Production of New Colouring Matters for Dyeing and Printing.
Year: 1893

page_text: Date of Application, 15th May 1893
Complete Specification Left, 9th Feb., 1894-Accepted, 10th Mar.,
1894
PROVISIONAL SPECIFICATION.
The Production of New Colouring Matters for Dyeing and
Printing.
We, READ HOLLIDAY & SONS LIMITED of Huddersfield in the County of
York, Chemical Manufacturers, and ROBERT HOLLIDAY of the same place,
Managing Director of the said Company do hereby declare the nature of this
invention to be as follows:-
:―
In the "Chemical News" of March 23rd 1883, there is an article by Raphael
Meldola on <<
some colouring matters belonging to the rosaniline series." In this he
describes the production of some naphthylated derivatives of rosaniline analogous
to phenylated blues; the sulphonic acids of which dye silk and wool of a deep
blue having a more reddish shade than the corresponding sulphonic acids of
triphenylrosaniline.
We have discovered that by heating rosaniline with excess of betanaphthylamine
at a much higher temperature than described by Meldola, and for a much longer
time, we obtain a blue much greener in shade than can be obtained by phenylating
rosaniline;
and that by using proper precautions in the inanufacture of the
sulphonic acids, we can. also obtain a sulphonic acid giving a greener shade
than any blue hitherto produced, from phenylated or naphthylated rosaniline that
we are aware of.
To carry the invention into effect we heat together 100 lbs. of rosaniline,
500 lbs. of betanaphthylamine and 5 lbs. of benzoic acid or glacial acetic acid at a
temperature of 160° C., the operation being continued until when a sample is taken
out, dissolved in alcohol and acetic acid, a drop of this solution on a piece of white
filter paper appears of a greenish blue colour by gas-light. Successive samples
treated in this way should pass through the stages of reddish blue, pure blue, to a
greenish blue, the time taken to reach this point being about five hours. The shade
of colour produced under these circumstances being much greener than can be
obtained by any phenylated blue.
The proportion of betanaphthylamine can be varied, a less quantity giving a less
green shade, and a larger quantity shortening the time taken by the operation and
giving a greener shade.
When the operation has reached the required shade it is cooled, and the
excess of betanaphthylamine washed out with a hot solution of muriatic acid and
water.
.
The sulphonation of the dried insoluble product is effected at a much lower
temperature than is required for phenylated rosanilines. The quantity of sulphuric
acid employed can be greatly varied.
As an example, we take, say, 100 lbs. of the crude product with 300 lbs. sulphuric
acid 66° Be. The operation is continued without any external heat till a sample
taken out and washed with cold water will not dissolve with a blue colour, and the
When this
washed product will dissolve in water with a slight excess of ammonia.
stage is reached the batch is poured into cold water, filtered and well washed. The
insoluble part being dried down with a slight excess of ammonia is ready for use as
a new colouring matter.
Sulphonated products of less or greater solubility can be obtained on the one
hand by stopping the sulphonation when the product is soluble in caustic soda, or

page_text: on the other by continuing the sulphonation until the product is soluble in water.
These sulphonic acids can be used in printing and dyeing.
Dated the 15th day of May 1893.
WM. BROOKES & SON,
55 & 56, Chancery Lane, London, Agents for the Applicants.
COMPLETE SPECIFICATION.
The Production of New Colouring Matters for Dyeing and Printing.
We READ HOLLIDAY & SONS LIMITED of Huddersfield in the County of
York, Chemical Manufacturers, and ROBERT HOLLIDAY of the same place,
Managing Director of the said Company, 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 "Chemical News" of March 23, 1883 there is published an article
by Raphael Meldola on some colouring matters belonging to the rosaniline series.
In this he describes the production of some naphthylated derivatives of rosaniline
analogous to phenylated blues, the sulphonic acids of which dye silk and wool of a
deep blue having a more reddish shade than the corresponding sulphonic acids of
triphenylrosaniline. We have discovered that by heating rosaniline with excess
of beta-napthylamine at a much higher temperature than described by Meldola
and for a much longer time, we obtain a blue, greener in shade than can be
obtained by phenylating rosaniline and that by using proper precautions in the
manufacture of sulphonic acids, we can also obtain a sulphonic acid giving a
greener shade than any blue hitherto produced from phenylated or naphthylated
rosaniline.
To carry the invention into effect we heat together 100 lbs. of rosaniline,
500 lbs. of betanapthylamine and 5 lbs. of benzoic acid or glacial acetic acid at a
temperature of 160° C. The operation is continued until a sample being taken
out, dissolved in alcohol and acetic acid, a drop of this solution on a piece of white
filter paper appears of a greenish blue colour by gas light. Successive samples
treated in this way should pass through the stages of reddish blue, pure blue to a
greenish blue, the time taken to reach this point being about 5 hours, the shade of
colour produced under these circumstances being much greener than can be obtained
by any phenylated blue.
The proportion of betanapthylamine can be varied, a less quantity giving a less
green shade, and a larger quantity shortening the time taken by the operation and
giving a greener shade.
When the operation has reached the required shade it is cooled and the excess
of betanapthylamine washed out with a hot solution of muriatic acid and water.
The sulphonation of the dried insoluble product is effected at a much lower
temperature than is required for phenylated rosanilines.
The quantity of sulphuric acid employed can be greatly varied.
As an example we take say, 100 lbs. of the crude product with 300 lbs. sulphuric
acid 66° Bé.
The operation is continued without any external heat till a sample taken out
and washed with cold water will not dissolve with a blue colour, and the washed
product will dissolve in water with a slight excess of ammonia. When this stage
is reached the batch is poured into cold water, filtered and well washed.
The insoluble part being dried down with a slight excess of ammonia is ready for
use as a new colouring matter.
Sulphonated products of less or greater solubility can be obtained on the one hand
by stopping the sulphonation when the product is soluble in caustic soda, or on the
other hand by continuing the sulphonation until the product is soluble in water:
These sulphonic acids can be used in printing and dyeing.
.

page_text: Having now particularly described and ascertained the nature of our said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is :-
1. The production of new colouring matters for dyeing and printing by heating
5 rosaniline with beta napthylamine, or with any suitable acid such as acetic or benzoic
until a greenish blue is produced.
2. Treating the blue shade napthylated rosaniline with sulphuric acid as and for
the purpose described.
3. The colouring matters produced by the process described.
9th day of February 1894.
WM. BROOKES & SON,
55 & 56, Chancery Lane, London, Agents for the Applicants.
WM. BROOKES & SON,
55 & 56, Chancery Lane, London, Agents for the Applicants.