Improvements in the Manufacture of Colouring Matters.
Year: 1890

page_text: Date of Application, 2nd Apr., 1890
Complete Specification Left, 2nd Dec., 1890-Accepted, 3rd Jan., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
We THE CLAYTON ANILINE COMPANY LIMITED of Clayton near Manchester in the
County of Lancaster and JOHN HALL of the same place Chemist to the said Company
do hereby declare the nature of the said invention to be as follows :—
According to this invention phenyl beta naphthylamine A. and B. sulphonic acid
and orthotolyl beta naphthylamine A and B sulphonic acid (referred to in the Specifi-
cation of our Application for Patent 10934 of 1889) separately or mixed are used for
the preparation of valuable colouring matters.
The preparation of the dyestuffs takes place in two stages, the first consists in the
formation of what may be called the intermediate compound by the combination of one
molecular proportion of a tetrazo diphenyl or tetrazo ditolyl salt with one molecular
proportion of any of the four acids. The second stage consists in the combination of
the intermediate compounds with amines or phenols or the sulphonic or carboxylic
acids of amines or phenols. We give the following to more clearly explain our
invention but we do not limit ourselves to the precise details.
28 parts by weight of benzidine sulphate suspended in 600 parts by weight of
water are diazotised which may be done in the manner well known to chemists
with 14 parts by weight of sodium nitrite and 30 parts by weight of hydrochloric acid.
The tetrazo diphenyl salt thus formed is poured into a solution of 32 parts by
weight of phenyl beta naphthylamine A. sulphonate of sodium in 1000 to 2000 parts
by weight of water together with sufficient sodium acetate to neutralize all the free
mineral acid. The intermediate compound separates quickly as a fine brown or brown.
red precipitate. After stirring for about an hour a solution of 32 parts by weight of
crystallized sodium naphthionate is added and sufficient sodium carbonate to neutralize
all free acid and keep the whole distinctly alkaline. It is stirred for some hours longer
until it forms a clear bright red liquid; when this stage is reached the formation of
colour is complete it is salted out filtered pressed and dried.
The colouring matter so obtained dyes cotton a fine blueish shade of red without a
mordant.
If the 32 parts of naphthionate of soda be replaced by 35 parts of beta naphthol
disulphonate of soda R (salt R) a blue-violet cotton dyestuff is obtained.
If the phenyl beta naphthylamine A sulphonate of sodium be replaced by an equal
weight of the isomeric B. salt, a colouring matter is obtained which dyes cotton a more
yellow shade of red than does that first described.
If the naphthionic acid be replaced by 14 parts by weight of salicylic acid an orange
colouring matter is obtained.
Further the benzidine sulphate may be replaced by an equivalent proportion of
tolidine sulphate; the shades obtained of course vary from the corresponding benzidine
derivatives for example by combining one of the intermediate compounds derived
from benzidine with Neville & Winter's alpha naphthol sulphonic acid a more or
less blue shade of maroon is obtained, whilst the tolidine derivative yields a blue. or
blue-violet.
Dated 1
1900
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
We THE CLAYTON ANILINE COMPANY LIMITED of Clayton near Manchester in the
County of Lancaster and JOHN HALL of the same place Chemist to 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:
According to this invention either the phenyl beta naphthylamine A sulphonic acid
or the phenyl beta naphthylamine B sulphonic acid or the orthotolyl beta naphthyl-
amine A sulphonic acid or the orthotolyl beta naphthylamine B sulphonic acid (referred
to in the Specification of our Application for Patent 10934 of 1889) or the last named
A and B acids mixed are used for the preparation of valuable colouring matters as
hereinafter described.
The preparation of the dyestuffs takes place in two stages the first consists in the
formation of what may be termed the intermediate compounds (insoluble bodies of a
more or less dark brown colour) by the combination of one molecular proportion of a
salt of tetrazo diphenyl or a salt of tetrazo ditolyl with one molecular proportion of
either of the four acids above named or of mixtures of the A and B acids of orthotolyl
beta naphthylamine. The second stage.consists in the combination of either of the
said intermediate compounds with amines or phenols or the sulphonic or carboxylic
acids of amines or phenols.
We give the following examples to more clearly explain this invention but we do
not limit ourselves to the precise details.
28 parts by weight of sulphate of benzidine suspended in 600 parts by weight of
water are diazotized, which may be done in the manner well known to chemists with
14 parts by weight of nitrite of sodium and 30.parts by weight of hydrochloric acid.
The tetrazo diphenyl salt thus formed is poured into a solution of 32 parts by weight
of phenyl beta naphthylamine A sulphonate of sodium in 1000 to 2000 parts by weight
of water together with sufficient sodium acetate (for the above proportions about
40 parts by weight) to neutralize all the free mineral acid. The whole is kept cool
by ice and well stirred. The intermediate compound separates quickly as a dark
precipitate of a fine brown or brown red colour. After stirring for about an
hour a solution of 32 parts by weight of crystallized naphthionate of sodium is
added together with sufficient sodium carbonate to neutralize all free acid and
keep the whole distinctly alkaline. The mixture is stirred for some hours longer
until it forms a clear bright red liquid. When this stage is reached the forma-
tion of colour is complete it is salted out filtered pressed and dried. The sodium
acetate may be replaced entirely by sodium carbonate that is to say the colour may
be made throughout in alkaline solution or the addition of sodium carbonate may be
left for some hours after the naphthionate of sodium has been added. It is advan-
tageous to use naphthionate of sodium in excess of the above given theoretical weight
the excess being recoverable by precipitating it as free naphthionic acid (by means of
hydrochloric acid) from the liquor obtained by filtering off the salted out colour.
The colouring matter obtained as hereinbefore described dyes unmordanted cotton
a fine red having a somewhat bluish shade.
If the 32 parts of naphthionate of soda be replaced_by_35_parts_of_beta naphthol
disulphonate of sodium R (salt R) a dyestuff is obtained which dyes unmordanted
cotton a blue-violet.
If the 32 parts of phenyl- beta- naphthylamine A- sulphonate of sodium be replaced
by the same weight of the isomeric phenyl- beta- naphthylamine- B- sulphonate of
sodium a colouring matter is obtained which dyes unmordanted cotton a more yellow
shade of red than does that first described.
If again instead of employing phenyl- beta- naphthylamine A sulphonate of sodium,
or the isomeric B sulphonate of sodium there be used 34 parts of orthotolyl- beta-
naphthylamine A sulphonate of sodium, or of the isomeric B sulphonate (or a mixture

page_text: of the two) colours are obtained which dye unmordanted cotton a blue shade of red if
the A sulphonate be used or a yellower shade of red if the B sulphonate be used, and
if a mixture of the A and B sulphonates be used intermediate shades are obtained
depending upon the relative proportions of the two in the mixture used.
If the naphthionic acid be replaced by 14 parts by weight of salicylic acid an orange
colouring matter is obtained.
If the 28 parts of benzidine sulphate used as aforesaid be replaced by its equivalent
weight (31 parts) of tolidine sulphate a colouring matter is obtained which however
does not give under the conditions described clear liquid, it is salted out pressed and
dried as hereinbefore described and the colour so obtained dyes unmordanted cotton
a fine red with a bluish shade which is faster against acids than is that obtained with
benzidine sulphate.
Similarly the benzidine sulphate can be replaced by tolidine sulphate in each of
the other preceding examples whereby we can obtain colours of different shades and
properties to those obtained by the use of benzidine sulphate and those colours in
the preparation of which both tolidine sulphate and naphthionate of soda are used,
though differing little in shade from the corresponding colours in the preparation of
which benzidine sulphate is used yet the former are faster to acids than the latter;
for another example the colour obtained by combining one of the intermediate com-
pounds derived from benzidine with Neville and Winters alpha- naphthol- sulphonic
acid is a more or less blue shade of maroon whilst the corresponding tolidine derivative
yields a blue or blue violet.
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 :-
First. In the manufacture of colouring matters the production of the herein before
named intermediate compounds by combining one molecular proportion of a salt of
tetrazodiphenyl or tetrazoditolyl with one molecular proportion of phenyl- beta-
naphthylamine A sulphonic acid, or of the phenyl-beta- naphthylamine B sulphonic
acid or of orthotolyl-beta- naphthylamine A sulphonic acid or of ortho tolyl beta
naphthylamine B- sulphonic acid or a mixture of the said ortho- tolyl- beta- naphthyl-
amine A and B sulphonic acids.
Second. The manufacture of colouring matters by first preparing the intermediate
compounds of the preceding claiming clause and then. combining the said compounds
with amines or phenols or sulphonic or carboxylic acids of amines or phenols.
Third. The preparation of colouring matters by the several processes particularly
described under the foregoing examples.
Dated this 2nd day of Decembe 1896.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.