Manufacture of Colouring Matters applicable to Unmordanted Fibres or Fabrics.
Year: 1893

page_text: Date of Application, 7th Dec., 1893
Complete Specification Left, 21st Mar., 1894-Accepted, 2nd June, 1894
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIÈRES
COLORANTES ET PRODUITS CHIMIQUES DE ST. DENIS, of 105, Rue
Lafayette, Paris, France.]
Manufacture of Colouring Matters applicable to Unmordanted Fibres
or Fabrics.
I, JOHN IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention to be as follows:-
This invention relates to the manufacture of black, bluish and greenish black,
colouring matters capable of dyeing unmordanted fibres or fabrics.
For this purpose, paraphenylenediamine, paraamidodimethyl aniline, Bernthsen's
mercaptan, of para amidodimethylaniline (according to description in Annales de
Liebig 251. "1.") azophenines, indamines or generally any bodies capable of
producing, by splitting, paradiamines, are heated with sulphur and caustic soda
producing a mass which, being pulverised, is directly applicable for dyeing. Besides
the substances above mentioned which may be classed as double substituted basic
combinations of benzene, may also be used in the same way compound amine and
phenol combinations of benzene, among which may be mentioned para amido phenol,
oxyazobenzol, azoxybenzol, or generally any bodies capable of producing by
splitting ortho or para amido phenol.
Dated this 7th day of December 1893.
ABEL & IMKAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Colouring Matters applicable to Unmordanted Fibres
or Fabrics.
I, JOHN IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, 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:-
It is known that certain fatty or aromatic organic matters of complex character,
such as wood sawdust, wool or waste of all kinds give, when heated with sulphur,
brown or yellowish brown colouring matters dyeing without mordants vegetable
fibres, but hitherto no colouring matters dyeing black, or bluish or greenish black
have been obtained from these substances.
My foreign correspondents have found that a whole class of colouring matters can
be obtained, directly dyeing vegetable fibres in black, blue black and blackish green
shades by similar reaction of sulphur on aromatic compounds of very definite
composition and having different chemical action.
For producing these colouring matters may be employed substances which may
be classed under two heads: namely
1. Doubly substituted basic combinations of benzine.
2. Joint amine and phenol combinations of benzine.
Under the first head it has been found that paraphenylene diamine and its

page_text: substitutes as well as the substances capable of producing it in the very reaction,
give by fusion with sulphur various brown and black colouring matters of great
intensity.
Under the second head it has been found that the amido combinations of phenol
and substances capable of producing' them, give by fusion with sulphur black and
bluish or greenish black colours of great intensity.
Example I. There are heated in an iron vessel 1 part of paraphenylene diamine,
0.5 sulphur, 1. caustic soda at 40° Bé. for 10 hours at a temperature of 180°
to 210° C.
The bronze black cooked mass is pulverised and can in this form be applied for
dyeing.
Example II. Under the same conditions, are heated 1 part of para amido phenol,
or, what is cheaper, the product of the reduction of the nitration of phenol (mixture
of ortho and para amidophenol), 0-5 sulphur, 1 caustic soda at 40 Bé. for 10 hours.
There is obtained a dark reddish brown mass, which when pulverised may be applied
to dyeing.
In Example I, for the paraphenylene-diamine may be substituted p. amido
dimethylaniline, Bernthsen's inercaptan (described in Liebig's Annalen 251,p.23,"1"),
amidoazobenzol and generally the azo compounds capable of giving by splitting and
reduction a paradiamine (chrysoidine, Brunswick black, &c.) azophenine and
indamines.
In Example II instead of para-amidophenol may be employed ortho-amidophenol,
oxyazobenzol, azoxybenzol, and the azo colouring matters capable of giving by
splitting and reduction ortho or para amidophenol.
The colouring matters of the first series are characterised by yellowish or greenish
black shades, they are very soluble in water, insoluble in acids. Once precipitated
by acid they are little soluble in the cold in alkalies, very soluble in sodium
sulphite; the solutions are very changeable in the air or in presence of any oxydant,
less changeable in air in their insoluble form.
The colouring matters of the second series are very soluble in water, alkalies,
alkaline sulphites, insoluble in acids, very changeable in the air whether in the
soluble or insoluble condition. The best mode of applying them is to dye in a
sodium sulphite medium.
All these colouring matters in the oxydised condition do not dye fibre, but in the
original condition that is to say in presence of sulphite, they have a very great
affinity for vegetable fibre and possess considerable colouring power. After dyeing,
these colouring matters become developed on the fibre under the action of air or any
oxidising agent.
Having now particularly described and ascertained the nature of my said 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 colouring matters by heating with
sulphur and caustic soda, paraphenylene diamine, para-amidodimethylaniline,
Bernsthen's mercaptan, azophenines, indamines or generally bodies capable of
producing paradiamines by splitting.
2. The herein described manufacture of colouring matters by heating with
sulphur and caustic soda ortho and para amidophenol, oxyazobenzol, azoxybenzol or
generally bodies capable of producing ortho or para-amidophenol by reduction and
splitting.
3. The colouring matters produced as above described.