US2273115A - Process of producing fast dyeings and the dyed fiber obtained thereby - Google Patents

Description

Patented Feb. 17, 1942 PROCESS OF PRODUCING FAST DYEINGS AND THE DYED FIBER OBTAINED THERE- Herbert Kracker, Willy Schumacher; and Vinzenz Schwind, Frankfort-on-the-Main, and Wilhelm Seidenfaden, Olfenbaoh-on-the-Main, Germany, assignors to General Aniline & Film.

Corporation, New Delaware York, N. Y., a corporation or No Drawing. Application December 12, 1940,

Serial No. 369,744.

In Germany June 15, 1939 14 Claims.

The present invention relates to a process of producing fast dyeings and to the dyedfiber obtained thereby.

We have found that valuable dyeings of good properties of fastness are obtained on naturalor artificial cellulosefibers and on animal fibers as well as on mixtures of animal fibers with cellulose fibers by applying to the material to be dyed a compound derived from 1.3.5-triazine and containing either at .least one substituted or unsubstituted radical which contains an aminogroup capable of being diazotized and at least one radical capable of coupling with diazo-compounds, or a radical which contains simultaneously the amino-groupcapable of being diazo tized and the position capable of coupling with diazo-compounds, as well as at least one amgroup and a group lending solubility in'water, then diazotizing the compound and causing it to combine with itself. The self-coupling may be performed or completed, for instance, byadding to the diazo-bath an agent neutralizing the acid or having an alkaline action, after the diazotization is finished,-or by passing the goods through a bath having an alkaline action subsequently to the diazotization process.

The radical containing the amino-group capable of being diazotized and the radical capable of coupling with diazo-compounds may be linked to the triazine radical by a carbon-, oxygen-, nitrogenor sulfur-bond.

As radicals capable of coupling with diazocompounds there may, for instance, be used the radicals of naphthols, of ortho-hydroxycarboxylic acids, of beta-ketocarboxylic acids, of 2-amino- S-naphthol-l-sulfonic acid, of 2-amin0-8-naphthol-fi-sulfonic acid, of. 1-amino-8-naphthol-3.6-'

disulfonic acid, of 1-amino-3-dimethylaminobenzene or of pyrazolones. As further radicals the most various inorganic or organic radicals may be used.

Most of the compounds used in the present process are substantive. Owing to the substantivity of these compounds for cellulose fibers it is possible to obtain on cellulose and regenerated terials may, for instance, be prepared asdescribed in German patent specification No. 634,213.

The following examples serve to illustrate the invention, but thereto:

(1) 1 kilo of mixed yarn consisting of 50 parts Q and 80 grams of ammonium sulfate. 600 grams of sodium sulfate are then added and the ma- ;terial is further treated for half an hour at 80 C. It is then rinsed, diazotized in the cold for half an hour in a solution containing per 30 liters of water 25 grams of sodium nitrite, 25

: grams of sodium dibutylnaphthalene, sulfonate and cc. of hydrochloric acid of 20 B. The

material is then treated for half an hour in a oxide, rinsed and dried. A brown dyeing of good properties of fastness is obtained.

When this dyeing is after-treated in the heat in an acetic 'acid solution with potassium bi-' chromate, chromium fluoride or copper sulfate, brown tints of an essentially improved fastness to water, to perspiration'mnd to washing are obtained.

(2) 1 kilo of a mixture consisting of 50 parts of wool and 59 parts of staple fiber from viscose is treated-for 1 hour at C. in a bath con-' they are not intended to limit it taining per 30 liters of water 50 grams'of a condensation product of the following formula:

NIH 0 NH: f I II N=N HN-O C-NH $0311 soirr on (obtainable by condensing cyanuric chloride with 1 mol of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 1 mol of the reduced monoazo-dyestufl from diazotized para-nitraniline and .2- amino-5-hydroxynaphthalene-'Z-sulfonic acid, and 1 mol of para-phenylenediamine) and 30 grams of ammonium sulfate. 600 grams of sodium sulfate are then added and the material is further treated for half an hour at 80 C. It is then rinsed, diazotized and developed as described in Example 1.

A red-brown dyeing of good properties of fastness is obtained. By treating the dyeing with metal salts in the heat its properties of fastness are essentially improved.

The following table illustrates the shades of a number of other dyeings obtainable by selfcoupling according to the present invention:

Parent component Shade Subdued golden-yellow, after-treated with metal salts. orange-brown.

2 Condensation product. from cyenurlo chloride, 1 mol of Z-amino-8-hydroxy-naphthalene-G-sulfonic acid, 1 mol Red-brown.

oi the reduced monoazo-dyestuff irom diazotized para-nitraniline and phenol, and 1 mol of para-phenylenediamine, corresponding with the formula:

3 Condensation product from cyanuric chloride, 1 mol of 3-aminobenzoyl-2-amino-5-hydroxynaphthalene-7- D0.

of para-phenylenediamine, corresponding with the formula:

I NH

sulionic acid, 1 mol oi the reduced monoazo-dyestufi from diazotized para-nitraniline and phenol, and 1 mol Parent component Shade phenylene-diamine, corresponding with the formula:

para-phenyienediamine, corresponding with the formula:

HOaS Condensation product from phenylenediamine,

corresponding with the formula:

Condensation 1 mo] of para-phenylenediamine, corresponding with the formula I; i NEG-NH: Condensation product from cyanuric chloride 1 moi of the reduced monoazo-dyestnfl from phenylenediamine, corresponding with the formula:

Condensation product from cyanuric chloride, 1 mol of l-aminwhydroxynaphthalone-3.6-disuifonic acid, 1 mol of the reduced monoazo-dyestufl from diazotized pare-nitraniline and phenol, and 1 moi of para- Condensation product from cyanuric chloride, 1 mol of 2-amino-5-hydroxynaphthalene-7-sulionic acid,

1 moi of the reduced monoazo-dyestufl from diazotized para-nitraniline and salicylic acid,

and i moi of coon cyanuric chloride, 1 moi of 2-amino-8-hydroxy-naphthalene-ti-suiionic acid, 1 mol oithe reduced monoazo-dyestufl from diazotizedpara-nitraniiine and salicylic acid, and 1 moi of para- COOH product from cyanuric chloride, 1 moi of 3-aminobenzoyl-2-amino-5-hy xynaphthalene-7- sulfonic acid, 1 mol 0! the reduced monoazo'dye-stufl from diazotized para-nitraniline an salicylic acid, and

GOOH

1 mol of l-amino-s hydroxynaphthaienedfi-disulfonic acid, diazotized para-nitraniline and salicylic acid, and 1 mol of para- Yellow-brown.

Yellow-brown, aftertreated with metal salts: more yellow shade.

Leather-brown, aftertreated with metal salts: more yellow shade.

Khaki-olive.

Parent component Shade Condensation productirom cyunutic chloride, 1 mol oi mino-o-hydroxynephthaleuefl-sulionio acid, 1 mol 0! the reduced monoazo-dyestufl from dimmed parsrnitmnfline and phenol with subsequent methyletion, and 1 mol of para-phenylenediamine, corresponding with the formula:

I H NH Condensation product from cyanurlc chloride, 1 mol oi 2-amiuo-8-hydroxinaphthalenedisulionic acid, 1 me] the reduced monoezo-dyestufl from diawtized para-nitrnuflino and phenol with subsequent methylation, and 1 mol 0! para-phenylenediamine, corresponding with the iormula:

F NE

Condensation product from cyanuric chloride. 1 mol 0! 3-en1inobenzoyl-2-amino-5-hydroxynaphthelene-7- sullonic acid, 1 mol of the reduced XDOIJDQZO-GYBSCUQI'DI? dieeotized para-nltraniline and phenol with sub sequent methylation, and 1 mol of para-phenylenedlamme, corresponding with the formula:

ILHONH:

Condensation product from cyanurlc chloride, 1 mol of 1-emino-8-hydroxynaphthelene-3.6- disulfonic acid, 1 mol of the reduced monoazo-dyestufl lrom dinzotized para-nitranillne and phenol with subsequent methyletion, and 1 mol of pera-phenylene-diamine, corresponding with the formula:

I NH

Condensation product irom cyenuric chloride, 1 mol of 2-emlno5-hydrox aphthalene-7-suliouic acid, 1 mol of the reduced monoum'dyestufitrom diswtimd ara-nitranilinp an Zmmino-b-hydroxynaphthaiene-7- sulionic acid in an acid solution, and 1 mol of pump enylenedimnme, corresponding with the formula;

Copper-brown.

Red-brown.

Parent component Shade Condensation product from cyanuric chloride, 1 mol of 2-amino-sehydroxynaphthalene-e-sulionic acid. lmol oi the reduced monoazo-dyestud from dlazotized para-nitraniline and 2-amino-5-hydroxynaphthalene-7- sulfonic acid in an acid solution, and 1 mol of paraphonylenediamine, corresponding with the formula:

OH /N\ N N Hols Condensation product from cyanuric chloride, 1 mol of 3'- sulionic acid, 1 mol ofthe reduced monoozo-dyestufi from the formula:

aminobenzoyl-2-vamino-5 hydroxy-naphthalene-7- diazotized para-nitraniline and 2-amino-5-hydroxynaphthalene-7-sullonlc acid in an acid solution, and 1 mol of para-phenylenediamine, corresponding with Hols NH: /N\ M -i F O I NH 'soln Condensation product from cyanuric chloride, l mol of l-amino-S-hydroxynaphthaLene-lLfi-disulionic acid,

1 mol of the reduced monoazo-dyestufl from diazotized para-nitraniline and 2-amin hydroxynaphthalene- 7-sulfonic acid in an acid solution, and 1 mol of paraphenylenediamine, corresponding with the formula:

The saponifled condensation product lrom eyanurlc chloride,

ionic acid,

1 mol of the reduced monoewdyeetufl from (11 1 mol oi 2-arnino-5-hydrox ynaphthalene-7-sulazotized nitranill he and I-acetylamino- 5-hydroxynaphtha1ene-7-eulionic acid in an alkaline solution, and 1 mo of aniline, corresponding with the formula:

The saponified condensation product from cyanuric chloride, lmol oi 2-amino8-hydroxynaphthaiene-li-sulionic acid, lmol oi the reduced monoazo-dyestufi lrom diazotized para-nitraniline and 2-acetylamino-5-hydroryullilaphtheleneJ-sulionic acid in an alkaline solution, and 1 mol of aniline, corresponding with'the orm Y 4 Bordeaux, alter-treated with metal salts: more yellow shade.

Bordeaux, alter-treated with metal salts: more yellow shades.

Garnet.

Intense garnet.

Shade The saponified condensation product from cyanuric chloride, 1 mol of 3-aminobenzoyl-2-emino-5-hydroxynaphthalene-7-sulfonic acid, 1 mol of the reduced monoazo-dycstufi from diazotized para'nitmniline and 2- ncetylamino-5-hydroxy-naphthalene-7-sullonic acid in an alkaline solution, and 1 mol of aniline, corresponding with the formula:

NH-C 0- I NH- C The saponified condensation product frorn cyanuric chloride, 1 mol of 1-amino-S-hydroxynaphthalene-3.6-

disulfonic acid, 1 mol of the reduced monoazo-dyestufi from diezotized para-nitraniline and 2 acetylamino 5-hydroxynaphthalene-i-sulfonic acid in an alkaline solution, and 1 mol of aniline, corresponding with the formula:

SIOaH N nms- NH:

i W- O N N -OH H soaH NHO The reduced condensation product from cyanuric chloride, 1 molof2-arnino-5-hydroxy-naphthalene-7- sullonlc acid, 1 mol of the monoazo-dyestuff from diazotized para-nitranlhne and aminohydroquinonedimethylether, and 1 mol of aniline, corresponding with the formula:

The reduced condensation product from cyanuric chloride, 1 mol of 2-a1nino-S-hydroxynaphthalene-fisullonic acid, 1 mol of the monoazo-dyestufi from diazotized para-nitraniline and aminohydroquinonedimethylether, and 1 mol of aniline, corresponding with the formula:

0 H O C H:

N N HOaS- C H:

The reduced condensation product from cyanuric chloride,- 1 mol of 3aminobenzoy1-2-amino-5-hydroxynaphthalene-7-sulfonic acid, 1 mol of the monoazo-dyestufl from diazotized para-nitraniline and aminohydroquinonedimethylether, and 1 mol of aniline, corresponding with the formula:

The reduced condensation product from cyanurlc chloride, 1 mol of l-amino-8-hydroxynapththalene-3.6-

disulfonic acid,1 mol of the monoazodyestufl from diazotized para-nitraniline and aminohydroqulnonedimethylethcr, and 1 mol of aniline, corresponding with the formula:

Dark garnet.

Currant.

Red-brown.

Brown Violetish garnet.

Parent component Shade The reduced condensation product from cyanuric chloride, mol oi Z-amino-5-hydroxynaphthalene-7-sulionic acid, 1 mol of the mcnoazo-dyestufi from diamtized ara-nitranillne and 2-ernino-5-hydroxynaphthalene-7- sulionic acid The reduced condensation acid, 1 mol of the monoazo-dyestufl from diazotized para-nitraniline and Mimi suironic acid ll! The reduced mndensation naphthalene-7-sulfonic eci in an alkaline medium, and 1 mol oi anil ne, corresponding with the formula:

product from cyanuric chloride, l moi oi 2-amino-S-hydroirynaphthaleneJi-suiionic noo-hyd goxynaphthaiene-iin an alkaline medium, and 1 mol of aniline, corresponding with the formu 80 all N=NONE1 OH H dproduct from cyenuric chloride, 1 moi of 3'-aminobeuzoyl-2-amino-5-hydroxy- 1 mol of the monoazo-dyestufl from diazotized paramtraniline and 2-amino-5- hydroxynaphthalene-7-su1ionic acid in an alkaline medium, and 1 mol of aniline, corresponding with the iormul HOaS The reduced condlensation product from cyanurlc chloride, 1 mol oi 1-amino-8-hydroxynaphthaiene-3.6-

disulionic acid nephthalene-7-sulfonic acid in an alkaline medium, and 1 mol of aniline,

The reduced condensation product irom cyanuric chloride 1 acid,

HOrS

The reduced condensation product from cyenuric chloride,

omc acid, 1 mol 'of the monoazo-dyestufl from diazotized naphthalene-T-suifonic acid in an alkaline medium,

BIOIH OaH 1 mol ofrthe monoazo-dyestufi from diazotized 2-chloro-4-nitraniline and 2-amino-B-hydro iene-7-sulionic acid in an alkaline medium,

, mol 0! the monoazo-dyestufl from diazotized para-nitraniiine and 2-amino-5-hydroxycorresponding with the formula:

mol of 2-amino-5-hydroxynaphthalene-7-sulionic xyuaphthaand 1 mol of aniline, corresponding with the lormula:

SOaH

1 mol oi l-aminohydroxyuaphthaiene-m- 2-chloro-4-hltraniline and :2'amlno-5-hydroxyand 1 mol of aniline, corresponding with the formula:

Dark garnet.

Violetish dark-blue.

Bordeaux-garnet.

Currant,

Garnet.

Parent component Shade The reduced condensation product from cyanuric chloride, 1 mol' of 1-amino-8-hydroxynaphthslene-3.6- Garnet.

disulionic acid, 1 mol of the reduced monoazo-dyestufi from diazotized pare-nitraniline and salicglic acid, and 1 moi of the monoazo-dyestufl from diazotized 2-methyl-5-methoxy-4-nitraniiine and l-amino-8- ydroxy' naphthalene-3.6-disu1ionic acid in an alkaline medium, corresponding with the formula:

som N coon -r W O G 0H 1k /N a soin NH 011 051 N=N Nu,

H033 SOaH CH:

The sappnified condensation product irom cyanuric chlorideyi moi oi 2-amino-5-hydroxynaphthalene-7- Dark garnet.

suliomc acid, 1 mol of the reduced monoazo-dyestufl from diazotized Z-chIoroA-nitraniline and 2-aoctylamino-5-hydroxynaphthaiene-7-sulionic acid in an alkaline medium, and 1 mol of aniline, corresponding with the formula: N

Hols Nil-(I'll (f-NH-QN:

N N v 1103s ,NH: H NH The saponifled condensation product from cyanuric chloride, 1 mol of 3'-aminobenzoyl-2-amino-5-hydroxy- Dark violet.

naphthalene-7-sulionic acid, 1 mol of the reduced monoazo-dyestuf! from diazotized 2-chioro-4-nitraniline and 2-acetyl-amino-5-hydrcxynaphthalene-7-sulionic acid in an alkaline medium, and 1 mol oi aniline, corresponding with the iormula:

Hols NHCOQ N on N N H 01 Hols NH,

Condensation product from cyanuric chloride, 1 mol of 1-(4'-aminophenyl)-3-methyl-5-pyrazoione, 1 mol oi Reddish yellow.

?.h6-dai)chl )1rho-1A-diaminobenzene and 1 mol oi 4-amino-1.1-azobenzene-4-sulionic acid, corresponding with e rm N=NOSOaH Condensation product from cyanuric chlorid 1 mol oi 1-(3'-aminophenyl)-5-pyrszolone-3-carboxyiio acid -1 Brownish yellow.

nfiihohzfit-diehlltlgo-lA-diaminobenune and mol oi 4-amino-l.1-azobenzsne4-sulionic acid, corresponding e orm Parent component I Shade Condensation product from cyannrlc chloride, l mol of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 1 mol Yellowish red.

of ZG-dIchIoro-IA-Qiaminobenzene and 1 mol of4-amino-l.1-azobenzene-4'-aullonic acid, corresponding with thelormular Cl N H0 NH-(fi C-NH- NH:

' N\ N l on NH Condensation product from cyanurlo chloride, 1 mol of 2-amino-5-hydroxynaphthalene-7-eullonic acid and Dark brown. 1 mol of 4.4-diamino-2-methyl-5-methoxy-l.1'-ozobenzeno, corresponding with the probable formula:

v 1 OCH;

- I H c1 5 Condensation product from c yanurlc chloride, 1 mol of l-amino-fi-hydroxynaphthaleneJ-stflionlc acid, 1 mol Intense current.

of 4.4'-d.lamino-2-methyl-5-methoxy-l.l-azobenzeneand lmol of l-amlnobenzeneA-sullonic acid, correspond-, lng with the probable formula:

J OCH: V

Nil-1 (IJ-NH-C N= NH: N N HO Ha (I) NH Condensation product from cyannric chlorid 1 mol of 2-amino-5-hydroxynophthalene-7 nullonic acid, 1 mol- Middle red-brown.

o! 2.6-dichloro-L4-diaminobenzena and 1 mo 0! the reduced monoano-dyestufl from diazotired para-nltraniline and salicylic acid, corresponding with the formula:

' COOH N=N OH Condensation product from cy'anuric chloride, 1 mol of l-amino's-hydroxyna mun; onic acid and Reddish brown.

1 mol of 4.4'-diamino-2-methyl--methoxy-l.l'mbenzene, corresponding wit the probable formula:

iarent component Shade Condensation product from cyanuric chloride, 1 mol of 1-amino-8-hydroxynaphthalene-i-sulfonic acid, 1 mol of 2.6-dich1oro-1A-diam1nobenzene and 1 mol of the reduced monoazo-dycstufi from diazotized para-nitraniline and salicylic acid, corresponding with the formula:

SOaH

(IJOOH Condensation product from cyanuric chloride 1 mol of l-amino-6-hydroxynaphthaiene-7-sulionic acid, 1 mol of 2.6-d1ch. loro-l.4-diaminobenzeue and 1 moi of the reduced monoazo-dyestufl from diazotized para-nitrani- 11116 and salicylic acid, corresponding with the formula:

COOH

Condensation product from cyanuric chloride, 1 mol of 1-amlno-8Fhydroxynaphthalene-fi-sulfonic acid and 1 mol of 4.4-diamino-2-methyl-5-methoxy-1.1-azobenzene, corresponding with the probable formula:

OH NH- Condensation product from cyanuric chloride, 1 mol of l-amino-8-hydroxynaphthalene5-sulfonic acid, 1 mol of 2.6-dich1oro-1A- diaminobenzene and 1 mol of the reduced monoazo-dyestufl from diazotized paranitraniline and salicylic acid, corresponding with the formula:

Yellowish brown.

Intensely reddish brown.

Reddish brown.

Brown.

Parent component Shade spending with the probable formula:

the formula:

of 2.6-dichloro-lA-diaminobenzene and and salicylic acid, corresponding with the formula:

COOH

Condensation roduct from cyanuric chloride, 1 mol of 2-amino 8-h droxyna hthalcne-B-sulfonic acid 1 m l of 4.4-diam1 1 1o-2-methy1-5-methoxy-1.l-azobenzene and 1 mol of l-amino 0 46 Condensation product from cyanuric chloride 1 mol of Z-amino-S-hydroxyna hthalene-G-suiionlc acid 1 m l of 4-amino-l.1-azobenzene-4-sulfonic acid and 1 mol 0! 2.6-dichloro-1A-diaminobenzene, corresponding with 47 Condensation product from cyanuric chloride, 1 mol of 2-amlno-8-hydroxynaphthalene-6-sulfonic acid, 1 mol 1 mol of the reduced monoazo-dyestufl from diazotized paranitraniline on c1 Nil-4" e-NH NB:

N N no 1 Intense cunant. nzenc-4-sulfonic acid, cone- OCH:

Brownish red.

Yellow-brown.

' fibers with cellulose fibers, which comprises applying to the fiber acompound derived from 1.3.5- triazine containing an azo group, a group conferring solubility in water, a diazotizable amino group and a grouping which is capable of coupling with a diazo compound, then diazotizing the compound on the fiber and causing self 5 coupling by an alkaline treatment. 2. Process of producing fast brown dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber the condensation product from cyanuric chloride, 1 mol of z-amino-ii-hydroxyv naphthalene-G-sulfonic acid,- 1 mol of the reduced monoazo-dyestufi from diazotized para- 55 phenylenediamine, corresponding with the formula then diamtizing the compound on the fiber and causing self-coupling by an alkaline treatment.

3. Process of producing fast brown dyelngs on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises apnitranilineand salicylic acid and 1 mol of paraplying to thefiber the condensation product mm cyanuric chloride, 1 mol of 2-amino-8-hydroxynaphthalene-fi-sulfonic acid, 1 mol of the reduced monoazo-dyestufi from diazotized para-nitraniline and salicyclic acid and 1 mol of paraphenylenediamine, corresponding with the formula:

1m H000 f OH ll ONm-OHN-Jk /C-NH@ N SOaH then diazotizing the compound on the fiber and causing self-coupling by an alkaline treatment.

5. Process of producing fast red-brown dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber the condensation product from cyanuric chloride, 1 mol of 2-amino- 8-hydroxynaphthalene-6-sulfonic acid, 1 mol of the reduced monoazo-dyestufi from diazotized para-nitraniline and phenol, and 1 mol of paraphenylenediamine, corresponding with the formula:

then diazotizing the compound on the fiber, causing self-coupling by an alkaline treatment and treating the dyeing with an agent yielding metal.

6. Process of producing fast leather-brown dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber the condensation product from cyanuric chloride, 1 mol of 2- amino-S-hydroxynaphthalene-6-sulfonic acid, 1 mol of the reduced IIlOl'lOflZO-(WBStllfi from'diazotized para-nitrantline and salicyclic acid, and 1 mol of para-phenylenediamine, corresponding with the formula:

011 N COOH i Q G NH-C C-NH N N OH II 5 HO:S N\ /N r NE then diazotizing the compound on the fiber and causing self-coupling by an alkaline treatment.

7. Process of producing fast leather-brown dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers withcellulose fibers, which comprises applying to the fiber the condensation product from cyanuric chloride. 1 mol of 2- amino-8-hydroxynaphthalene-6sulfonic acid, 1 mol of the reduced monoazo-dyestufi from diazotized para-nitraniline and salicyclic acid, and 1 mol of para-phenylenediamine, corresponding with the formula:

OH N 00011 i 3 NH-O C-NH N=N on F NH then diazotizing the compound on the fiber, causing self-coupling by an alkaline treatment and treating the dyeing with an agent yielding metal.

8. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 1.

9. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 2.

10. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 3.

11. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 4.

12. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 5.

13. Fiber dyed with an azo-compound obtain able on the fiber by the process claimed in claim 6.

14. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 7.

HERBERT KRACKER. WILLY SCHUMACHER. VINZENZ SCHWIND. WILHELM SEIDENFADEN.