UNITED STATES Pitjlllillitl'll @FFICE.

ARTHUR GEORGE GREEN, OF LEEDS, ENGLAND. _

PRODUCTION OF ANILIN BLACK (3N FIBERS AND FABRICS.

sees-is. Speci?cation of Letters Patent. Patented May 31, 195149.

31o Brewing. Application ?led January 15, 1908. Serial No. 410,934.

To all whom it may concern." longed steaming is necessary, as for instance

Be it known that I, ARTHUR GEORGE in printing together with tannin colors. It
GREEN, of The University, Leeds, York is also applicable to the dyeingvand printing
shire, England, consulting chemist, have in of linen, ramie, or silk, or of mixtures of
CH vented certain new and useful Improve
these fibers with one another or with cotton.
ments Relating to the Production of Anilin The new process is characterized and dis 60
Black upon Fibers and Fabrics, of which tinguished from all other known processes
the following is a speci?cation. of producing anilin black, by the fact that
In the ordinary method of producing an it does not require the presence of an oxidiz~
10 aged or oxidation black upon textile ing agent in the padding or printing mix
?bers or fabrics, the material is padded or ture, the oxidation of the anilin to the 65
printed with a solution containing a salt of aged condition known as emeraldin or to
anilin, usually the hydrochlorid, together nigranilin being effected solely or mainly by
with an oxidizing agent, usually sodium or the oxygen of the air. The possibility of
15 potassium chlorate, and an oxygen carrier, dispensing with an oxidizing agenhend thus
_ usually a salt of copper or vanadium. Uponof avoiding the tendering or weakening of
thematerial thus prepared the black is then the ?ber due to oxycellulose formation, de
developed by hanging in a Warm chamber pends on the discovery that, a small quan
more or less saturated with, moisture tity of a paradiamin or of a para~amid0~
20 (aged). In order to further complete phenol or other substance capable of'produc
the oxidation, the material is frequently sub mg an indamm by condensation with analin, 75
jected to a ?nal treatment With a hot solu it added to a mixture containing analin and
tion. of a bichromate ( chromed). In ap a suitable oxygen carrier, such as a salt of
plying this process to cotton fabrics, great copper, greatly accelerates the oxidation of
25 care is required in order to prevent the the anilin by atmospheric oxygen. Further
weakening or tendering of the cotton whereas in the ordinary processes of produc 80
fiber. The conditions as to humidity and ing an aged black the quantity of min
temperature of the aging chamber, the du eral acid employed cannot be materially re
ration of agin and other circumstance duced below the proportion of one equiva
so have to be care ally and exactly controlled, lent of the latter to one equivalent of base,
and even with the exercise of all possible under the new conditions here set forth a
precautions a certain weakening of the ma mixture which is basic may be used with sat
terial can scarcely be avoided. The cause of isfactory results for the purpose. Still fur
this weakening is two-fold: the oxidi-7._~ ther, the hydrochloric acid or other mineral
$5 ing action exerted by- the oxits of chlorin acid may be wholly or in part replaced by
produced from the chlorate, which tend to an organic acid, such for instance as formic 90
convert the cotton into oxycellulose; (ii). the acid, without materially affecting the
destructive action of the hydrochloric acid quality of the black obtained. In either
or other mineral acid set free from its com 'asc, whether a basic mixture is employed
40 bination with anilin. or a mixture containing an organic acid, the
The present invention relates to Ya new and tendering ot the tiber- by free mineral acid
improved method of producing anjilin black, liberated during aging or steaming is
which is not attended by the above disad avoided. own when these operations are
vantages, and in which all weakening or, unusually prolonged. The action of the para?
5 tendering of the cotton fiber may be avoided diamin or para-amidophenol is believed to
Without the exercise of any extreme care. be a on t u lytic one, since the quantity employed
At the same time a fuller utilization of the need only be small in proportion to the and
anilin is rendered possible, the danger ol. iin, and may be varied within Wide limits.
?re from spontaneous inflammation is re 'lhose substances bring about the oxidation
50 moved, the risk of injury to the health of of the anil in by intermediate formation of
the workpcople greatly diminished, the complex indannns, from which they are con 105
manufacture is simplified and greater speed stantly regenerated. in footy any other
of pl'?dlliitldil is attainable. The process compound, such as a nitroso compound or
may also be applied in cases in which pro~ quinone imid, capable of giving rise tom
 2 959,516

damins under the conditions employed, may will give rise to an indamin by condensa
be used for the same purpose. tion with anilin, such, for instance, as one
As suitable oxygen-carriers the chlorids of the follow1ngz~~
of copper have been found to give the best
results, and in order to prevent the prema~ Quinone mono-mild . . . . . . . . . . . . . . ,C5H4<g

70
ure formatitm of oxidation-products in the Quinonc diimidi . . . . . . . . . . i . v . . . . . ..C6H<Rv%

padding or printing mixture, it has been Quinone mono- or dychlorimi'd t \

found preferable to employ the copper in Para-nitrose-phenol . _ . i . . . . .. ...CH4(XO)tOH)[1:4]

Para-nitroso-rtimethylanilin . . . .CBIL (NO).N (C H3)? [1:4]

the form of a cuprou, salt. A convenient lara-nitrososdiethylanilin . i . . v . v . .,CGHANO).Nt(T-;H5)2tl:4]

method of otter-ting this is to add to the mix l'ara-amidirphenyl-qutnoue-mono' t)

imitt, 75
ture cupric (:hlorid or other cupric salt, to
gether with a sultite in quantity sutlicicnt
to reduce the cupric salt to the cuprous state, and their'analogues, homologucs,or deriva
and a sullicieut amount of a soluble chlorid, tires.
such as soilium chlorid, potassium chlorid, The following examples of suitable con 80
or ammonium chlorid, to keep the cuprous positions for padding mixtures are given
chlorid in solution. Mixtures thus prepared in order to illustrate the general method of
are quite stable, and remain clear and color carrying out this invention; the details may
less on exposure to air for a considerable however be varied within wide limits as set
period. Just as in the ordinary method of forth above. 85
producing anilin black, so here also the Example L-The padding mixture is re
analin may be replaced wholly or in part pared by adding a solution composed of 4:8
by its homologues such as orthotoluidin or parts of cupric chlorid, 110 parts of am
mctaxylidin. monium chlorid, and 14- parts of sodium
No claim is made to any process for the metabisultite in 500 parts of cold Water, to 90
production of a black from a mixture of a solution composed of 50 parts of anilin,
anilin and a paratiliamin in which the oxida 2 parts of paraphenylcnediamin,15 parts of
tion is e,tlected substantially by means of a hydrochloric acid (30 percent. HCl) and
chlorate. 15 parts of formic acid (90 per cent.) in
The mixtures: composed as above are ap~ ' 1,500 parts of cold water. - 95
plied to textilr'j tibers and fabrics in the usual
manner, namely, by padding or printine'. prepared
Exampleby II.-'lhe
adding a solution
padding composed
mixture of
In the latter case the mixture is suitably 48 parts of cupric ehlorid, 140 parts of am
thickened by means of any of the usual monium chlorid, and 14: parts of sodium
[.JClitlllllg agents. Oxidation is then ef metabisultite in 500 parts of cold water, to 100
fected by exposure of the material to air, a solution composed of 50 parts of anilin,
etl'cctcd either by passage through the ordi 4t- parts of pa raphenylenediamin, 30 parts of
.nary rapid ager, by hanging in a moist formic acid (90 per cent.) in 1,500 parts of
40
atmosphere, by steaming, or by any other cold water. '
convenient means. Finally it is washed and Example i1l.~-lhe padding mixture is
dried; or tlttnltlillg' to circumstances it may prepared by adding a solution composed of
be subjected to a linal treatment with a bi 48 parts of cupric chlorid, H0 parts of am
chromate either alone or in presence of other monium ohlorid, and 1st parts of sodium
materials as at, present employed in the metabisultite in 500 parts of cold Water, to
after-treatment of an aged7 anilin black, a solution composed of 50 parts of anilin, 110.
with the object of further oxidizing the 4 parts of paraphenylenediamin, and 50
emeraldin, 'or of rendering the black less parts of hydrochloric acid (30 per cent),
liable to green. in 1,500 parts of cold water.
Among the various paradiamins and para What I claim and desire to secure by Let
amidophenols which are suitable for the pur I ters Patent is :~
pose of this invention, the following may 1. A process for the production of emer
be specially mentioned :- aldm and amlm black upon textlle ?bers and
lara-plienylone
li!X':l-|)lItll)'ltHutliilmiiL.
dianiin sult'o
fabrics, comprising oxidation of an anilin
lara-pht-nyleuediumiu irbox) base substantially by atmospheric oxygen in -
Puru-tolylcnedtumin the presence of a copper salt associated with 120
, ~11 . ..
a substance capable of producing an in
lliethyl paiapltrn) lenc diamin. . . i
damin by condensation with anilin.
it. A process for the production of emer!
(it) aldin and anilin black upon textile ?bers and
fabrics, comprising oxidation of an anilin 125
and their analogues, homologues, or deriva base substantially by atmospheric oxygen in.
tives. the presence of a copper salt associated With
In place of para-diamins and paras-amido a paradiamin.
phenols, there may be used any other sub 3. A process for the production of emer
stance which under the conditions employed aldin and anilin black upon textile ?bers and
130
 $959,516 8

fabrics. comprisinq oxidation of an, aniiin and" afterward subjecting the material to
base sol:stantiaily y atmospheric oxygen iii a tmospiierio _ oxiiiation. ,
ins presence of a copper salt associated Wlilil 6. A process for the production of emeri
pamphenylenediamin. , v v
ziiciin and aniiin black upon textilel'?bers and
4:, A. pi'ocess for the production of emer fabrics, comprising the application to the
sidin :ind- anilin black upon textiie ?bers same of a mixture containing enili-n, hydro
and fabrics, comprising the application to chloric acid, a cupiic salt, a sul?te,_a_so1ub1e 25
the some of mixture containing an amlm chlorici and a paradiamin, as paraphenylene
'base, in]. acid, a salt of cooper and $5111) diamin, and subsequent subjection of the
T10 stance capable ofa-sproducing an indemin by material to atmospheric oxidation. .
condensation with alinin, and afterward \ in witness whereof, I have hereunto signed _
subjecting the material to atmospheric oxi my name in the presence of two subscribing
dation'. ' _ Witnesses.
5. A. process for the production of emer
aliiiii and. a'iiiiinbiack upontextile fibers and ARTHUR GEORGE GREEN.
fabrics, comprising the application to the Wiii'iesses: _ ' ' -

same oi ' 'fture containing an amino. Tease, THOMAS LAING Wi-HTEHEAD,

eniacicio iii of copper and a paradmmin, liosisc'r MILTON SPEAsPomT.