Improvements in the Production upon Fibres and Fabrics of Colors Varying from Black or Brown-black to Blue-black and Blue.
Year: 1887

page_text: Date of Application, 19th July, 1887
Complete Left, 16th Apr., 1888
Complete Accepted, 18th May, 1888
Improvements in the Production upon Fibres and Fabrics of Colors
Varying from Black or Brown-black to Blue-black and Blue.
We AUGUSTE GILLIARD, PROSPER MONNET and JEAN MARIE CARTIER, all of 6 Quai
de Retz, Lyons, France, Manufacturers of Coloring Matters, do hereby declare the
nature of this invention to be as follows:-
We produce on fibres and fabrics fast colors varying from black or brown-black to
blue-black and to blue by the direct oxidation on the fibres or fabrics of the following
substances.
1. A mixture of a salt of a simple diamine such as hydrochlorate of para-phenylene
diamine and of one or more molecules of salts of simple mono-amines such as hydro-
chlorates of aniline or ortho-toluidine.
2. Hydrochlorates of leuco-thionine and leuco-tolylene-thionine employed alone or
mixed with a salt of diamine and a salt of simple amine in variable proportions.
3. The products of condensation obtained by the action of simple amines on salts of
diamines.
We will describe successively examples of the modes of preparing these mixtures
and products which produce colors by direct oxidation on fibres and fabrics.
I. Preparation of the mixtures of salts of simple mono-amines and diamines. The
mixture comprises for example:
:-
Commercial hydrochlorate of para-phenylenediamine 55.47 parts
These quantities correspond to the molecular weight of each of these substances and
give by oxidation a very fast brown-black. By doubling the amount of hydrochlorate
of aniline the color of the black approaches or tends towards blue. We can substituto
for the hydrochlorate of aniline in the same proportions hydrochlorate of some other
simple amine or hydrochlorates of leuco-thionine or leuco-tolylene-thionine &c.

page_text: II. Preparation of the substitution products. When para-phenylene-diamine is
heated with sulphur by the known processes a substituted base is obtained viz. :-
leuco-thionine. We have discovered a new substituted diamino homologous with the
preceding viż.-leuco-tolyl-thionine. We prepare it by heating one molecule of para-
tolylene-diamine with 1 molecules of sulphur at 160° Centigrade for 3 hours and
afterwards forming the salt by treating the product of the reaction with dilute hydro-
chloric acid by prolonged ebullition. By filtration and desiccation hydrochlorate of
the leuco-tolyl-thionine is obtained in the dry state.
III. Preparation of the products of condensation. When a molecule of hydrochlorate
of para-phenylene-diamine and a molecule of aniline are heated at 2000 Centigrade
for 8 hours in an enamelled cast iron retort fitted with a coil, ammonia is disengaged,
NC® H$
and there is formed a condensed monophenylated diamine of the formula C³H* _H.
NH'
The raw product of the reaction is dissolved in acidulated water by hydrochloric acid,
then dried and it constitutes the product.. of. condensation which we will call hydro-
chlorate of mono-phenylated para-phenylene-diamine.
Oxidation on fabrics and fibres. To effect this oxidation we employ as a special
oxidation mordant a solution composed of:
Chlorate of soda ---
Vanadate of ammonia previously dissolved in water
acidulated with hydrochloric acid
Ordinary water the quantity sufficient to make 50 litres.
No. 1.
- .3 kilogrammes
}
7 grammes
We will call this solution
Preparation of the solution of the product to be oxidized. Whatever be the product
to be oxidized, a mixture of salts of diamine and amine, condensed or substituted
products, a solution is made of 6 kilogrammes in a sufficient quantity of cold water to
make 50 litres; this solution we will call No. 2.
Dyeing. We take for example cotton in skeins or hanks. The cotton is. wetted
with pure water and wrung so that it may not retain more than 50 per cent. of its
weight of water. The cotton is dipped in a mixture of equal volumes of the solutions
No. 1 and No. 2, and wrung so that it may only retain its own weight (the weight of
the cotton considered dry) of the liquid of the bath. Thus impregnated the cotton is
left in parcels of about 100 kilogrammes in open wooden boxes and left at the ambiant
temperature, say 15° to 20° Centigrade. After remaining about 24 hours in, the
boxes the oxidation is finished and the cotton dyed black is washed and dried.
The oxidation of the mixtures of the salts of simple diamine and amine gives colors
varying from brown-black to deep black; the products of condensation produce blue-
black. The oxidation of the leuco-thionines gives a blue more or less purple. The
mixture in suitable proportions of all these substances permits of varying the colors
as may be required.
The colors may be applied to the dyeing and printing of silk, woollen and cotton
fibres and fabrics.

page_text: Varying from Black or Brown Black to Blue Black and Blue.
We AUGUSTE GILLIARD, PROSPER MONNET and JEAN MARIE CARTIER, all of 6 Quai
de Retz, Lyons, France, Manufacturers of Coloring Matters, 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 :-
;
We produce on fibres and fabrics fast colors varying from black or brown-black to
blue black and to blue by the direct oxidation on the fibres or fabrics of the following
substances:-
:―
1. A mixture of a salt of a simple diamine such as hydrochlorate of para-phenylene-
diamine and of one or more molecules of salts of simple mono-amines such as hydro-
chlorates of aniline or ortho-toluidine.
2. Hydrochlorates of leuco-thionine and leuco-tolylene-thionine employed alone or
mixed with a salt of diamine and a salt of simple amine in variable proportions.
3. The products of condensation obtained by the action of simple amines on salts of
diamines.
We will describe successively examples of the modes of preparing these mixtures and
products which produce colors by direct oxidation on fibres and fabrics.
I. Preparation of the mixtures of salts of simple mono-amines and diamines. The
mixture comprises for example:
nomial hidrochlorate of nom-phenylenediamine
55 47 marts
These quantities correspond to the molecular weight of each of these substances
and give by oxidation a very fast brown black. By doubling the amount of hydro-
chlorate of aniline the color of the black approaches or tends towards blue. We
can substitute for the hydrochlorate of aniline in the same proportions hydrochlorate
of some other simple amine or hydrochlorates of leuco-thionine or leuco-tolylene-
thionine, &c.
II. Preparation of the substitution products. When para-phenylene-diamine is
heated with sulphur by the known processes a substituted baso is obtained viz.: leuco-
thionine. We have discovered a new substituted diamine homologous with the
preceding viz. louco-tolyl-thionine. We prepare it by heating one molecule of para-
tolylene-diamine with 1 molecules of sulphur at 160° Centigrade for 3 hours and
afterwards forming the salt by treating the product of the reaction with dilute hydro-
chloric acid by prolonged ebullition. By filtration and desiccation hydrochlorate of
the leuco-tolyl-thionine is obtained in the dry state..