Claims
- 1. In a process for dyeing a synthetic fibre material from an organic water-immiscible solvent by the exhaustion process, the improvement comprising employing a dispersion of a dyestuff of the formula: ##STR152## wherein D is the radical of an aromatic carbocyclic or aromatic-heterocyclic diazo component;
- Q.sub.1 is hydrogen; C.sub.1 -C.sub.4 -alkyl; C.sub.1 -C.sub.4 alkoxy; halogen; C.sub.2 -C.sub.5 alkylcarbonylamino which is unsubstituted or substituted with hydroxyl, halogen, CN, or C.sub.1 -C.sub.4 -alkoxy; phenylcarbonylamino which is unsubstituted or mono-, di, or tri-substituted with C.sub.1 -C.sub.4 -alkyl; C.sub.1 -C.sub.4 -alkoxy, halogen, hydroxyl, formylamino, or ureido;
- Q.sub.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or halogen;
- Q.sub.3 is hydrogen, C.sub.2 H.sub.4 OCONHQ.sub.4, C.sub.1 -C.sub.4 -alkyl which is unsubstituted or substituted with CN, Cl, -CONH.sub.2 or C.sub.1 -C.sub.2 -alkoxy;
- Q.sub.4 is hydrogen, amino, C.sub.1 -C.sub.4 -hydroxyalkylamino, OH, methyl, or hydroxphenyl; and
- A' is C.sub.1 -C.sub.4 -alkylene; in the dyeing liquor.
- 2. The process of claim 1 wherein A' is --C.sub.2 H.sub.4 --.
- 3. The process of claim 1 wherein Q.sub.4 is hydrogen.
- 4. The process of claim 1 wherein D is a radical of the formula ##STR153## T.sub.1 is H, NO.sub.2, CN, halogen, or --CONH.sub.2 ; T.sub.2 is H, NO.sub.2, CN, CONH.sub.2 or SO.sub.2 NH.sub.2 ;
- T.sub.3 is H, NO.sub.2, CN, halogen, or C.sub.1 -C.sub.4 -alkylsulfonyl; and
- T.sub.4 is H or halogen.
- 5. The process of claim 4 wherein Q.sub.1 is formylamino.
- 6. In a process for dyeing a synthetic fibre material from an organic water-immiscible solvent by the exhaustion process, the improvement comprising employing a dispersion of a dyestuff of the formula:
- Y.sub.1 --Ar--N.dbd.N--B--Y.sub.2
- wherein
- Ar is unsubstituted or substituted benzene free of ionic groups;
- B is unsubstituted or substituted pyrazolone, aminopyrazole, indole, or imidazole; and
- Y.sub.1 and Y.sub.2 independently of one another are hydrogen or --X--A--OCONR.sub.1 R.sub.2, wherein X is a direct bond or a bridging group, A is alkylene, R.sub.1 is hydrogen or alkyl, and R.sub.2 is hydrogen, alkyl, cycloalkyl, aralkyl, aryl or substituted or unsubstituted amino, with the proviso that Y.sub.1 and Y.sub.2 are not simultaneously hydrogen; in the dyeing liquor.
- 7. Process of claim 6 wherein R.sub.1 and R.sub.2 are hydrogen.
- 8. The process of claim 1 wherein said dyeing liquor further includes a non-ionic auxiliary or mixtures thereof in the amount of from about 0.05% to about 2% by weight of said organic solvent.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 2328160 |
Jun 1973 |
DT |
|
Parent Case Info
This is a continuation, of application, Ser. No. 474,990, filed May 31, 1974, now abandoned.
The invention relates to an exhaustion process for dyeing synthetic fibre materials, which is characterised in that dispersions of azo dyestuffs which contain at least one grouping of the formula ##STR1## wherein
X denotes a direct bond or a bridge member,
A denotes an alkylene radical,
R.sub.1 denotes hydrogen or alkyl and
R.sub.2 denotes hydrogen, alkyl, cycloalkyl, aralkyl, OH,
An optionally substituted amino group or aryl are used in organic water-immiscible solvents.
Suitable azo dyestuffs for this purpose are those of which the diazo component can belong either to the aromatic-carbocyclic or to the aromatic-heterocyclic series, and of which the coupling component is a benzene compound or heterocyclic compound customary in azo dyestuff chemistry.
The radical of the formula I which characterises the dyestuffs to be used can be present 1 to 3 times in the basic molecule.
Preferred radicals I are those with R.sub.1 and R.sub.2 = hydrogen.
The bridge members X are, for example, the following: --NY--, --O--, --S--, --CO--, --CONY--, --SO.sub.2 -- and --SO.sub.2 NY wherein
Y denotes hydrogen, optionally substituted alkyl or the radical ##STR2##
Suitable alkylene radicals A are straight-chain or branched C.sub.1 -C.sub.4 -alkylene radicals which can be interrupted by hetero-atoms, such as O and S, and can be substituted by nonionic substituents, such as OH, Halogen or ##STR3##
Suitable alkyl radicals R.sub.1, R.sub.2 and Y are those with 1 to 6 C atoms which are saturated or unsaturated and can be substituted, preferably monosubstituted by OH, halogen, CN, C.sub.1 -C.sub.4 -alkoxy or C.sub.2 -C.sub.5 -alkoxycarbonyl.
Suitable cycloalkyl radicals R.sub.2 are cyclohexyl radicals which can optionally be substituted by methyl or chlorine.
Suitable aralkyl radicals R.sub.2 are benzyl and phenylethyl radicals.
Suitable amino groups R.sub.2 are those of the formula --NR.sub.3 R.sub.4 wherein
R.sub.3 and R.sub.4 denote hydrogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -hydroxyalkyl and
R.sub.4 also denotes phenyl or tolyl.
Suitable aryl radicals R.sub.2 are phenyl radicals which are optionally substituted by OH, C.sub.1 -C.sub.4 -alkyl, halogen or C.sub.1 -C.sub.4 -alkoxy.
By halogen there is preferably to be understood, within the scope of this invention, F, Br and above all Cl.
Azo dyestuffs to be used preferentially correspond to the formula ##STR4## wherein
D denotes the radical of an aromatic-carbocyclic or aromatic-heterocyclic diazo component,
Q.sub.1 denotes hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, alkylcarbonylamino which is optionally monosubstituted by OH, halogen, CN or C.sub.1 -C.sub.4 -alkoxy, phenylcarbonylamino which is optionally monosubstituted to trisubstituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen or OH, formylamino or ureido,
Q.sub.2 denotes hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or halogen,
Q.sub.3 denotes hydrogen, C.sub.1 -C.sub.4 -alkyl which is optionally substituted by CN, Cl, CONH.sub.2 or C.sub.1 -C.sub.2 -alkoxy, or denotes -C.sub.2 H.sub.4 OCONHQ.sub.4,
Q.sub.4 denotes hydrogen, amino, C.sub.1 -C.sub.4 -alkylamino, C.sub.1 -C.sub.4 -hydroxyalkylamino, OH, methyl or hydroxyphenyl and
A' denotes C.sub.1 -C.sub.4 -alkylene, preferably -C.sub.2 H.sub.4 --.
Q.sub.2 preferably represents H.
The radical D preferably represents a benzene or thiadiazole radical which is optionally substituted by non-ionic radicals, non-ionic radicals being understood both as the group ##STR5## and as other radicals customary in dyestuff chemistry, such as Cl, Br, CN, NO.sub.2, C.sub.1 -C.sub.4 -alkyl, CONH.sub.2, SO.sub.2 NH.sub.2 and C.sub.1 -C.sub.4 -alkylsulphonyl.
Dyestuffs which are very particularly suitable for the dyeing process according to the invention are those of the formula II, wherein
D represents the radical ##STR6## wherein
T.sub.1 denotes H, NO.sub.2, CN, halogen or CONH.sub.2,
T.sub.2 denotes H, NO.sub.2, CN, CONH.sub.2 or SO.sub.2 NH.sub.2.
T.sub.3 denotes H, NO.sub.2, CN, halogen or C.sub.1 -C.sub.4 -alkylsulphonyl and
T.sub.4 denotes H or halogen.
Further dyestuffs to be used preferentially correspond to the formula
Ar denotes a benzene-type diazo component which is free of ionic groups,
B denotes a heterocyclic coupling component of the pyrazolone, aminopyrazole, indole or imidazole series and
The dyeing of synthetic fibre materials from organic solvents by the so-called exhaustion process is generally known. Organic water-immiscible solvents which can be used are those of boiling point between 60.degree. and 170.degree. C, for example aliphatic chlorohydrocarbons or aliphatic fluorohydrocarbons and fluorochlorohydrocarbons, as well as aromatic chlorohydrocarbons and fluorohydrocarbons.
Tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane have proved particularly suitable. Mixtures of these solvents can also be used.
The dyeing liquors can contain up to 3 percent by weight of water, based on the weight of the organic solvents.
Furthermore, an addition of non-ionic auxiliaries to the dyeing liquors has proved of value in some cases. Non-ionic auxiliaries which can be used are in particular the known surface-active ethoxylation and propoxylation products of fatty alcohols, alkylphenols, fatty acid amides and fatty acids as well as their mixtures; the auxiliaries are employed in an amount of 0.05-2 percent by weight, based on the weight of the organic solvents. Instead of adding the auxiliaries directly to the dyeing liquors, they can also be used with advantage for pasting the dyestuffs containing carbamate groups, and can in this way be added to the dyeing liquors in the form of a dyestuff/auxiliary paste.
The synthetic fibre materials to be dyed according to the invention are above all fibre materials of aromatic polyesters, cellulose esters, polyacrylonitrile, synthetic polyamides and polyurethanes. The fibre materials can be in the most diverse stages of processing, for example in the form of filaments, flocks, tops, yarn, piece goods, such as woven fabric or knitted fabric, or made-up goods.
The dyeing according to the invention is preferably carried out in closed apparatuses, at temperatures of 60.degree. to 170.degree. C. The dyeing times lie between 5 and 90 minutes.
The dyestuffs, containing carbamate groups, to be used according to the invention are largely insoluble in the organic water-immiscible solvents. They are distinguished by good affinity and good general fastness properties.
A further subject of the present invention are new azo dyestuffs of the formulae ##STR7## wherein
V.sub.1 denotes NO.sub.2, CN, C.sub.1 -C.sub.4 -alkylsulphonyl, Cl, Br or H,
V.sub.2 denotes H, chlorine, methyl, methoxy or ethoxy,
V.sub.3 denotes H, methoxy or ethoxy,
V.sub.4 denotes C.sub.1 -C.sub.4 -alkyl, cyanoethyl or -V.sub.5 -OCONHV.sub.6,
V.sub.5 denotes C.sub.1 -C.sub.4 -alkylene and
V.sub.6 denotes H or C.sub.1 -C.sub.4 -hydroxyalkyl; ##STR8## wherein
V.sub.7 represents carbamoyl or sulphamoyl and
V.sub.2 -V.sub.5 have the abovementioned meaning and
V.sub.6 represents H, methyl, ethyl, hydroxyethyl, phenyl, tolyl or hydroxyphenyl; ##STR9## wherein
V.sub.1, V.sub.3, V.sub.4 and V.sub.5 have the abovementioned meaning,
V.sub.2 represents formylamino, C.sub.2 -C.sub.5 -alkylcarbonylamino,
H.sub.2 NCONH- or benzoylamino and
V.sub.6 represents H, methyl, ethyl or hydroxyethyl; and also ##STR10## wherein
V.sub.1 ' represents CN,
W.sub.1 represents H, Cl, Br, CN, CF.sub.3, CH.sub.3, OCH.sub.3 or CONH.sub.2,
W.sub.2 represents H, Cl, Br, CN, CF.sub.3 or CH.sub.3,
W.sub.3 represents H or CH.sub.3,
V.sub.2 represents H, Cl, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, NHCHO, C.sub.2 -C.sub.5 -alkylcarbonylamino, H.sub.2 NCONH or benzoylamino,
V.sub.3 represents H, CH.sub.3, OCH.sub.3 or OC.sub.2 H.sub.5,
V.sub.4 represents C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy-C.sub.2 -C.sub.4 -alkyl radicals which are optionally substituted by 1 or 2 nitrile groups, or represents -V.sub.5 -OCONHV.sub.6,
V.sub.5 represents C.sub.2 -C.sub.4 -alkylene which is optionally substituted by a further OCONHV.sub.6 group and
V.sub.6 represents H, OH, C.sub.1 -C.sub.4 -hydroxyalkyl or C.sub.3 -C.sub.4 -dihydroxyalkyl.
Very particularly preferred new dyestuffs are
(a.sub.1) those of the formula IV, wherein
V.sub.1 represents Cl, Br, NO.sub.2 or CN,
V.sub.5 represents -C.sub.2 H.sub.4 - and
V.sub.4 represents cyanoethyl or -V.sub.5 OCONHV.sub.6 and the remaining radicals have the abovementioned meaning;
(a.sub.2) and also those of the formula IV, wherein
V.sub.1, V.sub.3 and V.sub.6 represent H, V.sub.2 represents H or CH.sub.3,
V.sub.4 represents cyanoethyl or V.sub.5 -OCONHV.sub.6 and
V.sub.5 represents -C.sub.2 H.sub.4 -;
(b) those of the formula V, wherein
V.sub.4 represents cyanoethyl or -V.sub.5 -OCONHV.sub.6,
V.sub.6 represents H and the remaining radicals have the abovementioned meaning;
(c) those of the formula VI, wherein
V.sub.2 represents acetylamino,
V.sub.4 represents cyanoethyl or -V.sub.5 -OCONHV.sub.6,
V.sub.5 represents -C.sub.2 H.sub.4 - and
V.sub.6 represents hydrogen and the remaining radicals have the abovementioned meaning; and
(d) those of the formula VII, wherein
V.sub.1 ' is the o- or p-position to the azo bridge,
W.sub.1 denotes Cl or CN,
W.sub.2 denotes H, Cl or CH.sub.3,
W.sub.3 denotes H or CH.sub.3,
V.sub.2 denotes H, CH.sub.3, formylamino, NHCONH.sub.2 or acetylamino, preferably H,
V.sub.3 denotes H, OCH.sub.3 or OC.sub.2 H.sub.5,
V.sub.4 denotes C.sub.2 H.sub.5, C.sub.2 H.sub.4 CN, C.sub.2 H.sub.4 OC.sub.2 H.sub.4 CN or CH.sub.2 CHCNCH.sub.2 CN, preferably C.sub.2 H.sub.4 CN,
V.sub.5 denotes --C.sub.2 H.sub.4 -- and
V.sub.6 denotes H or C.sub.2 H.sub.4 OH.
The new dyestuffs are obtained according to methods which are in themselves known, for example by diazotising corresponding anilines and coupling with corresponding coupling components. Suitable diazo components are: 2-cyano-4-nitroaniline, 2,4-dicyanoaniline, 2,5-dicyanoaniline, 2,4-dicyano-6-chloroaniline, 2,4-dicyano-3,5-dimethylaniline, 2,5-dichloro-4-cyanoaniline, 2,4-dinitro-6-bromoaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-cyano-aniline, 2,6-dicyano-4-nitro-aniline, 2-cyano-4-nitro-6-methylsulphonylaniline, 2-cyano-4-nitro-6-chloro-aniline, 2-cyano-4-nitro-6-bromo-aniline, 4-carbamoylaniline and 4-sulphamoylaniline.
Suitable coupling components are: ##STR11##
The new dyestuffs can, however, also be obtained by, for example, reacting azo dyestuffs containing the grouping
X and A have the abovementioned meaning and
Z represents H with compounds of the formula
Q denotes chlorine or bromine and in the case that Z denotes phenoxycarbonyl, reacting with amines of the formula NHR.sub.1 R.sub.2 in a manner which is in itself known (compare, for example, GB Pat. No. 1,241,705).
Those dyestuffs which contain nitrile groups in the 2,6-position of the diazo component are advantageously obtained by reaction of corresponding 2,6-dihalogenoazo dyestuffs with CuCN or CuCN-forming substances in aprotic polar organic solvents at temperatures of about 60.degree.-120.degree. C in a known manner (compare GB-PS No. 1,125,683).
The new dyestuffs are particularly suitable for dyeing the abovementioned types of fibres from organic solvents by the exhaustion process, and for the continuous dyeing of, preferably, polyester fibres with aqueous and non-aqueous padding liquors.
US Referenced Citations (5)
Foreign Referenced Citations (7)
| Number |
Date |
Country |
| 1,360,450 |
May 1963 |
FR |
| 1,061,926 |
Jul 1959 |
DT |
| 1,810,063 |
Jun 1970 |
DT |
| 2,145,412 |
Mar 1972 |
DT |
| 6,703,009 |
Feb 1967 |
JA |
| 1,468,908 |
Mar 1977 |
UK |
| 1,237,017 |
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UK |
Continuations (1)
|
Number |
Date |
Country |
| Parent |
474990 |
May 1974 |
|
Patent Grant
4083685
