900
"
180
"
"
دو
59
red M.T. (dyestuff from trimethyl-m-amido phenyl am-
monium m-toluidine y -8-naphthol.
dyestuff from trimethyl-m-amido phenyl
m-nitrobenzene azo-resor-
ammonium
yellow A.
blue K
Glauber's salt and
sulphuric acid.
at 50°C, brought to 85° C within
cinol.
Y
dyestuff from diazo-safranine + B-naphthol.
The previously dressed material is introduced
hour and kept at this temperature at this

page_text: temperature till the cotton is sufficiently dyed, completing this dyeing process by a
further bour's boil.
IV. COPPER COLOUR UPON 50 KILOS VIGOGNE YARN
The bath is prepared with:
1.250 Kilos half wool brown R
{
5 Kilos Glauber's salt and
sulphuric acid of 66° Bé.
"
duced at 50° C, brought to boil within
50 PER CENT WOOL
50 PER CENT COTTON
azo dyestuff from trimethyl-m-amido phenyl
ammonium, m-toluidine and chrysoïdine.
The previously well washed yarn is intro-
hour and dyed for of an hour, whilst being
well worked.
228
COMI LEID
SPECIFICATION.
"A Method for Dyeing Half Wool with Basic Azodyestuffs in an
Acid Bath."
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (which has been communicated to me from abroad by The Farbwerke
vormals Meister Lucius and Brüning, of Hoechst a/Main, Germany, Chemical
Manufacturers) and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement :-
The simultaneous working of wool and cotton are of great importance in the
manufacture of spun and woven goods of all kinds. Dyers accordingly have
endeavoured to find suitable methods for the equal dyeing of those two fibres, that is
to say, to improve the present system.
These efforts, however have not been thoroughly successful, the present methods
being very deficient:
Two methods are now mostly employed in dyeing half wool. The one consists, in
first dying the wool with acid dyestuffs in an acid bath, secondly, in mordanting the
cotton in cold baths containing tannin, thirdly in fixing the absorbed tannin by
passing the material through fixing baths (mostly antimonial or ferruginous) and
finally in dyeing the cotton thus previously mordanted with basic dyestuffs in a fourth
bath to the desired shade..
This method is cumbersome and uncertain on account of its many operations and
the difficulty of producing in two dye-fluids the shade desired on wool and cotton.
When the coal-tar industry put on the market tetrazo dyestuffs derived from para-
diamines, the second important method for dying half wool was formed and applied.
The said diamine dyestuffs possess as is known, the property of dyeing wool as well
as cotton in neutral or weak alkaline baths.
By a proper choice of dyestuffs, an appropriate regulation of the temperature when
dyeing and the addition of quantities of more or less alkaline salts, it is possible to
produce the most varied shades on half wool in a single bath. This method is popular
on account of its simplicity, but it has one great drawback, namely, that the quality
of the goods suffers enormously as the fibre of the wool boiled in neutral or mostly
alkaline baths loses its most valuable properties.

page_text: This disadvantage is so great, that in the case of many articles and after vain
efforts with this single bath method, half wool dyers have returned to the old and
more troublesome system.
My foreign correspondents have succeeded in finding a method for dyeing half
wool, combining the advantages of the single bath method with the complete
preservation of the properties of the valuable wool material, thus proving to be an
essential technical progress in the half wool industry.
They have found, that such strongly basic disazo dyestuffs, resulting from the
linking of at least 3 aromatic residues and containing as a component an aromatic
ammonium base or amido-benzylamine or their derivatives, as also basic safranine azo
dyestuffs, are easily fixed on half wool in an acid bath, preferably in a sulphuric acid
bath, dyeing cotton and wool equally. The simple azo dyestuffs produced from an
aromatic ammonuim base or amidobenzyl-amine or their derivatives, do not possess
this property which is first obtained by the joining of a second residue combined
with an
azo group, yet the strongly basic character of the dyestuff must be
retained, as the presence of acid groups reduces the affinity of the fibre and sulpho
groups mostly neutralizing the same.
The following dyestuffs have been found suitable for the above purpose.
1) The disazo dyestuffs having as first component an ammonium base
(trialkyl-my p-amido-phenylammonium, p-methyl-o-amidophenyl-trialkylammonium,
trialkyl-o-and p-amidobenzylammonium) or dialkyl-o-and-p-amidobenzylamine, and
as component in middle position a-naphthylamine, p-xylidine, symmetrical
m-xylidine, m-toluidine, mn-chloraniline o-chloro-m-toluidine, o-anisidine, o-amido-p-
cresolmethylether, a-amido-6-naphtholether and as component in final position
dimethyl-and diethyl-m-amido-phenol, phenylene-and toluylene-diamine, chrysoidine,
resorcinol, B-naphthol, phenyl and tolyl-B-naphthylamine amidonaphthols,.
pyrazolones, besides
2) those secondary basic disazodyestuffs, which are obtained by the action of one
molecule each of 2 different diazo-compounds (of which one must be the diazo-
compound of an ammonium base or of a dialkyl-benzylamine, the other for instance
may be acetyl-p-phenylenediamine, ni-and p-nitraniline, a-naphthylaminé, 'aniline,
etc.) to 1 molecule of double co bining phenols, amido-phenols or diamine, such as
resorcinol, dialkyl-m-amidophenol, m-phenylenediamine.
3) These disazo-dyestuffs, obtained by the action of the diazo-compound of an
amido-azo body upon 2-7 oxynaphthaline trialky lammonium.
4) The basic safranine-azo-dyestuffs obtained by the action of diazosafranines or
diazoalkylsafranines upon phenols, amidophenols, naphthols dioxynaphthalines,
amidonaphthols, amidonaphthol ethers, amines or diamines.
For the dyeing of half wool. the bath is prepared with 2 percent. of sulphuric
acid relatively to the weight of the goods, with the carefully prepared solution of
the above mentioned dyestuff in the quantity suitable to the required shade, as well
as with 5 to 20 per cent. of Glauber's salt, the previously cleaned and wetted material
is introduced into the bath at 40° to 50° C.; which is then brought to boiling, whilst
being correspondingly worked, the boiling to continue for 1 hour.
The material is slightly washed, in case of dark colours with argillaceous or Fuller's
earth and dressed in the usual manner.
Instead of sulphuric acid, bisulphate of soda may be employed. If the wool is
intended to be much lighter than the cotton, then oxalic acid is substituted for part
or all the sulphuric acid.
The attraction for wool is increased by additions of neutral salts, such as Glauber's
and common salt.
Other acids as hydrochloric, acetic, tartaric, ethyl tartaric, lactic acids, also.acid-
salts such as alum, cream of tartar, etc. may be used and give results similar to those
obtained by sulphuric and oxalic acid. If necessary these basic azo colours can be
combined with basic or acid colours. In that case no silts are employed and only
organic acids, especially oxalic and acetic acid are used. The bath is advantageously
first prepared with the acid colours and the goods worked at the boil. Then the

page_text: basic azo colours are added to the bath and the dyeing is executed at about 70° C.
By working in this manner the basic azo colours, above mentioned, dye almost
exclusively the cotton. Therefore, by combining acid colours with basic azo colours
of similar or the same shade, uniform dyes are obtained, whereas a combination of
contrasting shades produces so called cross-dyed effects upon the wool and cotton
fibre.
This mode of working permits of a short, easy and sure dyeing to shade; the dyeing
in an acid bath preserves the natural feel, gloss and solidity of the wool and improves
thereby the half wool material to be dyed.
The process may be.illustrated by the following example

page_text: 13 grammes of the { dyestuff from trimethyl-m-amidophenylammonium and
m-nitrobenzene azo-resorcinol.
The previously dressed material is introduced at 50° C., brought to 85° C. within
hour and kept at this temperature till the cotton is sufficiently dyed, this dyeing
process being completed by a further hour's boil.
IV. COPPER COLOUR UPON 50 KILOS VIGOGNE YARN
50% COTTON
The bath is prepared with 600 litres of water; the carbonates contained therein
are neutralized by oxalic acid and 2 kilos acetic acid, 100 gramines Patent-blue V.
and 60 grammes naphthol-yellow S. are added to it. The goods are introduced
at 60° C., after having been properly prepared and the temperature is gradually
raised to the boil. After boiling 45 minutes to 1 hour the goods run for a certain
time without steam in order to cool down the hath to about 70°. Then 100 grammes
of trimethyl-m-amido-phenylammonium +in-toluidine + B-naphthol carefully
dissolved, are added and the dyeing is proceeded with at this temperature of 70° C.
for about I hour. By using the baths repeatedly 10% acetic acid are added first and
the new lot of pieces run in the old liquid for 15 minutes at 70° without
any addition of colouring matter in order to exhaust the trimethyl-m-amido-
phenylammonium + m-toluidine + B-naphthol, which was left over in the bath from
the first lot. Then the acid colour is added and the pieces are worked again as
described above.
VI. NAVY-BLUE ON 2 PIECES = 20 KILOS UNION CLOTH.
The bath is prepared with about 600 litres of water and the carbonates contained
therein are neutralised first with oxalic acid.
2 kilos of acetic acid, 150 grammes of Victoria Violet 4 B.S. and 60 grammes of
Patent-blue are added to the bath. The goods are introduced at 60° C., after having
been properly prepared and the temperature is gradually raised to the boil.
After boiling for to 1 hour the goods run for a certain time without steam in
order to cool down the bath to about 70° C. Then 200 grammes of diazo
safranine 8-naphthol and 200 grammes of diazo-safranine and phenylenediamine,
carefully dissolved, are added and dyeing is proceeded with at 70° C. for about 1
hour.
The goods are slightly washed in cold water and treated afterwards in a jigger
or padding machine with 400 grammes of tannin, 400 gramines of sulphuric acid
and 200 grammes of tartar emetic in the cold.
If the baths are used again, the description given in Example 5 applies also in this
case.

page_text: 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 :-
A method for dyeing half wool in spun goods or woven fabrics with basic
azo dyestuffs in a single bath by the addition of acids or acid salts with basic
polyazodyestuffs having as component an aromatic ammonium base or amido-
benzylamine or its derivatives or such basic azo dyestuffs as are obtained by the
action of diazosafranines or diazo-alkylsafranines upon phenols, amidophenols,
naphthols, dioxynaphthalines, amidonaphthols, amidonapatholether, amines or
diamines, substantially as described.