The Manufacture and Production of Improved Dyestuffs suitable for Dyeing Vegetable Fibre with or without a Mordant.
Year: 1891

page_text: Date of Application, 13th Mar., 1891
Complete Specification Left, 2nd Dec., 1891-Accepted, 2nd Jan., 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of Improved Dyestuffs suitable for
Dyeing Vegetable Fibre with or without a Mordant.
I JAMES YATE JOHNSON of 47 Lincolns Iun Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen on Rhine in the Empire of Germany to be as follows :-
:-
Up to the present time azo-dyestuffs derived from diazotised safranine compounds
have found no application in the dyeing industry, although some time ago dye
chemists experimented with them and in the year 1885 a German Patent No. 38310
was granted to Beyer and Kegel for the preparation of azo dyes by the com-
bination of certain diazotised safranines with naphthol-sulpho acids. On account
of their bad dyeing qualities these dyestuffs were never brought into commerce and
the Patent was very soon abandoned. The compounds resulting from the com-
bination of the safranine diazo-compounds with the naphthols themselves were not
included in this Patent but have been mentioned in chemical literature as insoluble
precipitates and have hitherto been regarded as entirely useless for the dyeing
industry.
Now the present invention is based on the discovery that these insoluble
precipitates which result from the combination of the diazo compounds of the
safranines with alpha- and beta-naphthol behave chemically as if they were
colouring matter bases and can by appropriate treatment be readily converted into
very valuable dyestuffs which are their compounds or salts with acids. These rew
dyestuffs possess in a very high degree the valuable property of dyeing cotton not
only when mordanted (say for instance with tannin and tartar emetie). but also
without the aid of a mordant. They yield various beautiful shades of colour
varying from dark violet to indigo-blue and are characterized by very great
fastness against washing and against the action of light. The new dyes can be
advantageously applied in a similar manner to other vegetable fibres and also
to silk.
To prepare these acid-compounds or salts of the azo-compounds it is preferred
to use hydrochloric or acetic acid but other acids such as for instance sulphuric,
nitric oxalic, and tartaric acids can be used.
The following safranine compounds yield good results but the invention is not
restricted to their use as others can also be employed.
Safranine T (obtained by oxidation of a mixture of molecular proportions of
toluylenediamine, ortho toluidine and aniline).
Phenososafranine.
Safranine A. S. (obtained by oxidation of a mixture of molecular proportions
of para-amido-dimethyl-aniline; ortho-toluidine and para-toluidine).
To further illustrate the nature of this invention the following directions for the
preparation of one of the new dyestuffs are given by way of example but I do not
bind myself to the precise details I shall give. The parts are by weight.
Diazotise about seven parts of safranine T dissolved in about seven hundred
parts of ice-water by the addition of about two parts of sodium nitrite dissolved in
about twenty parts of water and about twenty three parts of hydrochloric acid
(containing about thirty per cent. real hydrochloric acid HCl) proceeding in the
well known way. Run the solution so obtained into a solution of three parts of
beta naphthol in about one hundred and sixty parts of water and twenty five parts
of caustic soda-lye (containing about thirty five per cent, sodium hydrate NaOH).

page_text: This solution must also be ice-cold. Stir for several hours and then filter off the
blackish-violet insoluble precipitate wash well with water and press.
To obtain a new dyestuff from the above mentioned blackish-violet precipitate
(which as my foreign correspondents have found behaves like a colouring matter
base) suspend the whole in about four hundred parts of water and add sufficient
strong hydrochloric acid to precipitate the hydrochloric acid salt or compound
(which is one of the new dyestuffs) from the violet solution which first forms. If
the above directions have been carefully followed about forty six parts of hydro-
chloric acid (containing about thirty per cent. real acid HCI) will be about the
requisite quantity. Filter press and dry at a temperature of about thirty degrees
Centigrade or preserve for use in the form of paste. Or if desired the new dyestuff
can be prepared from the blackish-violet precipitate obtained as above described
by grinding the press cakes thereof with just sufficient strong hydrochloric acid
(thirty per cen'. HCl, as before mentioned) to form the soluble salt or acid
compound. The paste so obtained can be used directly for dyeing and printing.
The method of preparing the dyestuff by precipitation with hydrochloric acid
can be recommended in this case, but the second method is capable of more general
application with other azo-compounds and different acids. It is, as a rule, best to
preserve the dyestuffs in the form of paste as they are liable to deterioration
on drying.
In a similar manner new dyestuff's can be obtained from other safranine compounds
and instead of the hydrochloric acid other acids can as aforesaid be used.
The production of the new dyestuffs can readily be combined with the operation
of dyeing by introducing the insoluble precipitate of the azo-compound into the
dye bath and adding the requisite quantity of acid to the same. The dyestuff
is then produced in the bath which can at once be used for dyeing.
Dated this 13th day of March 1891.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of Improved Dyestuffs suitable for
Dyeing Vegetable Fibre with or without a Mordant.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin & Soda Fabrik of
Ludwigshafen on Rhine in the Empire of Germany) and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement:―
This invention relates to the manufacture of violet to blue dyestuffs of such
great intensity of colouring power and fastness both against the action of light
and against washing that they are superior to any artificial dyes of the same class,
hitherto known and compare favourably with indigo itself and they can often be
used with advantage instead of this dyestuff.
Up to the present time azo-dyestuffs derived from diazotized safranine compounds
have found no application in the dyeing industry, although some time ago dye-
chemists experimented with them and in the year 1885 a German Patent No. 38310
was granted to Beyer & Kegel for the preparation of azo-dyes by the combination
of certain diazotized safranines with naphthol-sulpho-acids. On account of their
bad dyeing qualities these dyestuffs were never brought into commerce and the
Patent was very soon abandoned. The compounds resulting from the combination
of the safranine diazo-compounds with the naphthols themselves were
included in this Patent but they have been mentioned in chemical literature as
insoluble precipitates, and have hitherto been regarded as entirely useless for the
dyeing industry..
not

page_text: Now the present invention is based upon the discovery that these insoluble
precipitates which result from the combination of the diazo-compounds of the
safranines with alpha- and beta-naphthol behave chemically as if they were
colouring matter bases, and can, by appropriate treatment, be readily converted
into their compounds or salts with acids which are new and very valuable dyestuffs.
These new dyestuff's possess in a very high degree the valuable property of dyeing
cotton not only when mordanted (say, for instance with tannin and tartaremetic)
but also without the aid of a mordant. They yield various beautiful and intense
shades of colour varying from dark violet to indigo-blue which as aforesaid are
characterized by very great fastness against washing and against the action of
light. The new dyes can be advantageously applied in a similar manner to other
vegetable fibres and also to silk.
To prepare these acid-compounds or salts of the azo-compounds it is preferred to
use hydrochloric or acetic acid, but other acids such as, sulphuric, nitric, oxalic,
and tartaric, acids can be used.
The following safranine compounds yield good results,-Safranine T (obtained
by oxydation of a mixture of molecular proportions of toluylenediamine, ortho-
toluidine and aniline);
Phenosafranine;
Safranine A. S. (obtained by oxidation of a mixture of molecular proportions of
para-amido-dimethyl-aniline ortho toluidine and para-toluidine).
The invention is not restricted to the use of these safranines as all safranines
which yield diazo-compounds on treatment with nitrous acid in acidulated aqueous
solution can be employed.
To further illustrate the nature of this invention and the manner in which it
can be carried into effect the following directions for the preparation of one of the
dyestuffs are given by way of example but I do not limit myself to the precise
details I shall give.
The parts are by weight.
Diazotize about seven parts of safranine T dissolved in about seven hundred
parts of ice-water by the addition of about two parts of sodium nitrite dissolved in
about twenty parts of water and about twenty-three parts of hydrochloric acid
(containing about thirty per cent. real hydrochloric acid HCl), proceeding in the
well known way. Run the solution so obtained into a solution of three parts of
beta-naphthol in about one hundred and sixty parts of water and twenty-five parts
of caustic-soda-lye (containing about thirty five per cent. sodium hydrate NaOH).
This solution must also be ice cold. Stir for several hours and then filter off the
blackish-violet insoluble precipitate, wash well with water and press.
The process as far as it has as yet been described in this example is not, taken
by itself, regarded as new. To obtain a new dyestuff from the above mentioned
blackish-violet precipitate (which, as my foreign correspondents have found, behaves
like a colouring matter base), either of the following methods may be used.
A.
Suspend the whole precipitate in about four hundred parts of water and add
sufficient strong hydrochloric acid to precipitate the hydrochloric acid salt or
compound (which is one of the new dyestuffs) from the violet solution which first
forms. If the above directions have been carefully followed about forty-six parts
of hydrochloric acid (containing about thirty per cent. real acid HCI) will be about
the requisite quantity.
Filter press and dry at a temperature of about thirty degrees Centigrade or
preferably preserve for use in the form of paste.
B.
The blackish-violet precipitate, that is the safranine-azo-naphthol compound
obtained as above described, may advantageously be converted into the new dyestuff
in the form of paste by the following modification of the process.

page_text: Grind the press cakes of the insoluble azo compound with just sufficient strong
hydrochloric acid (thirty per cent. HCl as aforesaid) to form a paste soluble in
water of the salt or acid-compound. This paste can be directly used for dyeing
and printing. It is best to preserve the dyes in the form of paste as they are liable
to deterioration on drying, especially if a little free mineral acid be present.
In a similar way other new dyestuff's can be tained from the safranine-azo-
naphthol compounds, which are prepared from other diazotizable safranines as
above defined, and alpha- or beta-naphthol. Instead of hydrochloric acid the
above mentioned other acids can be used but in cases where the acid used does not
precipitate the dye formed from its solution the method B should be used as the
method A is then inapplicable.
The production of the new dyestuffs can readily be combined with the operation
of dyeing or printing by introducing the insoluble precipitate of the azo-compound
into the dye-bath or into the printing mixture and adding the requisite quantity of
acid in each case to form the soluble compound. The new dyestuff is thus produced
in the bath or mixture as the case may be and can at once be used. This method
however is not recommended, as the best results are obtained by using the new dyes
in the form of paste obtained as above described.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what 1
claim is :-
:-
1. The manufacture of new violet to blue colouring matters by the combination
of processes herein before described, namely by first preparing a safranine-azo-
naphthol body and subsequently treating this with an acid, all substantially as
hereinbefore described.
2. The manufacture of new violet to blue colouring matters by combining
a safranine-azo-naphthol body with an acid substantially as hereinbefore described.
3. The manufacture or production of new violet to blue dyes in the operation
of dyeing or printing, substantially as described, namely, by introducing a safranine-
azo-naphthol body into the dye-bath or into the printing mixture and adding the
requisite quantity of acid in each case.
4. The manufacture of a new violet-blue dye by first preparing the insoluble
azo-compound from safranine T and beta-naphthol and then treating it with
hydrochloric acid as herein described in the example.
5. The manufacture of a new violet-blue dye by preparing the insoluble azo-
compound from safranine T and alpha-naphthol and then treating it with an acid,
substantially as described.
6. The manufacture of new blue to violet dyes by preparing the alpha- or beta-
naphthol azo-compounds of phenosafranine or safranine A S, and then treating
these with an acid.
7. As new products of manufacture the blue to violet dyes obtained substantially
as hereinbefore described and claimed and whether produced as paste or powder or
fixed on the material dyed or printed.
Dated this 1st day of December 1891
J. H. JOHNSON & Co.,
Agents.