The Manufacture or Production of New Azo Colouring Matters, and Processes for Dyeing and Printing therewith.
Year: 1892

page_text: Date of Application, 5th Oct., 1892
Complete Specification Left, 4th July, 1893-Accepted, 2nd. Sept., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of New Azo Colouring Matters, and
Processes for Dyeing and Printing therewith.
I HENRY EDWARD NEWTON, of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
In the Specification of application for Letters Patent No. 5112, dated
15th March 1892, in the name of Benjamin Willcox, communicated by my foreign
correspondents, valuable mono azo dye-stuffs are described, which are formed by
combining the diazo derivatives of aromatic amido carbonic acids with certain
naphthylamine sulpho acids.
The technical value of these products, consists in that they can advantageously
be employed for dyeing wool which is previously mordanted with metallic salts,
and that they may further be used for printing purposes, as they, after being fixed
on cotton fibre by means of metallic mordants, can further be diazotised and
combined with amines or phenols.
My foreign correspondents have described in the Specification of application for
Letters Patent No. 15636, dated 31st August 1892, analogous colouring matters
which are obtained by the combination of diazotised amido carbonic acids with
alpha naphthylamine ortho, mono sulpho acid, amidonaphtholsulpho acid, amido-
naphtholether sulpbo acid, amidonaphthoxyacetic acid, amidonaphthoxyacetic sulpho
acid, or paraxylidine (CH, NH, CH,:1:2:4).
:
The last named dye stuffs also can be employed for dyeing mordanted wool, and
for printing purposes, using in the latter case the methods which my foreign corre-
spondents have explained in the Specification of application for Letters Patent
No. 5815, dated 24th March 1892.
My foreign correspondents have now found, that the paraxylidine above
mentioned can be replaced by amidocresolethers, especially those derived from
ortho amido paracresol (CH, NH, OH = 1:2:4:), and metaamidoparacresol
| (CH, : NH,:OH = 1:3:4), and having the general formula:
:
:
in which by R a methyl group, an ethyl group, a propylbutyl or amyl group, or
analogous fatty or aromatic groups, such as, for example: pheyle, tolyle, xylyle,
benzyle, and the like, are understood.
The production of these coloring matters, obtained by means of amidocresol-
ether, is effected in an analogous manner to that of the products described in the
Specification of application for Letters Patent No. 15636, dated 31st August 1892.
In order to illustrate the method of producing these dye stuffs, the following
example is given, the parts mentioned being by weight.

page_text: COLORING MATTER PRODUCED BY COMBINING ONE MOLECULAR PROPORTION
OF DIAZOTISED META AMIDOBENZOIC ACID, WITH ONE MOLECULAR
PROPORTION OF META AMIDO PARA CRESOLETHYLETHER.
A solution prepared by dissolving 1.37 parts of meta amidobenzoic in 40 parts
of water, with the addition of 3.6 parts of hydrochloric acid (containing 20 per
cent. of pure acid), when cool, is mixed with a solution in water of 0.69 parts
of sodium nitrite. As soon
as the diazotation is finished, the whole liquid is
poured into a solution obtained by dissolving 1-9 parts of meta amido para-
cresolethylether hydrochlorate in about 10 parts of water, and, on stirring,
about 7 parts of sodium acetate, dissolved in a small quantity of water, are
added. After heating for a short time at from 35 to 40 degrees centigrade, the
resulting mixture is allowed to stand for 24 hours. The complete dye stuff is
then filtered off and purified by redissolving and precipitation in the usual
manner.
It dyes wool mordanted with chromium salts a yellow, and produces the same
shade in printing therewith cotton mordanted with chromium salts.
If meta amidobenzoic acid employed in the foregoing example, be replaced by
orthoamidobenzoic acid, paraamidobenzoic acid, orthoamidosalicylic acid, para-
amidosalicylic acid, amidoparahydroxybenzoic acid, ortho amidometacresol-
carbonic acid, paraamidoorthocresolcarbonic acid, amido auisic acid, or amido-
phthalic acid; or, if on the other hand, metaamidoparacresolethyl ether be
replaced by the isomeric orthoamidoparacresolethylether, or the analogous and
homologous alkylethers of orthoamidoparacresol and metaamidoparacresol,
including amidocresolbenzylether, the analogous monoazo dye stuffs are obtained.
The latter produce, in printing therewith cotton (by means of metallic mordants),
shades which are from yellow to brown, and are in general similar to those
produced on wool previously mordanted with chromium salts.
Of course the production of these monoazo coloring matters is not restricted to
the above mentioned method, but they can be obtained by means of all those
processes which may be used for the manufacture of analogous dye stuffs.
In place of the amido carbonic acids, also sulpho derivatives thereof, and other
substitution products thereof, can be employed, analogous dye stuff's being obtained
which in general shew similar dyeing properties.
The process for further diazotising the afore defined nono azo coloring matters
derived from amidocresol ethers, when fixed on the cotton fibre (with the aid of
metallic mordants), and coupling their diazo compounds with phenols or amines, in
general, is effected in the same manner as described in the Specifications of
applications for Letters Patent No. 5815" and 15636".
In order to further illustrate this method, the following example is given, the
parts being hr weicht
PRODUCTION OF CLARET RED FAST AGAINST THE ACTION OF SOAPING, WITH
THE EMPLOYMENT OF THE DYE STUFF RESULTING FROM DIAZOTISED
META AMIDO BENZOIC ACID AND METAAMIDOPARACRESOLETHYLETHER 4
IN EQUAL MOLECULAR PROPORTIONS.
The cotton material is printed with a paste prepared mixing 100 parts of a
20 per cent. paste of the coloring matter obtained from diazotised metaamido
benzoic acid and metaamidoparacresolethylether, 200 parts of water, 640 parts of
acetic acid starch tragacanth thickening, and 60 parts of chrome acetate (20 degrees 50
Baumé). After steaming for one hour, chalking, malting, soaping, and washing,
the printed cloth is placed in a bath of nitrous acid (produced by acidulating

page_text: a diluted solution in water of 10 parts of sodium nitrite), and agitated therein
for say 15 to 30 minutes. The material is then taken out, washed, and well
agitated in a solution of 20 parts of the sodium salt of beta naphthol. The
cloth immediately takes a claret red color on the parts printed. After half an
hour it is washed and soaped.
Similar shades are obtained by the employment of the other monoazo dye stuffs
above mentioned in place of the product from meta amido benzoic acid and meta
amidoparacresolethylether.
If the diazo compounds produced on the fibre be combined, in place of beta
naphthol, for instance, with phenol, in general brownish shades result, whilst
resorcinol yields a brownish red, alpha naphthol a brownish violet, beta naphthol
carbonic acid a violet, 18 dihydroxynaphthalene a bluish violet, alphanaphthyl-
amine a brownish violet, betanaphthylamine a claret red, ethylbetanaphthylamine
a violet, amidonaphthol a reddish brown, amidonaphtholether a violet black, and
metaphenylene diamine a brown.
The sulpho and carbonic acids of the last named components, when combined
with the diazo products on fibre, in general yield similar shades.
The following example is given in order to illustrate the employment of the
aforesaid coloring matters as intermediate products for dreing purposes
BY
PRODUCTION OF A BLUISH VIOLET WITH WHITE PATTERNS ON COTTON
EMPLOYING THE DYE STUFFS OBTAINED FROM DIAZOTISED AMIDO-
SULPHOSALICYLIC ACID AND META AMIDOPARACRESOLETHYLETHER.
4
The cotton cloth is padded with chrome mordant (for example chrome bisulphite),
and the pattern desired is discharged with citric acid or lemon juice. It is then
dyed with a neutral or moderately acid solution of the dye stuff obtained by the
combination of diazotised amidosulphosalicylic acid and meta amidoparacresol-
ethylether. After washing, it is placed for a short time (say 5 to 10 minutes) in
a bath of sodium nitrite, acidulated with muriatic acid, taken out, washed, and
finally well agitated in a watery solution of betanaphthol. The original brown
color of the diazo compound immediately changes into a beautiful bluish violet.
When the combination is complete, the material is taken out, washed, and soaped.
Shades, which are in general similar, result by employing, in place of the
aforesaid mono azo dye stuffs, those diazo coloring matters which are obtained by
further diazotising the mono azo products, and coupling the diazo derivatives thus
formed, with such amido compounds, the amido group of which may further be
changed into the diazo group by nitrous acid, the latter process being effected on
the fibre. By the further combination of the diazo products formed on the fibre,
with the known dye-stuff components, likewise fast shades are obtained.
In general, red, brown, violet, blue, green, or black shades result by printing
the above mentioned coloring matters derived from amidocresolalkylether on cloth
or yarn, or by dyeing therewith cloth or yarn, further diazotising the amido mono
azo or amido disazo dye stuffs thus fixed on the fibre, and coupling the resulting
diazo compounds with suitable dye stuff components, such as, for example, amines,
phenols, amidophenols, amidophenolethers of the benzene or naphthalene series,
sulpho derivatives, carboxylic derivatives, and other substitution products thereof.
The shades thus produced resist the action of washing and soaping.
The employment of the aforesaid dye stuffs derived from amidocresolalkylether
is not restricted to the proportions mentioned in the last two examples, but the use
thereof may be varied. Of course in place of chrome mordants, other metallic
mordants producing the same or a similar effect can be employed; the cloth padded
with a suitable mordant may be discharged in pattern to produce white or colored
patterns etc., as desired.
The nature of this invention, in so far as it relates to the employment of the

page_text: above mentioned dye stuffs, derived from amidocresolalkylethers as intermediate
products in dyeing and printing is not altered by such variations.
Dated this 5th day of October 1892.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of New Azo Colouring Matters, and
Processes for Dyeing and Printing therewith.
I, HENRY EDWARD NEWTON, of The Office for Patents, 6, Bream's Buildings,
Chancery Lane in the County of London, 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 :-
In the Specification of Letters Patent No. 5112, dated 15th March 1892, in the
name of Benjamin Willcox (communicated by my foreign correspondents), valuable
mono azo dye-stuffs are described, which are formed by combining the diazo
derivatives of aromatic amido carboxylic acids with certain naphthylamine
sulpho acids.
The technical value of these products consists in that they can be advantageously
employed for dyeing wool which is previously mordanted with metallic salts, and
that they may also be used for printing purposes, as, when fixed on cotton fibre
by means of metallic mordants, they can be diazotised, and combined with amines
or phenols. Analogous colouring-matters derived from the diazo derivatives of
aromatic amidocarboxylic acids and amidonaphtholmonosulpho acid G, 1:8,
amidonaphthol beta disulpho acid, alpha naphthylamine-ortho-mono-sulpho acid,
alpha naphthylamine beta mono sulpho acid (beta or delta of Clève), or amido-
naphtholetherbeta mono sulpho acid, are mentioned by my foreign correspondents
in the 'Specification of the Letters Patent No. 5815, dated 24th March 1892.
:
:
My foreign correspondents have further described in the Specification of
application for Letters Patent No. 15636, dated 31st August 1892, analogous
colouring-matters which are obtained by the combination of diazotised amido-
carboxylic acids with paraxylidine (CH, NH, CH, 1:2:4), or salts thereof.
The last named dye-stuffs can be employed for dyeing mordanted wool, and for
printing purposes, using, in the latter case, the methods which my foreign
correspondents have explained in the Specification of Letters Patent No. 5815,
dated 24th March 1892, and in the Specification of application for Letters Patent
No. 15,636, dated 31st August 1892.
My foreign correspondents have now found that the paraxylidine above
mentioned, can be replaced by amidocresolethers, especially those derived from ortho
amido para cresol (CH, NH, OH = 1:2:4) and meta amido para cresol
(CH, NH, OH = 1:3:4), and having the general formula:
:

page_text: FIRST EXAMPLE.
COLOURING-MATTER PRODUCED BY COMBINING ONE MOLECULAR PROPORTION
OF DIAZOTISED METAMIDOBENZOIC ACID WITH ONE MOLECULAR
PROPORTION OF METAMIDO PARA CRESOL ETHYLETHER.
A solution prepared by dissolving 1.37 parts of metamidobenzoic acid in 40 parts
of water, to which is added 3-6 parts of hydrochloric acid (containing 20 per cent.
of pure acid), when cool, is mixed with a solution, in water, of 0.69 parts of sodium
nitrite. When the diazotisation is complete, the whole liquid is poured into a
solution prepared by dissolving 1.9 parts of metamidoparacresolethylether hydro-
chloride in about 10 parts of water. About 7 parts of sodium acetate dissolved in
a small quantity of water are then mixed with the liquid, and, after heating, during
a short time at from 35 to 40 degrees centigrade, the mixture is allowed to stand
during 24 hours. The resulting dye-stuff is then filtered off, and purified by
dissolving and precipitating in the usual manner.
It dyes wool mordanted with chromium salts, a yellow, and produces the same
colour on printing therewith cotton mordanted with chromium salts. The analogous
monoazo dye-stuffs are obtained if the metamidobenzoic acid employed in the
foregoing example be replaced by orthamidobenzoic acid, paramidobenzoic acid,
orthamidosalicylic acid, paramidosalicylic acid, amidopara hydroxybenzoic acid,
orthamidometacresolcarboxylic acid, paramido ortho cresolcarboxylic acid, amido-
anisic acid, or amidophthalic acid, or, if, on the other hand, metamidopara
cresolethylether be replaced by the isomeric orthamido para cresolethylether, or
the analogous and homologous alkylethers of orthamido para cresol or metamido
para cresol, including amidocresolbenzylether.
These latter produce, on cotton treated. with metallic mordants, shades which
vary from yellow to brown, and are in general similar to those produced on wool
previonsly mordanted with chromium salts.
Of course, the production of these monazo colouring-matters is not restricted to
the above mentioned method, but they can be obtained by means of all the methods
of producing analogous dye-stuffs known to chemists.
In place of the amidocarboxylic acids, sulpho derivatives thereof, and other
substitution products thereof, can also be employed, analogous dye-stuffs being
obtained which in general possess similar dyeing properties.
The process for further diazotising the aforesaid monazo colouring-matters
derived from amidocresolethers, when fixed on the cotton fibre (with the aid of
metallic mordauts), and coupling their diazo compounds with phenols or amines, is
in general effected in the same manner as described in the Specifications of Letters
Patent No. 58150, and of the application for Letters Patent No. 15,636.
In order to further illustrate this method, the following example is given, the
narte haine br maight
PRODUCTION OF CLARET-RED-COLOUR, WHICH WITHSTANDS SOAPING, BY
MEANS OF THE DYE-STUFF RESULTING FROM DIAZOTISED METAMIDO
BENZOIC ACID AND METAMIDO PARACRESOLETHYLETHER IN EQUAL
2.)
MOLECULAR PROPORTIONS.
per
The cotton material is printed with a paste prepared by mixing 100 parts of a
cent. paste of the colouring-matter obtained from diazotised metamidobenzoic
acid and metamidoparacresolethylether, 200 parts of water, 640 parts of acetic
acid, starch tragacanth thickening, and 60 parts of chromium acetate (20 degrees
Baumé). After steaming during one hour, chalking, treating with malt, soaping,
and washing, the printed cloth is placed in a bath of nitrous acid (produced by

page_text: PRODUCTION OF A BLUISH-VIOLET WITH WHITE PATTERNS OR COTTON, BY
EMPLOYING THE DYE-STUFF OBTAINED FROM DIAZOTISED AMIDOSULPHO
SALICYLIC ACID AND METAMIDOPARACRESOLETHYLETHER.
After "padding "the cloth with a chrome mordant, (for example, chromium
bisulphite), and, if necessary, "discharging" the patterns with citric acid or lemon
juice, it is dyed with a neutral or moderately acid solution of the dye-stuff from
diazotised amido sulpho salicylic acid, and metamidoparacresolethylether. It is
then washed, and afterwards placed for a short time (say, 5 to 10 minutes) in a
bath of sodium nitrite, acidulated with muriatic acid, from which it is removed after
about 10 to 15 minutes, washed, and finally well agitated in a watery solution of
the sodium salt of beta naphthol. When the combination is complete, the material
is taken out, washed, and soaped. In this manner, a beautiful bluish-violet is
produced on the undischarged parts.
In a manner similar to that mentioned in the Specification of the aforesaid
Letters Patent No. 5815", coloured figures can be discharged in place of white
figures.
In general, from red, brown, violet, to blue shades, result, by printing the above
mentioned colouring-matters derived from amidocresolalkylether on cloth or yarn,
or by dyeing therewith cloth or yarn, further diazotising the amidomonazo
colouring-matters thus fixed on the fibre, and coupling the resulting diazo
compounds with suitable dye-stuff components, such as, for example: amines,
phenols, amidophenols, amidophenolethers of the benzene or naphthalene series,
sulpho derivatives, carboxylic derivatives, or other substitution products thereof.
The shades thus produced withstand washing and soaping.
The above sccond and third examples are given, in order to illustrate the method
of producing fast colours on the fibre by means of the amidoazo products above
referred to. My foreign correspondents do not limit themselves to the above
proportions, as the latter can be varied, i.e., all methods employed in dyeing and
printing for analogous purposes, can be used, without the nature of this invention
being altered by such modifications.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, as communicated to me
from abroad, I declare that what I claim is :-
1. The process for producing amido dye-stuffs suitable for dyeing and printing

page_text: :
purposes, which process consists in coupling one molecular proportion of amido-
cresolether derived from orthamidoparacresol (CH, NH, OH = 1:2:4), or
metamidoparacresol (CH, NH: OH = 1:3: 4), or a salt thereof, with one mole-
cular proportion of one of the following acids, viz., orthamidobenzoic acid,
metamidobenzoic acid, paramidobenzoic acid, orthamidosalicylic acid, paramido-
salicylic acid, amidoparahydroxy benzoic acid, orthamidometacresol carboxylic
acid, paramidoorthocresol carboxylic acid, amidoanisic acid, amidophthalic acid,
or analogous amidocarboxylic acids, or substitution derivatives of the above
amidocarboxylic acids.
2. The employment of the amidoazo dye-stuffe defined in the foregoing first
claim, in the process described in the Specification of the Letters Patent No. 5815,
dated 24th March 1892, that is to say, for the production of fast colours on
the fibre.
3. The process for producing fast colours on the fibre, which consists either in
printing the amidoazo dye-stuffs (defined in the foregoing first claim), together with
a chromium salt or mordant, and a suitable thickening, on the fibre, or in dyeing
with the amidoazo dye-stuffs above referred to, the fibre mordanted with a chromium
salt or mordant, and (after or without discharging figures) subsequently treating
the thus printed or dyed fibre with moderately acidulated solutions of sodium
nitrite, and then with solutions which are prepared from the known dye-stuff
components (viz. phenols, amines, amidophenols, amidophenolethers of the benzene
or naphthalene series, or sulpho or carboxylic acids thereof), and rendered weakly
alkaline or acid, according to the nature of the components employed.
4. As new manufactures, the new amidoazo colouring matters obtainable by the
process described in the foregoing first claim, or by any other method producing
the same result.
5. Cotton fibres or textures printed or dyed in the manner described in the
foregoing third claim, or by any other process producing the same result.
Dated this 1st day of July 1893
NEWTON & SON,
Agents for the Applicant.