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

page_text: Date of Application, 31st Aug., 1892
Complete Specification Left, 29th May, 1893-Accepted, 8th July, 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.
1, 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 and communicated by my foreign
correspondents, mono azo dye-stuffs are described which are suitable for dyeing
wool with the aid of metallic mordants, and also are capable of being employed in
printing, as these dyes, when fixed on cotton fibre by means of metallic mordants,
can be diazotised, and combined with phenols, amines and the like, as described in
the Specification of application for Letters Patent No. 5815, dated 24th March 1892,
in the name of the said Benjamin Willcox.
: The aforesaid simple azo dyestuffs are obtained by acting with the diazo
compounds of amido carbonic acids, amidohydroxycarbonic acids, amidoalkyl-.
hydroxycarbonic acids, or sulpho acids thereof, on the so called alphanaphthylamine-
betamonosulpho acids of Clève. :
:
My foreign correspondents have now found that by combining diazotised amido
carbonic acids with other amidonaphthalenesulpho acids, for instance, alpha-
naphthylamineorthomonosulpho acid, amidonaphtholsulpho acid, amidonaphthol-
ethersulpho acid, amidonaphthoxyacetic acid, amidonaphthoxyaceticsulpho acid, or
such amines as contain no sulpho groups, especially with paraxylidine (CH, NH, :
CH, 1:24), amidoazo products are formed which can be employed for dyeing
and printing, that is to say, for dyeing wool mordanted, and, (as intermediate pro-
ducts) for producing azo dye-stuffs on fibre, and which in general possess the same
properties as the mono azo dyestuffs described in the Specification, of application
for Letters Patent No. 5112, dated 15th March 1892, before mentioned.
The production of these mono azo colouring-matters, obtained by the combination
of diazotised amidocarbonic acids with amines or amidosulpho acids, can be effected
in the manner described in the following example. The parts are by weight.
DYESTUFF
FIRST EXAMPLE.
"
OBTAINED BY COUPLING THE DIAZO PRODUCT OF
BENZOIC ACID WITH PARAXYLIDINE.
.
METAAMIDO-
13-7 parts of metaamidobenzoic acid are dissolved in 36 parts of muriatic acid
(20 per cent.) and 400 parts. of water. The resulting liquid, after cooling, is mixed
with a solution of 6.9 parts of, sodium nitrite in 20 parts of water, and when the
diazotation is complete, the liquid is poured into a solution prepared by dissolving
16 parts of paraxylidine hydrochlorate in 100 parts of water. Whilst stirring,
67. parts of sodium acetate (dissolved in a small quantity of water) are added, and
after heating to from 35 to 40 degrees centigrade, the mixture is allowed to stand
for about 24 hours. The dye stuff is filtered off, dissolved in sodium carbonate, and
precipitated again by adding acids, preferably acetic acid, to the alkaline solution.
The product obtained by filtering off can be, directly employed for dyeing and
printing. It dyes wool 'mordanted with chremium salts a yellowish, shade, and
1 produces the same colour when printed on cotton together with chromium.salts.
In an analogous manner, other dye-stuffs are produced, either by employing, in
DYESTUFF
OBTAINED BY COUPLING TIE DIAZO PRODUCT OF METAAMIDO-
BENZOIC ACID WITH PARAXYLIDINE.
13-7 parts of metaamidobenzoic acid are dissolved in 36 parts of muriatic acid
(20 per cent.) and 400 parts of water. The resulting liquid, after cooling, is mixed
with a solution of 6.9 parts of sodium nitrite in 20 parts of water, and when the
diazotation is complete, the liquid is poured into a solution prepared by dissolving
Whilst stirring,
16 parts of paraxylidine hydrochlorate in 100 parts of water.
67. parts of sodium acetate (dissolved in a small quantity of water) are added, and
after heating to from 35 to 40 degrees centigrade, the mixture is allowed to stand
for about 24 hours. The dye stuff is filtered off, dissolved in sodium carbonate, and
precipitated again by adding acids, preferably acetic acid, to the alkaline solution.
The product obtained by filtering off can be, directly employed for dyeing and
printing. It dyes wool mordanted with chromium salts a yellowish, shade, and
1 produces the same colour when printed on cotton together with chromium.salts.
In an analogous manner, other dye-stuffs are produced, either by employing, in

page_text: place of metaamidobenzoic acid of the foregoing example, the corresponding
quantity of ortho amido benzoic acid, paraamidobenzoic acid, orthoamidosalicylic
acid, paraamidosalicylic acid, amidoparahydroxybenzoic acid, orthoamidometacresol-
carbonic acid, paraamidoorthocresolcarbonic acid, amidoanisic acid, amido-
phthalic acid, analogues and substitution products thereof, especially sulpho
acids thereof, or by replacing paraxylidine by analogous amines or substituted
amines, for instance, alphanaphthylamine orthomonosulpho acid, amidonaphthol-
sulpho acid, amidonaphtholether sulpho acid, amidonaphthoxyacetic acid, amido-
naphthoxyaceticsulpho acid.
These simple monoazo dyes produce on wool mordanted with chromium salts,
shades varying from yellow to red, whilst by printing them together with chromium
salts on cotton, intense yellow, brown, or red shades result.
Of course, the aforesaid colouring matters can be obtained in other ways; in
general, all those methods known in chemistry for the production of analogous azo
dye stuffs can be used.
The said dyestuffs are of specially high value, as they are not only suitable for
dyeing wool mordanted, but can also be employed for producing red, brown, blue,
violet, green, or black disazo colouring matters on fibre, according to the process
described in the Specification of application for Letters Patent No. 5815, dated
24th March 1892, before mentioned, viz., either by printing the said dye stuffs
together with mordants on cotton cloth, yarn, and the like, or by dyeing said
materials after a treatment with mordants, and subsequently treating said goods
with moderately acid solutions of sodium nitrite, and weak alkaline or acid baths of
phenols, amines, amidophenols, sulpho or carboxylic acids thereof.
The employment of such colouring matters as. are derived from the diazo
derivatives of ortho-, meta-, and paraamidobenzoic acid, ortho- and paraamido-
salicylic acid, amidocresotinic, amidoparahydroxy benzoic acid, amidoanisic acid,
amidophthalic acid, sulpho products thereof, with amidonaphthols, alphaamido-
naphtholethers, amidonaphthoxyacetic acid, amidonaphthoxyaceticsulpho acid,
amidonaphtholmonosulpho acid G, amidonaphtholmonosulpho acid K, amido-
naphtholmonosulpho acid B, described in the German Patent No. 58352,
1.8 amidonaphtholbetadisulpho acid, alphanaphthylamine, alphanaphthylaminebeta-
monosulpho acids, amidonaphtholethermonosulpho acid; for producing disazo
colours upon fibre, is described in the Specification of application for Letters
Patent No. 5815, dated 24th March of 1892, before.mentioned.
The process described in the last named application can also be employed for
the aforesaid dyestuffs obtained from the diazoderivatives of amidocarbonic acids,
and paraxylidine or analogous amines.
In order to illustrate the method of diazotising. on fibre these amidoazo dyes,
fixed on fibre by means of chromium or similar salts, and combining the so-formed
diazo compounds with phenols or amines, the following examples are given; the
parts being by weight.
PRODUCTION OF A RED COLOUR, FAST TO THE ACTION OF WASHING, BY
'MEANS OF THE COLOURING MATTER FROM DIAZOTISED METAAMIDO-
BENZOIC ACID AND PARAXYLIDINE.
The cotton material is printed with a paste prepared by mixing 100 parts of a
20 per cent. paste of said dye-stuff, 200 parts of water, 640 parts of acetic acid
starch tragacanth thickening, and 60 parts of chrome acetate (20 degrees Baumé).
After steaming for one hour, chalking, malting, soaping, washing, the printed cloth
is placed in a bath of nitrous acid (produced by acidulating a diluted solution of
10 parts of sodium nitrite), and agitated therein for, say, 10 to 20 minutes.
The material is then taken out, washed, and well agitated in a solution of
20 parts of the sodium salt of betanaphthol. The cloth immediately takes a red
colour on the parts printed. After half an hour, it is washed and soaped.

page_text: PRODUCTION OF A BLUISH CLARET-RED BY MEANS OF THE DYE STUFF
FROM DIAZOTISED AMIDO SALICYLIC ACID AND PARAXYLIDINE.
The cloth, " padded" with chrome mordant (for instance, chrome bisulphite),
after "discharging" the pattern if desired with citric acid or lemon juice, is dyed
with a neutral or moderately acid solution of the dye stuff from diazo salicylic acid
and paraxylidine. After washing, it is placed in a bath of sodium nitrite,
acidulated with muriatic acid, taken out after about 10 to 15 minutes, washed, and
finally well agitated in a solution of the sodium salt of betanaphthol. When the
combination is complete, the material is taken out, washed, and soaped. In this
manner, a beautiful bluish claret-red results at the places not "discharged."
"
be
In a similar manner as mentioned in the Specification of application for Letters
Patent No. 5815%, in place of white figures, also coloured figures can
discharged."
The dye-stuff of the foregoing third example can be replaced by the analogous
colouring matters obtained from the diazo derivatives of the other amidocarbonic
acids and paraxylidine, or the paraxylidine employed can be replaced by analogous
amines or substituted amines.
All these dye stuffs, when fixed on fibre, either by printing thereon a paste
containing the dye together with mordants, or by dyeing cloth previously
mordanted, are further diazotised, and the diazo compounds are combined with
beta naphthol or other phenols, or amines, amidophenols, amidophenolethers, sulpho
and carboxylic acids thereof,-very different shades being thus produced, which are
"fast" against the action of washing and soaping.
My foreign correspondents have found that in general similar shades result
when the aforesaid mono azo dyes are replaced by such disazo-colouring matters as
result by further diazotising the aforesaid mono azo dye stuffs, and combining their
diazo products, so formed, with amido compounds, the amido groups of which, after
the combination, can be further diazotised on fibre. By combining the said diazo
products obtained on fibre with the known dye-stuff components, fast shades, varying
from red, brown, blue, violet, green, to black, are produced.
NEWTON & SON,
Agents for the Applicant.

page_text: 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 15 March 1892, granted
to Benjamin Willcox, for an invention.communicated by my foreign correspondents,
monoazo dye stuffs are described which are suitable for dyeing wool with the aid of
metallic mordants, and also are capable of being employed in printing, as, when
fixed on the fibre by means of metallic mordants, these dyes can be diazotised and
combined with phenols, amines, and the like, as described in the Specification of
Letters Patent No. 5815, dated 24th March 1892, and granted to the said
Benjamin Willcox.
The aforesaid simple azo dye-stuffs are obtained by acting with the diazo
compounds of amines, amidophenols, amidophenolethers, or substituted products
thereof, especially sulpho or carboxylic acids of all these components (including
Clève's alpha naphthylaminebetamonosulpho acid, beta or delta) on Clève's alpha-
naphthylamine betamonosulpho acids (beta or delta).
=
My foreign correspondents have now found, that by combining diazotised amido-
carboxylic acids with paraxylidine (CH3: NH, CH, 1:2:4), or salts thereof,
amidoazo products are formed which can be employed for dyeing and printing, that
is to say, for dyeing mordanted wool, and (as intermediate products) for producing
azo dye-stuffs on fibre, and which in general possess the same properties as the
mono azo dye stuffs described in the Specification of the Letters Patent No. 5112
dated 15th March 1892, before mentioned.
The production of these mono azo coloring matters obtained by the combination
of diazotised amidocarboxylic acids with paraxylidine, can be effected in the manner
described in the following example. The parts are by weight.
FIRST EXAMPLE.
DYE STUFF OBTAINED BY COUPLING THE DIAZO PRODUCT OF AMIDOSULPHO
BENZOIC ACID (NH,: SO,H: COOH = 1:3:5) WITH PARAXYLIDINE.
217 parts of amido sulpho benzoic acid are dissolved in 36 parts of muriatic
acid (20 per cent.), and 400 parts of water. The resulting liquid is cooled, and
mixed with a solution of 6.9 parts of sodium nitrite in 20 parts of water, and when
the diazotisation is complete, the mixture is poured into a solution prepared by
dissolving 16 parts of paraxylidine hydrochloride in 100 parts of water. 67 parts
of sodium acetate (dissolved in a small quantity of water) are then mixed with the
liquid, and after heating to from 35 to 40 degrees C., the mixture is allowed to
stand for about 24 hours. The dye stuff is filtered off, dissolved in a solution of
sodium carbonate, and again precipitated by adding acid, preferably acetic acid, to
the alkaline solution. The product obtained by filtering off can be directly
employed for dyeing and printing. It dyes wool mordanted with chromium salts,
a yellowish shade, and produces the same color when printed on cotton together
with chromium salts.
In an analogous manner, other dye-stuffs are produced by employing, in place of

page_text: amidosulphobenzoic acid of the foregoing example, the corresponding quantity of
orthoamidobenzoic acid, paraamidobenzoic acid, orthoamidosalicylic acid, paraamido-
salicylic acid, amidoparahydroxybenzoic acid, orthoamidometacresolcarboxylic acid,
paraamidoorthocresolcarboxylic acid, amidoanisic acid, amidophthalic acid, analogues
and substitution products thereof, especially sulpho acids thereof. The coloring
matter from diazotised metaamido benzoic acid and paraxylidine is not claimed.
These simple monoazo dyes produce on wool mordanted with chromium salts,.
shades varying from yellow. to red, and on printing them together with chromium
salts on cotton, intense yellow, brown, or red shades result.
The aforesaid coloring matters can be prepared not only by following the
directions above given, but by all the methods of producing analogous or similar
azo dye stuffs known to chemists.
The said dye-stuffs are of specially high value, as they can also be employed for
producing red, brown, blue, violet, green, or black disazo coloring matters on fibre,
according to the process described in the Specification of the Letters Patent
No. 5815, dated 24th March 1892, before mentioned, viz., either by printing
the said dye-stuffs, together with mordants, on cotton cloth, yarn, and the like,.
or by dyeing the said materials (after treatment with mordants), and subsequently
treating the said goods with moderately acid solutions of sodium nitrite, and weak
alkaline or acid baths of phenols, amines, amidophenols, amidophenolethers, sulpho.
or carboxylic acids thereof.
are derived from the diazo
The employment of such coloring matters as
derivatives of ortho, meta, or paraamido benzoic acid, ortho or paraamidosalicylic
acid, amidocresotinic acid, amidoparahydroxybenzoic acid, amidoanisic acid, amido-
phthalic acid, or the sulpho derivatives thereof, with amidonaphthol monosulpho
acid G, 1:8-amidonaphthol betadisulpho acid, alphanaphthylamine orthomonosulpho
acid (described in the German Patent No. 56,563, dated 21st January 1890), and
the alphanaphthylaminebetamonosulpho acids (beta or delta) obtained by Clève, or
amidonaphtholether betamonosulpho acids, is described in the Specification of the
Letters Patent No. 5815, dated 24th March of 1892, before mentioned.
The process described in the last named Letters Patent can also be employed for
the aforesaid dye-stuffs obtained from paraxylidine, and the diazo-derivatives of the
aforesaid amido carboxylic acids (including meta amido benzoic acid).
In order to illustrate the method of diazotising these amido azo dyes, when fixed
on fibre by means of chromium or similar salts, and of combining the so-formed
diazo compounds with phenols or amines, the following examples are given, the
parts being by weight.
PRODUCTION OF A RED COLOR WHICH WITHSTANDS WASHING, BY MEANS OF
THE COLORING MATTER FROM DIAZOTISED AMIDOSULPHO BENZOIC ACID
AND PARAXYLIDINE.
The cotton material is printed with a paste prepared by mixing 100 parts of a.
20 per cent. paste of the said dye stuff, 200 parts of water 640 parts of acetic acid
starch tragacanth thickening, and 60 parts of chromium acetate (20.degrees Beaumé).
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 acidulating a
diluted solution of 10 parts of sodium nitrite), and agitated therein during, say,
10 to 20 minutes. The material is then taken out, washed, and well agitated in a
solution of 20 parts of the sodium salt of betanaphthol. The cloth immediately
assumes a red color on the printed parts. After half an hour, it is washed and
soaped. Similar shades are produced by the employment of the other above-
named amidoazo dye-stuffs, instead of the product from diazotised amidosulpho
benzoic acid and paraxylidine.
If the diazo compound of the last-mentioned. amido azo dye-stuff be combined,

page_text: PRODUCTION OF A BLUISH CLARET-RED BY MEANS OF THE DYE-STUFF FROM
DIAZOTISED AMIDOSALICYLIC ACID AND PARAXYLIDINE.
After "padding" the cloth with a chrome mordant (for instance, chromium
bisulphite), and, if necessary, "discharging" the pattern with citric acid or lemon
juice, it is dyed with a neutral or moderately acid solution of the dye-stuff from
diazosalicylic acid and paraxylidine. It is then washed, and afterwards placed 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 solution of the
sodium salt of betanaphthol. When the combination is complete, the material is
taken out, washed, and soaped. In this manner, a beautiful bluish claret-red is
produced on the "undischarged " parts.
In a manner similar to that mentioned in the Specification of the aforesaid
Letters Patent No. 5815%, colored figures can be discharged" in place of white
figures.
Instead of the dye-stuff of the foregoing third example, the analogous matters
obtained from the diazo derivatives of the other amidocarboxylic acids and
paraxylidine can be used.
All these dye stuffs, when fixed on fibre, either by printing thereon a paste
containing the dye-stuff, together with mordants, or by dyeing previously mordanted
cloth, are further diazotisable, and the resulting diazo compounds can be combined
with beta naphthol or other phenols or amines, amidophenols, amidophenolethers,
sulpho or carboxylic acids thereof, very different shades being thus produced, which
withstand washing and soaping.
The above examples two and three are given in order to illustrate the method of
producing fast colors on the fibre by means of the amido azo 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 the said inven-
tion and in what manner the same is to be performed, as communicated to me,
I declare that what I claim is :-
1. The process for producing amidoazo dye-stuffs suitable for dyeing and printing
purposes, which process consists in coupling one molecular proportion of para-
xylidine (CH₂: NH, CH₂=1:2:4), or a salt thereof, with one molecular

page_text: proportion of one of the following acids, viz., ortho amido benzoic acid, paraamido
benzoic acid, ortho amidosalicylic acid, paraamidosalicylic acid, amidoparahydroxy-
benzoic acid, orthoamidometacresolcarboxylic acid, paraamidoorthocresolcarboxylic
acid, amidoanisic acid, amidophthalic acid, or analogous amido carboxylic acids,
or substitution derivatives of the above amidocarboxylic acids. (The coloring
matter from diazotised metaamido benzoic acid and paraxylidine is hereby
disclaimed.)
2. The employment of the amidoazo dye stuffs defined in the foregoing first
claim (including the dye-stuff from diazotised metaamido benzoic acid and para-
xylidine) 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 colors
on the fibre.
3. The process for producing fast colors on the fibre which consists either in
printing the amido azo dye stuffs (of the foregoing claims), 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, amido phenolethers, the 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 amido azo coloring matters obtainable by the
process described in the foregoing first claim, or by any 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 process producing the same result.
Dated this 24th day of May 1893.
NEWTON & SON,
Agents for the Applicant.