IL28297A - Dyeing and printing of polymers and copolymers of acrylonitrile or asymmetric dicyanoethylene or of acid-modified aromatic polyesters - Google Patents

Description

I/We FARBENFABRIKEii' BAYER AKfIENGESELLSCHAFT, a German Company, of Leverkusen Bayerwerk, Germany do hereby declare the nature of this invention and in what manner the same is to "be performed, to be particularly described and ascertained in and by the following statement:- '. : .

DYEING AND PRINTING OP POLYMERS AND COPOLYMERS OP . ACRYLONITRILE OR ASYMMETRIC DICYANOETHYLENE OR OF ACID-MODIFIED AROMATIC POLYESTERS- It has been found that shaped articles, such as fibres, foils, fabrics and the like, obtained from polymers or copolymers of acrylonitrlle or asymmetric dicyanoethylene, or. from ^acid-modified aromatic polyesters can be dyed and printed in very fast shades by using as dyestuffs compounds which a roups and cor in the above formula R represents hydrogen, an alkyl or. aryl group, a carboxylic acid ester group, an optionally N-sub-stituted carbonamide group, or an alkoxy group; R1 means hydrogen or an alkyl, aralkyl, cycloalkyl or aryl radical; R2 means hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical; means hydrogen, an alkyl, cycloalkyl or an aryl radical; ^ means hydrogen, halogen, such as CI and Br, alkoxy, aralk xy, aryloxy, acyloxy, alkyl, aralkyl, aryl, nitro, cyano, trifluoromethyl and carboxylic acid ester groups, optionally N-substituted carbonamide groups, acyl groups and alkylsulph.ony or arylsulphonyl groups, and X is an anion; the aromatic and (cyclo)aliphatic radicals, including the benzene rings according to the above formula, may carry further substltuents (nonrionic substituents), with the exception of sulphonic acid and carboxylic acid. groups.

, Suitable aryl radicals R, R , and R4 are preferably those of the benzene series, such as phenyl, ." 4-methylphenyl- 4-chlorophenyl, 4-methoxyphenyl, 2- methoxy phenyl or 2- chloro phenyl.. Suitable carboxylic acid ester groups are, for example,- the carboxylic acid methyl or ethyl ester; suitable car bonamide groups are, • for example, the carboxylic acid methylamide and dimethyl -o amide g roup.

Suitable alkyl radicals R, R^, R2, R^ and R4 are, in particular, lower' alkyl radicals containing 1 - 5 carbon atoms, such as methyl, ethyl and butyl radicals which may also contain non-ionic substituents. Suitable 5 · non-ionic substituents are, for. example, lower alkyl • . and alkoxy radicals containing 1 - 4 carbon atoms; aralkyl, .'.such as benzylj aralkoxy, such as benzyloxy; aryl, such as. phenyl, and phenyl radicals substituted by non-ionic ,r . radicals, e.g. chloropfaenyl, methyl phenyl, ethyl'phenyl, 0 nitrophenyl, cyanophenyl etc.'; aryloxy groups, such as phenyloxy; halogen substituent.s, , especially CI and Er; carboxylic acid ester groups, especially carboxylic acid methyl ester and ethyl ester groups, optionally N-substituted car bonamide group s, lower alkyl groups being preferred as . N- subs i uents which may be further substituted, e.g. by CI, Br and OH the cyano, nitro, hydroxy! or amino group; alkyl sulphonyl, such .as methyl sulphonyl and ethyl sulphonyl; aryl sulphonyl, such as benzene- sulphonyl and jg-tfol.uene- sulphonyl; acyloxy groups, such as acetoxy and propionyl- oxy; acylamino groups, ·. such 'as acetylamino, propionyl- The dye stuff was obtained in the following manner: 216 Parts by weight 4-chlorbbenzophenone and .7 parts by weight l-methyl-2-phenylindole are dissolved at 0°C In 1800 parts by volume of chloro benzene, followed by the addition of l60 parts by weight bf anhydrous zinc chloride. 306 Parts phosphorus oxychloride are subsequently introduc ed into the reaction mixture which is stirred at 120 - 125°C for l8 hours. The compound, which precipitates in crystalline form upon cooling, is stirred for some time, filtered off with suction^ washed with cold chloro benzene and dried; 20 Parts by weight of this compound are introduced into 60 parts by weight 4-,phenelidine heated to 90°C and the melt, which instantly adopts a blue-green colour, is stirred at 100°C for j hours. The hot melt is poured on to 500 parts by volume of ic e- water and 50 parts by volume hydrochloric acid (d = Γ.19) , whereupon the dye stuff precipitates in crystalline form. After stirring for several hours, it is filtered off with suction and. purified by recrystalllsation from 10$ acetic acid with the addition of sodium chloride..

Wit the same good result, those dye stuffs can ■ also be used for the dyeing of polyacrylonitrile which are obtained by the reaction of the aromatic amines set out in the Table below with the condensation product of 4- chloro benzophenone and l-methyl-2-phenyl-indole.

Aniline derivative Shade of dyeing on poly- acrylonitrile. aniline bluish green 4^ hydroxy ethoxy aniline bluish green 4*tpluidine , bluish green 3-tpluidine bluish green 2-toluidine greenish blue , 4- chloro aniline bluish green 2- chloroaniline blue-green 3- chloroaniline greenish blue 1- ainino-4-methyl-3- bluish green chlorobenzene 3,4-dichloroaniline ^ strongly bluish green 4- me thyl sulphonylaniline bluish green N-acetylphenylene diamine-l , 4 turquoise 4-ahisidine bluish green 3- anisidine bluish green 2- aminoTl,3-dl ethylbenzene greenish blue ' 5 aminb-l j; 3-di ( trif luor o- grey- blue • me thyl) -benzene 4- amino-3 -methyl-l-cy clo- green-blue ; hexylbenzene - amino-l , 3~dimethylbenzene bluish green 2 ,6- diiso ropylan-ilihe . greenish blue 2-amino-l-ethylbenzene gree r-blue . . · 4- am ino-i 3 -di me t hylb enz ene green-blue' 2-isopropylaniline green-blue " 2-amino^l , 4-dime thylbenzene green-blue of warm water at 50°C and the pH value is adj usted to 2 by the addition of 140 parts by volume of a 20$ sodium acetate soluti on. . The precipitation of . the dyestuff is. completed by the addition of 30 parts by weight of sodium chloride and the reaction mixture is stirred for some hours. The dye resin is separated, dis solved in 4000 parts by- olume of boiling water, the solution is clarified with active charcoal and the dye stuf f precipitated, when the solution is somewhat cooler, by the addition of 90 parts by volume of a soluti on of zinc chloride in an equal amount, by weight of water. The dyestuf f is stirred for some time, filtered off ..with suction and w shed with a 10 sodium chloride soluti on.

With the same good result, the dyestuffs can be used which were obtained by the r eac tion of the indole derivati es set out in the Table below, instead of 1 -methyl -2 -phenyl! ndole: .

Indole derivati e Shade on polyacrylonitrile fibres :2-phenylindole bluish - green 2-methylindple greenish blue 1, 2-di'methylindo 1e greenish blue l-methyl÷2-phenyl -5- blue-g reen methoxyindo le 1 -ethyl-2-phehyl- •bluis green-.indole 1 -eth 1-2-methy1- blue indole 1 -ethyl-2-phenyl- . green-blue -methy1-indole 1 ,5-dimethyl-2- . bluish green phenylindole 1 -cyanoethyl-2- bluish green Indole derivative Shade on polyacrylonitrile fibres 1 -cyanoethyl-2-methyl- indole 1 -ethyl-2-phenyl-7- chloroindole 1 ,6-dimethyl-2- phenylindole - 1 -isobutyl-2-phenyl- indole 1 -ethyli-2-phenyl-6- . meth lindole ' 1 -n-butyl-2-phenyl- 6-meth'ylindole 1 -n-butyl-2-phenyl- . indole • Example.5: .·· Fibres of polyacrylonitrile are introduced at. 40°C into an aqueous bat having a goods-to-llquor ratio , ,Aminobenzophenone 'Indole Shade o - poly- acrylonitrile 4-dimethylamino-4 ' - . 2-methylindole bordeaux · . methoxybenzophenone , 4-dimethylamino-41 - .'·;■ -phenylindole reddish black ' methoxybehzophenone ..4-dimethylamino-4' - - .2-methylindole bluish .bordeaux methylbenzophenone 4-dimethylamino'-4 ' - 2r henylindo1e blue-green ' .methylbenzophenone . 4-dimethyl-amiho-3' - 2rmethylindole reddish blue . chl r.obenzoph0.none 4-dimethylaminO-j5l- 2-phenylindole. green sh . blue, chloro-benzophenone • 4-dimethy1amino-21 - 2-methylindole bluish violet ... .chloro-benzophenone · 4-dimethylamino-2·' - ■- ' · 2-phenylindole greenish, blue , chloro-ben'zophehqne .:. 4-diethylamino-4 ' - . " .2-tilethy1indo1e violet ,'. .methylbenzophenone , 4-dimethylamino-2 ' ,5 ' · 1 ,2-dimethyl- „ -blue dichloro-benzophenone indole 4-dimethylamlho-2 ' , 5 ' · 1-methyl-2- greenish, blue dichloro-benzophenone phenylindole 4-dimethylamino-2 ' , 5 '· 2-me.thyUndole reddish . blue dlchloro-benzophenone ■ 4-dimeth lamino-21 ,5 ' - 2-phenylindole greenish blue dlchl'oro-benzoph'enone 4-dlmethylamln'o-"3 ' - - 1,2-dimethyl- greenish blue rr.ethyl-4' -nitro- indole · ··,' · -. benzophenone 4-dlm'ethylamlno- ' - 1 -methy1-2- blue-green methyl-4' -nitro-- . · phenylindole benzophenone , .··' ·· 4-( p-ethoxyphenyl) - ' T 2-dimethy1· blaciogrey. methylamirio.-4 ' - .. . : indole ' methoxybenzophenone"' ·. ,4- ( p-ethoxyphenyl) - . 1 -methyl-2- blue-green methylamino-^' -.. phenylindole methoxybenzophenone.

Aminobenzophenone. Indole Shade on poly- aerylonitrile 4-phenylmethylamino- 2-methylindole greenish blue 2 ',5' -dichloro- benzophenohe ' 4½henylmethylamino- 2-phenylindole bluish green 2!,5'-dichloro- benzophenone : -dimethylamiho-3 ' - 1 ,2-dimethylindole blue-grey nitro-4' -methoxy- benzophenone - -direthylamino-5 ' - 1 -methyl-2- bluish green nitro-4 ' -methoxy- phenylindole benzophenone 4-dimethylamino-5'- ,2rdimethylindole greenish blue me hyl-4 -nitro- benzophenone 4-dimethylaniino-31 - 1-methyi-2- blue-green methy1-4 '-nitrb- phenylindole benzophenone 4-dimethylamino-j51 - 1 -methy1-2- greenish blue hi rp-benzophenone phenylindole 4-dimethylamino-3!'7 ,2-dimethylindole blue .;■">-.' . nitro-benzophenone -dimethylam no-5, - 2-methylindole. currant-blue .nitro-41 -methoxy- benzophenone • 4-dimethylamino- ' -phenylindole bluish green hitro-41 -methoxy- benzpphenone 4-dimethylamino-31 - 2-phenylindo1e bluish green 'methy1-41 -nitro- ·.. benzophenone 4-dimethylamino-5 · - 2-methylindole greenish blue methy1.-4 -nitro- benzophenone 4-dimethylamino-^' - 2-methylindole reddish blue nitrobenzophenone 4-dimethylamino.-5f - 2-phenylindble greenish blue nitrobenzpphenone 4-diethylamino-j5' - 1 , 2rdiniethylindole greenish blue hitro-41 -methoxy- benzophenone Aminobenzophenone Indole Shade on poly acrylonltrile 4-diethylamino-21 - 1 -cyanoethyl-2- greenish blue ohlorobenzophenone phenylindole -dimethylamino-4' - 1 -cyanoethyl-2- currant methoxybenzophenone phenylindole 4-diethylamino- 1 -cyanoethyl-2- reddish dark blue benzophenone methylindole 4-dimetti lamino-4, - 1 -cyanoethyi-2- currant-blue methoxybenzophenone methylindole 4-diethylamino- ' - .1 -cyanoethyl-2- currant-blue methoxybenzophenone methylindole 4-dl-n-propylamino- 1,2-dimethyl- greenish blue 2' ,5'-dichl0ro- indole benzbphenone 4-di-n-propylamino- 1-methyl-2- greenish blue 2,,5'-dichloro- phenylindole benzophenone 4-di-n-propylamino- 1 -methyl-2- blue 1 -ohlorobenzophenone phenylindole 4-di-n-propylamino- 1,2-dimethyl- blue 2 ' -ohlorobenzophenone indole 4-diethylamino- 1 -ethy1-2-phenyl- blue-grey benzophenone 7-chloroindole 4-N-phenylmethylamino- 1 -cyanoethyl-2- blue-green 21 -ohlorobenzophenone phenylindole 4- (N-p-ethoxyphenyl- .1 -cyanbethyl-2- blue-green N-methyl) -amino- ' phenylindole benzophenone . 4-phenylmethylamino- 1 -cyanoethyl-2- greenish blue 2 ' -ohlorobenzophenone methylindole 4- (Nrp-ethoxypheny1- 1 -cyanoethyl-2' blue-green N-methyl) -amino- ' methylindole benzophenone 4-(p-methylphenyl- 1 -methyl-2- bluish green methy1 ) -aminophenylindole benzophenone 4-(p-methylphehyl- 1 ,2-dimethyl^ greenish blue methyl) -aminoindole benzophenone 4'-N-(p-ethoxyphenyl- , 1 ,2-dimethyl- greenish blue methylamino ) -21 - indole ohlorobenzophenone Aminobenzophenone Indole Shade, on poly* aerylonitrile 4-N- (p-ethoxyphenyl- 1 -methyl-2- bluish green methylamino)-21 - pheriylindole chlorobenzophenone 4-diethylamino- : 1,6-dimethyl-2- blue-green benzophenone phenylindole ■ 4-diethylamino-41 -·· 1,6-dimethyl-2- greenish grey methoxybenzophenone phenylindole-..,-· 4-diethylamino-2f- 1 ,6-dimethyl-2- greenish blue, ohlorobenzophenone phenylindole 4-diethylamino- 1 -isobutyl-2-: greenish blue benzopherione phenylindole 4-diethylamino-4'- ' 1-isobutyl-2- blue-grey me hoxybenzophenone phenylindole 4-diethylamino-2 ' - . 1 -isobutyl-2- .. greenish blue chlorobenzophenone . phenylindole 4-phenylmethylaminb- 2-phenylindole olive 2 ' -chlorobenzophenone 4-phenylmethylamino- 2-methyUndole greenish blue 2 ' -!chlorobenzophenone 4-phenylmethylamino- . 1-isobutylr2- bluish green 21 -chlorobenzophenone phenylindole 4-phenylmethylamino-, 1 ,7-dimethyl-2- bluish green 2 ' -chlorobenzophenone pheriylindole 4-diethylamino- 1 -ethyl-2-phenyl- blue-green' benzophenone 6-methylindole 4-diethylamino^1 - 1 -ethyl-2-phenyl- greenish grey methoxybenzophenone 6-me.thyUndole 4-diethylamino-21 - 1 -ethyl-2-phenyl- ', greenish blue, chlorobenzophenone 6-methylindole 4-phenylmethylamino- 1 -ethyl-2-phehyl- bluish green, 2' -chlorobenzophenone 6-methylindole 4-diethylamino- 1 -n-butyl-2-phenyl- blue-green benzophenone 6-methylindole 4-diethylamino-4f- 1 -n-buty1-2-phenyl- grey-green methoxybenzophenone 6-methylindole . 4-diethylamino-2 '-. 1 -n-buty1-2-phenyl- greenish blue chlorobenzophenone 6-methylindole 4-phenylmethylamino- 1 -n-fbutyl-2-phenyl- bluish, green 2 ' -chlorobenzophenone 6-methylindole Aminobenzophenone Indole Shade on poly- acrylonitrile -diethylamino-3- 1 -me hyl-2- greenish dark grey bromo-4* -methoxy- phenylindole benzophenone 4-diethylamino-3- 1 ,2-dimethylindole bluish violet bromobenzbphenone 4-diethylamino-j5- 1 -methyl-2- " greenish blue bromobenzophenone phenylindole 4-dimethylamino-2- 1-me.thyl-2- bluish green methylbenzophenone phenylindole 4-:dimethylamino-2- 1 , 2-!dime.thylindole greenish blue methylbenzophenone 4?-dimethylamino-2- 1-ethyl-2 -. bluish green methylbenzophenone ' phenylindole 4-diethylamino-21 1 , 2-dimethylindole greenish blue bromobenzophenone 4-dlethylamino-2 ' - 1 -methyl-2 - greenish blue, bromobenzophenone phenylindole 4-dlethylamino-2'- 1-ethyl-2- greenish blue bromobenzophenone phenylindole 4-phenylmethylamino- 1 -methyl-2- bluish green 21 -bromobenzophenone phenylindole 4-phenylmethylamino- 1 , 2-dimethylindole greenish blue 2 ' -bromobenzophenone 4-phenylmethylamino- 1 -ethyl-2-phenyl- bluish green 21 -bromobenzophenone indole 4-amino-2 ' -chloro- 1 , 2-dimethylindole bluish red benzophenone 4-amino-2 ' -chloro- 1 -methy1-2- bluish violet benzophenone phenylindple 4-dimethylamino-2- . 1 ,2-:dimethylindole greenish blue methyi-2 -bromobenzophenone 4-dimethylamino-2- 1-methyl-r2- greenish blue methyl-2' -bromophenylindole benzophenone 4-dimethylamino-2- 1 , 2-dimethylindole violet-tinted methyl-21 -chloro- blue benzophenone 4-dimethylamino-2- -methyl-2- greenish blue methyl- ' -chloro- phenylindole Aminobenzophenone Shade on poly- acrylonitrile 4-ethylbenzylamino- 1 -methy1-2- blue-green benzophenone phenylindole 4-ethylbenzylamino- 1 ,2-dimethylindole reddish blue benzophenone 2-chloro- ' -methyl- 1 -methy1-2- greenish blue benzylamino- phenylindole benzophenone 2-chloro- -ethyl- 2-phenylindole , bluish green benzylamino-benzophenone 2-chloro-4'-ethyi- 2-methylindole blue-grey benzylamino-benzophenone 4-ethylbenzylamino- 2-methylindole reddish blue * benzophenone 4-ethylbenzylamino- 2-phenylindole . blue-green benzbphenone 4-phenylmethylamino- l-methyl-2-. greenish blue-grey 5' -bromobenzophenone phenylindole 4-phenylmethylamino- 1 ,2-dimethylindole bluish bordeaux 3' -bromobenzophenone 4-ethylbenzylamino- 1-methyl-2- greenish blue 2-methyl-2 ' -bromophenylindole benzophenone 4-ethylbenzylamino- 1 , 2-dimethylindole greenish blue 2-methyl-2, -bromobenzophenone 4-amino-2',5,-di- 1-methyl-2- red-viole chlorobenzophenone phenylindole 4-amino-2,,5l-di- 1 ,2-dimethylindole yellowish red chlorobenzophenone 4-diethylamino-2- 1 ,2-dimethylindole currant-grey ethyl-4 ' -methoxy-benzophenone 4-diethylamlno-2- 1 -methyl-2- grey-green ethy1-4' -methoxy- phenylindole benzophenone 4-ethylbenzylamino- 1 -methyl-2- bluish green 2 ' -methyl- ' -methoxy- phenylindole . benzophenone Aminobenzophenone Indole Shade- on poly- acrylonitrlle 4-ethylbenzylamino- 1 , 2-dimethylindole grey-green 2* -methyl-4 ' -methoxy-benzophenone ·: V ''' 4-diethylamino-2- . ,1 -methyl-2- greenish blue ethoxy-2 '-chloro- ''. phenylindole benzophenone ' 4-diethylamino-2- 1 ,2-dimethylindole bluish violet ethoxy-21 -chloro-benzophenone 4-chroroethyl-n-butyl- 1 ,2-dimethylindole reddish blue aminobenzopherione 4-chloroethyl-n-butyl- 1 -methy1-2- . . greenish blue aminobenzopherione ·' phenyllndole 4-chloroethyl-methyl- 1 2-dimethylindo e reddish blue aminbbenzophenone 4-chioroethyl-methyl- :1-methylr2- greenish'blue aminobe zophenone phenylindole 4-di-n-propylamino- .1 Tn-butyl-2-phenyl- blue-green benzophenone '6-methylindole · 4-di-n-propylamlno- . 1 -n-butyl-2rphehyl- greenish blue benzophenone indole . 4-oCnaphthyl-methyl- 1 -methyl-2- greenish grey amino-4 ' -methoxy- .phenylindole -benzophenone 4-oC-haphthyl-methyl- - 1 ,2-dimethyliridole ' bluish violet amlno-41 -methoxy-benzophenone 4-O-naphthyl-methyl- 1 ,2-dimethylindole greenish blue amino-benzophenone 4-o-naphthyl-methyl- 1 -methyl-2- bluish green amino-benzophenone phenylindole 4-o-naphthyl.-methy1- ." 1 -methyl-2- . blue-green amirio-2 ' -chloro- ■ -' phenyllndole benzophenone ^ 4-o-riaphthyl-methyl- 1/2-dimethylindole greenish1 blue amino-2,1 -chloro- -benzophenone ' 4-ethylbenzylamino- 1 -methyl-2- greenish blue 21 -bromobenzophenone ph'enylindole 4-ethyibenzylamino- 1 ,2-dimethylindole - blue Aminobenzophenone Indole Shade on poly- aerylohltrile -diethylamino-2f- 1-methyl-2- greenish blue methoxybenzophenone phenylindole 4-die.thylamino-21 -,, 1 2-dimethyiindole greenish blue methoxybenzophenone 4-o£-naphthyl-methyl- 1-methyl-2- blue-green amino-2' -bromo- : phenylindole benzophenone 4-oL-riaphthyl-methyl- 1 , 2-dimethylindole greenish blue amino-^'-bromo-benzophenone 4-diethylamino-21 - 1 -methyl-2r greenish blue methylbenzophenone plenylindole 4-diethylamino-21 -' 1 , 2-dimethylindole. bluish violet methylbenzophenone 4-phenylmethylamino- -methyl-2- bluish green 21 -methoxybenzophenone phenylindole 4-phenylmethylamino~ 1 , 2-dimethylindole greenish blue 21 -methoxybenzophenone 4-B-chloroethyl-ethyl- 1 -methyl-r2- · bluish green amino-2-methyl-2'- . phenylindole chiorobenzophenone 4-B-chloroethyl-ethyl- 1 ,2-dimethyliridole grenish blue amino-2-methyl-2- -chiorobenzophenone 4-phenylme hylamino- 1 -methyli-2- . blue-green '2 ' -methylbenzophenone phenylindole 4-phenylmethylamino- 1 , 2-dimethylindole blue 21 -methylbenzophenone 4-diethylamino-j5, - 1 -methyl-2- , greenish blue methoxybenzophenone phenylindole ■ 4-diethylamino-31 - 1 ,2-rdime.thyllndole reddish blue methoxybenzophenone 4-ethyl-benzylamino- 1-methyl-2- greenish grey 4 ' -methoxybenzophenone phenylindole 4-ethyl-benzylamino- 1 , 2-dimethylindole currant 41 -methoxybenzophenone 4-phenylmethyl-amino- 1 -methyl-2- . green 1 -methoxybenzophenone phenylindole 4-phenylmethyl-amino- 1,2-dimethylindole greenish blue -methoxybenzophenone the preparation of which is described beiow. The bath is heated to boiling temperatur e within 20 - 30 minutes and kept at this temperature for 30 - 60 minutes.. The poly-aery lonit rile fibres are subsequently rinsed and dried. They exhibit a bluish red dyeing of very good light fastness.

The dyestuff was obtained as follows: 19. Parts ' by weight 4-aminobenzophenone and 14.5· parts by weight 1, 2-dimethylindole are introduced, into 200. parts by weight o alcohol, and 50 parts by weight of concentrated hydrochloric acid ( d = 1.19) are added at 30°C to .the r eaction mixture. When the mixtur e has been heated to 80°C , it is stirred at the same temperatur e for 3 hours . 120 Parts , by volume of alcohol are subsequently di stilled off and the deep -coloured r esidue is added to a mixture of 250 parts by volume of a saturated sodium chloride solution and 250 -parts by weight of ic e. The dyestuf f suspension is stirred overnight, filt ered off with suction and the dyestuf f is purified by recrystallisation from water and precipitation with sodium chloride. .

With the same good, result, those dyestuf f s can . be used for the dyeing of polyacrylonitrile which are is separated from the dye resin, the dyestuff dissolved in 500 parts of boiling water and precipitated with 10 parts by weight of zinc chloride and . 20 parts by weight of sodium chloride in the form of a zinc double salt.

Example 7 ; Acid-modified polyglycol. terephthalate fibres of the type DACRON® 64 (E. I. Du Pont de Nemours and Company) and as, for instance, described in the Belgian Patent Specification 5 9, 179 and the U. S. Patent Specification 2, 895* 816 are introduced at 20°C into a dye-bath containing per litre 3 g of sodium sulphate, 0.5 to 2 g of an oleylpolyglycol ether, prepared with 50 mol of ethyleneoxide, 2.5 to 5 g of diphenyl and .0.2 g of the dyestuff of Example 1 and which has been adjusted to a pH of 4.5 to 5.5 with acetic acid. The liquor-to-.goods ratio is 40 : 1. The temperature of the dye-bath is heated within j50 minutes to 98°C and the bath kept at this temperature for 60 minutes. The dyed fibres are subsequently rinsed with water and dried. A bluish green dyeing of very good. astness properties is obtained.

Example 8 : Acid-modified polyglycol. terephthalate fibres as described in Example 7 are introduced at 20°C into a dye-bath containing per litre 6 to 10 g of sodium sulphate, 0. to f g of βη· oleylpolyglycol ether prepared with 50 rnol of ethyleneoxide, 0 to 15 g' of dimethylbenzyl-dodecyl-ammoniumchloride and 0.3 g of the dyestuff of Example 1 and which has been adjusted to a pH of to 5 with acetic acid. The liquor-to-goods ratio is 40 : 1. The temperature of the dye-bath is heated Within ,30 minutes to, 120°C and the bath kept at this temperature for 60 minutes. The dyed fibres are subsequently rinsed with water and dried. One obtains a bluish green dyeing of very good fastness properties.

The dyestuffs mentioned in the preceding Examples may likewise be used for the dyeing of acid-modified aromatic polyester fibres according to the methods described in Examples J and 8 thus yielding valuable shades which are similar or equal to the shades obtained on polyacrylies

Claims (1)

1. insufficientOCRQuality