Improvements in the Manufacture of Colouring Matters.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
We, the Firm of LEPETIT DOLLFUS & GANSSER, of 13, Fatebenefratelli, Milan,
in the Kingdom of Italy, Manufacturers of Dye Stuffs, do hereby declare the
nature of this invention to be as follows:-
Since the discovery of Cachou de Laval by Croissant and Bretonniere obtained
by heating saw dust, turf, faeces in a word residues of organic substances belong-
ing to the fatty series, with sulphides of soda, (and after the first Patent of R.
Vidal, viz. French Patent No. 231,188 dated July 1st 1893.) only aromatical com-
pounds have been submitted to the reaction with sulphides of alkalis excepting
however, nitrocellulose mentioned in a patent of the Vidal fixed aniline
dyes German Patent No. 103302.
In the course of their studies relating to the action of sulphide of soda on
organic. substances, the communicators have found that compounds of the fatty
series and particularly fats, oils and their derivatives are adapted for the pro-
duction of dyestuffs of great intensity dyeing cotton or vegetable fibres without
mordants and which are quite different from Cachou de Laval by reason of their
greater dyeing power as well as their reactions.
The shades obtained on cotton by means of these new dyestuffs are somewhat
uniform, varying from brown to a brownish-black or black. The various oils or
greases or derivatives of the same do not give dyestuffs of the same value, that is
these dyestuffs, although giving analogous shades, differ in their greater or less
dyeing power. The shades on cotton are very fast to diluted alkalis and acids, to
boiling soap solutions and do not bleed on white cotton; they are of a good fas'
ness to light.
As derivatives of the fatty series we include the oils and greases, the fatty
acids, the oxy-acids of the same series and their salts, the oils made more or less
soluble by sulphuric acid, (generally known under the name of Turkey red oils).
the derivatives obtained by the action of nitrosyle chloride or nitrous acid on cer-
tain oil or fatty acids as elidine, azelain, elaidates and the like, tho sulphur
derivatives, the chlorinated compounds, their salts, ethers and the aldehydes cor-
responding to acids of the fatty series.
Instead of sulphides of soda or potash. mixtures may be used which are able
to yield alkali sulphides by heating. We have made the surprising discovery
that sometimes the best results are obtained by using a mixture of carbonate of

page_text: soda and sulphur instead of sodium sulphides or instead of mixtures of caustic
soda and sulphur.
The new dyestuffs obtained with the herein before mentioned substances are
amorphous, like dusty coke, easily soluble in water. The presence of sodium
monosulphide increases the solubility. The aqueous solutions have a colour vary-
ing from bottle-green to a bright green, green-blue or even blue, in every case
they dye cotton brown, brownish black or black in the presence of common salt.
The new dyestuffs differ from Cachou de Laval in the following respects.
1st. They have a greater dyeing power, they dye to a shade twice as dark as
Cachou de Laval on cotton, using the same weight of both.
2nd. They are not so fast as Cachou de Laval to light and to the action of
chlorine or bleaching power.
3rd. Whilst Cachou de Laval shades obtained by direct dyeing, treated with
oxydizing agents as diluted solutions of basic ferric sulphate (nitrate of iron),
nitrous acid, red prussiate of soda, bichromate of soda and acid, only undergo
little change, the direct brown black shades on cotton obtained by the new-dye-
stuffs prepared with the herein mentioned bodies from the fatty series are turned
into a nice red-brown or yellow brown very similar to the shades dyed by means
of cutch and bichromates.
We must insist on the fact that little modifications in the modus operandi of
manufacturing the new dyestuffs, such as small variations of temperature, pro-
portions of the mixture, of time of heating, etc. often cause great differences in
the properties of the dyestuffs.
According to what has been stated above it is difficult to formulate a deter-
mined receipt in order to prepare the direct dyestuffs of the present specification
by heating the mentioned fatty substances with sulphide of soda or sulphur and
alkali we give then a table indicating in a general way the proportions to be
used for some fatty bodies or derivatives of the same, but we wish to remark
that the figures given may be varied within rather wide limits.

page_text: 100° C. and afterwards the carbonate of soda and operate as described above, heat-
ing at least to 330° C. during 8-10 hours.
Dated this 19th day of September 1899.
HASELTINE, LAKE, & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicants.
Improvements in the Manufacture of Colouring Matters.
We, the Firm of LEPETIT DOLLFUS & GANSSER, of 13, Fatebenefratelli, Milan,
in the Kingdom of Italy, Manufacturers of Dye Stuffs, 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: —
Since the discovery of Cachou de Laval by Croissant and Bretonniere obtained
by heating saw dust, turf, faeces, in a word residues of organic substances belong-
ing to the fatty series, with sulphides of soda, (and after the first Patent of R.
Vidal, viz. French Patent No. 231,188 dated July 1st 1893) only aromatic com-
pounds have been submitted to the reaction with sulphides of alkalis excepting
however nitrocellulose mentioned in the Specification of the Vidal fixed aniline
dyes German Patent No. 103302.
In the course of their studies relating to the action of sulphide of soda on
organic substances, the communicators have found that compounds of the fatty
series and particularly fats, oils and their derivatives are adapted for the pro-
duction of dyestuffs of great intensity dyeing cotton or vegetable fibres without
mordants and which are quite different from Cachou de Laval by reason of their
greater dyeing power as well as their reactions.
The shades obtained on cotton by means of these new dyestuffs are somewhat
uniform, varying from brown to a brownish-black or black. The various oils or
greases or derivatives of the same do not give dyestuffs of the same value, that is
these dyestuffs, although giving analogous shades, differ in their greater or less
dyeing power. The shades on cotton are very fast to diluted alkalis and acids, to
boiling soap solutions and do not bleed on white cotton; they are of a good fast
ness to light.
As derivatives of the fatty series we include the oils and greases, the fatty
acids, the oxy-acids of the same series and their salts, the oils made more or less
soluble by sulphuric acid, (generally known under the name of Turkey red oils),
the derivatives obtained by the action of nitrosyle chloride or nitrous acid on cer-
tain oil or fatty acids as elidine, azelain, elaidates and the like, the sulphur
derivatives, the chlorinated compounds, their salts, ethers and the aldehydes cor-
responding to acids of the fatty series.
Instead of sulphides of soda or potash, mixtures may be used which are able
to yield alkali sulphides by heating. We have made the surprising discovery
that sometimes the best results are obtained by using a mixture of carbonate of
soda and sulphur instead of sodium sulphides or instead of mixtures of caustic
soda and sulphur.
The new dyestuffs obtained with the herein before mentioned substances are
amorphous, like dusty coke, easily soluble in water. The presence of sodium
monosulphide increases the solubility. The aqueous solutions have a colour vary-
ing from bottle-green to a bright green, green-blue or even blue, in every case
they dye cotton brown brownish black or black in the presence of common salt.
The new dyestuffs differ from Cachou de Laval in the following respects.

page_text: 1st. They have a greater dyeing power, they dye to a shade twice as dark as
Cachou de Laval on cotton, using the same weight of both.
2nd. They are not so fast as Cachou de Laval to light and to the action of
chlorine or bleaching power.
3rd. Whilst Cachou de Laval shades obtained by direct dyeing, treated with
oxvdizing agents as diluted solutions of basic ferric sulphate (nitrate of iron),
nitrous acid, red prussiate of soda, bichromate of soda and acid, only undergo
little change, the direct brown black shades on cotton obtained by the new-dye-
stuffs prepared with the herein mentioned bodies from the fatty series are turned
into a nice red-brown or yellow brown very similar to the shades dyed by means
of cutch and bichromates.
It should be distinctly understood that little modifications in the modus
operandi of manufacturing the new dyestuffs, such as small variations of tempera-
tures, proportions of the mixture, of time of heating, etc. often cause great differ-
ences in the properties of the dyestuffs.
According to the above statements it is difficult to formulate a deter-
mined receipt in order to prepare the direct dyestuffs of the present specification
by heating the mentioned fatty substances with sulphide of soda or sulphur and
alkali we give then a table indicating in a general way the proportions to be
used for some fatty bodies or derivatives of the same, but we wish to remark
that the figures given may be varied within rather wide limits.

page_text: 2. The herein described process for the manufacture of dyestuffs for dyeing
cotton direct, by heating gradually at temperatures varying from 100-350° C.,
sulphides of sodium or potassium, or caustic soda or potash and sulphur with oils
and greases, acids and oxv-acids of the fatty series, their salts, ethers and the deri-
vatives of the same as such obtained by a treatment with sulphur, hydrogen sul-
phide, sulphuric acid, nitrous acid, chlorine, nitrosyle chloride.
3. The process which consists in heating mixtures capable of yielding sulphides
of sodium or potassium at high temperatures, as for instance carbonate or bicar-
bonate of soda or potash and sulphur with the herein before mentioned deriva-
tives of the fatty series.
4. As new products of manufacture, the new dyestuff's dyeing cotton directly and
giving shades varying from brown to black, produced by the processes herein
before specified or by any other means affording the same result.
Datod this 10th day of June 1900
HASELTINE, LAKE, & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicants.