An Improved Process of Dyeing Animal Fibres and Fabrics, Horn, Feathers, Leather, and Albuminous Substances Generally.
Year: 1892

page_text: Date of Application, 20th Aug., 1892
Complete Specification Left, 12th May, 1893-Accepted, 19th Aug., 1893
PROVISIONAL SPECIFICATION.
An Improved Process of Dyeing Animal Fibres and Fabrics, Horn,
Feathers, Leather, and Albuminous Substances Generally.
I, FRITZ OBERMAYER, of 3 Landskrongasse, Vienna, in the Empire of Austria,
Doctor of Medicine, do hereby declare the nature of this invention to be as
follows:-
It has already been ascertained that wool and silk can be dyed in a vivid manner
by the action of an acidified solution of nitrite and the combination of the diazo
substances produced, with an alkaline solution of phenols, such as phenol, resorcine,
pyrogallic acid, alpha naphthol and beta naphthol. This process is however, not
susceptible of practical application, as the strongly alkaline solutions of phenol
necessary for this purpose injure the animal fibre too much.
In my researches in connection with albuminous substances I have repeated the
above mentioned reaction and have found that not only the said animal fibres but
generally all albuminous substances and substances resembling albumin can be
diazotized by means of nitrous-acid and combined in a suitable manner, without
injury to the structure and appearance, not only with phenols and their sulpho
acids and carbonic acids, which are employed in the industry of the azo colouring
matters, but also with certain aromatic amines, fast vivid dyes being produced
which may be advantageously adapted for industrial employment more especially
by reason of the simplicity of the manipulations and cheapness of the phenols and
amines used.
My invention comprises not only a method of dyeing the above mentioned
substances, but also the further diazotizing of the dyes produced with amines and
the combination of the same with amines, and furthermore the shading of azo
substances obtained in this and the aforesaid manner by the action of solutions of
metallic salt.
I will now proceed to describe in succession the following methods ;—
I. The diazotizing method carried out by me and recognized as the best, which
method is however only partly included in the scope of my present invention.
11. The combination of the diazo substances produced according to I with
phenols and amines, or their sulpho acids and carbonic acids.
III. The method of producing diazo substances from the amidoazo substances
obtained according to II with amines.
IV. The treatment of the diazo substances produced, or the azo, amidoazo and
diazo dyes, with various metallic salts for the purpose of shading the same.
In each of these four methods the operations which must be carried out for the
various kinds of the industrially important albuminous substances will hereinafter
be described and explained by examples.
1. DIAZOTIZING METHOD.
The trials made have demonstrated that it is of importance in the diazotizing
method to employ the solutions of nitrous acid in a very dilute state, that is to say
solutions of about one-tenth to two per cen'. of commercial sodium nitrite with a
proportion of about 80 per cent., acidified with an equivalent quantity of hydro-
chloric acid or sulphuric acid, and in a cold state preferably for a period of from
12 to 24 hours, the said solutions being excluded from the light.
Only by fulfilling these conditions is it possible to obtain equal dyes.
It should here be observed that the customary rinsing (moving) of the ware is

page_text: also of great value in this and the other operations for obtaining uniformity. The
diazotizing method does not differ materially for silk, wool, leather, hair, feathers,
horn and other albuminous substances. It should be noticed that dilute solutions
of nitrous acid dye the albuminous substances less intensively yellow and that more
concentrated solutions dye them more intensively yellow, which has then also an
influence upon the dye produced in the combination with phenols and amines.
For diazotizing wool and silk, unoiled wool or scoured silk is put in the solution
of nitrite prepared as above stated, and left therein for from 12 to 24 hours, with
repeated rinsing of the same. In this instance the proportion between the liquor
and ware should be such that the wool or silk is just covered by the solution.
Moreover care should be taken to exclude the light as completely as practicable,
with a period of action of 12 hours the night is suitably chosen for this purpose.
Then the ware is taken out and thoroughly washed with water and preferably at
once caused to combine with amines or phenols.
Hair, feathers, horn and leather are treated in the same manner, with the single
exception that the period of action is prolonged to 36 hours.
The diazo substances produced are very sensitive to light. When they are
treated with solutions of various metallic salts or oxidizing agents, copper chloride,
ferric chloride, zinc acetate, potassium bichromate in a solution of tartrate, with
the exception of stannous chloride, more or less intensively brown or brown-red
colours are obtained which are likewise very sensitive to light and are not therefore
suitable for an industrial utilization for dyeing purposes. When however, the said
diazo substances are treated with a dilute hydrochloric solution cf stannous
chloride at say 60 degrees centigrade a cream colour offering great resistance to
light is produced in a very short time with an apparent reduction of the diazo
substance for all the said albuminous substances and substances resembling
albumin.
II. COMBINATION OF THE DIAZO ALBUMINOUS SUBSTANCES WITH PHENOLS
AND AMINES OR THEIR SULPHO ACIDS AND CARBONIC ACIDS.
I have found that the combination of the diazo albuminous substances, such as
diazotized wool, silk, leather, feathers, horn, hair, with phenols takes place without
injury to the said substances in the simplest manner, if the phenols are employed
in a neutral aqueous solution heated to 80 degrees, or if use is made of cold,
slightly ammoniacal solutions of alkaline phenolates without an excess of free
alkali. Furthermore I have found that the neutral salts of the amines or the
slightly acetic solution of the amines, if heated to 80 degrees centigrade or even in
a cold solution, can likewise be employed for the combination to obtain dyes. The
solutions of phenols and amines used for this purpose vary a little as regards their
concentration, which has an influence upon the intensity of the dye produced. In
general it will be sufficient to employ per litre from 1 to 20 grammes of the phenols,
alkaline phenolates, alkaline salts, sulpho acids or carbonic acids or phenols, salts
of amines or amidosulpho acids.
The addition of ammonia to the solution of alkaline phenolates, in case the
dyeing is to take place in the cold state amounts to about two-tenths per cent. of
ammonia.
EXAMPLE 1.
The wool diazotized according to I is put in a solution of alkaline beta naphthol,
containing 5 per thousand of beta-naphthol and two-tenths per cent. of ammonia at
the ordinary temperature, and is left therein for 12 hours with frequent rinsing,
and then thoroughly washed. The beautifully red-brown dye produced resists the
action even of hot solutions of soap. Acids effect a lightening of the shade.

page_text: TABLE A.
Diazo albuminous substances combined with aniline chloride give a dark-red
yellow dye (1) but with phenol a yellow dye with a tinge of red (2), with resorcine
dark orange yellow (3), with tannin dark yellow with a tinge of red (4), with alpha
naphthol scarlet red (5), with beta naphthol light scarlet red with a tinge of
yellow (6), with alpha naphthyl-amine chloride light red brown (7), with beta
naphthyl-amine chloride orange yellow (8), with meta phenylenediamine chloride
dark violet red (9), with benzidine acetate a wood brown dye with a tinge of
red (10).
With all these dyes the solutions are neutral and the dyes resist the action of
soap, with the exception of 5 and 6 which become somewhat darker when treated
with soap.
The above mentioned dyes relate to those of wool.
The quantity of the liquid in proportion to the diazo albuminous substance
should be such that the latter substance is always covered by the liquid. The
baths can be used repeatedly, the proper proportions of the phenol or amine being
re-established from time to time. Feathers, hair, horn, leather are treated in like
manner; feathers and leather may however be combined only in a cold or luke-
warm bath with amines or phenols.
The phenols and amines or the sulpho acids and carbonic acids which are to be
employed in the aforesaid method are as follows:-
Phenol, o-nitrophenol, tiophenol, cressal, thymol, cumol (pseudo), resorcine,
pyrogallic acid, tannin, alpha naphthol, beta naphthol, dinitro beta naphthol,
dioxynaphthaline, salicylic acid, aniline, o and p toluidine, xylidine, cumidine,
m phenylenediamine p phenylene diamine, toluylenediamine, alpha naphthylamine,
beta naphthylamine, naphthylenediamine, benzidine, tolidine, dianisidine, sodium
beta naphthylamine sulpbide, 2.6.
(Brönner) Alpha naphthylamine-sulphide 1.4.

page_text: mentioned in the Table A becomes yellow brown with a tinge of red, 2 light brown
with a tinge of red, 3 light yellow brown, 4 light havannah with a tinge of red,
5 dark brown red of a lighter shade, 6 dark brown red, 7 dark brown, 8 havannah
brown with a tinge of red, 9 dark bordeaux, 10 dark wood brown with a reddish
tinge.
By treatment during about fifteen minutes in a neutral aqueous solution containing
from one-half to two per cent. of zinc acetate at the temperature of 100 degrees
centigrade, the dye designated by 1, of those mentioned in the Table A, becomes
roe brown, 2 light brown, 3 light yellow brown with a tinge of red, 4 light
havannah, 5 dark bordeaux, 6 bordeaux red, 7 red brown, 8 dark orange, 9 dark
bordeaux darker, 10 dark brown.
By treatment during about 3 to 5 minutes in a solution containing one per cent.
of potassium bichromate plus an equivalent quantity of sulphuric acid at a
temperature of from 30 to 80 degrees centigrade the dye designated by 1, of those
mentioned in the Table A, becomes dark yellow with a greenish tinge, 2 dark
yellow with a greenish tinge, 3 brown yellow, 4 dark yellow, 5 deep dark brown
with a tinge of red, 6 red brown, 7 dark wood brown, 8 light havannah brown,
9 light brown, 10 black with a brownish tinge; whilst the dye designated by 11,
of those mentioned in the Table B, becomes dark red brown, 12 black 13 deep dark
wood brown, 14 black with a tinge of light red, 15 deep dark brown, 16 black
somewhat reddish.
All the dyes resist the action of soap, with the exception of 5 and 6 which
become somewhat darker. The dyes mentioned refer to those of wool.
By the present process the animal fibres, fabrics and albuminous substances
are dyed throughout, as microscopic sections show; this determines not only a
special fastness but the appearance is also very beautiful and vivid. The dyes
obtained do not rust. A great number of these dyes resist the action of alkalies
and an equally great number resist the actions of acids. The process does not
injure the fibre and, by reason of the invariable employment of azo colour matter
components, is extremely simple and very cheap. For dyeing mixed fabrics
consisting of different animal fibres the improved process can be used with success,
as the operations for the several animal fibres do not differ from each other. By
maintaining the same conditions as regards concentration, temperature and period
of action, I always obtain equal dyes.
Dated this 20th of August 1892.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.
.
COMPLETE SPECIFICATION.
An Improved Process of Dyeing Animal Fibres and Fabrics, Horn,
Feathers, Leather, and Albuminous Substances Generally.
I, FRITZ OBERMAYER, of 3 Landskrongasse, Vienna, in the Empire of Austria,
Doctor of Medicine, 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 dyeing of animal fibres, fabrics, horn, feathers,
leather and albuminous substances generally.
It has already been ascertained that wool and silk can be dyed in a vivid manner
by the action of an acidified solution of nitrite and the combination of the diazo
substances produced, with an alkaline solution of phenols, such as phenol, resorcine,
pyrogallic acid, alpha naphthol and beta naphthol. This process is however pot
susceptible of practical application, as the strongly alkaline solutions of phenol
necessary for this purpose injure the animal fibre too much. In my researches in
connection with albuminous substances I have repeated the above mentioned

page_text: reaction and have found that not only the said animal fibres but generally all
albuminous substances and substances resembling albumin can be diazotized by
means of nitrous acid and combined in a suitable manner, without injury to the
structure and appearance, not only with phenols and their sulpho acids and
carbonic acids, which are employed in the industry of the azo colouring matters,
but also with certain aromatic amines, fast vivid dyes being produced which
may be advantageously adapted for industrial employment more especially by
reason of the simplicity of the manipulations and cheapness of the phenols and
amines used.
My invention comprises not only a method of dyeing the above mentioned
substances, but also the further diazotizing of the dyes produced with amines
and the combination of the same with amines, and furthermore the shading of
azo substances obtained in this and the aforesaid manner by the action of solutions
of metallic salt.
I will now proceed to describe in succession the following methods:
I. The diazotizing method carried out by me and recognized as the best, which
method is however only partly included in the scope of my present invention.
II. The combination of the diazo substances produced according to I with
phenols and amines, or their sulpho acids and carbonic acids.
III. The method of producing diazo substances from the amidoazo substances
obtained according to II with amines.
IV. The treatment of the diazo substances produced, or the azo, amidoazo and
diazo dyes, with various metallic salts for the purpose of shading the same.
In each of these four methods the operations which must be carried out for the
various kinds of the industrially important albuminous substances will hereinafter
be described and explained by examples.
I. DIAZOTIZING METHOD.
The trials made have demonstrated that it is of importance in the diazotizing
method to employ the solutions of nitrous acid in a very dilute state, that is to say,
solutions of about one-tenth to two per cent. of commercial sodium nitrite with a
proportion of about 80 per cent., acidified with an equivalent quantity of hydro-
chloric acid or sulphuric acid, and in a cold state preferably for a period of
from 12 to 24 hours, the said solutions being excluded from the light. Only by
fulfilling these conditions is it possible to obtain equal dyes.
It should here be observed that the customary rinsing (moving) of the ware is a
also of great value in this and the other operations for obtaining uniformity. The
diazotizing method does not differ materially for silk, wool, leather, hair, feathers,
horn and other albuminous substances. It should be noticed that dilute solutions
of nitrous acid, dye the albuminous substances less intensively yellow and that
more concentrated solutions dye them more intensively yellow, which has then also
an influence upon the dye produced in the combination with phenols and amines.
For diazotizing wool and silk, wool freed from oil or scoured silk is put in the
solution of nitrite prepared as above stated, and left therein for from 12 to 24 hours,
with repeated rinsing of the same. In this instance the proportion between the
liquor and ware should be such that the wool or silk is just covered by the solution.
Moreover care should be taken to exclude the light as completely as practicable;
with a period of action of 12 hours the night is suitably chosen for this purpose.
Then the ware is taken out and thoroughly washed with water and preferably at
once caused to combine with amines or phenols.
Hair, feathers, horn and leather are treated in the same manner, with the single
exception that the period of action is prolonged to 36 hours.
The diazo substances produced are very sensitive to light. When they are
treated with solutions of various metallic salts or oxidizing agents, copper chloride,
ferric chloride zinc acetate, potassium bichromate in a solution of tartrate, with the
exception of stannous chloride, more or less intensively brown or brown-red colours

page_text: are obtained which are likewise very sensitive to light and are not therefore
suitable for an industrial utilization for dyeing purposes. When however the said
diazo substances are treated with a dilute hydrochloric solution of stannous chloride
at say 60 degrees centigrade a cream colour offering great resistance to light is
produced in a very short time with an apparent reduction of the diazo substance,
for all the said albuminous substances and substances resembling albumin.
II. COMBINATION OF THE DIAZO ALBUMINOUS SUBSTANCES WITH PHENOLS
AND AMINES OR THEIR SULPHO-ACIDS AND CARBONIC ACIDS.
I have found that the combination of the diazo albuminous substances, such as
diazotized wool, silk, leather, feathers, horn, hair, with phenols takes place without
injury to the said substances in the simplest manner, if the phenols are employed
in a neutral aqueous solution heated to 80 degrees, or if use is made of cold, slightly
ammoniacal solutious of alkaline phenolates without an excess of free alkali.
Furthermore I have found that the neutral salts of the amines or tbe slightly
acetic solution of the amines, if heated to 80 degrees centigrade or even in a cold
solution, can likewise be employed for the combination to obtain dyes. The
solutions of phenols and amines used for this purpose vary a little as regards their
concentration, which has an influence upon the intensity of the dye produced. In
general it will be sufficient to employ per litre from 1 to 20 grammes of the phenols,
alkaline phenolates, alkaline salts, sulpho acids or carbonic acids or phenols, salts of
amines or amidosulpho acids. The addition of ammonia to the solution of alkaline
phenolates, in case the dyeing is to take place in the cold state, amounts to about
two-tenths per cent. of ammonia.

page_text: In water.
stirring. The silk now dyed deep blue black is thoroughly washed
Alkalies cause a tinge of blue, the dye perfectly resists the action of weak acids.
5. For example the following phenols and amines give the dyes hereinafter
mentioned.
TABLE A.
Diazo albuminous substances combined with aniline chloride give a dark red
yellow dye (1), but with phenol a yellow dye with a tinge of red (2), with resorcine
dark orange yellow (3), with tannin dark yellow with a tinge of red (4), with
alpha naphthol scarlet red (5), with beta naphthol light scarlet red with a tinge of
yellow (6), with alpha naphthylamine chloride light red brown (7), with beta
naphthylamine chloride orange yellow (8), with meta phenylenediamine chloride
dark violet red (9), with benzidine acetate a wood brown dye with a tinge of
red (10).
With all these dyes the solutions are neutral and the dyes resist the action
of soap, with the exception of 5 and 6 which become somewhat darker when treated
with soap.
The above-mentioned dyes relate to those of wool.
The quantity of the liquid in proportion to the diazo albuminous substance
should be such that the latter substance is always covered by the liquid. The
baths can be used repeatedly, the proper proportion of the phenol or amine being
re-established from time to time. Feathers, hair, horn, leather are treated in like
manner; feathers and leather may however be combined only in a cold or lukewarm
bath with amines or phenols.
The phenols and amines or the sulpho acids and carbonic acids which are to be
employed in the aforesaid method are as follows:-
Phenol, o-nitrophenol, tiophenol, cresol, thymol, cumol, (pseudo), resorcine,
pyrogallic acid, tannin, alpha naphthol, beta naphthol, dinitro beta naphthol,
dioxynaphthaline, salicylic acid, aniline, o and p toluidine, xylidine, cumidine,
m phenylene diamine, p phenylene diamine, toluylene diamine, alpha naphthylamine,
beta naphthylamine, naphthylene diamine, benzidine, tolidine, dianisidine, sodium
beta naphthylamine sulphonate 2·6 (Brönner), sodium alpha naphthylamine-
sulphonate 1.4.
III. THE PRODUCTION OF DIAZO DYES BY THE AID OF THE DYES
OBTAINED UNDER II WITH AMINEs.
The dyes obtained under II by means of amines owe their colour evidently to
amidoazo substances. In fact they can be diazotized by placing them in dilute
solutions of nitrous acid, of equal concentration, as stated under I, and paired with
phenols and amines thereby obtaining partly a greater intensity of the dyes and
partly shades of the same.
The method is in this case exactly like the method hereinbefore described
under I and II, both in respect of the various albuminous substances-silk, wool,
feathers, leather, hair, horn-and also in respect of the operations and the
concentration of the solutions. The following table explains some of the dyes
obtained by me in this manner.
TABLE B.
Amidoazo substances No. 7 of the Table A, diazotized and combined with
meta-phenylenediamine receive black colours with a slight tinge of red (11) whilst
combined with benzidine they receive a dark red-brown dye (12).
Amido azo substances, No. 8 of the Table A, diazotized and combined with
alpha naphthylamine, receive a red brown dye (13), whilst with benzidine they
receive a dark wood-brown dye (14).
Amido azo substances, No. 9 of the Table A, diazotized and combined with
alpha naphthol, receive a brown red dye (15), whilst with benzidine they receive a
wood-brown dye (16).

page_text: By treatment during about three minutes in a solution containing from one-half
to two per cent. of copper chloride and two-tenths per cent. of hydrochloric acid at
a temperature of from 50 to 80 degrees centigrade the dye designated by 1 in the
Table A becomes light wood brown, 2 wood brown, 3 light red brown, + light wood
brown, 5 dark brown red, 6 dark red violet, 7 black-brown, 8 havannah brown,
10 dark wood brown; whilst of the dyes mentioned in the Table B the dye
designated by 11 becomes deep dark brown almost black, 12 deep dark brown,
13 dark wood brown, 14 dark wood brown, 15 dark brown red, 16 wood brown.
By treatment during about 3 minutes in a solution containing from one-half to
2 per cent. of ferric chloride and two-tenths per cent. of hydrochloric acid at a
temperature of from 50 to 80 degrees centigrade, the dye designated by 1
mentioned in the Table A becomes yellow brown with a tinge of red, 2 light brown
with a tinge of red, 3 light yellow brown, 4 light havannah with a tinge of red,
5 dark brown red of a lighter shade, 6 dark brown red, 7 dark brown, 8 havannah
brown with a tinge of rel, 9 dark bordeaux 10 dark wood brown with a reddish
tinge.
By treatment during about fifteen minutes in a neutral aqueous solution con-
taining from one-half to two per cent. of zinc acetate at the temperature of
100 degrees centigrade, the dye designated by 1, mentioned in the Table A,
becomes roe brown, 2 light brown, 3 light yellow brown with a tinge of red, 4 light
havannah, 5 dark bordeaux, 6 bordeaux red, 7 red brown, 8 dark orange, 9 dark
bordeaux darker, 10 dark brown.
By treatment during about 3 to 5 minutes in a solution containing one per cent.
of potassium bichromate plus an equivalent quantity of sulphuric acid at a
temperature of from 30 to 80 degrees centigrade the dye designated by 1
mentioned in the Table A, becomes dark yellow with a greenish tinge, 2 dark
yellow with a greenish tinge, 3 brown yellow, 4 dark yellow, 5 deep dark brown
with a tinge of red, 6 red brown, 7 dark wood brown, 8 light havannah brown,
9 light brown, 10 black with a brownish tinge; whilst the dye designated by 11,
mentioned in the Table B, becomes dark red brown, 12 black, 13 deep dark
wood brown, 14 black with a tinge of light red, 15 deep dark brown, 16 black
somewhat reddish.
All the dyes resist the action of soap, with the exception of 5 and 6 which
become somewhat darker. The dyes mentioned refer to those of wool.
By the present process the animal fibres, fabrics and albuminous substances are
dyed throughout, as microscopic sections show; this determines not only a special
fastness but the appearance is also very beautiful and vivid. The dyes obtained do
B

page_text: not rust. A great number of these dyes resist the action of alkalies and an equally
great number resist the action of acids. The process does not injure the fibre and,
by reason of the invariable employment of azo colour matter components, is
extremely simple and very cheap. For dyeing mixed fabrics consisting of different
animal fibres the improved process can be used with success, as the operations for
the several animal fibres do not differ from each other. By maintaining the same
conditions as regards concentration, temperature and period of action, I always
obtain equal dyes.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
First. The process of diazotizing leather, feathers and horn by putting the same
in dilute solutions of nitrous acid, substantially as hereinbefore set forth under the
heading I.
Second. The process of dyeing animal fibres and animal fabrics and also mixed
fabrics consisting of various animal fibres, such as silk, wool, hair, leather and horn,
by diazotizing the same in the manner hereinbefore set forth under the heading I
and by combination with the phenols and amines or their sulpho acids and carbonic
acids mentioned under the heading II, substantially as specified under the same
heading II.
Third. The process of producing diazo dyes by further diazotizing the amidozo
dyes mentioned in the second claim and obtained by the use of amines, and by
combination of the substances produced with the phenols and amines or sulpho
acids and carbonic acids mentioned under the heading II, substantially as herein-
before set forth under the heading III.
Fourth. The process, herein set forth under the heading IV, of shading the dyes
obtained according to the second and third claims by treatment with solutions of
metallic salts or oxidizing agents, copper chloride, ferric chloride, zinc acetate,
potassium bichromate and sulphuric acid.
Fifth. The animal fibres and animal fabrics dyed according to the processes set
forth in the second and fourth claims.
Dated this 12th day of May 1893.
HASELTINE, LAKE & Co.,
.45, Southampton Buildings, London, W.C., Agents for the Applicant.