Improvements in the Manufacture of Colouring Matters.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
I, HENRI RAYMOND VIDAL, of 95, Boulevard Beaumarchais, Paris, in the
Republic of France, Chemical Engineer, do hereby declare the nature of this
invention to be as follows:-
In the Specification of my previous Patent No. 19880 dated July 1, 1890 I
described the formation of direct cotton-colouring agents obtained by the treat-
ment with toluquinone or hydrotoluquinone of ammonia in the presence of
sulphur alone or of sulphur and alkaline sulphides.
I subsequently found, that these identical colouring agents which originated
(before) in the conversion of toluquinone into amido-cresols, 1, 2, 5 and 1, 3, 6,-
by reason of the transformation of a hydroxyl group, being in the ortho or
meta position in relation to the methyl group,-may be obtained more readily
by starting with benzol ozo-cresols obtained from ortho or meta cresol.
Thus I heat
30 kilogrammes of benzol-azo-ortho-cresol
40 kilogrammes of soda and
8 kilogrammes of sulphur in a pan or digester in an oil bath, stirring the
mixture as it is heated, and generally raising the temperature to 180° Centi-
grade and, after distillation with aniline, to 240° Centigrade.
The heating is continued for from 6 to 8 hours.
For the benzol-azo-ortho-cresol 1 may substitute benzol-azo-meta-cresol in the
formula of the reaction which has been given; or a mixture of benzol-azo-ortho-
cresol and benzol-azo-meta-cresol, resulting from the action of di-azo-benzol upon
commercial cresol--which may or may not be freed from para-cresol,-may be
employed.
The products obtained show the following characteristics:-
(1) The derivative from the benzol-azo-ortho-cresol takes the shape of a black
brittle substance, which becomes blue-black on being dissolved in water and,
under the action of acids, yields up a liberal amount of a black precipitate
soluble in alkaline sulphides and taking, when dissolved therein, a blackish
brown colour, while, when it is dissolved in alkaline meta-bi-sulphites, in an
acid medium, it turns a dirty yellow. It dyes direct a deep black: in the first
mentioned medium, vegetable fibre; in the second, animal fibre; without
necessitating any oxidation.
These dyes resist air, light and the various chemicals.
(2) The derivative from benzol-azo-meta-cresol is in the form of a deep-black
brittle substance, soluble in water, when it turns a blackish yellow, and precipi-
tating under the action of acids.
The precipitated product is soluble in alkaline sulphides and in solutions of
meta bi-sulphite of soda and potash. It dyes direct; in the former case, vege-
table fibre in the latter, animal fibre.

page_text: the benzol-azo-ortho-cresol black is soluble in water, when it becomes blue black,
and will dye vegetable fibre some very rich black shades; while the benzol-azo-
meta-cresol black, when dissolved in water, turns a dirty yellow and dyes vege-
table fibre very rich blue shades.
As compared with the hydroquinone black described in the Specification of
prior Patent No. 19880 of July 1, 1893 my new black dyes are distinguishable
by the fact that, when dissolved, they assume blue-black and blackish-yellow
shades and, in the dyeing bath, from the very outset impart to cotton a solid
black colour. They consequently necessitate no oxidation and no fixing and
dye in a perfectly uniform manner; whereas the black dyes obtained from
hydroquinone, and by the analogous improvements and processes described in the
Specification of Patents 23578 of 1893 and 9443 of 1894, will dissolve into
bottle" green and impart a green colour to vegetable fibre; they only dye
black when subsequently subjected to oxidation. Moreover these blacks do not
dye in such a perfectly uniform manner.
Dated this 10th day of December 1898
Dated this 10th day of December 1898.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.
Improvements in the Manufacture of Colouring Matters.
I, HENRI RAYMOND VIDAL, of 95, Boulevard Beaumarchais, Paris, in the
Republic of France, Chemical Engineer, 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 my previous Patent No. 19880 dated July 1, 1893 I
described the formation of direct cotton-colouring agents obtained by the treat-
ment with toluquinone or hydrotoluquinone of ammonia in the presence of
sulphur alone or of sulphur and alkaline sulphides.
I subsequently found, that these identical colouring agents which originated
(before) in the conversion of toluquinone into amido-cresols, 1, 2, 5 and 1, 3, 6,-
by reason of the transformation of a hydroxyl group, being in the ortho or
metha position in relation to the methyl group, may be obtained more readily
by starting with benzol azo-cresols obtained from ortho or meta cresol.
Thus I heat 30 kilogs. of benzol-azo-ortho-cresol 40 kilogs. of soda and
8 kilogs. of sulphur in a pan or digester, in an oil bath, stirring the mixture
as it is heated, and gradually raising the temperature to 180° Centigrade and,
after distillation of the aniline produced to 240° Centigrade.
The heating is continued for from 6 to 8 hours.
For the benzol-azo-ortho-cresol I may substitute benzol-azo-meta-cresol in the
formula of the reaction which has been given; or I may substitute therefor a
mixture of benzol-azo-ortho-cresol and benzol-azo-meta-cresol, obtained from the
action of di-azo-benzol upon commercial cresol, which may or may not have
been freed of its para-cresol.
The products obtained show the following characteristics:-
(1) The derivative from the benzol-azo-ortho-cresol takes the shape of a black
brittle substance, which becomes blue-black on being dissolved in water and,
under the action of acids, yields up a liberal amount of a black precipitate
soluble in alkaline sulphides and taking, when dissolved therein, a blackish
brown colour, while, when it is dissolved in alkaline meta-bi-sulphites, in an
acid medium, it turns a dirty yellow. It dyes direct a deep black in the first-

page_text: mentioned medium, vegetable fibre; in the second, animal fibre; without
necessitating any oxidation.
These dyes resist air, light and the various chemicals.
(2) The derivative from benzol azo meta cresol is in the form of a deep-black
brittle substance, soluble in water, when it turns a blackish yellow, and precipi-
tating under the action of acids.
The precipitated product is soluble in alkaline sulphides and in solutions of
meta bi-sulphite of soda and potash. It dyes direct: in the former case, vege-
table fibre; in the latter, animal fibre.
These two black dyes differ from each other in the following characteristics:
the benzol-azo ortho cresol black is soluble in water, when it becomes blue black,
and will dye vegetable fibre some very rich black shades; while the benzol-azo-
meta-cresol black, when dissolved in water, turns a dirty yellow and dyes vege-
table fibre very rich blue shades.
As compared with the hydroquinone black described in the Specification of my
prior Patent No. 19880 of July 1, 1893 these new black dyes are distinguishable
by the fact that, when dissolved, they assume blue-black and blackish-yellow
shades and, in the dyeing bath, from the very outset impart to cotton a solid
black colour. They consequently necessitate no oxidation and no fixing and
dye in a perfectly uniform manner; whereas the black dyes obtained from
hydroquinone, and by the analogous improvements and processes described in the
Specifications of Patents 23578 of 1893 and 9443 of 1894, will dissolve into
"bottle" green and impart a green colour to vegetable fibre: they only dye
black when subsequently subjected to oxidation. Moreover, these blacks do not
dye in such a perfectly uniform manner.
Having now particularly described and ascertained the nature of my said in-
vention and in what manner the same is to be performed, I declare that what I
claim is:
A process of preparation of the colouring matters which I previously obtained
from toluquinone; such process consisting in subjecting ortho and meta benzol-
azo-cresols, either taken separately or mixed, to the action of sulphur in the
presence of soda or alkaline sulphides; the mixed benzol-azo-cresols being
obtainable for the purpose from cresols as commonly used in the trade, which
may or may not have been previously freed of its para-cresol.
Dated thie 11th day of July 1800
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.