Note: Descriptions are shown in the official language in which they were submitted.
2S~L
- 1 -
1-15146/=/CG~ 1106
Process for dye;ng synthetic polyamide materials w;th f;bre-
reactive anthraquinone dyes
The present invention relates to a process for dyeing
synthetic polyamide materials in ozone-fast shades with
fibre-reactive sulfo-containing anthraquinone dyes.
It is repeatedly found that synthetic polyamide mate-
rials dyed with anthraquinone dyes do not meet present-day
demands on the ozone fastness of dyeings.
It is the object of the present ;nvent;on to prov;de
a process for dyeing synthetic polyam;de materiaLs with
anthraquinone dyes which produces dyeings of very good ozone
fastness.
This object is achieved according to the invention
w;th the process descr;bed here;nafter. The dye;ngs produced
thereby meet the stated demands on ozone fastness.
The present invention accordingly provides a process
for preparing ozone-fast dyeings on synthetic polyamide fibre
materials from aqueous liquor with selected anthraquinone
dyes which comprises using at least one anthraquinone dye
which contains one or two fibre-reactive groups and one or
two sulfo groups.
The process according to the invention produces dye-
ings on synthetic polyamide fibre materials of very good
ozone fastness.
Suitable anthraquinone dyes are ~elected anthraqu;n-
one dyes hav;ng one or two fibre-reactive groups and one or
two sulfo groups, for example the anthraqu;none dyes g;ven
in the ~olour Index as react;ve blues.
~'~
:,,
.,'',
.,
~ r-
~L~7~
-- 2
In a preferred embodiment of the process according
to the invention, a dye of the formula
O NHAl --(S03H) 1-2
.~ \.. / \./ ~--A2 (1),
~ \t~! ---tX)1-2
_ 3
`
in which the ring L can be substituted by hydroxyl, halogen
or sulfo, A1 is hydrogen, C1_g-alkyl~ C5_7-cYcloalkyl,
phenyl or phenyl-C1_8-alkyl, A2 is hydrogen or halogen,
such as chlorine or bromine, or is preferably a sulfo group,
A3 is unsubstituted or C1_~-alkyl-, C1_4-alkoxy-, phenoxy-,
c1_4-alkYlphenoxy~ or naphthoxy-substituted phenyl or
; phenyl-c1-g-alkyl~ and X is a fibre-reactive radical which
is bonded either directly or via a bridge member, is used~
An alkyl radical A1 in the formula ~1) can be
a straight-chain or branched alkyl radical, for example
methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, iso-
buty~, tert.-b~ty~, penty~, hexy~, hepty~ or octy~ D
A Cs_7-cycloalkyL radical Al can ~e for examp~e
a~ u~s~stitute~ cyc~o~e~y~ ra~ica~ or a cyc~o~eY~y~
radical whlch is substituted by alkyl, such as methyl.
A pheny~ radical A1 in the formuia (1) can be a
phenyl radical which can be substituted by C1_4-alkyl,
c1_4-aLkoxy or haLogen and can be further substituted by a
su~fo group and a fibre-reactive radical; the phenyl radi-
cal is preferably substituted by a sulfo group and a fibre-
reactive radica~.
,~ .
:`:
Phenyl-c1-8-alkyl radicals A1 and A3 ;n the
formula (1), independently of each other, can each be for
example a benzyl, phenethyl, phenylbutyl or phenyl-sec.-butyl
radical which ;s preferably substituted by a sulfo group
and at least one fibre-reactive radical.
A phenyl radical A3 in the formula (1) can be a
phenyl radical which is substituted by C1_4-alkyl, in parti-
cular methyl, C1_4-alkoxy, in particular methoxy, phenoxy,
C1-c4-alkylphenoxy~ such as methylphenoxy or naphthoxy
and which can be further substituted by a sulfo group and
preferably one or two fibre-reactive radicals.
F;bre-reactive radicals X are to be understood as
meaning radiGals which are capable of reacting ~ith the
hydroxyl groups of cellulose, with the amino, carboxyl,
hydroxyl and ~hioL groups of ~ool and silk, or with the
amino and, where relevant, carboxyl groups of synthetic
polyamides to form covalent chemical bonds.
X is preferably a fibre-reactive radical of the
aliphatic, aromatic or heterocyclic series which is bonded
to the radical A1 and/or A3 either directly or via a
bridge member.
X is preferably bonded to the radical A1 and/or A3
either directly or v;a an amino group which can be monoalky-
lated, for example via -NH-, -N(CH3)-, -N(C2Hs)- or
-N~C3H7)-, or via a br;d9e member conta;ning an amino
group.
A fibre-react;ve radical X in the formula (1) can be
for example one of the following aliphatic or aromatic radi-
cals:
vinylsulfonyl~ ~-chloroethylsulfonyl, ~-sulfatoethyl-
sulfonyl, ~-acetoxy-ethylsulfonyl, phosphonooxyethylsulfonyl,
~thiosulfatoethylsulfonyl, N-methyl-N-~-sulfatoethyl-
sulfonyl)-amino, acryloyl, monochloroacryloyl~ dichloro-
acryloyl or trichloroacryloyl such as -CO-CCl=CH2,
-CO-CH=CH-Cl, -CO-CCl=CH-CH3; monobromo3cryloyl~ dibromo-
acryloyl or tribromoacryloyl such as -CO-CBr=CH2, -CO-CH=CH-Br,
-CO~CBr-CH-CH3i and also -CO-CCl=CH-COOH, -CO-CH=CCl-COOH,
~7~ria~
-- 4 ~
-CO-CBr=CH-COOH, -CO-C~=CBr-COOH; -CO-CCl=CCl-COOH, -CO-CBr=
CBr-COOH; precursors of the acryloyl radical and of the
derivatives of the acryloyl radical, such as ~-chloropropionyl,
~-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonyl-
propionyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloro-
prop;onyl, 2,~-d;bromoprop;onyl; and also 2-fluoro-2-chloro-
3,3-d;fluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclo-
butane-1-carbonyl or -1-sulfonyl, ~-(2,2,3,3-tetrafluorocyclo-
but-1-yl)-acryloyl,~- or ~-alkylsulfonylacryloyl orarylsulfonyl-
acryloyl groups such as ~- or ~-methylsulfonylacryloyl,
propiolyl~ chloroacetyl, bromoacetyl, 4-(~-chloroethyl-
sulfonyl)-butyryl, 4-vinylsulfonyl-butyryl, 5-(~-chlorethyl-
sulfonyl)-valeryl, 5-vinylsulfonyl-valeryl, 6~ chloroethyl-
sulfonyl)-caproyl, 6-vinylsulfonyl-caproyl; and also
4-fluoro-3-nitrobenzoyl, 4-fluoro-3-n;trophenylsulfonyl,
4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl,
2-fluoro-5-methylsulfonylbenzoyl~
The fibre-reactive radical X can also be a member of
the heterocyclic series, for example a 2,4-dichlorotriazin-
6-yl or monohalogenopyrimidinyl, dihalogenopyrimidinyl or
trihalogenopyrimidinyl radical, such as 2,4-dichloro-
pyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2,4-
dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or
-5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-
monochloromethyl- or -5-dichloromethyl- or -5-trichloro-
methyl or -5-methylsulfonyl-pyrimidin-6-yl, 2,5-dichloro-4-
methylsulfonylpyrimidin-6-yl, 2-fluoro-4-pyrimidinyl,
2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-
pyrimidinyl, 2-fluoro-5,6-dichloro-4-pyrimidinyl, 2,6-di-
fluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyr-
imidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro-
5-nitro-6-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-
4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-
cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-
trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-
pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-
bromo-6-chloromethyl-4-pyrimidinyl, 2,6-di~luoro-5-chloro-
~'~ 7~
methyl-4-pyrimidinyl, 2,6-difluoro-5-nitro-4-pYrimidinYl, 2-
fluoro-6-methyl-4-pyr;m;dinyl, 2-fluoro-5-chloro-6-methyl-
4-pyrimidinyl, 2-fluoro-5 chloro-4-pyr;midinYl, 2-fluoro-6-
chloro-4-pyr;mid;nyl, 6-trifluorome~hyl-5-chloro-2-fluoro-4-
pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrim;d;nYl,
2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethYl-
4-pyr;midinyl, 2-fluoro-5-phenyl- or -5-methylsulfonYl-4-
pyrimidinyl, 2-fluoro-5-carboxamido-4-pyrim;d;nyl, 2-
fluoro-5-carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-
trifluoromethyl-4-pyr;m;dinyl, 2-fluoro-6-carboxam;do-4-
pyrimidinyl, 2-fluoro-6-carbo-methoxy-4-pyr;m;dinyl, 2-
fluoro-6-phenyl-4-pyrimid;nyl, 2-fluoro-6-cyano-4-pyr;m;d;nyl,
2,6-difluoro-5-methylsulfonyl-4-pyrimid;nyl, 2-fluoro-5-
sulfonamido-4-pyr;m;dinyl, 2-fluoro-5-chloro-6-carbomethoxy-
4-pyrimidinyl, 2,6-difluoro-5-tri-fluoromethyl-4-
pyrimid;nyl; 2,4-bis-methylsulfonyl pyrimidin-4-yl, 2,5-
bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methyl-
sulfonyl-pyrim;din-4-yl, 2-phenylsulfonyl-pyr;m;d;n-
4-yl, 2-methylsulfonyl-5-chloro-6-methylpyr;midin-4-yl, 2-
methylsulfonyl-5-bromo-6-methyl-pyrimidin-4-yl, 2-
methylsulfonyl-5-chloro-6-ethyl-pyrimidin-4-yl, 2-
methylsulfonyl-5-chloro-methylpyrimidin-4-yl, 2-
methylsulfonyl-5-n;tro-6-methylpyrimidin-4-yl, 2,5,6-tris-
methylsulfonyl-pyr;midin-4-yl, 2-methylsulfonyl-5,6-
d;methylpyrimidin-4-yl, 2-ethylsulfonyl-5-chloro-6-
methyl-pyrimidin-4-yl, 2-methylsulfonyl-6-chloro-pyrimidin-
4-yl, 2,6-bis-methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-
methylsulfonyl-6-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-5-
sulfo-pyrimidin-4-yl, 2-methylsulfonyl-6-carbomethoxy-
pyrim;din-4-yl, 2-methylsulfonyl-5-carboxy-pyrimidin-4-yl,
2-methylsulfonyl-5-cyano-6-methoxy-pyrim;d;n-4-yl, 2-methyl-
sulfonyl-5-chloro-pyrimidin-4-yl, 2-sulfoethylsulfonyl-6-
methyl-pyrimidin-4-yl~ 2-methylsulfonyl-5-bromo-pyrimidin-
4-yl, 2-phenylsulfonyl-5-chloro-pyrimidin-4-yl, 2-carboxy-
methylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2,4-dichloro-
pyrimidine-6-carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-
5-carbonyl or -5-sulfonyl~ 2-chloro-4-methylpyrimidine-5-carbonyl,
5~L
2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio
4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloro-
pyr;mid;ne 5-carbonyl, 2,4,6-trichloropyrimidine-5-
carbonyl, 2,4-d;chloropyrimidine-5-sulfonyl, 2,4-dichloro-6-
methylpyrim;d;ne-5-carbonyl or-5-sulfonyl~ 2-methyl-
sulfonyl-6-chloropyr;midine-4- and -5-carbonyl, 2,6-bis-
(methylsulfonyl)-pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-
6-chloropyrim;d;ne-5-carbonyl, 2,4-bis-(methylsulfonYl)-
pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methyl-
pyrimidine-5-sulfonyl or -5-carbonyl~ 2-chloroquinoxaline-3-
carbonyl, 2- or 3-monochloroquinoxaline-6-carbonyl, 2- or 3-
monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5
or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl,
1~4-dichlorophthalazine-6-sulfonyl or -6-carbonyl, 2,4-
dichloroquinazoline~7- or -6-sulfonyl or -carbonyl, 2,4,6-
trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4-(4',5'-
dichloropyridaz-6'-on-1'-yl)-phenylsulfonyl or -carbonyl,
~-~4',5'-dichloropyridazin-6'-on-1'-yl)-propionyl, 3,6-dichloro-
pyridazine-4-carbonyl or -4-sulfonyl, 2-chlorobenzothiazole-5-
or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl-benzo-
thiazole- or 2-alkylsulfonylbenzothiazole-5- or -6-carbonyl
or -5- or -6-sulfonyl, such as 2-methylsulfonylbenzothiazole-
or 2 ethylsulfonylbenzothiazole-5- or -6-sulfonyl or -car-
bonyl, 2-phenylsulfonylbenzothiazole-S- or -6-sulfonyl or
-carbonyl and the corresponding 2-sulfonylbenzothiazole-5- or
-6-carbonyl or -sulfonyl derivatives which contain sulfo
groups in the fused-on benzene ring, 2-chlorobenzoxazole-5- or
-6-carbonyl or -sulfonyl, 2-chlorobenzimidazole-5- or -6-
carbonyL or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or
-6-carbonyl or -sulfonyl, 2-chloro-4-methyl 1,3-thiazole-5-
`carbonyl or -4- or -5-sulfonyl; ammonium-containing tri-
azine rings, such as 2-trimethylammonium-4-phenylamino- or -4-
(o-, m- or p-sulfophenyl)-amino-triazin-6-yl, 2-(1,1-dimethyl-
hydrazinium)-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-
aminotriazin-6-yl, 2-(2-isopropylidene-1,1-dimethyl)-hyd-
razinium-4-phenylamino- or -4-(o-, m- or p-sulfophenyl)-amino-
triazin-6-yl, 2-N-aminopyrrolidinium- or 2-N-aminopiperid-
~ ~.
~7~S~
-- 7inium~4-phenylamino- or -4-to-, m- or p-sulfophenyl)-amino-
triazin-6-yl, and also 4-phenylamino- or 4-(sulfophenylamino)-
triazin-6-yl radicals which, in the 2-pos;tion, contain 1,~-
bis-azabicycloC2.2.2~octane or 1,2-bis-azabicycloCO.3.3]-
octane via a quaternary nitrogen bond, 2-pyridinium-ll-phenyl-
amino- or -4-(o-, m- or p-sulfophenyl)-amino-triazin-6-yl and
corresponding 2-oniumtriazin-6-yl radicals which are sub-
stituted in the 4-position by alkylamino, such as methylamino,
ethylamino or ~ -hydroxyethylamino, or alkoxy, such as
methoxy or ethoxy, or aryloxy, such as phenoxy, or sulfo-
phenoxy groupsn
An interesting fibre-reactive radical can also be
a chloro- or fluoro-1,3,5-triazine radical of the formula
F, C1
V
where the substituent V on the triazine ring can be in par-
ticular:
halogen, for example chlorine or fluorine, C1_8-
alkoxy, for example methoxy, cyclohexyloxy, phenoxy, C1_6~
alkylmercapto, such as methylmercapto, phenylmercapto, -NH2,
alkylamino, N,N-dialkylamino, cycloalkylamino, N,N-dicyclo-
alkylamino, aralkylamino and arylamino groups, mixed-substituted
amino groups, such as N-alkyl-N-cyclohexylamino and N-alkyl-N-
arylamino groups, and also amino groups which contain
heterocyclic radicals which can have further fused-on carbo-
cyclic rings, and amino groups in which the amino nitrogen
atom is a member of an N-heterocyclic ring which can contain
further hetero atoms, as well as hydrazino and semicarbazido.
The abovementioned alkyl radicals can be straight-chain or
branched and of low molecular weight or higher molecular
weight and are preferably alkyl radicals having 1 to 6 carbon
atoms; cycloalkyl, aralkyl and aryl radicals can be in par-
ticular cyclohexyl, benzyl, phenethyl, phenyl and naphthyl
radicals; heterocyclic radicals can be in particular furan,
thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzi-
midazole, benzothiazole and benzoxazole radicals; and aminogroups in which the amino nitrogen atom is a member of an
N-heterocyclic ring are preferably radicals of six-membered
N-heterocyclic compounds Hhich can contain nitrogen, oxygen
or sulfur as further hetero atoms. The abovementioned alkyl,
cycloalkyl, aralkyl and aryl radicalsr the heterocyclic
radicals and the N-heterocyclic rings can be further substi-
tuted, for example by: halogen, such as fluorine, chlorine
or bromine, nitro, cyano, trifluoromethyl, sulfamoyl,
carbamoyl, C1_4-alkyl, c1_4-alkoxY, acylamino groups,
such as acetylamino or benzoylamino, ureido, hydroxyl,
carboxyl, sulfomethyl or sulfo~ Examples of such amino
groups are: -NH2, methylamino, ethylamino, propylamino,
;sopropylam;no, butylamino, hexylamino, ~-methoxyethylamino,
~-methoxypropylamino, ~-ethoxyethylamino, N,N-dimethylamino,
N,N-diethylamino, ~-chloroethylamino, ~-cyanoethylamino,
~-cyanopropylamino, ~-carboxyethylamino, sulfomethylamino,
~-sulfoethylamino, ~-hydroxyethylamino, N,N-d;-~-hydroxy-
ethylamino, ~-hydroxypropylamino, benzylamino, phenethyl-
amino, cyclohexylamino, phenylamino, tolu;dino, xylidino,
chloranilino, anisidino, phenetidino, N-methyl-N-phenylam;no,
N-ethyl-N-phenylamino, N-~-hydroxyethyl-N-phenylamino, 2-,
3- or 4-sulfoanilino, 2,5-disulfoanilino, 4-sulfomethyl-
anilino, N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino,
2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino,
4-sulfonaphth-1-ylamino, 3,6-disulfonaphth-1-ylamino, 3,6,8-
trisulfonaphth-1-ylamino, 4,6,8-trisulfonaphth-1-ylamino,
1-sulfonaphth-2-ylamino, 1,5-disulfonaphth-2-ylamino,
6-sulfonaphth-2-ylamino, morpholino~ piperidino, piperazino,
hydrazino and semicarbazido.
In particularly preferred embodiments of the process
according to the invention9
~ ~ 7
_ 9 _
a) a dye of the formula
0 NH
::~ ll 1 2
\ /~
. i il il i_S03H (2)
0 NH~ 3 0-1
(X) 1-2
.
.~
in which X is as defined under the formula (1~ and the
phenyl ring L1 can be monosubstituted, disubstituted,
tr;substituted or tetrasubstituted by C1_4-alkyl, C1_4-
alkoxy or phenoxy, is used;
b) a dye of the formula
_
0 NH-A . _-- (S03H) 1-2
; :I~ ,¢ ,il~ ~i (3),
\ 2 / ( ) 1-2
_
which A4 is a C1_6-alkyl or Cs_7-cycloalkyl radical,
X is as defined under the formula t1) and the phenyl ring L2
can be monosubstituted, disubstituted or trisubstituted by
C1_~-alkyl, C1_4-alkoxy, phenoxy or c1_4-alkYlphenoxy,
is used;
'~
.,
~ ~ 7
- 10 -
c) a dye of the formula
0 NH-A --(S03H) 1-2
:~
~ ! il i! i --(x) 1-2
/ \ / \.~ ._.
~ ~H-(Cl 8-A1ky1~n)--~L3 ~ (4),
; ;n wh;ch A4 is as defined under the formula (3), X is as
def;ned under the formula (1) and the phenyl ring L3 can be
monosubstituted or disubstituted by C1_4-alkyl or C1_4-
alkoxy, is used;
d) a dye of the formula
;
0 NH- (cl_8-alkYlene) o ~ ~ 3
T i1 i1 i (s),
~ / \ / \ ~
o NH-(Cl_8 alkyl~0_l \ _ Xso H
;n wh;ch X ;s as def;ned under the formula (1), ;s used.
In very particularly preferred embodiments of the
process according to the invent;on
e) a dye of the formula (2) or (3) is used;
f) use is made of anthraquinone dyes of the type defined by
the invention ;n which X ;s a fibre~reactive radical of
the aliphatic, aromatic or heterocyclic series which can be
bonded v;a a bridge member of the formula
.~ . .. .
~ ~7~
N{ (CO)
R4
0-1
.~
or via ~ICH --N- or -CH2-N , and R4 is hydrogen or C1_4-
COOH R4 R4
alkyl;
g) use is made of anthraquinone dyes of the type defined by
the invention in which X is a chloroacetyl, bromoacetyl,
acryloyl, ~ ,~-dichloropropionyl,~ ~ -dibromopropionyl,
~-bromoacryloyl or ~-chloroacryloyl radical which is bonded
via -NH-, -CJH-NH- or -CH2-NH- or is a radical of the
formula COOH
-~U- ~ \ / rr ~ ~U ~ \ F~ Cl
R5 F, C1
in which Rs is C1_6-alkoxy, c1_6-alkYlmercapto or a
radical of the formula ~R6 where R6 and R7,
\R
independently of each other, are each hydrogen~ C1_6-alkyl
or subs~ituted or unsubstituted phenyl or naphthyl, or is a
vinylsulfonyl, ~-sulfatoethylsulfonyl, ~-acetoxyethylsulfonylf
~-chloroethylsulfonyl or ~ '-sulfatoethylsulfonyl)-propion-
ylaminomethyl radical~
In three particularly interesting embodiments of the
process according to the invention, use is made of
~7~
- 12 -
h) an anthraqu;none dye of the formula
O NH
Il 1 2
11 11 i-S03H
' 'T~ 1\. ./ 2
O NH ~ -G (6)
= .
in which G1, G3 and G5 are each methyl, G4 is ~-di-
bromopropionylaminomethyl, ~-chloroacryloylaminomethyl~
~-bromoacryloylaminomethyl, ~ '-sulfatoethylsulfonyl)-
-propionylaminomethyl,~,~-dibromopropionylamino,
~r
-CH ( COOH) -NH-CO-¢H
or chloroacetylaminomethyl and G2 is hydrogen, sulfo,
chloroacetylaminomethyl or -CH~COOH)-NH-CO-CH~r-CH2Br or
;n which G1 is hydrogen or methoxy, Gz, G3 and Gs are
each hydrogen and G4 is sulfatoethylsulfonyl, chloro-
acetylamino, ~3-dibromopropionylamino, vinylsulfonyl,
2-methoxy-4-fluoro-s-triazinylarnino or 2-ehtylamino-4-fluoro-
s-trizinylamino or in which G1, G2, G4 and Gs are
each hydrogen and G3 is chloroacetylamino, ~ ~ -dibromo-
propionylamino, 2,6-difluoro-5-chloro-pyrimidin-4-ylamino
or 2-chloro-4-amino- or 4-N,N-dimethyl-amino-s-triazinyl-
amino, or in which G1 is methyl, Gz is ~-sulfatoethyl-
sulfonyl and G3, G4 and Gs are each hydrogen~ or in
which G1 or G2 is sulfo, G3 ;s~-bromoacryloylamino
or N-methyl-N-~3- ~ -chloroethylsulfonyl~-benzoyl~-amino
and G2 or G1 and G4 and 65 are each hydrogen, or
G1, G2 and Gs are each hydrogen, G3 is methyl and
G4 is chloroacetylamino, or in which G1 is methyl,
Gz is 2,6-difluoro-5-chloropyrimidinylamino, G4 is
sulfo and G3 and Gs are each hydrogen;
", i
: . ,
~ r~
- 13 -
i) a dye of the formula (6) in which G1, Gz, G4 and
Gs are each hydrogen and G3 is chloroacetylamino or
~,~)-dibromopropionylamino, or in which G1, G2, G3 and
Gs are each hydrogen and G4 is vinylsuLfonyl, chloro-
acetylamino, 2-methoxy- or 2-ethylamino-4-fluoro-s-triazinyl-
amino or in which G1, G3 and G5 are each methyl, G2 is
hydrogen and G4 is chloroacetylaminomethyl, ~,~-dibromo-
propionylaminomethyL or -CH~COOH)-NH-CO-CHBr-CH2Br, or
in which G1 is methoxy, G2, G3 and Gs are each
hydrogen and G~ is ~-sulfatoethylsulfonyl~ or in which
G1, G3 and Gs are each hydrogen and G2 and G4 are
each chloroacetylaminomethyl or -cH(cooH)-N~-co-cHBr-cH2Br~
or in which G1, G3 and Gs are each methyl, G2 is
~, ~ -dibromopropionylamino and G4 is sulfo, or in which G1
is sulfo, G2, G4 and Gs are each hydrogen and G3 is
~-bromoacryloylamino, or in ~hich G1 is methyl, G2 is
2,6-difluoro-5-chloropyrimidYlamino, G3 and Gs are each
hydrogen and G4 is sulfo; and
j) an anthraquinone dye of the formula ~1) in which A1
is cyclohexyl, A2 is hydrogen, A3 is 4-(4'-methyl-
phenoxy)-phenyl and X is chloroacetylaminomethyl and the
dye contains only one sulfo group or ;n which A1 is
isopropyl, A2 is hydrogen and A3, together with X, is
a phenyl-sec. butyl radical which is substituted in the
phenyl ring by sulfo and chloroacetylaminomethyl or is a
4-phenoxyphenyl radical which is substituted in the phenoxy
radical by sulfo and acryloylaminomethyl, or in which A2
is hydrogen and A1 and A3, together with X, are both a
4-~-bromoacryloylamino-3-sulfophenyl radical or a phenyl-
sec.-butyl radical which is substituted in the phenyl ring
by sulfo and chloroacetylaminomethyl.
Of the dyes indicated in j), preference is given to the
dye of the ~ormula (1) in which A1 is cyclohexyl, A2 is
hydrogen and A3 iS 4-(4'-methylphenoxy)-phenyl, the phenyl
ring of the phenoxy group being substituted by sulfo and
chloroacetylaminomethyl.
A particularly important embodiment of the process
Sf~
- 14 -
accord;ng to the invention comprises using a dye of the
formula (6) in which G1, G2, G4 and Gs are each
hydrogen and G3 is ~,~-dibromopropionylamino, or in which
G1, G3, G4 and Gs are each hydrogen and G2 is vinyl-
sulfonyl, chloroacetylamino, 2 methoxy-4-fluoro-s-triazinyl-
amino or 2-ethylamino-4-fluoro-s-triazinylamino, or in which
G1 is methyl~ G2 is 2,6-difluoro-5-chloropyrimidinylamino,
G3 and Gs are both hydrogen and G4 is sulfo, or in
which G1 is methoxy, G2, G3 and Gs are each hydrogen
and G4 is p~-sulfatoethylsulfonyl~ or in which G1~ G3 and
Gs are each methyl, G2 is hydrogen or -CH(COOH)-NH-CO-
CHBr-CH2Br and G4 is ~,~-dibromopropionylaminomethyl or
~cH(cooH)-NH-co-cHBr-cH2Br~ or in which G1, G3 and Gs
are each methyl, G2 is D~-dibromopropionylamino and G4
is sulfo, or in which G1 is sulfo, G2, G4 and Gs are
each hydrogen and G3 is ~-bromoacryloylamino~
Very particularly important embodiments of the
process according to the invention comprise using the dye
of the formula
.
1l NH 2
o\ ~- C~3 ~CH2NHCOCH2Cl
~--CH3 ( 7)
.=,~
CH3
or the dye of the formula
\ / \o/ ~o/ 3
- C~3 ~cH2~HcocH2cl (8),
H ~ / 3
~= b
CH3 2 2
or the dye of the formula
~ ~ ~. R, ,~ ,S03H
i1 11
~H~ -NH-CO-CH2Cl (9),
,~= o
~ 5
- 15 -
or the dye of the formula
.--~
~H--~ H ~
CH -NH-C0-CH Cl
-~ CH3 (10)
03H
In the process according to the invention, it is
also possible to use mixtures of two or more anthraquinone
dyes of the type defined. In particular, use is made of
a mixture of two anthraquinone dyes whose individual
components each contain one or two fibre-reactive groups
and one or two sulfo groups.
Preferably, each individual component of the mixture
corresponds to one of the anthraquinone dyes specified above
under the formula (1).
It is very particularly preferred to use in the
process according to the invention mixtures of anthraquinone
dyes of the formulae t2), t3), t4) or t5), i.e. mixtures
in which one component corresponds to a dye of the formula
t2), t3), (4) or t5) and the other component corresponds
to a dye of the formula t2), t3), t4) or t5). In particular,
use is made of a mixture of two anthraquinone dyes in which
one component corresponds to a dye of the formula t2) and
the other component corresponds to a dye of the formula
t2) or t3).
In an important mixture of anthraquinone dyes which
can be used in the process according to the invention, one
component corresponds to a dye of the formula t7), t8) or
a dye of the formula t3) in which A4 is cyclohexyl,
L2 is substituted bY P-methylphenoxy and X is chloro-
acetylaminomethyl, and the dye of the formula t3) contains
only one sulfo group, and the other component corresponds
to a dye of the formula (6) in which G1, G2, G4 and
~2~
~ 16 -
G5 are each hydrogen and G3 is ~,~-dibromopropionylamino,
or in which G1, G3, G4 and G5 are each hydrogen and G2
is vinyLsulfonyl, chloroacetylam;no, 2-methoxy-4-fluoro-s-
tr;az;nyla~;no or 2-ethylam;no-4-fluoro-s-tr;az;nylamino,
or ;n wh;ch G1 ;s methyl, and G2 ;s 2,6-d;fluoro-5-chloro-
pyr;m;dinylamino, G3 and G5 are both hydrogen and G4 ;s
sulfo, or ;n wh;ch G1 is sulfo, G2, G4 and Gs are each
hydrogen and G3 is ~-bromoacryloylamino, or in which G1,
G3 and Gs are each methyl, and G2 is ~,¦~-dibromo-
propionylam;nomethyl, -CH(COOH)-NH-C0-CHBr-CH2gr or
~C,~-dibromopropionylamino and G4 is hydrogen, -CH(COOH)-NH-
C0-CH~r-CH2Br or sulfo, or in which G1 is methoxy, G2,
G3 and Gs are each hydrogen and G4 is ~-sulfatoethyl-
sulfonyl.
In a part;cularly ;mportant m;xture of anthraquinone
dyes which can be used in the process according to the in-
vent;on, one component corresponds to the dye of the formula
(7) or (8) and the other component corresponds to the dye
of the formula (3) ;n wh;ch A4 is cyclohexyl, L2 is
substituted by p-methylphenoxy and X is chloroacetylamino-
methyl and the dye of the formula (3) contains only one
sulfo group.
In a further particularly important mixture of
anthraquinone dyes which can be used in the process accord-
ing to the invention, one component corresponds to the dye
of the formula t7) or (8) and the other component corres-
ponds to the dye of the formula (6) in which G1, Gz, G4
and Gs are each hydrogen and G3 is chloroacetylamino~
In a very particularly important mixture of anthra-
quinone dyes which can be used in the process according to
the invention, one component corresponds to the dye of the
formula (8) and the other component corresponds to the dye
of the formula (10). Prefarably the weight ratio of the
dyes of the formulae (8) to (10) is 90:10 to 70:30~ in
particular 80:20.
In general the weight ratio of the anthraquinone
dyes in the mixtures used according to the invention can
, ~ .
S~
vary within wide l;mits. A weight rat;o of 90:10 to 10:90
and in particular of 70:30 to 30:70, has been found to be
advantageous.
The anthraquinone dyes of the formula (1) or the
components of the mixtures used in the process according to
the invention preferably contain only one sulfo group.
The anthraquinone dyes used in the process accord-
ing to the invention are known per se or can be prepared
analogously to known methods. For ;nstance, the dyes of
the formula (1) can be prepared as indicated in German
Offenlegungsschr;ft 2,305,206, Sw;ss Patent 466,~70 and
British Patent 903,590.
The dyes used in the process according to the in-
vention are either in the form o-f the;r free sulfonic acid
or preferably ;n the form of its salts.
Examples of su;table salts are the alkali metal,
alkaline earth metal and ammonium salts and the salts of
organic amines. Examples are the sodium, lithium, potassium
and ammonium salts and the salt of triethanolam;ne.
The dyes used ;n the process according to the ;n-
vent;on generally conta;n further additives, such as sod;um
chloride or dextrin.
The process according to the invention for dyeing
synthetic polyamide mater;als can be appl;ed to the customary
dyeing methods.
The dyeing liquors, in addition to water and the
dyes, can contain further additives, for example wetting
agents, anti-foams, levelling agents or agents which affect
the nature of the text;le material, for example softeners,
f;re retardants or soil , water- or oil-repellent agents,
and water-softening agents and natural or synthetic thick-
eners, for example alginates or cellulose ethers.
The process according to the invention is par-
ticularly su;table for cont;nuous dyeing.
The dyes used ;n the process accord;ng to the in-
vention are d;stinguished by uniform build-up, good ex-
haustion properties and good fastness properties, in
~ ~7~
- 18 -
particular good ozone fastness.
The particularly noteworthy ozone fastness of the
dye;ngs obtained with the process accord;ng to the in-
vention on synthetic polyamide materials is determined by
American Associa~ion of Textile Chemists and Colorists test
methods 109-1975 and 129-1975.
The process according to the invention is suitable
for dye;ng synthetic polyamide materials, for example
nylon or Perlon, in particular nylon 6.6 and preferably
nylon 6.
Said textile material can be dyed at various stages
in processing, for example as fibre, yarn, woven fabric or
knitted fabric and in particular as carpet.
In a particularly interesting embodiment of the
process according to the invention, nylon carpets are con-
tinuously dyed with anthraquinone dyes of the formula (1)
or mixtures of anthraquinone dyes of the formula t1), in
particular the anthraquinone dyes of the formulae (2) or ~6).
If mixtures of dyes are used in the process accord-
ing to the invention, these can be prepared by mixing the
individual dyes. This mixing process is effected for ex-
ample in suitable mills, for example ball and pin mills,
and kneaders or mixers.
The mixtures of dyes can also be prepared by spray-
drying the aqueous mixtures of dyes.
The amounts in which the dyes or mixtures are
used in the dyebaths can vary within wide limits, depending
on the desired depth of shade~ but in general amounts of
0.001 to 6% by weight on weight of fibre has been found to
be advantageous.
The liquor ratio can be chosen from within a wide
range, from 1:1 to 5:1 for continuous dyeing methods and
from 5:1 to 50:1, preferably 8:1 to 25:1, for discontinuous
exhaust methods.
Dyeing is effected from aqueous liquor, for example
by the exhaust method, for example at temperatures between
70 and 130C, preferably at around the boil, i.e. at 95
'
5~
- 19 -
to 105C, or in the case of continuous dyeing methods at
temperatures between 60 and 98C. In continuous methods,
the liquor padded or sprayed on the cloth is preferably hot.
The pH of the dyeing liquor can vary within the
range from 5 to 9. In general, a pH of 6 to 8.5 has been
found to be advantageous. In the process according to the
invention it can be advantageous to vary the pH during the
dyeing, ;n particular to start the dyeing at a pH of 9
and to bring the dyeing l;quor to pH 5 in the course of
the dyeing.
The dye time for d;scontinuous exhaust methods is
generally 10 to 50 minutes. With continuous methods, the
dye time depends on the dyeing apparatus or machines
used a
In the following examples, parts are by weight.
The temperatures are given in degrees centigrade. Parts
by weight relate to parts by volume as the gramme relates
to the cubic centimetre.
Example 1: 10 parts of nylon 6 carpet yarn CAllied 3B-39]
are introduced at 40 into a dyebath which contains 500
parts of water, 1 part of NaH2po4, 0.15 part of
Na2HP04 and 0.02 part of the dye of the formula
O N~12
I ll l~ 1 3
~./-\./-\.~-
. _ .~
0 NH ~ \ /--NHCOCH2Cl
The temperature is uniformly raised to the boil in the
course of 30 minutes, and dyeing is continued at that tem-
perature for 1 hour. The blue-dyed yarn is then rinsed
and dried.
The ozone fastness of the dyeing obtained is tested
in accordance with AATCC CAmerican Association of Textile
Chemists and Colorists] test method 129-1975, and the colour
change is evaluated against the standard grey scale ~SNV
~:7~X~l
-- 20 --
(Swiss Standards Institute) standard 95805] where 1 is
worst and 5 is best.
The dyeing obtained with the above dye has a
fastness level of 4-5~
Replacing the dye given in the above example by one
of the dyes indicated in column II of the following table
or by one of the dye mixtures indicated likewise affords
blue dyeings having the fastness levels indicated in column
III of the table for the colour change after said o~one
fastness test.
. .
~ ;~7~5~
E x amp L e II III
~ .__ _ ._
o~ \ / \ /-~ ~S03H
2 I i1 i1 i . 4
~ 1 2
O NH2
- 2Z -
.
Exampl Dye of the formula Fastness level
~ .. . _ . _ _ _
4 1 N~ CH3
, 502CH2CH2oso3H
6 t~ S03H 4
~' 't' 't~ C~3 ,cH2NHcocEI2cl
\o=~/ 3
H3 CH2l~lcocH
~ ~7~r
- 23 -
._ . ~
Exampl Dye of the formu~a Fastness level i
I II III
__ ~ ..
~- 8 ,~ /S03H
7 ~ -CH 4
C~3 CH2NHcocH-cH
8 t~ 1/ C~ 4
\.=./ 3 1 ¦
CH3 ICH-NH-CO-CH- lCH2
COOH Br Br
. 9 .~ \ / \./ ~1/ 3 COOH 4
I~H0~ ~--CH3 Br Br
CHj ICH-NHCO- ICH- ICH2
COOH Br Br .
.
25~3~
- 2~ -
_
Exampl Dye of the-formula ¦Fastness level¦
II ! III
Mixture of
80 parts by weight of the dye of the formula
1~ " ,.
CH3 CH2NHCOCH2Cl
and 20 parts by weight of the dye of the formula 4 .
NH; ~ H
I~H~ 0- -~ ~-CH
H2NHCOCH2Cl . I
: Mixture of
80 parts by weight of the dye of the formula
,3~ ~- CH~ ~cH2NHcocH2cl
\.= ~/ 3
C~3 CH2NHCOCH2Cl. .
11 a~d 2~ part~ by ight of the dye of the form~la 4
b l~H--~ ~-0-~ -CH3 .
H2NHCOCH2Cl
.. __ . . __ . - ._~
~ ~ 7~ rj ~F~
- 25 -
_ _ _ _ .
Examplle Dye of the formula Fastness level¦
I II III
-Mixture of
90 parts by weight of the dye of the formula
~ \ / \ /e~ ~S03H '
. ~./ \./ \ ~ C\3 ~CH2NHcOcH2C
~ ~H - O\ / C 3
and C~ CH NHCOCX2Cl .
12 10 parts by weigh~ of the dye of the formula 4
; i~2
d ~H-~ -NHCOCH2C1 l i
Mixture of
50 parts by weight of the dye of the formula ¦ i
~ I .
.~ S03H
and CH3 CH2NHCOCH2C1
13 50 parts by weight of the dye of the formula 4
~ -NHCOCH2~1
.
:~ ~ 7~' ~
- 26 -
Example¦ 3ye oF the formu~a Fastness level
I ¦ II III
Mixture of
80 parts by.wei~ht of the dye of the formula
CH\3
and '.=.' 3 .
14 C~ CH NHCOCH Cl
gh~ o th2e dye 2f the formula 4
b ~ ~ ~-UHCOCH2C.
lS ~ 4
16 d ~ ~o U
_ c/~ r[~ .
,,
;...
................ ... .
. .
~ ~:7~
- 27 -
,
~xampl~ Dye of the formula Fastness level
I II III
._ ... . .. _ ___ . ____
17 ~ 3CO C CU
18 ~ _0_~ -CU3
H2NHCOCH2Cl
19 ~\/S\.`~lf 4
~ \~ ~
~ ;~7~S~3~L
-- 2~ --
_
Example Dye of the IfIrmUla III
-- ~ \0~ ./ 3 __
.. ~ ~' f `~ ~ ~ HcH ~cH3
Comparative example:
Replacing the 0.02 part of the dye in Example 1 by
0.02 part of the non-fibre-reactive dye of the formula
O NH2
I~ \il/ \il/ ~i-S03H
O NH ~ ~ ~ -NE~COCH3
produces a blue dyeing which, on testing in accordance
with the AATCC ozone fastness test method 129-1975, has a
fastness level in terms of colour change ~SNV standard
95805] of only 2-3.
