Note: Descriptions are shown in the official language in which they were submitted.
~2~9~Z
-]- 21489-6833
Process for the continuous trichromatic dyeing of synthetic
polyamide materials
The present invention relates to a process for the
continuous trichromatic dyeing of synthetic polyamide materials
with at least one blue-dyeing fibre-reactive sulfo-containing
anthraquinone dye, at least one red-dyeing sulfo-containing azo
dye and at least one yellow or orange-dyeing sulfo-containing azo
dye.
It is repeatedly found that trichromatic dyeings on
synthetic polyamide materials do not meet present-day demands on
the ozone fastness of dyeings.
It is the object of the present invention to provide a
process for dyeing synthetic polyamide materials with dyes which
are suitable for trichromatic combinations which produces dyeings
of very good ozone fastness.
This object is achieved according to the invention
with the process described hereinafter. The dyeings produced
thereby meet the stated demands on ozGne fastness.
The present invention accordingly provides a process
for the continuous trichromatic dyeing of synthetic polyamide
materials which comprises using at least one blue-dyeing fibre-
reactive sulfo-containing anthraquinone dye together with at least
one red-dying sulfo-containing azo dye and at least one yellow-
or orange-dyeing sulfo-containing azo dye.
More particularly, the invention provides a process for
the continuous trichromatic dyeing of synthetic polyamide
9(~2
-la- 21489-6833
materials which comprises usi.ng at least one blue-dyeing dye of
the formula
O NH2
`" ~ -SO3H
Gl\ /G2 (13)
O NH-~ G3
G5 G4
in which Gl, G3 and G5 are each methyl, G4 is ~ -chloroacryloyl-
aminomethyl or ~-bromoacryloylaminomethyl, ~, ~-dibromopropionyl-
aminomethyl, ~ '-sulfatoethylsulfonyl)-propionylaminomethyl,
dibromopropionylamino, -CH(COOH)-NH-CO-CHBrCH2Br or chloro-
acetylaminomethyl and G2 is hydrogen, sulfo or chloroacetylamino-
methyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which Gl is hydrogen
or methoxy, G2, G3 and G5 are each hydrogen and G4 is sulfato-
ethylsulfonyl chloroacetylamino,~ , ~-dibromopropionylamino, vinyl-
sulfonyl, 2-methoxy-4-fluoro-s-triazinylamino or 2-ethylamino-4-
fluoro-s-triazinylamino, or in which Gl, G2, G4, and G5 are each
hydrogen and G3 is chloroacetylamino,~ , ~-dibromopropionylamino,
2,6-difluoro-5-chloropyrimidin-4-ylamino or 2-chloro-4-amino-
or 4-N,N-dimethylamino-s-triazinylamino, or in which Gl is methyl,
G2 is ~ -sulfatoethylsulfonyl and G3, G4 and G5 are each hydrogen,
or in which Gl or G2 is sulfo, G3 is ~ -bromoacryloylamino or N-
methyl-N-[3-( ~-chloroethylsulfonyl)-benzoyl]-amino and G2 or G
3 Z~90~
-lb- 21489-6833
and G4 and G5 are each hydrogen, or Gl, G2 and G5 are eaeh hydrogen,
G3 is methyl and G4 is chloroacetylamino, or in which Gl is methyl
and G2 is 2,6-dichloro-5-chloropyrimidinylamino, G4 is sulfo and
G3 and G5 are each hydrogen, or at least one blue dye of the
formula
O NH-Yl
~ y ~ (S3 )1-2 (1)
NHY3 ~r ~ T)1_2
in which
Yl is eyelohexyl, Y2 is hydrogen, Y3 is 4-(4'-methylphenoxy)-
phenyl and T is ehloroaeetylaminomethyl and the dye eontains a
single sulfo group, or in whieh Yl is isopropyl, Y2 is hydrogen
and Y3 is a phenyl-sec.-butyl radieal whieh is substituted in the
phenyl ring by sulfo or chloroacetylaminomethyl or is a diphenyl
ether radical whieh is substituted in the phenoxy radieal by
sulfo and aeryloylaminomethyl, or in whieh Yl and Y3 both denote a
phenyl-see.-butyl radieal whieh is substituted in the phenyl ring
by sulfo and ehloroaeetylaminomethyl, and Y2 is hydrogen, or in
whieh Yl and Y3 both denote a 4- ~-bromoaeryloylamino-3-sulfophenyl
radieal and Y2 is hydrogen, together with at least one red dye of
the formula A NH2
B- ~ -N=N- ~
~ ~ (2)
SO3H
-Ic- 21~89-6833
in which A is hydrogen, substituted or unsubstituted Cl_4-
alkyl,
Rl Rl
2 \ , -C0-N or -S02R3, where Rl is Cl_4
R2 R2
alkyl, R2 is substituted or unsubstituted C5 7-cycloalkyl
or substituted or unsubstituted phenyl, and R3 is substituted
or unsubstituted phenyl or substituted or unsubstituted
phenoxy, and B is hydrogen, halogen, C2 4-alkanoylamino,
C5_8-cycloalkoxycarbonylamino, Cl_4-alkoxycarbonylamino,
Cl_4-alkylsulfonylamino or substituted or unsubstituted phenyl-
sulfonylamino, and with at least one yellow or orange dye of
the formulae
,~)-N=N- ~-N=N- ~
in which Bl, B2 and El are each hydrogen, Cl_4-alkyl or
Cl_4-alkoxy and X is straight-chain or branched Cl 4-
alkyl or straight-chain or branched C2 4-hydroxyalkyl, or
~-O-S02-~
Zl N = N - C-C -C~3
C ,N
Z3 03H
~Z~902
-ld- 21489-6833
in which Zl' Z2 and Z3, independent:Ly of one another are
each hydrogen, halogen, Cl_4-alkyl or Cl_4-alkoxy, or
mixtures o:E dyes of the formulae(3) and (4), or a yellow
dye of the formula
W ~ I 503H ~5)
in which Wl is hydrogen, Cl_4-alkyl, Cl_4-alkoxy, halogen,
C2_4-alkanoylamino or a substituted or unsubstituted aryl-
sulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-
gen, halogen, a substituted or unsubstituted alkyl, aryloxy
or aryloxysulfonyl radical or a radical of the formula
w5 w5
S2N \ or -CON W3 is a substituted or unsubstitu-ted
W6 W6
alkyl or aryl radical, W4 is hydrogen or alkyl and W5 and W6
independently of each other, are each hydrogen or substituted
or unsubstituted alkyl, cycloalkyl or aryl radical.
Trichromatic dyeing is to be understood as meaning the
additive colour mixture of suitably chosen yellow- or orange-,
red-and blue-dyeing dyes with which every desired shade of
the visible colour spectrum can be matched by a
~4~90;~
suitable choice of the mixing ratios of the dyes.
The process accord;ng to the invent;on produces
dyeings of good to very good ozone fastness.
Suitable blue-dyeing fibre-reactive sulfo-containing
anthraquinone dyes are for example the anthraquinone dyes
given in the Colour Index as reactive blues.
Suitable red-, yellow- and orange-dyeing sulfo-
containing azo dyes are for example the azo dyes given in
the Colour Index as acid reds, acid yello~s and acid oranges
respectively.
In a preferred embodiment of the process according
to the nvention, at least one blue dye of the formula
O NHYl
I~ 1 2_ 3 )1-2 ~1 )
11 l
O NHY3
in which the ring L can be substituted by hydroxyl, halo-
gen or sulfo, Y1 is hydrogen, C1_g-alkyl, Cs_7-cycloalkyl,
phenyl or phenyl-c1-g-alkyl~ Y2 is hydrogen or halogen,
such as chlorine or bromine, or is preferably a sulfo
group, Y3 is unsubst;tuted or C1_4-alkyl-, C1_4-alkoxy-,
phenoxy-, C1_4-alkylphenoxy or naphthoxy-substituted phenyl
cr phenyl-C1_8~alkYl, and T is a fibre-reactive radical
which is bonded either directly or via a bridge member,
is used together with at least one red dye of the formula
NH~,
B-~ -N=N--~ ~-
~ C--
HO--~ ~-
\S03H
in which A is hydrogen, substituted or unsubstituted C1_4-
alkyl,
z
-- 3 --
~S02~ , -CO-~ or -S02R3, ~here R1 is C1_4
alkyl, R2 is subst;tuted or unsubstituted C5_7-cycloalkyl
or substituted or unsubstituted phenyl, and R3 is substitu-
ted or unsubstituted phenyl or substituted or unsubstituted
phenoxy, and B is hydrogen, halogen, C2-4-alkanoylamin
Cs_g-cycloalkoxycarbonylamino, c1_4-alkoxYcarbonylamin
C1_4-alkylsulfonylamjno or substituted or unsubstituted
phenylsulfonylamino, and with at least one yellow or orange
dye of the formulae
~ 2 ~l (3)
;n which B1, B2 and E1 are each hydrogen, C1_4-alkyl or
C1_4-alkoxy and X is straight-chain or branched C1_4-alkyl
or straight-chain or branched C2_4-hydroxyalkyl, or
~< ~--O-S02--~ ~o
Z ~ (4)
C
H2 \1
Z~-/
in which Z1~ Z2 and Z3, independently of one another are
each hydrogen, halogen~ C1_4-alkyl or C1_4-alkoxy, or mix-
tures of dyes of the formulae (3) and (4), or a yellow dye
of the formula
C~2
-- 4 --
2 ~ 3 ~ S03H
W4 J
in which W1 is hydrogen, C1_4-alkyl, C1_4 alkoxy, haloge ,
C2-4-alkanoylamino or a substituted or unsubstituted
arylsulfonyl, aryloxy or arylcarbonyl radical, W2 is hydro-
gen, halogen, substituted or unsubstituted alkyl, aryloxy
or aryloxysulfonyl radical or a radical of the formula
-S2 ~ or -C0~ , W3 is a substituted or unsub-
stituted alkyl or aryl radical, W4 ;s hydrogen or alkyl, and
W5 and W6, independently of each other, are each hydrogen
or a substituted or unsubstituted alkyl, cycloalkyl or
aryl radical.
An alkyl radical Y1 in the formula (1) can be a
straight-chain or branched alkyl radical, for example
methyl, ethyl, propyl, isopropyL, butyl, sec.-butyl, iso-
butyl, tert.-butyl, pentyl, hexyl, heptyl or octyl.
A C5_7-cycloalkyl radical Y1 in the formula (1)
and a Cs_7-cycloalkyl radical R2 in the formula (Z3,
independently of each other, can be for example an unsub-
stituted cyclohexyl radical or a cyclohexyl radical which
is substituted by alkyl, such as methyl.
A phenyl radical Y1 in the formula (1) can be a
phenyl radical which can be substituted by C1_4-alkyl,
C1_4-alkoxy or halo9en and be further substituted by a
sulfo group and a fibre-reactive radical; the phenyl radi-
cal is preferably substituted by a sulfo group and a
fibre-reactive radical.
Phenyl-cl-8-alkyl radicals Y1 and Y3 in the formula
(1), independently of each other, can each be for example
-- 5 --
a benzyl, phenethyl, phenylbutyl or phenyl-sec.-butyl
radical which is preferably subst;tuted by a sulfo group
and at least one fibre-reactive radical.
A phenyl radical Y3 in the formula (1) can be a
phenyl radical which is substituted by C1_4-alkyl, in par-
ticular methyl, C1_4-alkoxy, in particular methoxy,
phenoxy, C1_4-alkylphenoxy, for example p-methylphenoxy,
or naphthoxy and ~hich is further substituted by a sulfo
group and preferably one or two fibre-reactive radicals.
Fibre-reactive radicals T are to be understood as
mean;ng radicals which are capable of reacting w;th the
hydroxyl groups of cellulose, w;th the amino, carboxyl,
hydroxyl and thiol groups of wool and silk, or ~ith the
amino and carboxyl groups of synthetic polyamides to form
covalent chemical bonds~
Alkyl radicals A, B1, B2, E1, R1, X~ Z1~ Z2 and
Z3 in the formulae (2), (3~ an~ (4), independently of
one another, can be straight-chain or branched alkyl radi-
cals, for example methyl, ethyl, propyl, isopropyl~ butyl,
sec~-butyl, isobutyl or tert.-butyl.
An alkyl radical A can be substituted, for exa~ple,
by halogen, such as chlorine or bromine or in particular
fluorine, but preferably an alkyl radical A is a C1_4-perfluoro-
alkyl radical, in particular a trifluoromethyl radical.
Substituted or unsubstituted phenyl radicals R2
and R3 can each be a phenyl radical which is substituted
by C1_4-alkyl, C1_4-alkoxy or halogen; R2 or R3 is prefer-
ably an unsubstituted phenyl radical.
A substituted or unsubstituted phenoxy radical R3
can be a phenoxy radical which is substituted by C1_4-alkyL,
in particular methyl, C1_4-alkoxy or halogen, in particular
chlorine; a phenoxy radical R3 is preferably a phenoxy
radical which is unsubstituted or substituted by chlorine.
Halogens B, Z1~ Z2 and Z3 in the formulae (2) and
(4) can each be fluorine or bromine or in particular
chlorine.
A C2_4 alkanoylamino ~ in the formula (2) can be
90;~ `
-- 6 --
for example an acetylamino, propionylamino or butyrylamino
rad;cal.
A Cs-C8-cycloalkoxycarbonylamino B can be in par-
ticular a cyclohexyloxycarbonylamino radical.
A C1-4-alkylsulfonylamino ~ can be a methylsul-
fonylamino, ethylsulfonylamino, propylsulfonYlamino, iso-
propylsulfonylamino, butylsulfonylamino, tert.-butylsul-
fonylamino, isobutylsulfonylamino or sec.-butylsulfonYl-
amino radical.
A phenylsulfonyLamino radicaL can be a phenyLsuL-
fonylamino radical which is substituted by C1_4-alkyl,
C1_4-alkoxy or halogen; it preferably is a phenylsulfonyl-
amino radical which is unsubstituted or substituted by
methyl.
Alkoxy radicals ~ 2r E1~ Z1~ Z2 and Z3 in the
formulae (3) and ~4) can each be for example a methoxy,
ethoxy, propoxy, isopropoxy, butoxy, sec.-butoxy, isobut-
oxy or tert. butoxy radical.
A hydroxyalkyl radical X in the formula (3) can be
a straight-chain or branched hydroxyalkyl radical, for
example a ~-hydroxyethyl, ~-hydroxypropyl, ~-hydroxybutyl
or ~-ethyl-~-hydroxyethyL radical.
A C1_4-alkyl W1 is methyL, ethyL, n-propyl,
isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl.
A C1_4-alkoxy W1 ;s methoxy, ethoxy, r,-propoxy,
isopropoxy, n-butoxy, sec.-butoxy, isobutoxy or tert.-
butoxy.
A C2_4-alkanoylamino W1 is for example acetylamino,
propionylamino or butyrylamino.
In a substituted or unsubstituted arylsulfonyl,
aryloxy or arylcarbonyl radical W1, aryl is preferably a radi-
cal of the benzene or naphthalene series which can be
further substituted, for example by C1_4-alkyl groups,
such as methyl and ethyl, C1-4-alkoxy groups, such as
methoxy and ethoxy, halogen, such as fluorine~ chlorine
and bromine, alkanoylamino groups having 1 to 6 carbon
atoms, such as acetylamino, and hydroxyl.
~Lg~O',~
Halosens W1 and/or W2 are fluorine, chlorine
or brom;ne.
In a substituted or unsubstituted aryloxy or aryl-
oxysulfonyl radical W2, aryl is a radical of the benzene
or naphthalene series which can be further substituted,
for example, by C1_4-alkyl groups, such as methyl and
ethyl, C1_4-alkoxy groups, such as methoxy and ethoxy,
halogen, such as fluorine, chlorine and bromine, alkanoyl-
amino groups having 1 to 6 carbon atoms, such as acetyl-
amino, and hydroxyl.
Substituted or unsubstituted alkyl radicals W2,
W3, W5 and W6, independently of one another, are each pre-
ferably a straight-chain or branched C1_12-alkyl, in parti-
cular C1_4-alkyl, radical which can be further substi-
tuted, for example by halogen, such as fluorine, chlorine
or bromine, hydroxyl, cyano, C1_4-alkoxy, such as methoxy
or ethoxy, and alkanoyl groups having 1 to 6 carbon atoms,
such as the acetyl or propionyl group, and benzoyl group.
The alkyl radical W3 can also be substituted by sulfo.
Examples of alkyl radicals W2, W3, Ws and W6 are:
methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-
butyl, iscbutyl and trifluoromethyl.
Substituted or unsubstituted aryl radicals W3, W5
and W6, independently of one another, are preferably mem-
bers of the benzene or naphthalene series and can be fur-
ther substituted, for example by C1_4-alkyl groups, such
as methyl, C1_4-alkoxy groups, such as methoxy and eth-
oxy, halogen, such as fluorine, chlorine or bromine, tri-
fluoromethyl, alkanoylamino groups having 1 to 6 carbon
atoms, such as acetylamino, hydroxyl and carboxyl. The
aryl radical W3 can also be substituted by sulfo. In
part;cular aryl radicals W3, W5 and W6 are each a phenyl
radical which can be substituted by methyl, trifluoro-
methyl and chlorine.
An alkyl radical W4 is preferably a straight-
chain or branched C1_12-alkyl and in particular a c1_~-alkYl
radical. Examples are~ methyl, ethyl, propyl, isopropyl,
~LZ~ 2
butyl, sec.-butyl, tert.-butyl, isobutyl, pent-1-yl,
pent-3-yl, hept-1-Yl, hept-3-yl and oct-1-yl.
Subst;tuted or unsubstituted cycloalkyl rad;cals
Ws and W6, ,ndependently of each other, are preferably
cycloalkyl groups having 5- to 7-membered rings, which can
be further substituted, for example by C1_4-alkYl, such as
methyl. In part;cular the cyclohexyl group comes into
consideration.
T ;n the formula (1) is preferabLy a fibre-reactive
radical of the aliphat;c, aromat;c or heterocyclic series
which ;s bonded to the radical Y1 and/or Y3 e;ther d;-
rectly or v;a a bridge member.
T ;s preferably bonded to the rad;cal Y1 and/or Y3
either directly or v;a an amino group ~hich can be mono
alkylated, for example via -NH-, -N(CH3)-, -N(C2H5)- or
-N(C3H7)-, or via a bridge member containing an am;no group.
A fibre-react;ve radical T ;n the formula t1) can
be for example one of the follow;ng al;phat;c or aromat;c
radicals:
vinylsulfonyl, ~-chloroethylsulfonyl, ~-sulfato-
ethylsulfonyl, ~-acetoxy-ethylsulfonyl, phosphonooxyethyl-
sulfonyl, ~-thiosulfatoethylsulfonyl, N-methyl-N-(~-
sulfatoethylsulfonyl)-am;no, acryloyl, monochloroacryloyl,
d;chloroacryloyl or trichloroacryloyl such as CO-CCl=CH2,
-CO-CH=CH-Cl, -CO-CCl=CH-CH3; monobromoacryloyl, di-
bromoacryloyl or tribromoacryloyl such as -CO-CBr=CH2,
-CO-CH=CH-Br, -CO-CBr=CH-CH3; and also -CO-CCl=CH-COOH,
-CO-CH=CCl-COOH, -CO-CBr=CH-COOH, -CO-CH=CBr-COOH~ -CO-
CCl=CCl-COOH, -CO-CBr=CBr-COOH; precursors of the acryloyl
rad;cal and of the der;vat;ves of the acryloyl rad;cal,
such as ~-chloroprop;onyl, ff-bromoprop;onyl, 3-phenyl-
sulfonyLprop;onyl, 3-methylsulfonylprop;onyl, 3-chloro-3-
phenylsulfonylpropionyl, 2,3-dichloroprop;onyl, 2,3-
d;bromoprop;onyl; and also 2-fluoro-2-chloro-3,3-d;fluoro-
cyclobutane 1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-
carbonyl or -1-sulfonyl, ~-(2,2,3,3-tetrafluorocyclobut-1-
yl)-acryloyl, ~- or ~-alkylsulfonylacryloyl or arylsulfonylacryloyl
groups such as ~- or ~-methylsulfonylacryloyl, propiolyl,
chloroacetyl, bromoacetyl, 4-(~ chloroethylsulfonyl~-
butyryl, 4-vinylsulfonyl-butyryl, 5-(~-chloroethylsulfonyl)-
valeryl, 5-vinylsulfonYl-valerYl, 6-(~ chloroethylsulfonyL)-
caproyl, 6-v;nylsulfonyl-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 T can also be a member
of the he-terocyclic series, for example a 2~4-dichlorotri-
azin-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-monochloro-
methyl- or -5-dichloromethyl- or -5-trichloromethyl- or
-5-methylsulfonyl-pyrimidin-6-yl, 2,5-dichloro-4-methyl-
sulfonylpyrimidin-6-yl, 2-fluoro-4-pyrimidinyl, 2,6-
difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl,
2-fluoro-5,6-dichloro-4-pyr;midinyl, 2,6-difluoro-5-methyl-
4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyrimidinyl, 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-pyrimi-
dinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-
difluoro-5-chloromethyl 4-pyrimidinyl, 2,6-difluoro-5-
nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-
fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-
4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-tri-
fluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoro-
methyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimi-
dinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-
5-phenyl- or -5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-
carboxamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4-
æ
- 10 -
pyrimidinyl, 2-fluoro-5-bromo-6-trjfluoromethyl-4-pyrim
dinyl, 2-fluoro-6-carboxamido-4-pyrimidinyl, 2-fLuoro-6-
carbomethoxy-4 pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimi-
dinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-
methylsulfonyl-4-pyrimidinyl, 2-fluorc-5-sulfonaMido-4-
pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimi-
dinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl; 2,4-
bis-methylsulfonylpyrimidin-4-yl, 2~5-bis-methylsulfonyl-
5-chloropyrimidin-4-yl, 2-methylsulfonyl-pyrimidin-4-yl,
2-phenylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-
6-methylpyrimidin-4-yl, 2-methylsulfonyl-5-bromo-6-methyl-
pyrimidin-4-yl, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimi-
din-4-yl, 2-methyLsulfonyl-5-chloro-methylpyrimidin-4-yl, 2-
methylsulfonyl-5-nitro-6-methylpyrimidin-4-yl, 2,5,6-tris-
methylsulfonyl-pyrimidin-4-yl, 2-methylsulfonyl-5,6-
dimethylpyrimidin-4-yl, 2-ethylsulfonyl-5-chloro-6-methyl-
pyrimidin-4-yl, 2-methylsulfonyl-6-chloro-pyrimidin-4 yl,
2,6-bis-methylsulfonyl-5-chloropyrimidin-4-yl, 2-methyl-
sulfonyl-6-carboxy-pyrimidin-4-yl, 2-methylsulfonyl-
5-sulfo-pyrimidin-4-yl, 2-methylsulfonyl-6-carbomethoxy-
pyrimidin-4-yl, 2-methylsulfonyl-5-carboxy-pyrimidin-4-yl,
2-methylsulfonyl-5-cyano-6-methoxy-pyrimidin-4-yl, 2-
methylsulfonyl-5-chloro-pyrimidin-4-yl, 2-sulfoethyL-
sulfonyl-6-methyl-pyrimidin-4-yl, 2-methylsulfonyl-5-bromo-
pyrimidin-4-yl, 2-phenylsulfonyl-5-chloro-pyrimidin-4-yl, 2-
carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidin-4-yl, 2,4-
dicnloropyrimidine-6-carbonyl or -6-sulfonyl, 2,4-
dichloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-
methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-
carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-
methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6 tri-
chloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-
sulfonyl, 2,4-dichloro-6-methylpyrimidine-5-carbonyl or -5-
sulfonyl, 2-methylsulfonyl-6-chloropyrimidin-4-yl and -5-
carbonyl, 2,6-bis-(methylsulfonyl)-pyrimidine-4- or -5-
carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2,4-
bis-lmethylsulfonyl)-pyrimidine-5-sulfonyl, 2-methyl-sulfo-
- 11 -
nyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl or -5-carbonyl;
2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinox-
al;ne-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl,
2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquin-
oxaline-5- or 6-sulfonyl, 1,4-dichlorophthalazine-6-sul-
fonyl 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'-dichloropyri-
dazin-6'-on-1'-yl)-propionyl, 3,6-d;chLoro-pyr;daz;n-4-
carbonyl or -4-sulfonyl, 2-chlorobenzoth;azole-5- or -6-
carbonyl or -5- or -6-sulfonyl, 2-arylsulfonylbenzoth;azole-
or Z-alkyLsulfonylbenzothiazole-5- or -6-carbonyl or -5- or
-6-sulfonyl, such as 2-methylsulfonylbenzothiazole- or 2-ethyl-
sulfonylbenzothiazole-5- or -6-sulfonyl- or -carbonyl~ 2-
phenylsulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl
and the corresponding 2-sulfonylbenzothiazole-5- or -6-
carbonyl or -sulfonyl der;vatives which contain sulfo groups
in the fused-on benzene ring, 2-chlorobenzoxazole-5- or
-6-carbonyl or -sulfonyl, 2-chlorobenzim;dazole-5- or -6-
carbonyl or -sulfonyl, 2-chloro-1-methylbenz;midazole-5-
or -6-carbonyl or -sulfonyl, 2-chloro-4-methyl-1,3-thiazole-
5-carbonyl or -4- or -5-sulfonyl; ammonium-containing tri-
az;ne rings, such as 2-trimethylammonium-4-phenylamino-
or -4-(o-, m- or p-sulfophenyl)-amino-tr;azin-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)-hydrazinium-4-phenylamino- or -4-(o-, m- or p-
sulfophenyl)-aminotriazin-6-yl, 2-N-aminopyrrolidinium-
or 2-N-aminopiperidinium-4-phenylamino- or -4-(o-, m- or
p-sulfophenyl)-aminotriazin-6-yl, and also 4-phenylamino-
or 4-(sulfophenylamino)-triazin-6-yl radicals which, in
the 2-position, contain 1,4-bis-azabicycloC2.2.2.]octane
or 1,2-bis-azabicyclo~0.3.3.]-octane via a quaternary
nitrogen bond, 2-pyridinium-4-phenylamino- or -4 (o-, m-
or p-sulfophenyl)-amino-triazin-6-yl and corresponding
2-oniumtriazin-6-yl radicals wh;ch are substituted in the
5~
- 1Z -
4-position by alkylamino, such as methylamino, ethylamino
or ~-hydroxyethylamino, or alkoxy, such as methoxy or
ethoxy, or aryloxy, such as phenoxy, or sulfophenoxy groups.
An interesting fibre-reactive radical can also be
a chloro- or fluoro-1,3,5-triazine radical of the formula
F, Cl
V
where the substituent V on the triazine ring can be in
particular:
halogen, for example chlorine or fluorine, C1_8-
alkoxy, for example methoxy, cyclohexyloxy, phenoxy,
C1_6-alkylmercapto, such as methylmercapto, phenylmer-
capto, -NH2, alkylamino, N,N-dialkylamino, cycloalkyl-
amino, N,N-dicycloalkylamino, aralkylamino, arylamino,
mixed-substituted amino groups, such as N-alkyl-N-cyclo-
hexylamino and N-alkyl-N-arylamino groups, and also amino
groups wh;ch contain heterocyclic radicals which can have
further fused-on carbocyclic rings, and amino groups in
which the amino nitrogen atom is a member of an N-hetero-
cyclic ring which can contain further hetero atoms, as
well as hydrazino and semicarbazido. The abovementioned
alkyl rad;cals 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 particular
cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radi-
cals; heterocyclic radicals can be in particular furan,
thiophene, pyrazole, pyridine, pyrimidine, quinoline, ben-
zimidazole, benzothiazole and benzoxazole radicals; and
amino groups in which the amino nitrogen atom is a member
of an N-heterocyclic ring are preferably radicals of six-
membered N-heterocyclic compounds which can contain nitro-
gen, oxygen or sulfur as further hetero atoms. The above-
mentioned alkyl, cycloalkyl, aralkyl and aryl radicals,
O~
- 13 -
the heterocyclic radicals and the N-heterocyclic rings can
be further substituted, for example by: halogen, such as
fluorine, chlorine or bromine, nitro, cyano, trifluoro-
methyl, sulfamoyl, carbamoyl, C1_~,-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, isopropylamino, butylamino, hexylamino,~ -
methoxyethylamino, ~-methoxypropylamino, ~-ethoxyethyl-
amino, N,N-dimethylamino, N,N-diethylamino,~ -chLoroethyl-
amino, ~cyanoethylamino, ~-cyanopropylamino, ~-carboxyethyl-
amino, sulfomethylamino,~ -sulfoethylamino, ~-hydroxy-
ethylamino, N,N-di-~-hydroxyethylamino,~-hydroxypropyl-
amino, benzylamino, phenethylamino, cyclohexylamino,
phenylamino, toluidino, xylidino, chloranilino, anisidino,
phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylam;no,
N-~-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino,
2,5-disulfoanilino, 4-sulfomethylanilino, N-sulfomethyl-
anilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-
sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfo-
naphth-1-ylamino, 3,6-disulfonaphth-1-ylamino, 3,6,8-
trisulfonaphth-1-ylamino, 4,6,8-trisulfonaphth-1-ylamino,
1-sulfonaphth-2-yl-amino, 1,5-disulfonaphth-2-yl-amino,
6-sulfonaphth-2-yl-amino, morpholino, piperidino, pipera-
zino, hydrazino and semicarbazido.
In particularly preferred embodiments o-f the pro-
cess accordin~ to the invention,
a) a blue dye of the formula
O NII2
- SO H
~ ( )N)o-l (6),
in ~hich T is as defined under the formula ~1) and the
phenyl ring L1 can be monosubstituted, disubstituted,
~2~0~
- 14 -
trisubstituted or tetrasubstituted by C1_4-alkyl, C1_4-
alkoxy or phenoxy, or a blue dye of the formuLa
/ \i/ ~- ~ (S3H)l 2
0 E~H--~ L2/- ~ (T)1-2
hich Y4 is a C1_6-alkyl or C5_7-cycloalkyl radical,
T is as defined in the formula (1) and the phenyl ring L2
can be monosubstituted, disubstituted or trisubstituted by
C1_4-alkyl, C1_4-alkoxy, phenoxy or C1_4-alkylphenoxy, or a
blue dye of the formula
0 ~H-Y
o~ ,.,!,.,!~. _ - (S03H) 1-2
!~ ! 1 - (T)l-2 (8~
~ O E`IH-(Cl 8-alkylene~-\ L3/~ ,_
in which Y4 is as defined under the formula (7), T is as
defined in the formula (1) and the phenyl ring L3 can be
monosubstituted or disubstituted by C1_4-alkyl or C1_4-
alkoxy, or a blue dye of the formula
o ~H-(Cl_6-alk'~l~ne)o_l \ >~
.~ \./ \./
~ ! ! ( 9),
/ \./ \.~ T
Il I ~o-
~O NE~-(Cl-6- alky1ene) ~ -
S03H
in which T ;s as defined in the formula ~1), is used;
~z~ o;~
b) at least one red dye of the formula (2) in which A ishydrogen, methyl, trifluoromethyl, ~ ~
-CON~ , -SO2N~ or -S02R3
2 2
where R~ is methyl or ethyl, R2 is cyclohexyl or phenyl,
and R3 is phenyl, methylphenyl, phenoxy or chlorophenoxy,
and B is hydrogen, chlorine, acetylamino, propionylamino,
cyclohexyloxycarbonylamino, phenylsulfonylamino or methyl-
phenylsulfonylamino, A and B not both being hydrogen at
the same time, is used; and
c) at least one yellow or orange dye of the formula
~CH3 ~l
N=N-~ -N N--~ O-X1 ~10),
Al
in which A1 is hydrogen or methyl, F1 is hydrogen or
methyl and X1 is methyl, ethyl, ~-hydroxyethyl,~ -hydroxy-
propyl, ~-hydroxybutyl or ~-ethyl-~-hydroxyethyl or a mix-
ture of at least one dye of the formula (10) and a yello~
dye of the formula
~ ~--O-S02--~ ~-
Z
N
.~ ~. ( 1 1 ),
Z + 1I SO H
6 ~ /- 3
in which Zs and Z6~ independently of each other, are
each hydrogen, methyl or chlorine, or a yello~ dye of
the formula
w~ I ~so3H
n~
- 16 -
in which W1 ;s hydrogen, methyl, chlorine, methoxy,
ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsul-
fonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl,
naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl, W2
is hydrogen, chlorine, methyl, tr;fluoromethyl, o-methyl-
phenoxy, o-chlorophenoxy, o-chlorophenoxysulfonyl, -S02NHz,
N-C1_2-alkylaminosulfonyl, N,N-dimethylaminosulfonyl, N-
methyl-N-~-hydroxyethylaminosulfonyl, N-methyl-N-cyclo-
hexylaminosulfonyl, N-phenylaminosulfonyl, N-o-methyl-
phenylaminosulfonyl, N-o-chlorophenyLaminosu~fonyl, N-m-
trifluoromethylphenylaminosulfonyl, N-ethyl-N-pheny'amino-
sulfonyl~ CONH2 or -CON(CH3)2, W3 is methyl or phenyl
and W4 is hydrogen~ methyl, ethyl or octyl, is used.
In particularly interesting embodiments of the
process according to the invention
d) a dye of the formula (6) or (7) is used:
e) use is made of anthraquinone dyes of the formulae (6)
to (9), in particular of the formulae (6) or ~7) in which
T is a fibre-reactive radical of the aliphatic, aromatic
or heterocyclic series which can be bonded via a bridge
member of the formula
~ ~ o l ~ ~ 3
o--1
or via -CH2-N- or -CH~-~(R4), and R4 is hydrogen or C1 4-alkyl;
COOHR4
f) use is made of anthraquinone dyes of the formulae (6)
to (9) in which T is a chloroacetyl, bromoacetyl, acryloyl,
~,~-dichloropropionyl, ~-~-dibromopropionyl, ~-bromoacryl-
oyl or ~-chloroacryloyl radical which is bonded via -NH,
-CH-NH- or -CH2-NH- or is a radical for the formulae
COOH
~2~
- 17 -
-NH ~ Cl ~! ,F, Cl
N~ ~ or N~ ~
R5 F, C1
in ~hich R5 is C1_6-alkoxy, c1_6-alkYlmercapto or a
radical of the formula _N~6 where R6 and R7,
~ 7
independently of each other, are each hydrogen, C1_6-alkyl
or substituted or unsubstituted phenyl or naphthyl, or is
a vinylsulfonyl, ~-sulfatoethylsulfonyl, ~-acetoxyethyl-
sulfonyl, ~-chloroethylsulfonyl or g-~'-sulfatoethylsul-
fonyL)-propionylaminomethyl radical;
g) use is made of preferably a blue anthraquinone dye of
the formula o NH
1 2
SO ~1
/ \ / \ ~
I\._./ 2 tl3),
\.=./ 3
G/ \G
in which G1, G3 and Gs are each methyl, G4 is q-chloro-
acryloylaminomethyl or d-bromoacryloylaminomethyl, d,~-
dibromopropionylaminomethyl, ~-(g'-sulfatoethylsulfonyl)-
propionylaminomethyl, ~,~-dibromopropionylamino
-CH ( COOH) -.~'H-CO-~H
H2Br
or chloroacetylaminoethyl and G2 is hydrogen, sulfo or chloro-
acetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2Br, or in which
G1 is hydrogen or methoxy, G2, G3 and Gs are each hydro-
gen and G4 is sulfatoethylsulfonYl, chloroacetylamino, ~g-
dibromopropionylamino, vinylsulfonyl, 2-methoxy-4-fluoro-s-
triazinylamino or 2-ethylamino-4-fluoro-s-triazinylamino, or
in ~hich G1, G2, G4 and GS are each hydrogen and G3 is
g~oz
- 18 -
chloroacetylamino, ~p,-dibromopropionylamino~ 2,6-difluoro-5-
chloropyrimidin-4-yl-amino or 2-chloro-4-amino- or 4-N,N-di-
methylamino-s-triazinylamino, or in which G1 is methyl, G2
is ~-sulfatoethylsulfonyl and G3, G4 and G5 are each
hydrogen, or in which G1 or G2 is sulfo~ G3 is ~- bromo-
acryloylamino or N-methyl-N-[3-(~-chloroethylsulfonyl~-ben-
Y mino and G2 or G1 and G4 and G5 are each hydro-
gen, or G1, G2 and G5 are each hydrogen, G3 is methyl
and G4 is chloroacetylamino, or in which G1 is methyL, G2
is 2,6-difluoro 5-chloropyrimidinylamino, G4 is sulfo and
G3 and Gs are each hydrogen; and
h) in particular a dye of the formula (13) in which G1, G2,
G4 and Gs are each hydrogen and G3 is chloroacetyl-
amino or ~v~-dibromoprop;onylamino, or in which G1, G2, G3
and G5 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 Gs are each methyl, G2
is hydrogen and G4 is chloroacetylaminomethyl, ~
dibromopropionylaminomethyl or -CHtCOOH)-NH-CO-CHBr-CH2Br,
or in which G1 is methoxy, G2, G3 and G5 are each
hydrogen and G4 is ~-sulfatoethylsulfonyl, or in which G1,
G3 and Gs are each hydrogen and G2 and G4 are each
chloroacetylaminomethyl or -CH(COOH)-NH-CO-CHBr-CH2sr, or in
which G1, G3 and Gs are each methyl, G2 is ~v~~
dibromopropionylamino and G4 is sulfo, or in which G1 is
sulfo, G2, G4 and Gs are each hydrogen and G3 is ~-
bromoacryloylamino, or in which G1 is methyl, G2 is 2,6-
difluoro-5-chloropyrimidylamino, G3 and G5 are each hydro-
gen and G4 is sulfo; or
i) use is made of a blue dye of the formula (1) in which
Y1 is cyclohexyl, Y2 is hydrogen, Y3 is 4-(4'-methyl-
phenoxy)-phenyl and T is chloroacetylaminomethyl and the
dye contains a single sulfo group, or in which Y1 is
isopropyl, Y2 is hydrogen and Y3 is a phenyl-sec.-butyl
radical which is subst;tuted in the phenyl ring by sulfo
and chloroacetylaminomethyl or is a diphenyl ether radical
which is substituted in the phenoxy radical by sulfo and
acryLoylaminomethyl~ or in which Y1 and Y3 both denote
a phenyl-sec.-butyl radical which is substituted in the
phenyl ring by sulfo and chloroacetylamino methyl, and Y2
is hydrogen, or in which Y1 and Y3 both denote a 4-~-bromo-
acryloylamino-3-sulfophenyl radical and Y2 is hydrogen.
Of the dyes given in i), preference is gi~en to
the dye of the formula (1) in which Y1 is cyclohexYl, Y2
is hydrogen and Y3 is 4-(4'-methylphenoxy)-phenyl, the
phenyl ring of the phenoxy group being substituted by
sulfo and chloroacetylaminomethyl.
In a particular~y important embodiment of the pro-
cess according to the invention, a blue dye of the formula
(13) in which G1, Gz, G4 and Gs are each hydrogen and G~
is ~ dibromopropionylamino, or in which G1, G3, G4 and
G5 are each hydrogen and G2 is vinylsulfonyl, chloro-
acetylamino, 2-methoxy-4-fluoro-s-triazinylamino or Z-
ethylamino-4-fLuoro-s-triazinylamino, or in which G1 is methyl,
G2 is 2,6-difluoro-5-chloropyrimidinylamino~ G3 and G5
are each hydrogen and G4 is sulfo, or in which G1 is methoxy,
G2, G3 and G5 are each hydrogen and G4 is ~-sulfato-
ethylsulfonyl, or in which G1, G3 and G5 are each methyl,
G2 is hydrogen or -CH(COOH)-NH-CO-CHBr-CH29r and G4 is ~,g-
dibromopropionylaminomethyl or -CH(COOH)-NH-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, is used together with a red dye of
the formula (2) and the yellow or orange dyes of the for-
mulae (3) and/or (4) or ~5)~
In very particularly important embodiments of the
process according to the invention, the blue dye of the
formula
R ~H2
S O ~{
Cl
.=./ 3 (14),
c~3
1;~4~90~
- 20 -
or the dye of the forMula
S03H
I i1 i1 i
C~3 ~CH2~1cOcH2Cl
\.=./ 3 (15),
CH3 CH2~HCOCH2Cl
or the dye of the formu~a
~ ~R ~2~So3H
!~ ,ii, i!, ~! (16),
~H--~ NH-C0-CH2Cl
=--
or the dye of the formula
_ --
~H- ~ H ~-
.~ \o/ \ /
11 11
- ~./ \ / \ ,~ ,CH2-'.~H-CO-CH2Cl (17),
O ~H - ~ CH3
03H
;s used.
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 ;ndividual component of the mix-
ture 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
~J~ 2
- 21 -
dyes of the formulae (6), (7), (8) or (9), i~e. mixtures
;n which one component corresponds to a dye of the formula
~6), (7), (~) or (9) and the other component corresponds
to a dye of the formula (6), (7)~ (~) or (9)~ In parti-
cular, use is made of a mixture of two anthraquinone dyes
in which one component corresponds to a dye of the formula
(6) and the other component corresponds to a dye of the
formula (6) or (7).
In an important mixture of anthraquinone dyes
wh;ch can be used in the process according to the inven-
t;on, one component corresponds to a dye of the formula
(14), (~15~ or a dye of the formula t7) in which Y4 is
cyclohexyl, L2 is substituted by p-methylphenoxy and T is
chloroacetylaminomethyl, and the dye of the formula ~7)
contains only one sulfo group, and the other component
corresponds to a dye of the formula (13) in which G1, G2,
G4 and Gs are each hydrogen and G3 is ~,~-dibromo-
propionylamino, or in which G1, G3, G4 and G5 are each
hydrogen and G2 is vinylsulfonyl, chloroacetylamino,
2-methoxy-4-fluoro-s-triazinylam;no or 2-ethylamino-4-
fluoro-s-triazinylamino, or ;n wh;ch G1 is methyl, and G2
is 2,6-difluoro-5-chloro-pyrimidinylamino, G3 and G5 are
both hydrogen and G4 is sulfo, or in which G1 is sulfo,
G2, G4 and G5 are each hydrogen and G3 is ~-bromoacryl-
oylamino, or in which G1, G3 and G5 are each methyl, and
G2 is ~,~- dibromopropionylaminomethyl, -CH(COOH)-NH-CO-
CHBr-CH2Br or ~,~-dibromopropionylamino and G4 is hydrogen,
-CH(COOH)-NH-CO-CHBr-CH2Br or sulfo, or in which G1 is
methoxy, G2, G3 and Gs are each hydrogen and G4 is
~-sulfatoethylsulfonyl.
In a particularly important mixture of anthraqui-
none dyes which can be used in the process according to
~he ;nvention, one component corresponds to the dye of
the formula (14) or (15) and the other component corres-
ponds ~o the dye of the formula ~7) in which Y4 is cyclo-
hexyl, L2 is substituted by p-methylphenoxy and T ;s
chloroacetylaminomethyl and the dye of the formuia (7)
02
- 22 -
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 (14) or (15) and the other component
corresponds to the dye of the formula (13) in which G1, G2,
G4 and G5 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 (15) and the other component corresponds to
the dye of the formula (17). Preferably the weight ratio
of the dyes of the formulae (15) to (17) 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
vary ~ithin ~ide limits. A weight ratio 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 of the anthraquinone dyes used
in the process according to the invention preferably con-
tain only one sulfo group.
In the process according to the invention, the
red dye used is preferably
j) a red dye of the formula (Z) in ~hich A is hydrogen, N-
methyl-N-cyclohexylsulfamoyl, phenylsulfonyl, N-ethyl-N-
phenylsulfamoyl, phenoxysulfonyl or trifluoromethyl and B
is hydrogen, acetylamino or cyclohexyloxycarbonylamino;
and in particular
k) a red dye of the formula (2) in which A is hydrogen
and B is acetylamino or cyclohexyloxycarbonylamino or A
is trifluoromethyl and B is acetylamino or A is phenylsul-
fonyl, N-methyl-N-cyclohexylsulfamoyl, N-ethyl-N-phenyl-
sulfamoyl or phenoxysulfonyl and B is hydrogen; and the
yellow or orange dye of the formulae (3) to (5~ is
l) the yellow dye of the formula
~5~102
- 23 -
~OCH3
\. ./ \ / \ / 3 (18)
S~3H
or the orange dye of the formula
OCH
HO S--~ ~-N=N--~ N=N~ -OCH t19
C~3
or a mixture of the yeLlow dye of the formula (18) with
the orange dye of the formula (19),
or a mixture of the dyes of the formulae (18) andlor (19)
w;th the dye of the formula
~ ~.-n-so2-.~ ~.
\Cl
~=N-~ -~C~-CH3
,~ ~ (20)
H2N' ~
~ Cl
i '!
HO3S ~-/
are used, in weight ratios of the dyes of formulae (18) and
(19) of 60:40 to 40:60 and in particular 1:1 and weight ratios
of the dyes of the formulae (18) or (19) and (20) of
80:20 to 20:80 and in particular 70:30 and weight ratios
of the dyes of the formulae (18), t19) and t20) of 60:20:20,
20:60:20 to 20:20:60 and in particular 1:1:1, or the yel-
low dye of the formula
-- --
-SO
N = N-- - ~ \ / 3 (21),
~./ H
o~
-- 24 --
In a very part;cularly preferred embodiment of the
process according to the invention, a blue dye of the
formula (14), (15), (16) or t17) or a mixture of the dyes
of the formulae (15~ and (17) is used in a weight rat;o
of in particular 70:30 together with a red dye of the
formulae H3C-N-~ /
SO2
il-N=N-~ (22),
~. o~
\SO3H
0- ~
SO =-
-N - N~ - (23) or
/ HO /
\S03H
ICF3 H2N~
C0 ~ ~- ~ ~ ( 2 4 ) and
c~3 \S03H
the yellow dye of the formula (18), (19) or (21) or the
mixture of the yellow dyes of the formulae (18) and (20)
;n a weight ratio of 70:30.
In a very particularly important embodiment of the
process according to the invention, a dye of the formula
(14) or (15) is used together with a dye of the formula
(22) and ~he dye of the formula (19).
The dyes used for trichromatic dyeing in the pro-
cess according to the invention are known or can be pre-
pared analogously to a known method. For instance, the
dyes of the formula (1) can be prepared as indicated in
German Offenlegungsschriften 2,305,206 and 3,142,852, in
lz~$~lo2
- 25 -
Sw;ss Patent 466,470 and ;n British Patent 903,590, the
dyes of the formula (2) are indicated in German Patents
702,932 and 2,063,907 and in German Offenlegungsschrift
2,712,170 and the dyes of the formulae (3) and (4) as in-
dicated in German Offenlegungsschrift 2,142~412 and German
Auslegeschrift 1,100,~46.
Mixtures of dyes used in the process according to
the invention can be prepared by mixing the individual
dyes, for example in suitable mills, for example ball and
pin mills, and in kneaders or mixers.
Mixtures of dyes can also be prepared by spray-
drying the aqueous mixtures of dyes.
The dyes used in the process according to the
invention are either in the form of their free sulfonic
acid or preferably in the form of its salts.
Examples of suitable salts are the alkali metal,
alkaline earth metal and ammonium salts and the salts of
organic amines. Examples are the sodium, lithium, potas-
sium and ammonium salts and the salt of triethanolamine.
The dyes used in the process according to the in-
vention generally contain further additives, such as sodium
chloride or dextrin.
The novel process for trichromatic dyeing can be
applied to the customary continuous dyeing methods. The
dyeing liquors, in addition to water and the dyes, can
contain further additives, for example wetting agents,
antifoams, levelling agents or agents which affect the
nature of the textile material, for example softeners,
fire 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 parti-
cularly suitable for dyeing from short liquors and employed
for example in continuous dyeing methods or/and continuous
foam-dyeing methods.
The dyes used in the process according to the
invention are distinguished in trichromatic dyeing by
~2~ Z
uniform build-up, good exhaustion properties, good shade
consistency even in different concentrations, good fastness
properties, in particular very good ozone fastness, and
good compatibility.
The process according to ~he invention is suitable
for the continuous dyeing of synthetic polyamide materials,
for example nylon or Perlon, in particular nylon 66 and
preferably nylon 6 materials.
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~
The particularly noteworthy good ozone fastness
of the dyeings obtained wi~h the process according to the
invention is determined by American Association of Textile
Chemists and Colorists test methods 109-1975 and 129-1975~
The amounts in which the dyes or mixtures are used
in the dyebaths can vary ~ithin wide limits depending on
the desired depth of shade; in general amounts of 0~001
to 6% by weight on weight of fibre have been found to be
advantageous.
The liquor ratio can be chosen within a wide range,
in particular from 1:1 to 1:5 in the case of continuous
dyeing methods.
Dyeing takes place from an aqueous liquor at tempera-
tures between 6û and 98C. Preferably the dyeing liquor
is hot when padded or sprayed on the cloth.
The pH range 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 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 cub;c centimetre.
Example 1: An aqueous solution containing per litre 0.65 9
of the dye of the formula
- ~L2~ )2
- 27 -
~OCH3
H03S~ N=N~ -N=N-~ OCH3 (19),
CH/
0.29 9 of the dye of the formuLa
H C N / H \
lso2 NH2~
il-N = N--~ ~- (21)
HO
\S03H
and 0.57 9 of the dye of the formula
O NH2
i il i S03H
./ \./ \.~ H3C~ ~C~2NHCOCH2Cl t15)
\.=./ 3
H3C CH2NHcocH2cl
as well as 3 9 of an anionic wetting agent is brought to
pH 8.2 with Na3P04.
300X on weight of fibre of this liquor are applied
to a non-prewetted nylon 6 grey state carpet at a liquor
temperature of 22 and a carpet speed of 8 metres per
minute. The impregnated carpet then passes into a steamer
where it is treated with saturated steam at 98 to 100
for four minutes.
The result after a wash in an open-width washer
is a carpet in a brown shade which is level in respect of
the surface of the carpet and in respect of the individual
- 28 -
fibre and has good ozone fastness.
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 CSNV
(S~iss Standards Institute) stanclard 95805] where 1 is worst
and 5 is best.
The dyeing obtained with the above dyes has a
fastness level of 4.
The above example is repeated, except that a hot
liquor at 90 is used in place of the cold liquor, afford-
ing without the use of a steamer or with a residence time
in saturated steam at 98 or 100 of one minute a carpet
likewise dyed in a level brown of good ozone fastness 4.
Example 2: An aqueous solution containing per litre 0.15 9
-
of the dye of the formula
~OCH3
HO3S~ --N=N--~ ~--N=N--~ ~--OCH3 (19),
=. =-- .=--
CH3
0.1 9 of the dye of the formula
3 1 \ /
1 2 ~H2\
i~ il-N=N--\ ~- (22),
SO3H
0~125 9 of the dye of the formula
3~)2
- 29 -
O NH2
Il l
;~ \i/ \j/ ~ SO H
./ \~/ \.~ H3C~ ~CH2NHCOCH2Cl (14),
O NH~ -CH3
2.0 9 of the ammonium sulfate ester of ethoxylated nonyl-
phenol and 0.5 9 of ethoxylated nonylphenoL is brought to
pH 8.0 with a mixture of Na2HP04 and NaH2P04 and is
heated to 96 to 9~. The hot solution is sprayed in a
sealed chamber through a number of nozzles under a pressure
of 3 atmospheres onto a nylon 66 carpet passing continu-
ously through the chamber. The residence time of the
carpet in the chamber is about 5 seconds. The liquor pick-
up is about 500% on weight of fibre. The result is a
nylon 66 carpet dyed a level brown of ozone fastness 3-4,
the ozone fastness being assessed as indicated in Example 1.
Example 1 is repeated, except that instead of the
combination of dyes of the formulae (19), (22) and (15)
which is mentioned in Example 1 the combination of dyes
which is indicated in the Table below in Examples 3 to 12
in column II is used in the amounts indicated there, like-
wise affording carpets which have been dyed a level olive to
brown shade and have good ozone fastness, the ozone fastness
being assessed as in Example 1 and the fastness level being
indicated in column III.
~$~
- 30 -
Table
.... ~
Ex- Dyes Fast-
ampLe ness
Level
3 0.84 g/l of the dye of the formula 3~4
3 \ ~ \ ;, OCH3
1.78 g/l of the dye of the formula
3 ~ \ /
t 11 ` ,
û.98 g/L of the dye of the formula
_ _
4 0.92 g/l of the dye of the formula (19) 4
1.67 g/l of the dye of the formula (22) and
0.76 g/l of the dye of the formula
.~ So3H
li ~ -W`CO-~
~zL~
- 31 -
Ex- Dyes Fast-
ample ness
level
0.90 g/l of the dye of the formula (19), 4
1.30 g/l of the dye of the formula ~22~ and
1.02 g/l of the dye of the formula
!~ C~3 ~03H (26)
\.=./ 3
G~3 ~'H-C0-CHBr-CH2Br
_ , .
6 0.92 g/l of the dye of the formuLa (19), 3-4
1.33 g/l of the dye of the formula (22) and
1.89 g/l of the dye of the formula
~._ / 3
.
7 0.86 g/l of the dye of the formula (19), 3-4
1.67 g/l of the dye of the formula (22) and
1.60 g/l of the dye of the formula
~,~ h~ U-CO-CU~CI
302
Ex- Dyes Fast-
ampl ness
_ level
8 1.18 g/l of the dye of the formula (19), 4
1.99 g/l of the dye of the formula (22) and
1.14 g/l of the m;xture of the dyes of for-
mulae (14) and (17), ~hich contains
80 per cent by weight of the dye of
the formula (14) and 20 per cent by
weight of the dye of the formula
(17), based on 100X of the mixture.
9 1.97 g/l of the dye of the formula 4
,._.~
1 li N - N~ \i/ 3H (21),
2.47 g/l of the dye of the formula (22) and
1.08 g/l of the mixture of the dyes of for-
mulae (14) and (17), ~hich contains
80X by weight of the dye of the
formula (14) and 20% by ~eight of
the dye of the formula (17), based
on 100X of the mixture.
.
1.89 g/l of the dye of the formula 4
._ ~, . _ ./ 3
~ N=N~ "-N=N- ~ -OCH3 ( )
S 3H
1.06 g/l of the dye of the formula
_.~ ~.
~ ~ / N ~1 (23) ~ ¦
-- ~ -
Ex- Dyes Fast-
ample ness
and
1.06 g/l of the dye of formula (14)
11 2~03 g/l of the mixture o-f the dyes of the 4
formula (18) and
\ ~ /C ~ 2 ~ ~ ~H (20) ,
where, based on 100X by we;ght, the
mixture contains 70X by weight of
the dye of the formula (18) and 30%
by weight of the dye of the formula
(20),
0.89 g/l of the dye of the formula
I ~-/ dO-.' \ and
1.30 g/l of the mixture of the dyes of the
formulae (15~ and (17), which conta ns
80X by weight of the dye of the
formula (15) and 20X by weight of
the dye of the formula (17), based
on 100X of the m;xture.
_
- ~29~ 02
- 34 -
Ex- Dyes Fast-
ample level
_ _
12 1.82 g/l of the dye of the formula (19), 4
2.32 g/l of the dye of the formula (22) and
I CH3 \~H~
Comparative Example 1
Example 1 is repeated, except that the 0.57 g/l of
the dye of the formula (15) is replace by 1.26 g/l of the
non fibre-reactive dye of the formula
S03H
!~ ,il, ,i!, ~i ~CH3 (28)
\ _ / 3
\SO ~NHCH2CH20H
afford;ng a carpet of brown shade which, according to the
test method for ozone fastness ~AATCC 129-1975] has a fast-
ness level for the change of sha~e rSNV standard 95805
of only 2.
Comparative Example 2
Example 1 is repeated, except that the 0.57 g/l
of the dye of the formula (15) is replaced by 1.D9 g/l of
the non fibre-reactive dye of the formula
- ~J~S~o;~
- 35 -
~'H2
.~ \~/ \ /-~ /S03~
C~3 /cl~2~ co-.~ ~. (29),
\ -./ 3
c~3
affording a carpet dyed in a brown shade ~hich, according
to the test method indicated in Comparative Example 1, has
an ozone fastness level of 2.
