Note: Descriptions are shown in the official language in which they were submitted.
1~01154
This invention relates to disperse azo dyestuffs
and more particularly to mixtures of two or more disperse monoazo
dyestuffs of closely related structure, to a process of
manufacture of the said mixtures and to the application of
the said mixtures to aromatic polyester textile materials
and aromatic polyester/cellulose unions
According to the present invention there is
provided a mixture of two or more monoazo dyestuffs of the
formula:
N02 X
2 ~ ~ \
W ~HCOR
' ' ".
wherein W is a chlorine atom or a bro~ine atom;
X is hydrogen or -OR and
R, R , Z and Y are lower alkyl groups;
:: . provided that the mixture contains at least one component
in which X = H and another in which X=OR .
Throughout this specification by "lower alkyl group"
we mean an alkyl group containing from 1 to 4 carbon atoms
As specific examples of lower alkyl groups represented
by R, R , Y and æ there may be mentioned methyl ethyl,
~: 20 n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl groups,
--1--
b~ ~
'
. ' ' ' :
11C~1154
In the case in which the mixture of dyestuffs as
deined above comprises two components, then these components
may be present in the mixture in amounts from 95:5 to 5:95
parts by weight, preferably from 20:80 to 80:20 parts by
weight,
When three or more component dyestuffs are present
in the mixture, no single dyestuff will comprise less than
5% by weight of the total weight of the mixture.
A preferred mixture of dyestuffs according to the
10 invention is that comprising two dyestuffs having the
formula:
2 xl / 2 5
2~ =R ~ ~
W NHCOCH3 C2H5
`
: ~' , .
: : ~ in which the two dyestuffs have W = Br, X = H and W = Br,
X = methoxy respectively,
: Another preferred mixture of dyestuffs according
,. :
to the invention is that comprising two dyestuffs of formula
(II) in which W~= Br, X = H and W = Br, Xl = ethoxyt
respectively,
: :Yet another preferred mixture of dye~tuffs according : -
~;~ 2~0 to~the~invention:is ;that comprising two dyestuffs of formula
(II) in which W:= Cl, X = H and W = Cl, Xl = methoxy,
respectively.
, ::: ~ ~: : '
~ 2-
., :
"~L7'
,: ; : ~ .: :
- . . .
,,.
. . - . . , . . ~ - ' . : : - :
llQllS4
Still another preferred mixture of dyestuffs accord-
ing to the invention is that comprising two dyestuffs of
formula (II) in which W = Cl, Xl = H and W = Cl, Xl = ethoxy,
respectively
It is further preferred that in each of the above-
defined mixtures the dyestuffs of formula (II) in which Xl =
H and the dyestuff of formula (II) in which Xl is either
methoxy or ethoxy should be in the proportions between
approximately 4:1 and approximately 2:1 by weight,
respectively
Particularly preferred is a mixture comprising two
dyestyfs of formula ~II) in which W = Br, X = H and W =
Br, Xl = methoxy, in the proportions of approximately 3:1
by weight respectively.
According to a further feature of the invention
there is provided a process for the manufacture of the
~:~ - mixtures o disperse monoazo dyestuffs of formula (I) which
comprises coupling a mixture of at least two coupling
.
~components of formula
X '
: NHCOR
wherein R, X, Y:and Z have the meanings stated above, with
a~t least one diazonium compound obtained by diazotisation
of an amine of the formula: ~
., - ~ .
-: . ~: , :
~ 3-
.
h
.
.
154
~2
2~ 2 (IV)
W
wherein W has the meaning stated above, provided that the
mixture of coupliny components contains at least one com-
ponent in which X is hydrogen and at least one component
in which X is o~ .
In the case in which two diazonium compounds are
employed in a process as defined above, these may be used
by individually diazotising the amines and adding ~he dia-
zonium compounds so obtained simultaneously or consecutively
to the mixture of coupling components, or the amines may
be diazotised in admixture and the mixed diazonium compounds
' ~ so obtained then added to the mixture of coupling components,
or the individually prepared diazonium compounds may be
mixed together before addition to the mixture of coupling
:`: components,
:The amine of formula (IV) may be 2, 4-dinitro-6-
chloroaniline or 2,4-dinitro-6-bromoaniline,
Examples of coupling components of formula (III) -:
: are 5-acetylamino-2-methoxy-N,N-diethylaniline, N,~-diethyl-
m-aminoacetani;lide,~ The diazotisation and coupling may be :~
carried out by methods conventionally used for these
reactions. Thus diazotisation of the amine or amines of
formula ~IV) may be carried out in nitrosylsulphuric acid
in known manner, followed by addition of the resulting
solution of the diazo compound to a solution or suspension
: : ~ of the coupling components in water or in a mixture of water
: ~ ~
.' ~ , ' :
-
. . .
.~, . . . .
. .
, . ' . i . . ~: . ' .: : . ~
11(~1154
and a water-miscible organic liquid, if necessary adjusting
the pH of the mixture to facilitate the coupling reaction,
and finally isolating the resulting dyestuff by conventional
methods.
In addition to preparing mixtures of dyestuffs
according to the invention from mixed coupling components
and a single diazo component or mixture of diazo components
as defined above, such mixtures may of course be obtained
- by mixing together the individually prepared component dye-
stuffs of the mixture, obtained by conventional diazotisation
and coupling reactions from an amine of formula (IV) and
a coupling component of formula (III)
The dyestuffs may be applied to polyester textile
materials by aqueous dyeing, padding or printing methods
in the form of aqueous dispersions which are prepared by
conventional methods, for example, by milling the dyestuffs
with water and a suitable dispersing agent such as the
:~ sodium salt of a naphthalene-2-sulphonic acid/formaldehyde
: condensate, and this colouration process constitutes a
::. 20 further feature of the invention
The dyestuff mixtures of the present invention
,
provide navy shades on aromatic polyester textile materials
which have very good build-up properties and high tinctorial
~: ; strength superior to the effect achieved by the application
of any single component of the dyestuff mixture on its own.
:. :
According to a yet further feature of the invention
there is provided a process.for the colouration of aromatic
polyester/cellulose unions which comprises applying to the
said unions by an aqueous dyeing, padding or printing
30. : process a:mixture of two or more disperse monoazo dyestuffs
;~ ~ - as hereinbe:fore defined.
~ _5_
.
' ~ ' ' ' ' . - ' ' ,
1154
It is known that the polyester component of a
polyester/cellulosic blend can be dyed with disperse dyes,
but these dyes suffer from the disadvantage that, particularly
when applied by a padding or printing process, they also
adhere to the cellulosic component. Because disperse dye-
stuffs have low fastness properties on cellulosic materials,
that portion of the applied dyestuffs which has stained the
cellulose is easily washed off and fades rapidly on exposure
to light. Consequently a polyester/cellulose union coloured
in this way has poor fastness properties due to loose dye on
- the cellulose, In order that the coloured union has the
maximum fastness properties it is essential that any
unfixed dyestuf f be removed. This is usually achieved by
a "reduction clear" treatment of the coloured union (i,e,
a treatment in a warm aqueous alkaline solution of sodium
hydrosulphite). However, the disposal of the liquors from
; ~ the "reduction clear" treatment causes ecological problems
due to the presence of the reducing agent, Also a reduction
clear treatment cannot be used after the cellulose poxtion
of the blend has been dyed with a dye which is sensitive to
this treatment,
Further, in the absence of a "reduction clear"
treatment, any dyestuff which is removed by, for example,
an~ordinary washing treatment can give rise, especially in
the case of printing, to back staining resulting in the
" ~ . ~
staining of other ~areas of the print, or dull tones.
The above described problems are minimised by the
use of mixtures o~ disperse monoazo dyestuffs as herein-
i: :
before d~fined, which cause a minimum of staining of the
; ~cellulose portion of ths blend,
~ :
~ 6-
:: : .
-:, ~ ~ , .
- : . - , .
ll~llS4
The process may be carried out by immersing the
polyester/cellulose union in a dyebath comprising an aqueous
dispersion of the two or more monoazo dyestuffs as defined
above, which dyebath preferably contains a non-ionic, cationic
and/or anionic surface-active agent, and thereafter heating
the dyebath for a period at a suitable temperature, The
dyeing process can either be carried out at a temperature
between 95 and 100C, preferably in the presence of a
carrier such as diphenyl,o-hydroxydiphenyl, methyl naphthalene,
methyl salicylate or trichlorbenzene, or at a temperature
from 120C to 140C, under superatmospheric pressure,
The process of the invention may also be carried out
by padding on to the polyester/cellulose union an aqueous
dispersion of two or more disperse monoazo dyestuffs as here-
inbefore defined, the dyestuffs then being fixed on the union
by steaming it for short periods at a temperature between
100 and 180C or baking it at temperatures between 160
i and 220C, If desired the padding liquor can contain the
: conventional additives, for example, dispersing agents,
thickeners, migration inhibitors or urea,
As a further method of application a thickened
: printing paste containing the two or more disperse monoazo
dyestuffs~in dispersed form can be applied to the surface of
~ the polyesterjcellulose union by any of the methods
': , conventionally used for applying printing pastes to textile
: materials, for example by block, screen or roller printing,
The printed textile material~ optionally after being dried,
`then steamed for short periods at temperatures between
:
.
~ ~ 100 and 180C, or is baked at temperatures between 160C
:~ 30 and 220C.~ Suitable thickening agents which are present in
~: the printi~ng paste include gum tragacanth, gum arabic,
alginates, for example, sodium or ammonium alginates, oil-
.
: ~ in-water or water-in-oil emulsions, or thickening agents of
. ~ -7-
,
-,
" ll(~llS4
synthetic origin based on ethylene/maleic anhydride copolymers
or polyacrylic acids The printing pastes can also contain
conventional additives such as urea, sodium m-nitrobenzene
sulphonate, diimides, acids or alkalis to assist in bringing
about fixation of the various dyestuffs.
After the dyeing, padding or printing process has been
carried out, the coloured textile material is then rinsed in
water.
The aromatic polyester/cellulose unions used in
the process of the invention can be any textile materials
which are mixtures of aromatic polyester fibres and
cellulose fibres. Such unions are usually in the form of
knitted, or preferably woven goods. The percentage of
aromatic polyester fibres is usually in the range of 20
to 95%, and preferably 30 to 85%, by weight of the weight
of the union The aromatic polyester fibres are preferably
polyethylene terephthalate fibres and the cellulose fibres
'~ are preferably cotton, linen, viscose rayon or polynosic
~ rayon fibres,
By the use of mixtures of disperse monoazo dyestuffs
as hereinbefore defined in the process of the invention the
aromatic polyester part of the polyester/cellulose union
is coloured in navy shades with excellent reserve of the
cellulose part of the union, i.e. the cellulose remains
uncoloured or virtually so Any staining of the cellulose
~which does occur can be removed by a "reduction clear"
treatment which is very much milder than that conventionally
; employed, with a corresponding reduction in the effluent
disposal problem
The process of the present invention can also be
appl1ed to the colouration of unions containing aromatic
--8--
~' ' .
,
11~1154
polyester and cellulose whereby the mixture of disperse
monoazo dyestuffs as hereinbefore defined is applied in
conjunction with one or more suitable colouring matters
for the cellulose, and this constitutes a still ~urther
feature of the invention.
Suitable colouring matters for the cellulose part
of the polyester/cellulose unions are Direct Dyestuffs,
Vat Dyestuffs, Sulphur Dyestuffs, Azoic Colouring Matters,
or Reactive Dyestuf~s.
The mixture of disperse monoazo dyestuffs for the -~
aromatic polyester part of the union and a colouring matter
from one of the above-defined classes for the cellulose
part of the union may in general be applied concurrently
or consecutively, by the conventional processes.
Though the dyes employed in this invention can be
applied to a polyester/cellulosic blend by all conventional
processes and together with all classes of dyes for cellulose,
;~ a particular advantage of these dyes is that since they have
good cellulose reserve and dyeings of high fastness can be
obtained using processes which do not involve a reduction
clearing treatment. This permits the use of simple and
economical processes, as exemplified below,
Thus, the polyester!cellulosic material may be padded
with a liquor containing disperse and reactive dyes, dried,
baked or steamed at high temperature to fix the disperse
dyes on the polyester component, padded in aqueous alkali,
:
steamed to fix the reactive dye on the cellulosic component,
washed and dried.
Alternatively, the pad liquor can contain alkali,
30 ~ and fixation of the reactive dye be achieved during drying
_ g_
.~
llQ1154
prior to baking, thus avoiding the need for an alkali pad-
steam treatment,
In batchwise processing the polyester component can
be dyed in any conventional manner, the dyeing given a mild
reduction clearing treatment, or no treatment at all, the
cellulosic portion then being dyed by any process, using
any class of dye for ~ellulose.
The cellulosic portion can first be dyed with a
reactive dye, the material rinsed until neutral, and the
polyester component then dyed with the mixture of disperse
dyes in a separate dyebath either under pressure or with
a carrier, washed and dried. Or the cellulose can be dyed
first with a reactive dye, after which the mixture of
disperse dyes is added to the exhausted dyebath, the pH
adjusted and any auxiliary products added, and the polyester
component dyed either at the boil with a carrier, or under
pressure.
The reactive dyestuffs used in the process of the
invention can be any water-soluble dyestuffs which contain
at least one fibre-reactive group, this being defined as
~ a group whose presence in the dyestuff molecule renders
`~ the dyestuff capable of chemically combining with hydroxy
groups present in cellulose textile materials so that the
dyestuff molecule becomes attached to the cellulose molecule
through a covalent chemical bond or bonds. Each fibre-
reactive group is attached to a carbon atom pxesent in the
dyestuff molecule and preferably to a carbon atom of an
aromatic ring, preferably a benzene ring, present in the
dyestuff molecule. The said dyestuffs are preferably dye-
stuffs of the azo, including monoazo and polyazo and metallised
azo dyes, anthraquinone, formazan, triphendioxazine, nitro
and phthalocyanine series containing at least one fibre-
reactive group,
-10-
l~Q11~4
As examples of fibre-reactive groups there may be
mentioned acylamino radicals derived from olefinically
unsaturated aliphatic carboxylic acids such as acryloylamino
and crotonylamino, or from halogen-substituted aliphatic
carboxylic acids such as ~-chloropropionylamino, ~-bromo-
propionylamino, ~ -trichlorocrotonylamino and tetra-
fluorocyclobutylacryloylamino Alternatively the fibre-
reactive group can be a vinyl sulphone, ~-chloroethyl sul-
phone, ~-sulphatoethylsulphonyl, ~-chloroethylsulphonamide
or an optionally N-substituted ~-aminoethylsulphonyl group
The fibre-reactive group is preferably a heterocyclic
radical having two or three nitrogen atoms in the hetero-
cyclic ring and at least one labile substituent attached
to a carbon atom of the heterocyclic ring As examples of
labile substituents there may be mentioned chlorine, bromine,
fluorine, quaternary ammonium groups, thiocyano, sulphonic
acid, hydrocarbylsulphonyl groups, groups of the formula
-SC - N wherein the
11
.~ . S
nitrogen atom carries optionally substituted hydrocarbon
; 20 or heterocyclic radicals, and groups of the formula:-
-- S -- C `~
\ S ,_
wherein the dotted line indicates the atoms necessary to
form an optionally substituted or fused heterocyclic ring.
,
11~1154
As specific examples of such fibre-reactive
heterocyclic radicalst there may be mentioned 3:6-dichloro-
pyridaæine-4-carbonylamino, 2:3-dichloroquinoxaline-5- or
6-(sulphonyl or carbonyl)amino, 2:4-dichloroquinazoline-6-
or 7-sulphonylamino, 2:4:6-trichloroquinazoline-7- or
8-sulphonylamino, 2:4:7- or 2:4:8-trichloroquinazoline-6-
- sulphonylamino, 2:4-dichloroquinazoline-6-carbonylamino,
1:4-dichlorophthalazine-6-carbonylamino, 4:5-dichloro-
pyridazon-l-ylamino, 2:4-dichloropyrimid-5-yl-carbonylamino,
: . 10 1-(phenyl-4'-carbonylamino)-4:5-dichloxopyridazone, 2:4-
and/or 2:6-dichloro- or bromo-pyrid-6-(and/or -4)ylamino,
difluorochloro-pyrimidylamino, trichloropyrimidylamino,
tribromopyrimidylamino, dichloro-5-(cyano, nitro, methyl
or carbomethoxy)pyrimidylamino, 2-methylsulphonyl-6-
chloropyrimid-4-ylcarbonylamino and 5-chloro-6-methyl-2-
methylsulphonylpyrimid-4-ylamino, and more particularly
. 1:3:5-triazin-2-ylamino radicals which contain a fluorine ~.
,~ or a bromine and, above all, a chlorine atom on at least
one of the 4- and 6- positions, for example 4:6-dichloro-
1:3:5-triazin-2-ylamino When the triazine nucleus contains
only a single halogen atom, preferably a chlorine atom,
then the third carbon atom of the triazine ring can be
: substituted by a hydrocarbon radical, such as methyl or
: phenyl, but more particularly by an optionally substituted
hydroxy, mercapto or amino group, such as methoxy, phenoxy,
; : a- and ~-naphthoxy, methylmercapto, phenylthio, methylamino,
diethylamino, cyclohexylamino and anilino and ~-alkylanilino
and substituted derivatives thereo~ such as anisidino,
toluidino, carboxylanilino, sulphoanilino, disulphoanilino
and sulphonated naphthylamino.
-12-
.
.
.. ... .
1154
Thus a preferred class of the reactive dyestuffs
comprises those dyestuffs which contain as the fibre~reactive
group a group of the formula:
~ `\
Cl - C C - N -
N ~ Cr_lH2r_
~ C/
Q
wherein r is 1 or 2, and Q is a chlorine atom, an optionally
substituted amino group or an etherified hydroxyl group.
The optionally substituted amino groups represented
by Q are preferably optionally substituted alkylamino,
anilino, or ~-alkylanilino groups, e g, methylamino, ethyl-
amino, ~-hydroxyethylamino, di(~-hydroxy-ethyl)amino, ~-
methoxyethylamino, ~-sulphatoethylamono, o-, m- and ~-
sulphoanilino, 4- and 5-sulpho-2-carboxyaniline, 4- and 5-
sulpho-2-methoxyanilino, 4- and 5-sulpho-2-methylanilino,
4-and 5-sulpho-2-chloroanilino, 4- and 5-sulpho-2-chloro-
anilino, 2,4-, 2,5- and 3,5-disulphoanilino, N-methyl-m-
and p-sulphoanilino.
If desired the fibre-reactive group can be of the
type:
~H Jl M J2
wherein Jl is a pyrimidine or triazine ring optionally
carrying a labile substituent, J is a pyrimidine or tria-
zine ring carrying at least one labile substituent and ~
is a bridging member which is linked to J and J through
optionally substituted imino groups, said imino groups
being linked together through an alkylene or arylene radical
such as ethylene, 1:4 -phenylene or 2-sulpho-1:4-phenylene.
-13-
'
.. . . . .
S4
Other linking groups of particular interest
represented by M are the divalent radicals of stilbene,
diphenyl, diphenyloxide, diphenylamine, diphenylurea,
diphenoxyethane and diphenylamino-s-triazine, which
contain a sulphonic acid group in each benzene nucleus,
It is preferred that Jl and J2 should each
represent a chloro-s-triazine group, Thus, a further class
of reactive dyestuffs comprises those dyestuffs which con-
tain as the fibre-reactive group a group of the formula:
~ N \
11
N~ " N Cr_lH2r-1 ¦
C ~ (7)
~ I M ~ ~ ~ l - Cl
., , I ~
Cp lH2p 1 C lH2
:
wherein r, ~ and ~ are each independently 1 or 2, and M and
- Q have the meanings stated above,
The group Q, as previously defined, includes within
its scope groups which contain a chromophoric system linked
~to the carbon atom of the triazine ring through -~H- or -O-. ~.
.~ ~ '.'''
-14-
1154
Such reactive dyestuffs can be obtained in conven- ;
tional manner for example by reacting a water-soluble
dyestuff containing a primary or secondary amino group
with a compound which contains the said fibre-reactive
group As examples of such compounds there may be
mentioned acryloyl chloride, cyanuric chloride, 2:4:6-
trichloropyrimidine, 2:4:6-trichloro-5-(cyano- or
chloro-)pyrimidine and 6-methoxy-2:4-dichloro-1:3:5-
triazine,
Other preferred reactive dyestuffs are those
containing one or more phosphorus acid groups,
particularly phosphonic acid groups, which are applied
to cellulose textile materials by the methods described
in U.K, Patent Specification ~o. 1411306.
By this process of the invention aromatic
polyester/cellulose unions are coloured in a variety
of shades which have excellent fastness to the tests
commonly applied to such textile materials, and there
is excellent reserve of the white unprinted portions
of such textile materials,
The preparation of certain coupling components
and dyestuffs for the particularly preferred mixtures
according to the present invention is described below,
Parts are by weight unless otherwise indicated, the
: ratio of parts by weight to parts by volume being that
of the kilogram to the litre.
-15-
11C~1154
Preparation of 5-acetylamino-2-methoxy-N,N-diethylaniline
18 parts of 5-acetylamino-2-methoxyaniline are
stirred in 50 parts by volume of water. Aqueous
sodium hydroxide solution (70O Tw) is added to adjust
the pH to 9-10, The mixture is heated to 65OC and a
dispersing agent )polyglycerolricinoleate,0,5 part)
is added followed by 29.4 parts of sodium bicarbonate
(e~uivalent to 3,5 mols per mole of the aniline ...
starting material). 54 parts of diethylsulphate ~3,5
mols per mol of mol of starting material) is then added
over a period of 2 hours at 65C, Reaction proceeded
smoothly, Stirring of the mixture at 65C was continued
for.a further 2 hours after addition of the diethyl-
sulphate to complete the reaction. The reaction mixture
. was cooled to room temperature and the 5-acetylamino-2-
methoxy-~,~-diethylaniline was collected, washed with
water (500 parts of volume) and dried at 70C,
~,~-Diethyl-m-aminoacetanilide is prepared in similar
manner starting from m-aminoacetanilide,
Preparation of the dyestuff _f formula (II) in which Xl ~.
is methoxy . .:
70 parts (by volume) of 100% sulphuric acid
: are added to 4 parts of water, 7 parts of sodium
nitrite are then added portionwise to the stirred acid .
at a rate such as to raise the temperature of the
mixture to 70~ 2C and to maintain it at that level, : :
On completion of the addition of sodium nitrite.the - .
.' .
-16-
,
~.
,
, . .
l~llS4
solution is stirred for 1 hour, the temperature being
allowed to fall to room temperature 26 2 parts of
2,4-dinitro-6-bromoaniline are added to the stirred
sodium nitrite solution at 25-28C during 30 minutes.
On completion of the addition the solution is stirred
for 2 hours at room temperature.
23,6 parts of 5-acetylamino-2-methoxy-N,N-
diethylaniline are stirred in 500 parts of water and
10 parts by volume o concentrated hydro-chloric acid
are added. Ice is added to the solution to lower the
temperature to 0C and anhydrous sodium acetate is
added to adjust the pH to 3-4. The diazotised amine
solution is then added dropwise during 30 minutes at
0C and pH 4 (controlled by the addition of ice and
sodium acetate) until only a trace of excess coupling
component remains as shown by testing the mixture
with diazotised p-nitroaniline, The mixture is stirred
for a further 15 minutes at 0-5C, and the dyestuff
is collected and washed free from inorganic contaminants
with water. The d~estuff is dissolved in boiling
acetone, the solution is filtered and the dyestuff is
re-precipitated by the addition of ice and water to
the acetone solution. The product is again collected,
washed with water and dried at 70C.
Preparation of the dyestuff of formula (II) in which
X is hydroqen
2,4-Dinitro-6-bromoaniline (2~ 2 parts~ is
diazotised and coupled with 20,6 parts of N,N-diethyl-
m-aminoacetanilide exactly as described for the
preceding preparation,
~lV1~54
The invention illustrated butnot limited by
the following Examples in which parts and percentages
are by weight
Example 1
10 Parts of the dyestuffs o~ formula (II) in
which W = Br, Xl = methoxy and W = Br, X = hydrogen
respectively are individually gravel milled with 12.8
parts of an aqueous solution of a dispersing agent
(sodium salt of a naphthalene-2- sulphonic acid/formal-
dehyde condensate), containing 39 2% by weight of theagent, and 77 2 parts of water After 48 hours milling
the particle size of each dyestuff in its dispersion
is 3-4 microns
~ 0.3 part of the 10% aqueous dispersion of the
dyestuff of formula (II) in which,W = Br, X
hydrogen, and 0,075 part of the 10% aqueous dispersion .::
, of the dyestuff of formula (II) in which.W = Br, X
methoxy, both dispersions being obtained as described
above, are transferred into a dyeing vessel. 0.5 part
by volume of a buffer solution is added, followed by
5 parts of polyester piece textile material. The dye-
bath is then made up to 50 parts with water and dyeing
~ is effected under superatmospheric pressure at 130C
:~ for 1 hour.
On completion of dyeing the dyed material is
stirred in a reduction clearing bath comprising 5
parts of sodium hydrosulphite, 3 parts by volume of
sodium hydroxide solution (70 Tw), 3 parts by volume
of a dispersing agent and 490 parts by volume of water,
for 30 minutes at 70C. The fibre is then thoroughly
washed in a soap solution, rinsed well in water and
-18-
.~.,~'i
ll~llS4
and dried.
The polyester is dyed in a navy blue shade having
very good build up and high tinctorial strength.
Example 2
- The dyeing procedure described in Example 1 is
repeated except that the 10% aqueous dispersion of the
dyestuff of formula (II) in which W = Br, Xl = H and the
10% aqueous dispersion of the dyestuff of formula (II) in
which W = Br, Xl - methoxy are used in the following amounts:-
(II W - Br,X - H(II)W = Br,Xl= methoxv
(a) 0.10 0,30
(b) 0,20 0,20
(c) 0,25 0.15 :
(d) 0.30 0,10
(c) 0,35 0,05
In each case a strong navy blue shade on polyester
textile material is obtained,
Example 3
The dyeing procedure described in Example 1 is
repeated except that the 0,075 part of the 10% aqueous
dispersion of the dyestuff of formula (II) in which W = Br,
X - methoxy is replaced by 0,1 part of a 10% aqueous
dispersion of one of the following dyestuffs of formula (I),
W, X, Y, Z and R in the table below have the same
significance as in formula (I),
-19-
lS4
W X Y Z R
ta) Br OCH3 CH3 CH3 CH3
(b) Br OCH3C3H7~n) C3H(n) CH3
(c) Br C4 9(-) C2H5 C2H5 CH3
(d) Br OCH3 C2H5 C2H5 C2H5
(e) Cl OCH3 C2H5 C2H5 3
(f) Br 0C2H5 C2H5 C2 5
: (g) Br 3 7(-1 C2H5 C2H5 3
(h) Br OCH3 C4Hg( ) C4Hg(~) CH3
(i) Br OCH3 CH3 C4H9(_) CH3
(j) Br OCH3 C2H5 C2H5 C3H7(n)
(k) Br OCH3 C2H5 C2H5 C3H7 (i80)
: Each dyestuff mixture when applied to aromatic
; polyester textile material as described in Example 1 gives a
strong navy blue shade
Example 4
The dyeing procedure described in Example 1 i9 repeated
except that the 0, 075 part of the 10% aqueous dispersion of
the dyestuff of formula (II) in which W = Br, X = methoxy
~:20 is replaced by 0,1 part of the same dyestuff dispersion, and
the 0.3~part of the 10% aqueous dispersion of the formula (II)
` ; ~ in which W = Br, X = hydrogen is replaced by 0.3 part of a
:10% aqueous dispersion of one of the following dyestuffs of
formula (I). W, X, Y, Z and R in the table below have the
same significances as in formula (I).
,~
.
~l~tllS4
W X Y Z R
(a) Br 2 5 C2 5 C2H5
(b) Cl HC2H5 C2H5 CH3
(c) Br HCH3 CH3 CH3
(d) Br H3 7(_) C3H7(_) CH3
(e) Br HC4Hg(_)C4Hg ~) CH3
(f) Br HCH3 CH2cH(cH3) 2 CH3 ~`
(g) Br HC2H5 C2H5 C3H7 ~)
Each dyestuff mixture when applied to aromatic
polyester textile material as described in Example 1 gives
a strong navy blue shade.
ExamPle 5
:,
0 3 part of a 10% aqueous dispersion of the dyestuff
of formula (II) in which W = Br, X = hydro~en, 0.5 par~ of
a 10% aqueous dispersion of the dyestuff of formula (II) in
which W = Br, Xl = methoxy and 0.05 part of a 10% aqueous
dispersion of the dyestuff of formula (II) in which W = Br,
X = ethoxy are mixed together. This mixture when applied
to aroma~ic polyester textile material by the method described
in Example 1 gives strong navy blue shades.
~ ~ .
Similar results are obtained if the dyestuff of
formula (II) in which W = Br, Xl = ethoxy is replaced by
the dyestuff of formula (I) in which W is bromine, X is
methoxy, Y and Z are each n-propyl and R is methyl.
Example 6
A mixture is made in the proportions given below,
of the 10% aqueous dispersions of four dyestuffs of formula (I)
in which Y and Z are each ethyl, R is methyl and W and X have
the meanings given below
-21- ~
~j :
, . ,
110~
- x -
Br H 1.5 part
Cl H 1 5 part
Br OCH3 0 5 part
Cl OCH3 0.5 part
This mixture when applied to aromatic polyester
textile material by the method described in Example 1 gives
strong navy blue shades.
Example 7
26.2 Parts of 2,4-dinitro-6~bromoaniline are
diazotised by the method described previously and the
diazonium compound so obtained is coupled with a mixture
of 6.0 parts of 5-acetylamino-2-methoxy-~ diethyl-
aniline and 15.4 parts of ~,~-diethyl-m-aminoacetanilide
by the method described previously. The mixed dyestuff
so obtained when applied in the form of an aqueous
dispersion to aromatic polyester textile material as
described in Example 1 gives strong navy blue shades
Example 8
The dyeing procedure described in Example 1 is
repeated except that the 0 3 part of a 10% aqueous
dispersion of the dyestuff of formula (II~ in which W = Br,
~: .
~ xI = hydrogen is replaced by 0.3 part of a l~/o aqueous
.
dispersion of the dyestuff of formula (II) in which W =
Cl, X ~= hydrogen, and the 0.075 part of the 10% aqueous
dispersion of the dyestuff of formula (II) in which W -
Br, X = methoxy is replaced by 0 1 part of a 10% aqueous
dispersion of one of the following dyestuffs of formula (I~.
:
W, X, Y, Z and R in the table below have the same signifi-
cance as iD formula (I)
:
~ ~ -22-
,
llalls4
W X Y Z R
(a) Cl OCH3 C2H5 C2H5 CH3
(b) Cl C2H5 C2H5 C2H5 CH3
(c) Cl OCH3 C2H5 C2H5 C2H5
(d) Cl OCH3 C3H7(n) C3H7(_) CH3
Each dyestuff mixture when applied to aromatic
polyester textile m~terial as described in Example 1
gives a strong navy blue shade.
ExamPle 9
A 67/33 woven blend of polyester/cotton fibres
is padded in a pad-liquor of the following constitution,
so that the material retains 50% of its weight of the
padding liquor,
1 part of the dyestuff of formula (II) in which
W = Br, X = hydrogen, as a 10% a~ueous dispersion,
4 parts of the dyestuff of formula (II) in which
W = Br, X = methoxy, as a 10% aqueous dispersion,
~- ~ 10 parts urea,
10 parts Matexil FA-MIV (a migration inhibitor
marketed by Imperial Chemical Industries Limited;
~ "Matexil" is a Registered Trade Mark)
:~ 10 parts sodium bicarbonate per 1000 parts of
: pad liquor
The dyes are preferably in the form of an aqueous
. ~ ~ dispersion, milled in the presence of an equal weight of
: a protective agent such as the sodium salt of a
naphthalene-2-sulphonic acid/formaldehyde condensate.
-23- :
.
, :~
:'
~.
,. ..
.
54
The padded material is dried for 30 seconds at
110C, baked for 60 seconds at 210C, rinsed in hot water,
treated for 30 seconds at 80C in a solution containing
2 g/litre Synperonic BD (a synthetic detergent marketed
by Imperial Chemical Industries Limited, "Synperonic" is
a Registered Trade Mark) rinsed in cold water and dried.
The above series of operations can conveniently be
carried out as a continuous sequence
The polyester portion of the blend is dyed to a
full, reddish navy shade while the cotton portion is
only slightly stained, and the fabric has good fastness
to light and washing.
Example 10
The padding procedure described in Example 9 is
repeated except that the dyestuff of formula (II) in
which W = Br, Xl = hydrogen and the dyestuff of formula
(II) in which W = Br, X = methoxy are used in the
following proportions:-
(II) W = Br, X = H (II) W = Br, Xl =
. M methoxy
(a) 1 0 3.0
(b) 2,0 2.0
: ~c) 2,5 l S
: ~ (d) 3.0 1.0
: (e) 3.5 0 5
In each case a similar result to that describedin Example g is obtained
Example 11
The padding procedure described in Example 9 is
30 repeated except that the 1 part of the dyestuff of formula :~
(II) in which W = Br, X = hydrogen.is increased to 3 parts,
and the 4 parts of the dyestuff of formula (II) in which
. -24-
' ' ' ~ '.
11~115~
W = Br, Xl = methoxy are replaced by 1 part of one of
the following dyestuffs of formula (I) W,X, Y, Z and
R in the table below have the same significance as in
formula (I).
W X Y z R
ta) Br OC~3 CH3 CH3 CH3
(b) Br OCH3 C3H7(n) . C3H7(n) CH3
(c) Br OC4Hg~) C2H5 C2H5 CH3
(d) Br OCH3 C2H5 C2H5 CH5
Cl OCH3 C2H5 C2H5 CH3
(f) Br C2H5 C2H5 C2H5 CH3
(g) Br OC3H7(_) C2H5 C2H5 CH3
(h) Bx OCH3 C4Hg(_) C4Hg ~) CH3
(i) Br OCH3 CH3 C4Hg(_) CH3
(i) Br OCH3 C2H5 C2H5 C3H7(n)
(k) Br OCH3 C2H5 C2H5 c3H7(iso)
In each case a similar result to that described in
Example 9 is obtained.
Example 12
The padding procedure described in Example 9 is
repeated except that the 4 parts of the dyestuff of
formula (II) in which W = Br, Xl = methoxy are reduced
to 1 part, and the 1 part of the dyestuff of formula (II)
in which W = Br, Xl = hydrogen is replaced by 3 parts of -
one of the foll~wing dyestuff of formula (I). W, X, Y,
Z and R in the table below have the same significance as
- . ..... ................................................................... : .
in formula (I)
-25-
. ,~'
-
154
W X Y Z R
(a) Br H 2 5 C2H5 C2H5
(b) Cl H C2~5 C2H5 CH3
(c) Br H CH3 CH3 3
(d) Br H C3H7(n) C3H7(_) CH3
(e) Br H C4Hg(_) C4H9(n) CH3
(f) Br H CH3 CH2CH(cH3)2 CH3
(g) Br H C2 5 C2Hs C3H7(n)
In each case a similar result to ~hat described
in Example 9 is obtained.
ExamPle-l3
The padding procedure described in Example 9 is
repeated except that the 1 part of the dyestuff of
~ formula (II) in which W = Br, X = hydrogen and the 4
I ~ parts of the dyestuff of formula (II) in which W = Br,
xl = methoxy are replaced by 3 parts of the dyestuff of
formula (II) in which W = Br, Xl = hydrogen, 0.5 part
of the dyestuff of formula (II) in which W = Br, X
methoxy and 0.5 part of the dyestuff of formula (II) in
which W = Br, Xl = ethoxy.
A similar result to that described in Example 9
is obtained.
If the dyestuff of formula (II~ in which W = Rr,
X = ethoxy is replaced by the same amount of the dyestuff
., ~
of formula (I) in which W is hromine~ R is methyl, X is
methoxy, and Y and Z are each n-propyl, a similar result
is obtained.
. ~ .
~ -26-
~ ' '
.
154
Example 14
The padding procedure described in Example 9
is repeated except that the 1 part of the dyestuff of
formula (II) in which W = Br, Xl = hydrogen and the 4 parts
of the dyestuff of formula (II) in which W = Br, Xl =
methoxy are replaced, in the proportions given below,
by four dyestuffs of formula (I) in which Y and Z are
each ethyl, R is methyl and W and X have the meanings
given below:-
W X
Br H 1.5 parts
Cl H 1.5 parts
Br OCH3 0.5 parts
Cl OCH3 0.5 parts
: A similar result to that described in Example 9
is obtained.
Example 15
A mixture of dyestuffs of formula (II) in
which W = Br, Xl = hydrogen and W = Br, Xl = methoxy
respectively is prepared as described in Example 7 and
converted into 10% aqueous dispersion.
When this dispersion is applied to a polyester/
cotton blend as described in Example 9 a similar result is
obtained,
Example 16
The padding procedure described in Example 9 is
repeated except that the 1 part of the dyestuff of
formula (II) in which W = Br, Xl = hydrogen and the
4 parts of the dyestuff of formula (II) in which W = Br,
Xl = methoxy are r placed by 3 parts of the dyestuff of
-27-
'
l~llS4
formula (II) in which W = C1, Xl = hydrogen and 1 part of
one of the following dyestuffs of formula (I) respectively.
W, X, Y, Z and R in the table below have the same signifi- -
cance as in formula (I),
W X Y Z R
(a) C2H5 C2H5 ~H3
(b) Cl C2H5 C2H5 C2H5 CH3
(c) Cl OCH3 C2H5 C2H5 C2H5
(d) Cl OCH3 C3H7~_) C3H7(-) CH3
In each case a result similar to that described
in Example 9 is obtained.
-
...
'
~ .
-28-
'
