PROCESS FOR DYEING NATURAL OR SYNTHETIC POLYAMIDE FIBRE MATERIALS WITH MIXTURES OF DYES

METHODE DE TEINTURE DE TEXTILES NATURELS OU SYNTHETIQUES DE POLYAMIDE AVEC DES COLORANTS MIXTES

English Abstract

Process for dyeing natural or synthetic polyamide fibre materials
with mixtures of dyes
Abstract of the Disclosure
A process for dyeing natural or synthetic polyamide fibre material
from an aqueous liquor with mixtures of dyes, in the presence of an
alkali metal salt or an ammonium salt and optionally in the presence
of an assistant, which process comprises dyeing said fibre material
with a mixture containing at least one 1:1 metal complex dye which
contains sulfo groups and at least one metal-free dye which contains
sulfo groups, in the presence of an alkali metal or ammonium
fluoride, an alkali metal or ammonium fluorosilicate, an alkali
metal or ammonium fluoroborate, an alkali metal or ammonium fluoro-
zirconate or an alkali metal or ammonium fluorosulfonate, at a pH
value in the range from 3 to 7.
The process of the invention is suitable for producing non-skittery
and level dyeings of good fastness properties on synthetic polyamide
material.

Claims

21489-6944
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for dyeing natural or synthetic polyamide
fibre material from an aqueous liquor with mixtures of dyes, in
the presence of an alkali metal salt or an ammonium salt and
optionally in the presence of an assistant, which process
comprises dyeing said fibre material with a mixture containing at
least one 1:1 metal complex dye which contains sulfo groups and
at least one metal-free dye which contains sulfo groups, in a
compound chosen from the group consisting of alkali metal
fluoride, ammonium fluoride, alkali metal fluorosilicate,
ammonium fluorosilicate, alkali metal fluoroborate, ammonium
fluoroborate, alkali metal fluorozirconate, ammonium
fluorozirconate, alkali metal fluorosulfonate and ammonium
fluorosulfonate, at a pH value in the range from 3 to 7.
2. A process according to claim 1, wherein dyeing is
carried out in the presence of sodium fluoride or potassium
fluoride.
3. A process according to claim 1, which comprises using
half to four times the amount by weight of a compound chosen from
the group consisting of alkali metal fluoride, ammonium fluoride,
alkali metal fluorosilicate, ammonium fluorosilicate, alkali
metal fluoroborate, ammonium fluoroborate, alkali metal

26 21489-694
fluorozirconate, ammonium fluorozirconate, alkali metal
fluorosulfonate and ammonium fluorosulfonate, based on the amount
by weight of dye employed.
4. A process according to claim 1, wherein the pH range of
3 to 7 is adjusted with an organic acid, and which optionally
comprises using, in addition to a compound chosen from the group
consisting of alkali metal fluoride, ammonium fluoride, alkali
metal fluorosilicate, ammonium fluorosilicate, alkali metal
fluoroborate, ammonium fluoroborate, alkali metal
fluorozirconate, ammonium fluorozirconate, alkali metal
fluorosulfonate and ammonium fluorosulfonate another ammonium or
alkali metal salt.
5. A process according to claim 1 wherein dyeing is
carried out in a pH range from 3 to 6.
6 A process according to claim 1, wherein dyeing is
carried out in the presence of a leveling assistant or a mixture
of levelling assistants.
7. A process according to claim 6, which comprises using
0.3 to 3 percent by weight based on the fibre material, of
levelling assistant or levelling assistant mixture.

26a 21489-6944
8. A process according to claim 1, which comprises using a
dye mixture that contains at least one 1:1 chromium complex azo
or azomethine dye containing 1 to 3 sulfo groups and at least one
metal-free dye containing 1 or 2 sulfo groups.

- 27 - 21489-6944
9. A process according to claim 8 for trichromatic dyeing,
which comprises using a, mixture of at least three 1:1 chromium
complex azo or azomethine dyes selected from dyes that give
yellow or orange, red and blue dyeings, and at least one
metal-free dye selected from dyes that give yellow or orange
and/or red and/or blue dyeings.
10. A process according to claim 8, wherein the 1:1
chromium complex azo or azomethine dyes correspond to formula
<IMG> (4)
wherein -(CO)O-1-O and -(O- or -NR1) are linked to D and K
adjacent to the azo bridge, D is a radical of the benzene or
naphthalene series which is unsubstituted or substituted by
halogen C1-C4alkyl, C1-C4alkoxy, nitro or sulfamoyl, K is a
phenyl, naphthyl, 1-phenyl-3-methylpyrazol-5-one, acetoacetamide
or quinoline radical, each unsubstituted or substituted by
halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfamoyl
or hydroxy, R1 is hydrogen, M is an alkali metal cation, and An
is an anion, and Y is a nitrogen atom or the -CH- group.

28 21489-6944
11. A process according to claim 1, which comprises using
mixtures of sulfo-containing 1:1 metal complex dyes and sulfo-
containing metal-free dyes in the weight ratio of 40:60 to 95:5.
12. A process according to claim 8, wherein the metal-free
sulfo-containing dyes are those of the monoazo, polyazo,
anthraquinone, xanthene or triphenylmethane series.
13. A process according to claim 1, wherein the fibre
material is synthetic polyamide material, silk or wool.
14. A process according to claim 13, wherein the fibre
material is wool.
15. A composition comprising at least one 1:1 metal complex
dye which contains sulfo group, at least one metal-free sulfo-
containing dye and half to four times the amount by weight of a
compound chosen from the group consisting of alkali metal fluo-
ride, ammonium fluoride, alkali metal fluorosilicate, ammonium
fluorosilicate, alkali metal fluoroborate, ammonium fluoroborate,
alkali metal fluorozirconate, ammonium fluorozirconate, alkali
metal fluorosulfonate and ammonium fluorosulfonate, based on the
amount by weight of dye employed.
16. A process according to claim 3, wherein the amount by
weight of a compound chosen from the group consisting of alkali

29 21489-6944
metal fluoride, ammonium fluoride, alkali metal fluorosilicate,
ammonium fluorosilicate, alkali metal fluoroborate, ammonium
fluoroborate, alkali metal fluorozirconate, ammonium
fluorozirconate, alkali metal fluorosulfonate and ammonium
fluorosulfonate is from one to three times the amount by weight
of dye employed.
17. A process according to claim 3, wherein the amount by
weight of a compound chosen from the group consisting of alkali
metal fluoride, ammonium fluoride, alkali metal fluorosilicate,
ammonium fluorosilicate, alkali metal fluoroborate, ammonium
fluoroborate, alkali metal fluorozirconate, ammonium
fluorozirconate, alkali metal fluorosulfonate and ammonium
fluorosulfonate is from two to three times the amount by weight
of dye employed.
18. A process according to claim 4, wherein the organic
acid is formic acid or acetic acid.
19. A process according to claim 4, wherein another
ammonium or alkali metal salt is alkali metal acetate or alkali
metal sulfate.
20. A process according to claim 19, wherein the alkali
metal salt is sodium acetate or sodium sulfate.

21489-6944
21. A process according to claim 5, wherein the pH range is
from 3.5 to 5.
22. A process according to claim 21, wherein the pH range
is from 4 to 5.
23. A process according to claim 7, wherein the amount of
levelling assistant, or mixture of levelling assistants, is 1 to
2 percent by weight, based on the fibre material.
24. A process according to claim 8, wherein the chromium
complex azo or azomethine dye contains 1 to 2 sulfo groups.
25. A composition according to claim 15, wherein the 1:1
metal complex dye is a 1:1 chromium complex dye.

Description

~73~54
-- 1 --
1-15356/+
Process fcr dyeing natural or synthetic polyamide fibre materials
with mixtures of dye3
The present invention relates to a novel proces~ for the non-~kit-
tery and level dyeing of natural and synthetic polyamide fibre
material3 from an aqueou~ liquor with mixtures of l:1 metal complex
dyes which contain sulfo groups and metal-free dyes which contsin
sulfo groups, in the presence of a 60urce of fluoride ions such a3
an alkali metal or ammonium fluoride, an alkali metal or ammonium
fluorosilicate, an alkali metal or ammonium fluoroborate, an alkali
metal or ammonium fluorozirconate or an alkali metal or ammonium
fluoro6ulfonate, and optionally in the presence of an assistant, in
which process dyeing is carried out at a fibre-preserving pH value
in the range from 3 to 7 with virtually cvmplete exhaustion of the
dyebath, and the dyeing 80 obtained has good allround fastnes~
properties, in particular good fastness to wet processing and light.
The invention further relates to the material dyed by the novel
proces~ and to a composition for carrying out said proce6s.
The disadvantage of the conventional methods of dyeing natural or
synthetic polyamide fibre materials with 1:1 metal complex dyes or
mlxtures thereof with metal-free acid dyes is that these dye~ or
mixtures must be applied in the pH range from about 1.9 to 2.8 in
order to obtain level dyeings. In addition to the duration of
dyeing, the pH of the dyebath is of decislve importance for dyeing
natural and synthetic polyamide fibre materials, especially for
dyeing wool, a~ the3e fibre msterial3, again in particular wool, are
severely attacked both in the 3trongly acidic and in the strongly
alkaline pH range.
.~

~2731S4
-- 2 --
Surprisingly> there has now been found a novel process that does not
have the shortcoming referred to above and which makes it possible
to dye natural or synthetic polyamide materials, in simple manner,
in the fibre-preserving pH range from 3 to 7, preferably from 3 to 6
and, most preferably, from 3.5 to 5.
Accordingly, the present invention relates to a process for dyeing
natural or synthetic polyamide flbre material from an aqueous liquor
with mixtures of dyes, in the presence of an alkali metal salt or an
ammonium salt and optionally in the presence of an assistant, which
process comprlses dyeing said fibre material with a mixture contain-
ing at least one 1:1 metal complex dye which contains sulfo groups
and at least one metal-free dye which contains sulfo groups, in the
presence of an alkali metal or ammonium fluoride, an alkali metal or
ammonium fluorosilicate, an alkali metal or ammonium fluoroborate,
an alkali metal or ammonium fluorozirconate or an alkali metal or
ammonium fluorosulfonate, at a pH value in the range from 3 to 7.
The eligible 1:1 metal complex dye~ which contain sulfo groups are
preferably monoazo or disazo dyes which contain a chromium ion as
metal ion. It is also possible to use 1:1 metal complex azomethine
dyes which preferably contain a chromium ion.
The eligible metal-free dyes which contain sulfo groups are prefer-
ably acid to strongly acid dyes selected from the series of the
monoazo or polyazo, anthraquinone, triphenylmethane or xanthene dyes
that may contain the customary substituents of acid dyes. These
sulfo-containing metal-free dyes may be substituted by fibre-reac-
tive radicals.
Depending on the desired depth of shade, the amounts in which the
dye mixtures are added to ths dyebaths may vary within wide limits.
In general, amounts from 0.01 to 10 percent by weight, based on the
goodff to be dyed, of one or more dye mixtures are advantag~ous.

i~31~;4
-- 3 --
It has long been known to dye natural or synthetic polyamide fibre
materials wlth 1:1 metal complex dyes or mixtures thereof with
metal-free ~yes in the presence of an alkali metal sulfate or alkali
metal chloride, for example sodlum sulfate and sodium chloride, and
optionally of an assistant. Surprisingly, the use of an alkali metal
or ammonium fluoride, of an alkali metal or ammonium fluorosilicate,
of an alkali metal or ammonium fluoroborate, of an alkali metal or
ammonium fluorozirconate or of an alkali metal or ammonium fluoro-
sulfonate, optionally in the presence of an assistant, makes it
possible to dye these materials in a fibre-preserving pH range to
give level dyeings with good penetration of the dye.
In the process of this invention, it is preferred to use sodium or
potassium fluoride as alkali metal fluoride.
The alkali metal fluorosilicate or ammonium fluorosilicate employed
in the process of this invention is the alkali metal salt or
ammonium salt of hexafluorosilicic acid. It is preferred to use
NazSiF6, K2SiF6 or (NH4)2SiF6.
The alkali metal fluoroborate or ammonium fluoroborate employed in
the process of ths invention is the alkali metal salt or ammonium
salt of fluoroboric acid. It is preferred to use NaBF4, KBF4 or
NH4BF4.
The alkali metal or ammonium fluorozircon~te smployed in the process
of this invention is an alkali metal hexafluorozirconate or ~mmonium
hexafluorozirconate, preferably Rz(ZrF6).
The alkali metal or ammonium fluorosulfonate employed in the process
of this invention is an alkali metal salt or an ammonium salt of
fluorosulfonic acid, and is preferably NaFSO3, KFSO3 or NH4FSO3.

~273154
-- 4 --
Preferred embodim~nts of the process of this invention comprise:
a) dyeing in the presence of an alkali metal fluoride or ammonium
fluoride, preferably sodium or potassium fluoride or ammonium
fluoride, optionally in the presence of an assistant or of a
mixturs of sssistants,
b) dyeing in the presence of an alkali metal fluorosilicate or
ammonium fluorosilicate, preferably sodium or potassium fluoro-
silicate or ammonium fluorosilicate,
c) dyeing in the presence of an alkali metal fluoroborate or
ammonium fluoroborate,
d) dyeing in the presence of an alkali metal hexafluorozlrconate or
ammonium fluorozirconate, preferably K2(ZrF6),
e) dyeing in the presence of an alkali metal fluorosulfonate or
ammonium fluorosulfonate, preferably KFSO3.
A particularly preferred embodiment of the process of thls invention
comprises dyeing in the presence of an alkali metal fluoride or
ammonium fluoride, an alkali metal fluorosilicate or ammonium
fluorosillcate, or of an alkali metal fluoroborate or ammonium
fluoroborate.
The amount in which the alkali metal or ammonium fluoride, alkali
metal or ammonium fluorosilicate, alkali metal or ammonium fluoro-
borate, alkali metal or ammonium fluorozirconate or alkali metal or
ammonium fluorosulfonate is added to the dyebaths may vary within
wlde limits. In general, half to four times the amount by weight,
preferably one to three times the amount by weight and, most
preferably, two to three times the amount by weight, of alkali metal
or ammonium fluoride, alkali metal or ammonium fluorosilicate, of
alkali metal or ammonium fluoroborate, alkali metal or ammonium
fluorozirconate or alkali metal or ammonium fluorosulfonate, based
on the amount by weight of dye, i8 advantageous.

~2~315~
-- 5 --
The asslstants which may be used in the process of this invention
sre known per se and are prepared by known methods. Preferably, they
are levelling a~sistants or mixtures of dlfferent levelling assist-
ants. Suitable levelling assistants are anionic, cationic, nonionic
and amphoteric compounds or mixtures thereof. - -
Examples of suitable anionic compounds are: substituted naphthalene-
sulfonic acids, sulfonic acid hemiesters of ethoxylates, salts of
alkanesulfonic acids of longer chain length, salts of alkylaryl-
sulfonic aclds, in particular dodecylbenzenesulfonic acids, fatty
acid amide sulfonic acids, and sulfuric acid hemiesters of fatty
amine polyglycol ethers. Representative examples of cationic
compounds are: polyglycol ethers of fatty amines, polyglycol ethars
of fatty acid amide-amines, and quaternary ammonium compounds.
Typical examples of nonionic compounds are: polyglycol ethers of
fatty alcohols, of alkylphenols, of resinic acids, and of fatty acld
alkylolamides. Typlcal examples of amphoteric compounds are:
reaction products of ethoxylated fatty amines and hydroxyethane-
sulfonic acids, reaction products of phenol and styrene, and
polyethylene glycol di-fatty acid esters.
It is preferred to use levelling assistant compositions containing
compounds of the formula
( CH2-cH2-o~so3M
m (1)
\( CH2-CH2-O~SO3M
wherein R i8 an alkyl or alkenyl radlcal of 12 to 22 carbon atoms, M
is hydrogen, an alkali metal or ammonium cation, and m and n ara
integers, the sum of m ~ n being from 2 to 14; or compounds of the
formula

~273154
-- 6 --
~ (CHz-CH2-O-~ H
R'- ~ P (2)
~ (CHz-CH2-~ ) H
A q
wherein R' independently of R has the meaning of R, A ls an anion, Q
is an unsubstituted or substituted al~yl radical and p and q are
integers, the ~um of p + q being from 2 to 50; or compounds of the
formula
OH
H-CH2- I-(CH2-CH2- ~ H
( H2)2
H-CH2- : (3)
H ( H2)2
R"- I-(CH2-~H2-O-~yH
whereln R" independently of R has the meaning of R and x and y are
integers, the sum of x + y being from 80 to 140; or a mixture
containing compounds of the formulae (l) and (2) or a mixture
containing compounds of the formulae (1), (2) and (3).
It is particularly preferred to use a mixture of levelling a~sist-
ants comprising 5 to 70 parts by weight of a compound of for-
mula (1), 15 to 60 parts by weight of the compound of formula (2),
and 5 to 60 part~ by welght of the compound of formula (3), based on
100 parts by weight of said mixture, wherein R, R' and R" in
formulae (1), (2) and (3) are independently an alkyl or alkenyl
radical of 16 to 22 carbon atoms.
It is advantageous to use a compound of formula (2), wherein A and Q
are derived from a quaternising agent selected from the group
consisting of chloroacetamide, ethylene chlorohydrin, ethylene
bromohydrin, epichlorohydrin, epibromohydrin or, preferably,
dimethyl sulfate.

~7:~i4
-- 7 --
In the process of this invention it is preferred to use a mlxture of
levelling assistantfi which, in addition to comprising the compounds
of the formulae ~1), (2) and (3), wherein the sum of p + q in
formula (2) is preferably from 20 to 50, also contalns an adduct of
50 to 100 moles of ethylene oxide with 1 mole of a Cls-C2~alkenyl
alcohol.
It is also pre~erred to use a mix~ure of levelling assistants which
contains the compounds of the formulae (1) and (2~, wherein the sum
of p + q in formula (2) is 4 to lQ.
It is further preferrsd to use a mixture of levelling assistants
which contains compounds of formula (2), wherein the sum of p + q in
formula (2) i9 30 to 40, and R' is a C1s-Cz2alkyl radical.
The amount in which the levelling assistant or mixture of levelling
as~istants i5 added to the dyebaths can vary within wide limits; but
in general an amount of 0.3 to 3 percent by ~eight, preferably of
1 or 2 percent by welght, based on the fibre material, of the
levelling assistant or mixture thereof, i9 advantageous.
The dyebaths may contain, as further assistants, mineral acids such
as sulfuric acid, sulfamic acid or phosphoric acid, or organic
acid~, preferably lower aliphatic carboxylic acid3 such as formic
acid, acetic acid or maleic acid. These acids are employed in
particular for ad~u~ting the pH of the dyebath. It i8 preferred to
ad~ust the pH of 3 to 7 with an organic acid, preferably with acetic
acid or formic acid.
Dyeing i8 preferably carried out in the p~ range from 3 to 6,
preferably from 3.5 to 5 and, most preferably, from 4 to 5.
The dyebath may contain, as further assistants, a salt other than
an alkali metal or ammonium fluoride, alkali metal or ammonium
fluorosilicate, alkali ~etal or ammonium fluoroborate, alkall

:12'73~54
-- 8 --
metal or ammonium fluorozirconate or alkali metal or ammonium
fluoro~ulfonate, in particular an ammonium salt or alkali metal
salt, for example am~onium sulfate, ammonium acetate or, prefer-
sbly, sodium acetate or sodium sulfate. It is preferred to use 0.1
to 10 percent by weight of ammonium salt or alkali metal salt, based
on the fibre material.
The dye mixtures employed in the proces of this invention are
preferably mixture3 that contain at least one 1:1 chromium complex
azo or azomethine dye containing 1 to 3, preferably 1 or 2, sulfo
groups, and at least one metal-free dye containing 1 or 2 sulfo
groups.
The sulfo-containing metal-free dye~ employed in the process of thls
invention are preferably those having good migration properties. The
migrating power of these dyes r,hall correspond to those of the 1:1
chromium complex azo or azomethine dyes.
A range from 25 to 50 % has proved advantageous as a good migrating
power (dyeing at pH 4 to 5 and measured as difference in strength).
The migrating power is determined on wool by treating a sample which
has been dyed to 1/1 standard depth of shade, together with an
undyed sample of the same weight, in a blank bath.
The treatment conditlons for determining the migrating power match
those indicated in Example 1. Evaluation i8 made by spectrophoto-
metric determination of the amount of dye present on the originally
undyed wool in percent of ths originally dyed wool.
Examples of metal-free sulfo-containing dyes are C.I. Acid Blue 1,
7, 13, 23, 40, 40:1, 43, 45, 47, 72, 147, 258 and 277; C.I. Acid
~ed 1, 5, 37, 42, 52, 57 and 361; C.I. Acid Yellow 10, 17, 25, 27,
99 and 219; C.I. Acid Orange 1, 3 and 156; C.I. Acld Green 3, 9 and
16; C.I. Acid Violet 9 and 36, C.I. Acid Brown 10, 11 and 248.

~2731~;4
In the process of this invention it i~ also posible to U58 mixtures
of several dye mixtures as defined herein.
A preferred mlxture of dye mixtures as de~Eined herein is:
a) at least two 1:1 chromium complex azo o~ azomethine dyes and at
least one sulfo-contalning metal-free dye; and
b) at least three 1:1 chromium complex azo or azomethine dyes and at
least one sulfo-containing metal-free dye; or
c) for trichromatic dyeing, at least three 1:1 chromium complex azo
or azomethine dyes selected from dyes that give yellow or orange,
red and blue dyeings, and at least one metal-free dye selected
fromm dyes that give yellow or orange and/or red and/or blue
dyeings.
By trichromatic dyeing i8 meant the additive blending of suitably
chosen dyes that give yellow or orange, red and blue dyeings with
which any desired shade of the visible colour spectrum can be
matched by suitable choice of the quantity ratios of the dyes.
1:1 Chromium complex azo or azomethine dyes employed in the process
of this invention are, in particular, those of the formula
r - ( or NRl) ~An
(4)
b ~--y~ _( S03Ml 1 -2
wherein -(CO) ~ and -(O- or -NRl) are linked to D and K ad~acent
to the azo brldge, D i8 the radical of a diazo component of the
benzene or naphthalene serie~, K i8 the radical of a coupling
component of the benzene, naphthalene or heterocyclic series or of
the acetoacet~rylide series, R1 is hydrogen or an unsubstituted or
substituted alkyl or phenyl radical, M is a cation and An is an
anion, and Y is a nitrogen atom or the -CH- group.

~273~54
-- 10 --
In the process of this invention it is preferred to use sulfo-con-
taining 1:1 chromium complex azo or azomethine dye~ of the for-
mula (4), wherein D i9 a radical of the benzene or naphthalsne
series which is unsub6tituted or substituted by halogen, C~-C4alkyl,
C1-C4alkoxy, nitro or sulfamoyl, K is a phenyl, naphthyl, l-phenyl-
3-methylpyrazol-5-one, acetoacetamide, preferably acetoacetanilide,
or a quinoline radical, each unsubstituted or ~ubstituted by
halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfamoyl or
hydroxy, R1 i9 hydrogen and M iB an alkali metal cation.
Y in formula (4) is preferably a nitrogen atom.
The sulfo-containing metal-free dyes employed in the process of this
invention are preferably those of the dyestuff aeries referred to
above, which dyes may be substituted by e.g. C1-C4alkyl groups such
as methyl, ethyl, propyl, isopropyl and butyl, or by C1-C4alkoxy
groups such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, or
C1-C6acylamino groups such as acetylamino and propionylamino,
benzoylamino, amino, C1-C4alkylamino, phenylamino, C1-C4alkoxy-
carbonyl, nitro, scetyl, cyano, trifluoromethyl, halogen such as
fluorine, chlorine and bromine, sulfamoyl, carbsmoyl, ureido,
hydroxy, carboxy and sulfomethyl.
The sulfo containing metal-free dyes may also be substituted by one
or more fibre-reactive radicals. Examples of suitable fibre-reactive
radicals are those listed in German Offenlegungsschrift 29 13 102.
In the proces~ of this invention it is preferred to use mixtures of
sulfo-containing 1:1 metal complex dyes and sulfo-containing
metal-free dyes ln the weight ratio of 40:60 to 95:5.
The sulfo-containing dyes employad in the proces~ of this invention
are either in the form of the free sulfonic acid or, preferably, of
the salts thereof.

~2731~i4
Examples of suitable salts are alkali metal, alkaline earth metal or
ammonium salts, or the salts of an organic amine. Representative
examples are the sodium, lithium, potassium or ammonium salts or the
salt of triethanolamine.
The sulfo-containing 1:1 metal complex dyes and the sulfo-containing
metal-free dye~ employed in the proce~s of this invention are known
per se and can be obtained by known methods.
The mixtures uf dyes used in the process of the invention may be
prepared by mixing the individual dyes. Mixing is carried out in
suitable mills, e.g. ball or pin mills, as well as in kneaders or
mixers.
Further, the mixtures can also be prepared by spray drying aqueous
dye mixtures.
In addition to containing the dye and the aforementioned assistants,
the dyebaths may contain further conventional auxiliaries, for
example wool protecting agents, wetting agents and antifoams.
The liquor to goods ratio may be chosen within a wide range from 1:6
to 1:80, preferably from 1:10 to 1:30.
Dyeing i-~ carried out from an aqueous bath by the exhaust process,
for example in the temperat~re range from 80 to 105C or 110C when
using a wool protecting agent that splits off formaldehyde, prefer-
ably in the range from 98 to 103C. The dyeing time is normally
from 30 to 120 minutes.
Special apparatus is not required for carrying out the process of
the invention. The conventional dyeing machines, e.g. for flocks,
tops, hank yarn, packages, piece goods and carpets, may be used.

~27:3154
- 12 -
The levelllng assistant and the alkali metal or ammonium fluoride,
alkali metal or ammonium fluorosilicatP, alkali metal or ammonium
fluoroborate, alkali metal or ammonium fluorozirconate or alkali
metal or ammonium fluorosulfonate ls conveniently added to the
aqueous dyebath and applied simultaneously with the dye. An alter-
native procedure is to treat the goods to be dyed first wlth the
levelling assistant and then to dye the good~, in the same bath,
after addition of the dye and of the alkali metal or ammonium
fluoride, alkali metal or ammonium fluorosilicate, alkali metal or
ammonium fluoroborate, alkali metal or ammonium fluorozirconate or
alkali metal or ammonium fluorosulfonate. It is preferred to put the
fibre material into a bath which contains acid and the asslstAnt and
has a temperature of 30 to 70C. Then the dye mi~ture and the
alkali metal or ammoni~m fluoride, alkali metal or ammonium fluoro-
silicate, alkali metal or ammonium fluoroborate, alkali metal or
ammonium fluorozirconate or alkali metsl or ammonium fluorosul-
fonate is added and the temperature of th0 dyebath i8 raised at a
rate of 0.75 to 3C per minute, optionally with a temperature stop
during the heating up phase, in order to dye in the indicated
temperature range from 80 to 105C, preferably for 30 to 120 min-
utes. Finally, the bath is cooled and the dyed material i8 rinsed
and dried in conventional manner.
Natural polyamide fibre material that may be dyed by the process of
this invention is, in particular, wool and also woolfpolyamide,
wool/polyester, wool/cellulose or woollpolyacrylonitrile blends a~
well as silk. The fibre material may be in a very wide range of
presenta~ion, for example as loose material, tops, yarn and piece
goods or carpets.
Synthetic polyamide material that may be dyed by the process of this
invention comprises all known synthetic polyamides. The fibre
material may be in a very wide range of presentation, for example as
loose material, tops, yarn and piece goods or carpets.

~2731S4
- 13 -
A particularly preferred embodiment of the process of this lnvention
comprises dyeing natural or synthetic polyamide fibre material,
preferably wool, with at least one dye mixture as defined above, in
the presence of sodlum fluoride, ammonium fluorosilicate or sodium
fluorosilicate, preferably in two to three times the amount by
weight, based on the amount by weight of 1:1 chromium complex dye,
and optionally in the presence of a levelling assistant comprising
compounds of the formula (2) or a mixture of compounds of the
formulae (1) and (2) or (1), (2) and (3), and in the presence of
sodium acetate, ammonium acetate or sodium s~lfate, in the p~ range
from 4 to 5.
The sulfo-containing metal-free dye~ used in the process of the
present invention may contain one or more fibre-reactive groups. In
the process of the invention it i5 preferred to use those mixtures
of 1:1 metal complex dyes as defined herein, wherein the metal-free
dyes are either all reactive dyes or are all devoid of fibre-react-
ive groups. It is most preferred to use sulfo-containing metal-free
dyes that do not contain fibre-reactive groups.
A very particularly preferred embodiment of the invention comprlses
the use of dye mixtures consisting of those metal-containing and
metal-free dyes which give dyeings of the same shade, i.e. for
example the use of a mixture of at least one sulfo-containing 1:1
metal complex dye and at least one sulfo-containing metal-free dye,
each of which dyes in a blue shade.
Compared with the known processes for dyeing natural or synthetic
polyamide fibre material, the proceas of this invention has the
following advantages in addition to those already mentioned above.
The material dyed under the dyeing conditions has better allround
fastness properties, in particular better wetfastness properties. A
further essential advantage is that the dyes are taken up almost
completely onto the fibre. When dyeing is complete, the dyebaths are
almost completely exhausted.

~27~1S~
- 14 -
The invention further relates to a composition for carrying out the
process of the invention. The compositioD is a solid mixture
containing at least one sulfo-containing 1:1 metal complex dye~
in particular a 1:1 chromium complex dye, and at least one sulfo-
containing metal-free dye, and an alkali metal or ammonium fluoride,
alkali metal or ammonium fluorosilicate, alkali metal or ammonium
fluoroborate, alkali metal or ammonium fluorozirconate or alkali
metal or ammonium fluorosulfonate.
The composition of this invention i9 prepared by mixing a sulfo-
containing 1:1 chromium complex dye and at least one sulfo-con-
taining metal-free dye with an alkali metal or ammonium fluoride,
alkali metal or ammonium fluorosilicate, alkali metal or ammonium
fluoroborate, alkali metal or ammonium fluorozirconate or alkali
metal or ammonium fluorosulfonate. Mixing is carried out, for
example, in suitable mills, e.g. ball or pin mills, as well as in
kneaders or mixers.
Preferred compositions contain sodium or ammonium fluoride or sodium
or ammonium fluorosilicate, in addition to the dye mixture.
The solid mixtures can be used for dyeing natural or synthetic
polyamide fibre materials. The same preferences apply to the solid
mixtures as to the process.
The invention is illustrated by the following Examples, in which
parts and percentages are by weight. The relationship of parts by
weight to parts by volume is the same as that of the gram to the
cubic centimetre. The indicated amounts of dye refer to commercially
available dye.

~2~3~
- 15 -
Example 1: 800 parts of worsted spun yarn are pretreated for
15 mlnutes at 50C in a dyebath containing, in 20,000 part3 of water
of 50C, 64 parts of godium sulfate, 24 parts of (NH4)zSiF6 and
12 parts of a levelling assistant consisting of:
24 parts of the anionic compound of formula
(CH2-CH2-0-~--S03NH4
R2_ ~ m
~CH2-CH2-0 ~ S03NH4
R2 - C16-C1ghydrocarbon radical; m + n ~ 7;
24 parts of the quaternary compound of formula
~ (CHz-CH2-0-t--H
R3- ~ P p ~ q = 34,
1 (CHz-CH2- ~ H
CH30-SOz-0
R3 - Czo-Cz2hydrocarbon radical;
5 parts of ammonium chloride
3 parts of oxalic acid and
44 parts of water, based on 100 parts of levelling assistant.
After addition of a solution of
2.2 parts of the 1:1 chromium complex of the dye of formula
c~3
S~3H ~ H0
~ N=N-C-C0-NH~
N~z

1~'731~;4
- 16 -
2.4 part~ of the 1:1 chromium complex of the dye of formula
N ~ CH3
OH HO/
il i
11
SO3H \,~
0.6 part of the 1:1 chromium complex of the dye of formula
H3~ 1~ HO
N----N~
03H
0.65 part of the 1:1 chromlum complex of the dye of formula
/ OH IOH ~03H
HO3s-~ /.-N-N t ~~ .
2.2 parts of the dye of formula
OCH3
~ N=~ --N=N--~ ~--OCN3
S~3H

12~31~i~
- 17 -
2.4 parts of the dye of formula
CH3~ H /-
~ 2 N~2
t~ N=N-~
.=.
S03H
and 1.2 parts of the dye of formula
~ ~2
i~ il il ~i-so3H
1~1 bH---~ NH--CO--CH2CH3
the dyebath is kept for 10 minutes at 50C and then heated to 98C
at a rate of 0.8C/mlnute. The pH is 4.6 at the commencement of
dyeing. After a dyeing time of 90 minutes at 98C, the dyebath is
cooled to 50C and drained off. The brown wool yarn i8 rinsed first
for 10 minutes at 505 and thsn for 10 minutes at room temperature
and dried in conv2ntional manner. The medium brown dyeing 80
obtained has excellent levelness and good fastness properties.
Exam~le 2: 100 parts of wool fabric are pretreated for 15 minutes at
40C in a dyebath containing, in 2000 parts of water of 40C,
8 parts of sodium sulfate, 1.2 parts of the levelling assistant
employed in Example 1 and 1.5 parts of 85 % formic acid. The pH of
the bath i8 4.3.
After addition of a solution of 1.9 parts of sodium fluoride and
0.695 part of the dye of formula

~2731S4
- 18 -
102
0.59 part of the dye of form~la
~ ~:=X \SO3Na
i1 c~3
0.26 part of the dye of formula
C~ D~ ~SO3Na
1CH 3
0.31 part of the dye of formula
~ r ~ Sl03Na
NaO3S- f ~ N-i~

~273i5~
-- 19 --
0.28 part of the dye of formula
C~;
~
NaO3S~ -N=N--~ ~ \Cl
C`H3
0.28 part of the dye of formula
H3C\ c(C6Hll)
~2 N~2
t~ N=N-.
~ / H0
SO3Na
and 0.27 part of the dye of formula
R ~H2
/SO 3 Na
i1 i1
CH3
iH~ CH3
~SO2NHCH2CH20H
the dyebath i8 kept for a further lQ minutes at 40C and then heated
to 70C at a rate of 1Clmin. After a dyeing time of 20 minutes at
70C, the dyebath i5 heated to 100C and dyeing is carried out for
90 minutes at thls temperature. The dyebath i8 then cooled to 60C
and drained off. The brown wool fabric is rinsed first for 5 minutes
at 50C and then for 5 minute~ at room temperature and drled in
conventional manner. The dyeing has excellent levelness and good
fastness propertie~.

73154
- 20 -
Example 3: 100 par~s of wool fabric are pretreated for 10 minutes at
40C in a dyebath containing, in 1000 parts of water of 40C,
8 part~ of sodium sulfate, 1.5 parts of the levelling assistant
employed in Example l and 2 parts of 85 % formic acid. The pH of the
bath i3 3.8. After addition of a solution containing
1.2 parts of the dye of formula
~. O
C~ ~ / NaO3S/ ~ \SO3Na
1CH 3
0.28 part of the dye of formula
R ~H2
/SO 3 Na
!~ ,i!, ,'!, ~! ~CH3
d ~H--~ ~-CH3
\SO2NHCH2CH20H
and 1.6 parts of K2(ZrF6),
the tyebath is kept for a further 10 minutes at 40C and then heated
to 100C at a rate of 0.8C/min. After a dyeing time of 90 minutes
at 100C, the dyebath i9 cooled to 60C and drained off. The blue
wool fabric is rinsed and dried in conventional manner. The medium
blue dyeing has excellent levelness and good fastness properties.
A comparably good result is obtained by using 1.8 parts of NazSiF6
instead of 1.6 parts of K2(~rF6).

~Z~31~;~
- 21 -
Example 4: lO0 parts of wool fabric are pretreated for lS minutes at
40C in a dyebath containing, in 1500 parts of water of 40C,
8 parts of sodium sulfate, 1.5 parts of the levelling assistant of
the following compo~itio~:
14.6 parts of the anionic compound of formula
( CH2-cH2-o~so3NHl~
R2-N/ m
~(CH2-CH2-O ~ SO3NH4
Rz ~ hydrocarbon radical of tallow amine, m + n = 8;
21 parts of the quaternary compound of formula
~ (CHz-CH2-O-~--N
R3-l ~ P p + q = 34,
/ (CHz~CH2~0-~-q-H
CH30-SOz-O
R3 ~ C20-C22hydrocarbon radical;
7 parts of the adduct of oleyl alcohol with 80 moles of sthylene
oxide; and
7 part~ of the compound of formula
ClaH3 7 - ~ - CH2-CH2-~-CHz -CH2-~(CH2CH20)yH
( H2CH20x H ~Hz CH2-CIH-OH
~H-OH ~-\
i~ \. 1~ ~i1
~-~ x + y ~ c. 100,
and 49.7 parts of water, based on 100 parts of levelling assistant
~ixture;
and 1.5 parts of 85 % formic acid. The pH of the bath is 4.5. After
additlon of a ~olution containing 1.94 parts of NaF, 1.66 parts of
the dye of formula

~Z~315~
- 22 -
NaO3S /~r~\
\.=./ \.= \SO3Na
C~ C~3
and 1.5 parts of the dye of formula
H~ ~NCOCH3
NaO3S ~ SO3Na
the dyebath is kept for a further 10 minutes at 40C and then heated
to 100C at a rate of 0.8C/min. After a dyeing time of 90 minutes
at 100C, the dyebath i8 cooled to 50C and drained off. The red
wool fabric is rinsed and dried in conventional manner. The deep red
dyeing 80 obtained has excellent levelness and good fastness
properties .
Example 5: 100 parts of wool fabric are pretreated for 15 mlnutes at
40C in a dyebath containing, in 2000 parts of water of 40C,
8 part3 of sodium sulfate, 1.2 parts of the levelling assistant
mixture employed in Example 1 and 1.5 parts of 85 % formic acid. The
pH of the bath i~ 4.3. To this dyebath are then added 1.4 parts of a
solid mixture consisting of:
0.425 part of NaF,
0.28 part of the dye of formula
C~,
~0
NaO3S~ -N=N-~
c~3

~3i5~
- 23 -
and 0.695 part of the dye of formula
~ 50
102
1.56 parts of a solid mixture Consisting of:
0.69 part of Na~,
0.59 part of the dye of formula
~r--I
and 0.28 part of the dye of formula
H3C c(C6Hl1)
~; 2 N~2
T ,, N ~,_,/
SO3Na
and 1.63 parts of a solid mixture consisting of
0.79 part of NaF,
0.26 part of the dye of formula

~'73~54
- 24 -
l - Clr - f
C~ ~- NaO3S ~ SO3Na
1CH 3
0.31 part of the dye of formula
~--IcL---1 j;O3Na
NaO 3 S~ N t il
._.~
and 0.27 part of the dye of formula
R ~H2
/SO3Na
il i
CH3
1~ ~H--.~ ~.--CH3
\SO2NHCH2CHzOH
The dyebath is kept for a further 10 minutes at 40C and then heated
to 70C at a rate of 1C/min. After a dyeing tim2 of 20 mlnutes at
70C, the dyebath iS heated to lOO~C and tyeing is carried out for
90 mlnutes at this temperature. The dyebath i8 then cooled to 60C
and drained off. The brown wool fabric ~s rinsed first for 5 minutes
at 50C and then for 5 minutes at room temperature and dried in
conventlonal manner. The dyeing has excellent levelness and good
fastne~3s properties.