Manufacture of New Substantive Black Colouring Matters.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
Manufacture of New Substantive Black Colouring Matters.
I, ALCIDE FRANÇOIS FOIRRIER, of 105, Rue Lafayette, Paris, France, Manu-
facturer, do hereby declare the nature of this invention to be as follows:-
The processes hitherto employed for obtaining sulphurated substantive colour-
ing matters, consist always in heating a more or less complex, polyamido,
amido-hydroxl, amido-sulpho, amido-hydroxyl-sulpho &c. aromatic substance
with sulphur or with sulphur and sodium sulphide.
Nevertheless in one case (D.R.P. 103646, and French Patent 271388) for
sulphur there has been substituted sulphur chloride acting directly upon a single
substance which generates the colouring matter, the same as formerly Bernthsen
had also employed sulphur chloride instead of sulphur in the preparation of
thiodiphenylamine (Studien in der Methylenblaugruppe; Annalen der Chemie-
230 page 73 à 211).
I have since found that other sulphur combinations are capable of trans-
forming complex aromatic polyamido or amidohydroxyl bodies into sulphurated
colouring matters similar to the substantive colouring matters hitherto obtained.
My process consists in treating together in the first place commercial sulphur
chloride and simple aromatic substances, such as aniline or phenol, then to sub-
ject the combination thus obtained to reaction with more complex polyamido
or amidohydroxyl bodies.
EXAMPLE I.
100 parts of phenol have added to them drop by drop with active agitation
200 parts of commercial sulphide chloride. Volumes of hydrochloric acid are
evolved, then the material is heated after the reaction appears to be at an end
to 150°-160° C. for an hour, and then it is added to 50 parts of paraphenylene-
diamine. The components form a homogeneous mixture which is kept for two
hours at 200° C. The mass obtained is hard and friable; it is insoluble in
water or acids; it is soluble in alkalies and especially in sodium sulphide.
The solution when precipitated by acid gives a greenish blue mass which a
trace of oxidant changes to blue black. The mass obtained is treated as
follows;-
100 parts of the product are introduced in small doses into 300 parts of
sodium sulphide melted in its water of crystallisation, slowly evaporated and
heated to 200° C. to complete the drying.
.
The colouring matter thus obtained dyes unmordanted cotton blue black.
In this Example 1 commercial cresol can be substituted for the phenol.
EXAMPLE II.
100 parts of phenol are treated as in Example I, but the mass obtained after
reaction of sulphur chloride, is treated with 5 parts of paramidophenol. The
product obtained is more brilliant than the former, it is, like it, insoluble in
water and acids, but very soluble in alkalies_and_alkaline_carbonates-as-well-as-

page_text: For use in dyeing the reaction product is melted in sodium sulphide and dried
as described above. It dyes cotton a more violet shade than the product of
Example I.
For the phenol in Example II may be substituted commercial cresol or any
phenolic substance, and for the paramidophenol a more complex hydroxyl such as
paraoxy-diamidodiphenylamine.
EXAMPLE III.
In a cast iron apparatus closed and provided with a reflux appliance and
agitator are charged 150 parts of aniline hydrochlorate, it is heated to 120°-
130° C. externally by an oil bath, then 240 parts of sulphur chloride are very
slowly added. There is a violent evolution of hydrochloric acid, and when this
becomes more slow, the temperature is gradually raised to 180° C. It is ascer-
tained that at this moment there is no longer any reflux in the cooling apparatus
then 120 parts of paraphenyldiamine are rapidly added, and the temperature
is raised to 200° C. for 8 hours.
The mass obtained is dry, spongy and brilliantly black. For its use and
application in dyeing this mass is introduced into 1000 parts of crystallised
sodium sulphide dissolved in very little water, it is agitated for several hours,
the temperature being kept at 120° C. until a homogeneous mass is obtained,
then the whole is dried at about 200° C. for several hours.
The colouring matter not treated with sodium sulphide, is insoluble in water,
acids and alkalies, but it is soluble in sodium sulphide, giving blueish or greenish
solutions. The solutions are precipitated by acids, sea salt and concentrated
alkalies.
EXAMPLE IV.
The operation is the same as in Example III, but 50 parts of paramidophenol
are substituted for the 50 parts of paraphenylenediamine.
"
The colouring matter obtained possesses the general characteristics of that of
Example III, but is more soluble it is slightly soluble in alkalies and the shades
which it produces on the unmordanted cotton are a little more bluish. In this
example may be substituted for the paramidophenol another amidohydroxyl such
as paraoxydiamidodiphenylamine.
Generally all these colouring matters dye unmordanted cotton in a boiling bath
little salt.
with
The shades obtained become much deeper when they are exposed to the air,
or when they are oxidised by ordinary oxidants, bichromates, acids &c.
All these colouring matters are rendered insoluble by salts of the heavy metals;
they give insoluble combinations with metallic oxides, in these conditions the
shades thus fixed on cotton have considerable resistance to ordinary and even
to concentrated lyes.
I do not limit my claim to the quantities of the reagents stated in the examples,
these being given rather as types of the preparation, and I reserve the right to
increase or diminish at will the proportions of the reagents and the temperatures.
Dated this 12th day of September 1899.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New Substantive Black Colouring Matters.
I, ALCIDE FRANÇOIS POIRRIER, of 105, Rue Lafayette, Paris, France, Manu- 50
facturer, do hereby declare the nature of this invention and in what manner the

page_text: same is to be performed, to be particularly described and ascertained in and by
the following statement:-
The processes hitherto employed for obtaining sulphurised substantive colour-
ing matters, consist always in heating a more or less complex, polyamido,
amido-hydroxyl-, amido-sulpho-, amido-hydroxyl-sulpho- &c. aromatic substance
with sulphur or with sulphur and sodium sulphide.
Nevertheless in one case, (in the German Patent 103646, and French Patent
271388) for sulphur there has been substituted sulphur chloride acting directly
upon a single substance which generates the colouring matter, just as formerly
Bernthsen had also employed sulphur chloride instead of sulphur in the pre-
paration of thiodiphenylamine (Studien in der Methylenblaugruppe: Annalen
der Chemie-230 page 73 à 211)..
I have since found that other sulphur combinations are capable of trans-
forming complex aromatic polyamido- or amidohydroxyl-bodies into sul-
phurised colouring matters similar to the substantive colouring matters hitherto
obtained.
My process consists in treating together in the first place commercial sulphur
chloride and simple aromatic substances, such as aniline or phenol, then to sub-
ject the combination thus obtained to reaction with more complex polyamido
or amido-hydroxyl bodies.
EXAMPLE I.
100 parts of phenol have added to them drop by drop with active agitation
200 parts of commercial sulphur chloride.. Volumes of hydrochloric acid gas are
evolved after the reaction appears to be at an end the material is heated to
150° 160° C. for an hour, and then it is added to 50 parts of paraphenylene-
diamine. The components form a homogeneous mixture which is kept for two
hours at 200° C. The mass obtained is hard and friable; it is insoluble in water
or acids; it is soluble in alkalies and especially in sodium sulphide.
The solution when precipitated by acid gives a greenish blue mass which a
trace of oxidant changes to blue black. The mass obtained is treated as
follows:-
100 parts of the product are introduced in small doses into 300 parts of
sodium sulphide melted in its water of crystallisation; the mixture is slowly
evaporated and heated to 200° C. to complete the drying.
The colouring matter thus obtained dyes unmordanted cotton blue black.
In this Example 1 commercial cresol can be substituted for the phenol.
EXAMPLE II.
100 parts of phenol are treated as in Example I, but the mass obtained after
reaction of sulphur chloride, is treated with 5 parts of paramidophenol. The
product obtained is more brilliant than the former; it is, like it, insoluble in
water and acids, but very soluble in alkalies and alkaline carbonates as well as
in sodium sulphide.
For use in dyeing, the reaction product is melted in sodium sulphide and dried
as described above. It dyes cotton a more violet shade than that produced by
the product of Example I.
For the phenol in Example II may be substituted commercial cresol or any
phenolic substance, and for the paramidophenol a more complex hydroxyl deriva-
tive such as paraoxydiamidodiphenylamine.
EXAMPLE III.
In a cast iron apparatus closed and provided with a reflux appliance and
agitator are charged 160 parts of aniline hydrochloride; it is heated to 120°
180° C. externally by an oil bath, then 240 parts of sulphur chloride are very
slowly added. There is a violent evolution of hydrochloric-acid-gas, and-when-
this becomes more slow, the temperature is gradually raised to 180° C. It is
ascertained that at this moment there is no longer any reflux in the cooling

page_text: apparatus then 120 parts of paraphenylenediamine are rapidly added, and the
temperature is raised to 200° C. for 8 hours.
The mass obtained is dry, spongy and brilliantly black. For its use and
application in dyeing this mass is introduced into 1000 parts of crystallised
sodium sulphide dissolved in very little water, it is agitated for several hours,
the temperature being kept at 120° C. until a homogeneous mass is obtained,
then the whole is dried at about 200° C. for several hours.
The colouring matter not treated with sodium sulphide, is insoluble in water,
acids and alkalies, but it is soluble in sodium sulphide, giving blueish or greenish
solutions. The solutions are precipitated by acids, common salt and concen-
trated alkalies.
EXAMPLE IV.
The operation is the same as in Example III, but 120 parts of paramidophenol
are substituted for the paraphenylenediamine.
The colouring matter obtained possesses the general characteristics of that of
Example III, but is more soluble; it is slightly soluble in alkalies and the shades
which it produces on unmordanted cotton are a little more bluish. In this
example may be substituted for the paramidophenol another amidohydroxyl
derivative such as paraoxydiamidodiphenylamine.
Generally all these colouring matters dye unmordanted cotton in a boiling bath
with a little salt.
The shades obtained become much deeper when they are exposed to the air,
or when they are oxidised by ordinary oxidants, bichromates and acid, and the
like.
All these colouring matters are rendered insoluble by salts of the heavy metals;
they give insoluble combinations with metallic oxides, in these conditions .the
shades thus fixed on cotton have considerable resistance to ordinary and even
to concentrated lyes.
I do not limit my claim to the quantities of the reagents stated in the examples,
these being given rather as types of the preparation, and I reserve the right to
increase or diminish at will the proportions of the reagents and the temperatures.
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:-
1. The herein described manufacture of substantive black colouring matters
by subjecting the products obtained by the action of sulphur chloride on simple
aromatic substances such as aniline or phenol, to reaction with more complex
polyamido- or amidohydroxyl-bodies such as paraphenylenediamine, paramido-
phenol, or diamido-oxydiphenylamine.
2. The colouring matters manufactured as above set forth.
ABEL & IMRAY,
Agents for the Applicant.