Improvements in the Production of Colouring Matters Dyeing with Mordants.
Year: 1894

page_text: COMPLETE SPECIFICATION.
[Communicated from abroad by the Firm of SANDOZ & Co., of Basel, in the
Swiss Republic, Manufacturing Chemists.]
Improvements in the Production of Colouring Matters Dyeing with
Mordants.
I, WILLIAM EDWIN HEYS, of 70 Market Street Manchester in the County of
Lancaster, 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:-
This invention relates to the production of colouring matters which are capable
of dyeing cotton and other fibres and fabrics with the aid of mordants.
My foreign correspondents have observed that 12 naphthoquinone 4 mono-
sulphonic acid combines very readily with aromatic compounds containing a free
amido group, the sulpho group being eliminated and 2 oxy-1 4 naphthoquinone
derivatives being formed. For example, upon the addition of aniline to an aqueous
solution of 12 naphthoquinone 4 potassium sulphonate, a bright vermillion
precipitate of ẞ oxy-anilido-a naphthoquinone takes place according to the
auration
SO,K (4)
= N(CH)(4)
P. diamines containing free amido groups re-act in quite an analogous way and
compounds result which are closely related to the indophenols. P. amidodimethyl-
aniline, for example, yields ẞ oxy-indophenol as a black-violet precipitate insoluble
in water. The thiosulphonic acids of such ẞ oxy-indophenols are of great technical
value, since they can be easily converted into valuable blue thiazine colouring
matters dyeing with mordants. Such oxy-indophenol thiosulphonic acids are easily
obtainable on addition of a cold aqueous solution of a 12 naphthoquinone
4 monosulphonate to a cold aqueous solution which can be either neutral or may
contain a little acetic acid or sodium carbonate, of the thiosulphonic acids of the
asymmetrically substituted aromatic P. diamines or P. diamine sulphonic acids
containing a free amido group.
The resulting oxindophenol thiosulphonic acids can be easily converted, under
suitable circumstances, into thiazine colouring matters dyeing with mordants
according to the general equation :
1

page_text: This conversion takes place, although in a very slow and incomplete manner, by
continuous boiling of the aqueous solutions, but more quickly on boiling the
aqueous solutions of these oxy- and sulpho-oxy-indophenol thiosulphonic acids in
the presence of zinc chloride.
can
My foreign correspondents have also observed that this conversion
advantageously take place on the fibre itself, most suitably on cotton. Thus, if the
oxy- or sulpho-oxy-indophenol thiosulphonic acids are printed on the fibre, in the
presence of chrome mordants, with or without acetic acid, and if these printed fibres
or fabrics are then steamed for from 1 to 2 hours at a pressure of from to 1 atmo-
sphere, the thiazine colouring matter is converted in statu nascendi into its insoluble
chrome lake, which is fast to washing, to acids, and to alkalies, and is fixed as such
directly on the fibre.
The thiazine colouring matters can be advantageously obtained as such from the
indophenol thiosulphonic acids by either of two methods :-
1. By boiling their aqueous solutions on addition of caustic alkalies.
2. By adding them to concentrated or to monohydrated, or to fuming sulphuric
acid containing a low percentage of anhydride.
Whilst the first method is preferable on account of its simplicity for the production
of the sulpho-oxy-indophenol thiosulphonic acids, the second method is excellent for
the non-sulphonated oxy-indophenol thiosulphonic acids, yielding thiazines insoluble
in water, which however, if prepared according to the second method can be
sulphonated in the same operation by using fuming sulphuric acid, or by acting at
first with monohydrated sulphuric acid and sulphonating afterwards by the addition
of fuming sulphuric acid containing a high percentage of anhydride. In both cases
the conversion into thiazines takes place at a temperature not higher than 50° C.
and the conversion into sulphonic acids is effected by heating at from 70° to 80° C.
until a sample is perfectly soluble in water containing sodium acetate, with a pure
blue coloration.
.
20.5 kilos. of 12 naphthoquinone 4 potassium sulphonate dissolved in 500 litres
of water are added at the ordinary temperature, to a solution of 20 kilos. of
P. amidodimethylaniline sodium thiosulphonate dissolved in 500 litres of water.
The
formation of the oxy-indophenol sodium thiosulphonate is completed instantly, the
mixture having an intense blackish-violet coloration. The product of the reaction
is precipitated by common salt as a bluish-black precipitate. It is easily soluble in
water with a blackish-violet colour. Acetic acid precipitates the free sulphonic acid
as a bluish powder soluble in excess of acetic acid with a reddish-violet colour.
Cold dilute mineral acids dissolve the precipitate without decomposition, producing
a reddish-yellow solution. On boiling, the solutions quickly decompose, forming
Boxy-a-naphthoquinone and P. amidodimethylaniline thiosulphonic acids. The
sulpho-oxy-indophenol thiosulphonic acids are formed in a perfectly analogous
manner on using asymmetrically substituted sulpho-P. phenylenediamine thio-
sulphonic acids.
30 parts by weight of oxy-indophenol sodium thiosulphonate from P. amido- 4
dimethylaniline thiosulphonic acid are well mixed at 70° C. or thereabouts, with
300 parts by weight of water and 340 parts by weight of tragacanth gum thickening.
After cooling, 30 parts by weight of acetic acid containing 40 per cent. of acetic
acid, and 50 parts by weight of chromium acetate of 20° Bé. are added, and the
whole is mixed and filtered through a sieve. This, printed on cotton previously 5
suitably oiled, and steamed from 1 to 2 hours at a pressure of from to 1
atmosphere, will produce a shade, dull violet before steaming, and converted

page_text: 30 kilos. of oxy-indophenol thiosulphonic acid from P. amidodiethylaniline
thiosulphonic acid are added with continuous stirring, to 90 kilos. of sulphuric
monohydrate. The mixture is kept for about 2 hours at a temperature of about
30° C., for about 2 hours more at about 50° C., and then, for the sulphonation of
the resulting thiazine, 90 kilos. of fuming sulphuric acid containing 70 per cent. of
anhydrous sulphuric acid are added to the thiazine, the whole mass being well
cooled. The mixture is then heated to about 80° C. until the sulphonation is
complete. The sulphonic acid is precipitated by pouring it into ice cold water.
It is separated by filtration and converted by boiling with a solution of sodium
acetate into its sodium salt, which is salted out, pressed, and dried.
The same colouring matter is obtained if 30 kilos. of oxy-indophenol thiosulphonic
acid are added to 150 kilos. of fuming sulphuric acid containing 35 per cent. of
anhydrous sulphuric acid, at about 20° C. The mixture has to be stirred for about
six hours and has then to be heated gently to 80° C. and kept at that temperature
until the sulphonation is complete. The resulting thiazine colouring matters dye
unmordanted wool from an acid bath, a blue-violet. Fibres mordanted with chrome
are dyed, from a bath containing acetic acid, bright blue to greenish blue shades
which, being fast to alkalies acids and light, are of great technical value.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, as communicated to me
by my foreign correspondents, I declare that what I claim is :-
1. The method of and process for the production of oxy- and sulpho-oxy-
indophenol thiosulphonic acids, which consists in allowing 12 naphthoquinone
4 monosulphonic acid to act on solutions of the thiosulphonic acids of P. amido-
dimethylaniline, P. amidodiethylaniline, P. amidomonoethylaniline, P. amidomono-
methylorthotoluidine, P. amidomonoethylorthotoluidine, P. aniidomethylbenzyl-
aniline sulphonic acid, P. amidoethylbenzylaniline sulphonic acid, P. amido-
diphenylamine sulphonic acid, or P. amidodibenzylaniline disulphonic acid, such
solutions being either neutral, rendered faintly acid by acetic acid, or alkaline by
sodium carbonate, substantially as hereinbefore described.
2. The method of and process for the conversion of the oxy- and sulpho-oxy-
indophenol thiosulphonic acids obtainable as herein before described, into thiazine
colouring matters on fibres or fabrics by printing the oxy- and sulpho-oxy-
indophenol thiosulphonic acids thereon with a chrome mordant and subsequently
steaming them under pressure, substantially as hereinbefore described.
3. The method of and process for the production of thiazine colouring matters

page_text: dyeing with mordants, by the conversion of the oxy- and sulpho-oxy-indophenol
thiosulphonic acids obtainable as hereinbefore set forth, by boiling their aqueous
solutions with dilute caustic alkalies, substantially as described.
4. The method of and process for the production of thiazine colouring matters
dyeing with mordants, by the conversion of the oxy- and sulpho-oxy-indophenol
thiosulphonic acids obtainable as hereinbefore set forth, by adding them to
concentrated, monohydrated, or fuming sulphuric acid containing a low percentage
of anhydrous sulphuric acid at a temperature not exceeding 50° C. whereby the
unsulphonated thiazines are formed which are then sulphonated by the addition of
fuming sulphuric acid and heating to 70° or 80° C. or by using at the beginning of
the operation a fuming sulphuric acid and heating to a temperature of 50° at first,
and finally to from 70° to 80° C., substantially as described.
Dated this 22nd day of February A.D. 1894.
WILLIAM E. HEYS.