Improvements in Dyeing and Printing with Azo Dye-stuffs.
Year: 1892

page_text: Date of Application, 20th June, 1892
Complete Specification Left, 20th Mar., 1893-Accepted, 6th May, 1893
PROVISIONAL SPECIFICATION.
Improvements in Dyeing and Printing with Azo Dye-stuffs.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which has been
communicated to me from abroad by the Farbenfabriken vormals Friedrich Bayer
and Co. of Elberfeld in the Empire of Germany to be as follows:-
It is known that azo colouring matters containing a hydroxylic and carboxylic
group in ortho position, possess the property of forming with chromium salts lakes
that mostly resist very well the action of washing and soaping.
My foreign correspondents have also shewn that two carboxylic groups in ortho
position likewise enable the azo-dye-stuffs to dye with the aid of mordants and
that certain dye-stuffs which do not contain the hydroxylic and carboxylic group
in ortho position (for example the azo colouring inatters derived from amido para
hydroxybenzoic acid) can still be employed for dyeing with the aid of mordants.
My foreign correspondents have further found that certain dye stuff's which
contain the hydroxylic and carboxylic group not in the same benzene or naphthaline
nucleus can still be used for dyeing and printing with the aid of chromium mordants
even if the solubility of the colouring matters be augmented by a sulpho group.
Good results are obtained especially with those azo dye stuffs which result from
the combination of diazotised ortho-meta- or para-amido-benzoic acid amido-alkyl-
hydroxy-benzoic acids (for example anisic acid) amido-phthalic acids, ortho- or
para-amido-salicylic acid amido-cresol-carbonic acid amido-para-hydroxy-benzoic
acid or sulpho acids of the aforesaid amido-carbonic acids with phenols dihydroxy-
benzenes naphthols dihydroxy-naphthalenes, amido-phenols, amido-naphthols and
sulpho carboxylic acids thereof.
Of the metallic mordants the chromium products have been found by my foreign
correspondents to be most adapted as the chromium lakes of the dye stuffs above
enumerated have the greatest resistance to the action of soaping and of alkali.
The process for printing with these dye stuffs in general is the following: The
respective colouring matters mixed with a suitable thickening and chromium salts
are printed on the material which is then steamed malted and soaped. For dyeing
purposes either fibres or yarns or fabrics which are mordanted with chromium salts
and are discharged, if desired, can be employed and be dyed in the bath of the
dye stuff used, or the colouring-matter can be fixed on the fibres or fabrics with
chromium fluoride or other chromium salts in a single bath.
The following are examples of the manner in which the invention may be

page_text: 1·8-naphthol-mono-sulpho acid symmetrical dihydroxy-benzoic acid (OH:OH :
COOH = 1:3:5) beta-naphthol-delta-sulpho-acid, beta-naphthol-alpha-sulpho
acid, and the like.
The colouring matters obtained from diazotised benzoic acids and one of the
components enumerated in the first column of the following table produce the
respective shades named after each.
Alnho_nonhthoLolnbo-culnhosid (OH · SO-1 red with a yellow
If the dye stuff employed in the first preceding example be replaced by the
combination from diazotised sulpho salicylic acid and beta-naphthol a bluish claret
red is obtained. The process for printing steaming and the like is effected in the
manner described in the first example.
By employing instead of beta-naphthol one of the compounds named in the
following table viz.: by combining them with diazo-sulpho-salicylic acids the
respective shades enumerated after each are obtained.
Alpha-naphthol
Beta-naphthol carbonic acid melting at 216 degrees
centigrade
1-8 dihydroxy-naphthalene
-
Beta-naphthol-sulpho-acid (OH: SO₂H=2:6)
Beta-naphthol-sulpho acid (OH: SO₂H=2:7)
-L
claret-red.
-
bluish black.
-
-
black.
-
-
red.
claret-red.
-
-
By combining diazotised phtalic acid with the compounds mentioned in the
following table the respective shades result which are enumerated after each.
Beta-naphthol
Alpha-naphthol
-
-
-
Beta-naphthol carbonic acid melting at 216 degrees
centigrade
1-8 dihydroxy-naphthalene
Beta-naphthol-alpha-mono-sulpho-acid (OH SO,H=2:6)
Beta-naphthol-alpha-mono-sulpho-acid (OH: SO H=2:7)
Alpha-naphthol-mono-sulpho-acid (OH: SO,H=1:8)
Alpha-naphthol-mono-sulpho-acid (OH: SO,H=1:5)
Alpha-naphthol-mono-sulpho acid (OH: SO₂H=1:4)
1.8-dihydroxy-naphthalene sulpho acids
-
-
-
-
->
brownish-red.
reddish orange.
claret-red.
black.
brownish red.
brownish red.
reddish orange.
red with bluish tinge
bluish-red.
bluish black.
In employing the colouring matters from ortho- and para- amido-salicylic acid
amido-cresol-carbonic acids or amido anisic acids, or sulpho acids thereof, in
general shades result which are more bluish than those obtained by means o

page_text: amido-benzoic acids, whilst the analogous dye-stuffs from amido-para-hydroxy-
benzoic acid yield shades similar to those which result from the colouring matters
derived from amido benzoic acids.
Dated this 20th day of Lu1000
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.
COMPLETE SPECIFICATION.
Improvements in Dyeing and Printing with Azo Dye-stuffs.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farbenfabriken vorm. Friedr. Bayer & Co.
of Elberfeld in the Empire of Germany) and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:-
It is known, that azo colouring matters containing a hydroxylic and carboxylic
group relatively in the ortho position possess the property of forming chromium
lakes that are mostly capable of withstanding washing and soaping
My foreign correspondents have shown that certain azo dye-stuffs containing
two carboxylic groups in ortho position are capable of dyeing with the aid of
mordants and moreover that dye-stuffs which do not contain the hydroxylic and
carboxylic group in ortho position (for example, the azo colouring-matters derived
from amido-para-hydroxy-benzoic acid) may also be employed in dyeing with the
aid of mordants.
My foreign correspondents have further found that even certain dye-stuff's which
contain the hydroxylic and carboxylic group in different benzene or naphthalene
nuclei can be used for dyeing and printing with the aid of chromium mordants,
and moreover that this is the case even when the solubility of the colouring-matters
is augmented by the presence of a sulpho group. Good results are obtained
especially with those azo-dye-stuffs which result from the combination of diazotised
ortho-, meta- or para-amido benzoic acid, amido-alkyl-hydroxy-benzoic acids (for
example anisic acid), amido-phthalic acids, ortho- or para-amido-salicylic acid,
amido-cresol-carboxylic acid, amido-para-hydroxy-benzoic acid; or sulpho acids of
the aforesaid amido-carboxylic acids with phenols, dihydroxy-benzenes, naphthols,
dihydroxy-naphthalenes, amido-phenols, amido-naphthols and sulpho or carboxylic
acids thereof.
Of the metallic mordants those containing chromium have been found by my
foreign correspondents to be best adapted for use, as the chromium lakes of the
dye-stuffs above enumerated best withstand soaping and the action of alkali.
The process for printing with these dye-stuffs in general is the following:
The respective colouring-matters, mixed with a suitable thickening and chromium
salts, are printed on the material which is then steamed, treated with "malt" and
soaped.
For dyeing purposes either fibres or yarns or fabrics which have been mordanted
with chromium salts and discharged, if desired can be employed and can be dyed
In a bath of the particular dye-stuff used, or the colouring matter can be fixed on
the fibres, yarns, or fabrics, by dyeing in a single bath containing chromium fluoride
or other suitable chromium salts.
The following are examples of the manner, in which the invention may be
carried out.
FIRST EXAMPLE.

page_text: 10 per cent. of the dye-stuff from diazotised meta-amido benzoic acid and beta-
naphthol-mono-sulpho acid (2:6) and 8 parts, by weight, of chromium acetate
(20° Baumé) and is then steamed during say an hour, chalked, treated with malt and
soaped for about 20 minutes at 25 degrees Réaumur.
The colouring-matter can be dyed either on oiled or unoiled material.
Very similar shades are produced by employing the dyestuffs from diazo-benzoic
acids and 18-naphthol-mono-sulpho acid, symmetrical dihydroxy-benzoic acid
(OH OH COOH=1:3:5), beta-naphthol-delta-sulpho acid, beta-naphthol-alpha
sulpho acid, and the like.
:
The colouring-matters obtained from diazotised amido-benzoic acids and one of the
components enumerated in the first column of the following table produce the shades
respectively named after each.
If instead of the dye-stuff employed in the first preceding example the corre-
sponding quantity of the colouring-matter obtained from diazotised amido-sulpho-
salicylic acid and beta-naphthol be used, a bluish claret-red is obtained. The process
of printing, steaming and the like is effected in the manner described in the first
example.
By employing instead of beta naphthol one of the compounds named in the
following table, viz. by combining them with diazo-sulpho-salicylic acid the
respective shades enumerated after each are obtained.
Alpha-naphthol
Beta-naphthol-carboxylic acid (melting at
216 degrees centigrade)
1: 8-dihydroxy-naphthalene
Beta-naphthol-sulpho-acid (OH: SO,H=2:6)
Beta-naphthol-sulpho-acid (OH: SO,H=2:7)
Claret-red.
Bluish-black.
Black.
Red.
Claret-red.
By combining diazotised amido-phthalic acid with the compounds mentioned in
the following table the shades result which are respectively enumerated after each.
Beta-naphthol -
Alpha-naphthol
Beta-naphthol-carboxylic acid melting at
216 degrees centigrade
18-dihydroxy-naphthalene
Beta-naphthol-beta-mono-sulpho acid (OH:
SO₂H=2:6)
-
-
Beta-naphthol-delta-mono-sulpho acid (OH:
Brownish-red.
Reddish-orange.
Claret-red.
Black.
Brownish-red.
DL1

page_text: Alpha-naphthol - mono-sulpho acid (OH:
SO,H=1:8)
-
-
Alpha-naphthol - mono-sulpho - acid (OH:
$0,H=1:5)
Alpha-naphthol - mono-sulpho
$0₂H=1:4)
acid (OH:
1: 8-dihydroxy-naphthalene sulpho acids
Reddish-orange.
Red with bluish tinge.
Bluish-red.
Bluish-black.
The colouring-matters from ortho- and para-amido-salicylic acid, amido-cresol-
carboxylic acids, or amido-anisic acids or sulpho acids thereof, afford shades which
are generally bluer than those obtained by means of amido-benzoic acids, whilst.
the analogous dye-stuffs from amido-para-hydroxy-benzoic acid yield shades similar
to those which result from the colouring-matters derived from amido-benzoic
acids.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The process of dyeing with the colouring-matters obtainable by the combination
of diazo-benzoic acid, diazo-sulpho-benzoic acid, diazo-salicylic acid, diazo-sulpho-
salicylic acid, diazo-cresol-carboxylic acid, diazo-sulpho-cresol-carboxylic acid,
diazo phthalic acid, diazo-sulpho-phthalic acid, diazo-para-hydroxy-benzoic acid,.
diazo-sulpho-para-hydroxy-benzoic acid, diazo-alkyl-hydroxy-benzoic acid or diazo-
alkyl-hydroxy-sulpho-benzoic acid with phenol, dihydroxy-benzene, naphthol,.
dihydroxy-naphthalene, amido-phenol, amido-naphthol, sulpho-, carboxylic- or
sulpho-carboxylic acid thereof, which process of dyeing consists either in dyeing
fibres yarns or fabrics mordanted with chromium salts (and discharged, if desired)
in the baths containing the above defined colouring-matters or in fixing the said
dye-stuffs on the fibres, yarns or fabrics, by the aid of chromium salts (the latter
process being effected in a single bath).
2. The process of printing with the colouring-matters defined in the preceding
first claim, which process consists in printing the respective dye-stuffs mixed with
chromium salts and suitable thickenings on the materials and subsequently steaming,.
treating with "malt" and soaping the materials thus treated.
3. Fibres, yarns or fabrics dyed or printed by means of the processes claimed in
the foregoing first and second claiming clauses or by means of any other process.
producing the like result.
1
1 1009
B. WILLCOX.