GB2030169A

GB2030169A - Improvements in or relating to organic compounds

Info

Publication number: GB2030169A
Application number: GB7932096A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1978-09-19
Filing date: 1979-09-17
Publication date: 1980-04-02
Also published as: JPS5543190A; IT7950185A0; GB2030169B; ES484254A1; FR2436801A1; DE2936489A1; CH636369A5; BR7905959A; ZA794964B; BE878658A

Abstract

The present invention relates to a mixture of disperse dyestuffs containing at least one compound of formula I, <IMAGE> and at least one compound of formula II <IMAGE> in which D, is a disperse dye diazo component radical, R1, is hydrogen, alkyl, alkoxy or acylamino, R2, is hydrogen, alkyl or alkoxy which is optionally substituted, R3, is hydrogen, alkenyl, chloro- or bromo-alkenyl, linear alkyl which is optionally substituted, R'3, is hydrogen, alkenyl, chloro- or bromo alkenyl, linear or branched alkyl, which is optionally substituted, R4, is a sulphur-free acyloxy or alkoxy-carbonyl radical, one of R5 and R'5 is hydrogen and the other is methyl, the D's R1's, R2's and R4's being identical, which mixture contains 15 to 85% compound of formula I and 85 to 15% compound of formula II, and has good dispersion stability and is useful for dyeing disperse dye dyeable substrats with good build-up power and gives dyeings have good wet-fastness.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to mixtures of disperse dyestuffs which mixtures possess improved properties over the individual dyestuffs.

More particularly, the present invention provides a mixture of disperse dyestuffs containing at least one compound of formula I,

and at least one compound of formula II

in which D, is a disperse dye diazo component radical, R1, is hydrogen, alkyl, alkoxy or acylamino, R2, is hydrogen, alkyl or alkoxy which is optionally mono-substituted by a substituent selected from halogen, cyano, acyl, acyloxy, hydroxyl, alkoxy, phenyl and phenoxy, R3, is hydrogen, alkenyl, chloro- or bromo-alkenyl, linear alkyl which is optionally substituted by up to two substituents selected from halogen, acyloxy, hydroxyl, and alkoxy or mono-substituted by a cyano, acyl, phenyl or phenoxy group, R3, is hydrogen, alkenyl, chloro- or bromo alkenyl, linear or branched alkyl, which is optionally substituted by up to two substituents selected from halogen, acyloxy, hydroxyl, and alkoxy or mono-substituted by a cyano, acyl, phenyl or phenoxy group, R4, is a sulphur-free acyloxy or alkoxy-carbonyl radical, one of F5 is R5 is hydrogen and the other is methyl, the D's, R1's, R2,s and F4,s being identical, any alkyl groups or moieties and any alkoxy groups in such dyestuffs contain 1 to 8 carbon atoms, any alkenyl groups 2 to 4 carbon atoms, and said mixture contains 15 to 85% compound of formula I and 85 to 15% compound of formula II.

It will be appreciated that the compounds of formula I and formula II are free from acetal groupings i.e.

By halogen is meant chlorine, bromine or iodine.

The preferred halogens are chlorine and bromine.

By 'acyl' is meant groups of formula R-Y- and R'-Z wherein R is a alkyl, alkenyl, C5.7 cycloalkyl, phenyl or a heterocyclic group, (preferably alkyl, alkenyl (C5.7) cycloalkyl or phenyl), which alkyl is optionally mono-substituted by halogen, hydroxy, (C1.2) alkoxy, phenyl or phenoxy and which phenyl is optionally substituted by up to two substituents selected from halogen, (C1.2) alkyl and (C1.2) alkoxy, Y is -O-CO-, or - OSO2-(-O-bound to R)or - SO2 R ' is hydrogen or has one of the significances of R, Z is -CO-, -NR"CO- or -NR"SO2- (-N bound to R'), and R" is hydrogen or has one of the significance of R and acyloxy and acylamino are to be understood accordingly.

When the alkyl and/or alkoxy groups in the dyestuffs are substituted they are preferably monosubstituted or are substituted by a hydroxyl group and a further substituent. Preferably the alkyl and alkoxy radicals contain 1 to 4, more preferably 1 or 2 carbon atoms. Preferred alkenyl groups contain 3 carbon atoms. The preferred cycloalkyl is cyclohexyl.

Preferred diazo component radicals are those of the benzene series (optionally disazo component radicals) and diazo component radicals of the benzothiazolyl, thiophene orthiazolyl series.

More preferably, D is thiophene-2 substituted by up to two nitro groups; benzothiazolyl-2 in which the benzene nucleus is substituted by up to two substituents selected from chlorine and nitro; or phenyl substituted in the para position by nitro, alkylsulphonyl, aminosulphonyl, mono- or dialkylaminosulphonyl or phenylazo (in which the benzene nucleus is optionally substituted by up to three substituents selected from methyl, methoxy, chlorine, bromine and nitro) and optionally bearing up to two further substituents selected from halogen, nitro, cyano or alkylsulphonyl.

Representative mixtures are those containing at least one compound of formula la

and at least one compound of formula Ila

in which D' is a radical of formula (a), (b), (c) or (d)

wherein R6 is hydrogen, chlorine, bromine, iodine, nitro or cyano, R7 is nitro, (C1-2)alkylsulphonyl, amino-sulphonyl, mono- or di(C1.2) alkylamino-sulphonyl or phenylazo in which the benzene ring is optionally substituted by up to three substituents selected from methyl, methoxy, chlorine, bromine and nitro, F8 is hydrogen, chlorine or bromine, Rg is hydrogen, chlorine, bromine, iodine, cyano or (C1-2) alkylsulphonyl, with the proviso that one of F8 and Rg is hydrogen, R11 is hydrogen, methyl, methoxy, ethoxy, formylamino, alkyl (C1-4) carbonylamino, alkyl (C1-2) carbonylamino monosubstituted by hydroxyl, chlorine, bromine, cyano, phenyl, (C1-3) alkoxy or phenoxy, alkoxy-(C1.4) carbonylamino, ethoxycarbonylamino monosubstituted by hyd roxy, (C1d2-3) alkoxy or (C1.2) alkoxyethoxy, benzoylamino or (C1.2) alkylsulphonylamino, R12 is hydrogen, methyl, (C1.2) alkoxy, (C1.2)-alkoxyethoxy or (C1-2) alkoxy monosubstituted by chlorine, bromine, cyano or phenyl, R13 is hydrogen, linear (C1-4) alkyl, (C2-3)- alkenyl, linear (C2-3) alkyl mono-substituted by (C1-2) alkoxy, cyano, formyloxy, alkyl (C1-4) carbonyloxy, alkoxy (C1-3) carboyl, benzoyloxy or alkoxy (C1-3) carbonyloxy, R13' has one of the significances of R13 but where the alkyl and substituted alkyl radicals are linear or branched, R14 is formyloxy, alkyl (C1-4) carbonyloxy, benzoyloxy, phenoxyacetoxy, alkoxy (C1.4)- carbony loxy, alkoxy (C1-4) carbonyl, alkoxy (C1.2) ethoxycarbonyl, alkoxy (C1-2) ethoxycarbonyloxy, alkoxy (C1-2) alkyl (C1.2) carbonyloxy, mono- or di (C1-4) alkyl) aminocarbonyloxy or phenyl aminocarbonyloxy wherein the benzene nucleus is optionally substituted by up to two substituents selected from chlorine, bromine, methyl and methoxy, whereby in such mixture D', R11, R12, and R14 in the compound of formula la is identical with that of the compound of formula Ila.

More preferred mixtures are those wherein D' is a group of formula (d), especially those wherein R6 is F8,, where R6" is hydrogen, chlorine, bromine or nitro, R7 is nitro, F8 is hydrogen and Rg is R9' where R9' is hydrogen, chlorine, bromine, ,cyano or methylsulphonyl.

Even more preferred mixtures are those wherein D' is a group of formula (d) wherein R6 is R6, R7 is nitro F8 is hydrogen, Rg is Rg, R11 is R11' where R11' is hydrogen, methyl, alkyl (C1-2) carbonylamino, chloro- or bromoalkyl-(C, 2) carbonylamino, alkoxy (C1-2) carbonylamino or alkoxy-(C1.2) ethoxycarbonylamino, R12 is R12', where R12' is hydrogen, methoxy or ethoxy, R13 is R13a, wherein R13a is linear (C2-3) alkyl, allyl or linear (C2-3) alkyl monosubstituted by cyano, alkyl (C1-2) carbonyloxy, alkoxy (C1-2)- carbonyl or alkoxy (C1-2) carbonyloxy, F1,3 has one of the significances of R13a but where the optionally substituted (C2-3) alkyl may be linear or branched and R14 is alkyl-(C1-2) carbonyloxy or alkoxy (C1-2) carbonyloxy.

The preferred coupling component in the mixtures of the invention are those where R5 is hydrogen, F5 is methyl, R1 is R11, R2 is R12, R3 is R13, R3' is R13' and R4 is acyloxy especially alkyl (C1-2) carbonyloxy or alkoxy-(C1.2) carbonyloxy, especially those wherein R11 is F11, F12 is R12', R13 is R13a and R;3 has one of the significances R13a but where the optionally substituted alkyl may be linear or branched.

The following mixtures of the compounds of formula la and Ila are most preferred (i) those where D' is a radical (d) wherein R6 is chlorine or bromine, especially chlorine, R7 is nitro, F8, Rg, R11 and R2 are hydrogen, Ra3 and R;3 are cyanoethyl, R14 is alkyl (C1.2) carbonyloxy, especially acetoxy, R5 is methyl and R5' is hydrogen; (ii) those where D' is a radical (d) wherein R6, R8, R11 and R12 are hydrogen, R7 is nitro, Rg is cyano, R13 and Ra3 are cyanoethyl, R14 is alkyl (C1.2) carbonyloxy, especially acetoxy, F5 is methyl and R5' is hydrogen;; (iii) those wherein D' is a radical (d) wherein Re and R > , independently, are chlorine, or bromine, especially chlorine, R7 is nitro, R8, R11 and F12 are hydrogen, Ra3 and R,3 are cyanoethyl, R14 is alkyl (C1.2) carbonyloxy, especially acetoxy, F5 is methyl and R5 is hydrogen; (iv) a mixture of the following three dyes::

in which each Rg is chlorine, bromine or iodine, especially bromine, each R11 is alkyl (C1.2)- carbonylamino, especially acetylamino, each F12 is (C1.2) alkoxy, especially ethoxy and each R15 is (C1.2) alkyl, especially methyl, especially a mixture containing approximately 25% (i) 50% (2) and 25% (3).

The preferred method of preparing the mixtures according to the invention is to couple a diazotised amine with a mixture containing at least one compound of formula IV and at least one compound of formula V,

whereby at least 15 mol % of a compound of formula IV and at least 15 mol % of a compound of formula V is present.

Diazotization and coupling are carried out in accordance with known methods.

It will also be appreciated that the mixtures of the invention may also be obtained by admixing dyes of formula I and II together, preferably at the time of making the dyeing preparation.

The dyestuff mixtures according to the present invention are made up into dyeing preparations by known methods, for example by grinding in the presence of disperse agents and/or fillers, followed by drying. It will be appreciated that when the mixtures are obtained by admixing dyes of formula I and 11, the dyeing preparation can be made by admixing the already ground dyes of formula land II or by grinding the already mixed dyes of formula I and II.

The dyestuff preparations containing the mixtures according to the present invention are useful for dyeing or printing textiles comprising or consisting of synthetic, semi-synthetic, hydrophobic, high-molecular weight organic substrates from aqueous suspensions. Preferred substrates are textiles of linear, aromatic polyesters, cellulose 21/2 acetate, cellulose triacetate and synthetic polyamides. Dyeing, padding or printing may be carried out in accordance with known methods, for example as described in French Patent No.

1,445,371.

It is known that some disperse dyes exist in the thermoinstable form which causes problems in that they do not build-up into the fibre which leads to uneven dyeings having poor rubbing and wash fastness and which causes special difficulties for cross-wound spool dyeing. Such dyestuffs can be converted to the thermostable form by heat-treatment. However with the dyestuff preparations made with some of the mixtures according to the present invention the above-mentioned disadvantages do not occur and thus, the further conversion e.g. heat-treatment step is unnecessary.

Further, the mixtures of the invention have good dispersion stability, have good build-up power and give dyeings with good ru bbi ng- wet-fastn esses.

The following Examples further serve to illustrate the invention. In the Examples all parts are by weight, unless otherwise stated, and all temperatures are in degree centigrade.

Example 1 17.3 Parts 2-chloro-4-nitroaniline are stirred overnight in a mixture of 44 parts conc. hydrochloric acid and 100 parts water. 60 Parts ice are added thereto and a solution of 6.9 sodium nitrite in 25 parts water are added dropwise over a period of 30 minutes at 0 - 3 . After 21/2 hours when diazotization is completed some undissolved product is filtered off and a mixture of 11.6 parts N-(2'-acetoxyethyl)-N-(2'-cyanoethyl)aminobenzene, 12.3 parts N-(2'acetoxypropyl)-N-(2'-cyanoethyl)-aminobenzene and 20 parts acetic acid are added dropwise over a period of 45 minutes at 0 to 3 to the clear diazonium salt solution. The coupling reaction is completed by the addition of 50 parts sodium acetate.The precipitated dyestuff mixture is filtered, washed with 4000 parts water and dried.

The dyestuff mixture without conversion to the thermostable form may be up into a dyeing preparation in accordance with known methods with the addition of a dispersing agent, e.g. a commercially available ligninsulphonate which preparation has good dispersion stability.

Example 2 16.3 parts 2-cyano-4-nitroaniline are added at 5 to 10 to 100 parts (95%) sulphuric acid. At the same temperature, 32 parts (40%) nitrosylsulphuric are added dropwise and the whole is stirred for 3 hours. The so obtained diazonium salt solution is poured onto a mixture of 300 parts ice and 100 parts water. Some undissolved product is filtered off and a mixture of 11.6 parts N-(2'-acetoxyethyl)-N-(2'cyanoethyl)aminobenzene, 12.3 parts N-(2'-acetoxypropyl)-N-(2'-cyanoethyl)-aminobenzene and 30 parts acetic acid is added dropwise at 0 to 3 to the clear solution. After 3 hours the precipitated dyestuff mixture is filtered, washed free of acid and dried. Dyestuff preparations made therefrom without conversion have good dispersion stability.

Example 3 A mixture of 16.2 parts N-(2'acetoxyethyl)-N-(2'-cyanoethyl)aminobenzene, 7.4 parts N-(2'-acetoxypropyl) N-(2'-cyanoethyl)amino benzene and 30 parts acetic acid are added dropwise to the clear diazonium salt solution obtained as described in Example 2 at 0 to 3 . The precipitated dyestuff mixture is filtered and washed free from acid. The presscake is subsequently stirred in 300 parts water. The homogenous suspension is put in a steel autoclave and is stirred for 3 hours at 105 - 110 . After cooling and filtering, a thermostable dyestuff mixture is obtained which may be made up into useful dyestuff preparations.

Example 4 13.8 Parts 4-nitroaniline are dissolved in 80 parts water at 70 - 80" with the addition of 28 parts conc.

hydrochloric acid. The solution is cooled to 0 to 2" by adding 200 parts ice and diazotization is quickly carried out with a solution of 6.9 parts sodium nitrite in 14 parts water. Some solid product is filtered off and over a period of 60 minutes a mixture of 13.9 parts N-(2'-acetoxyethyl)-N-(2'-cyanoethyl)aminobenzene, 9.85 parts N-(2'-acetoxypropyl)-N-(2'cyanoethyl)aminobenzene and 20 parts acetic acid is added dropwise at 0 to 3 to the clear diazonium salt solution. After the addition of 40 parts sodium acetate coupling is complete and the precipitated dyestuff mixture is filtered, washed and dried.The mixture, without conversion, is made into a finely divided dyeing preparation with the addition of dispersing agent, which preparation gives orange dyeings on polyester fibres.

Example 5 At 0 to 30 a mixture of 18.6 parts N-(2'-acetoxy-ethyl)-N-(2'-cyanoethyl)aminobenzene, 4.9 parts N-(2'-acetoxypropyl)-N-(2'-cyanoethyl)aminobenzene and 20 parts acetic acid are added dropwise over a period of 45 minutes to the diazonium-salt solution prepared as described in Example 1. 50 Parts sodium acetate are added to complete the coupling reaction. The precipitated dye mixture is filtered, washed with 4000 parts water and dried in vacuo for at least 48 hours at 100-105".

After heat treatment to convert the mixture to the thermostable form the dye mixture is made up into an excellent finely dispersed dyestuff preparation.

Example 6 69 parts sodium nitrite are added portionwise to 1200 parts conc. sulphuric acid at 60-70 with energetic stirring. Stirring is continued for a further 10 minutes and the mixture is cooled to 30 whereupon 207 parts 2,6-dichloro-4-nitroaniline are added. Diazotization is complete after 3 hours. The yellow-brown solution is poured onto a mixture of 3400 ice and 2500 parts water. A mixture of 116 parts N-(2'-acetoxyethyl)-N-(2'cyanoethyl)aminobenzene, 123 parts N-(2'-acetoxypropyl)-N-(2'-cyanoethyl)aminobenzene and 200 parts acetic acid are added dropwise with stirring at 0 to 5 to the obtained aqueous diazonium-salt solution. The precipitated dye mixture is filtered, washed acid-free, dried and, without conversion to the thermostable forms is made up in accordance with known methods, with the addition of a ligninsulphonate into a fine dispersion. The preparation has very good dispersion stability combined with good build-up power on polyester material.

Example 7 A mixture of 46 parts N-(2'-acetoxyethyl)-N-(2'-cyanoethyl)aminobenzene, 197 parts N-(2'-acetoxypropyl) N-(2'-cyanoethyl)aminobenzene and 200 parts acetic acid are dropped into the diazonium salt solution of Example 6 at 0 to 5 . The precipitated dye is filtered and washed acid free. A dispersion stable dye mixture is obtained which gives satisfactory dyeings without conversion to the thermostable form.

Example 8 600 Parts water and 194 parts 1 -acetylamino-4-ethoxy-3-amino benzene are put in an autoclave which is rendered oxygen free by pasing nitrogen therethrough. The whole is heated to 55 and the amine is reacted for 2 hours with a mixture consisting of 52.8 parts ethyleneoxide and 69.6 parts propylene oxide whereupon the temperature rises to 62". The mixture is stirred for 6 hours at 60 and then cooled to 5 . Excess ethyleneand propyleneoxide are removed by means of a water jet pump and then passing nitrogen therethrough.

The autoclave is opened and the crystalline precipitated product is filtered, washed with a little cold water and dried in vacuo at 60".

148 Parts of the dried product are dissolved in 150 parts glacial acetic acid. At 80-90" over a period of 1 hour 122 parts acetic acid an hydride are added dropwise. The mixture is then heated to 110 and stirred for 3 hours at this temperature until there are no more traces of nonesterified material (tested by thin layer chromatography). The mixture of coupling components is cooled to room temperature.

With energetic stirring 31.1 parts sodium nitrite are added at 60 to 70 to 540 parts conc. sulphuric acid.

Stirring is continued for a further 10 minutes at 60", the mixture cooled to 1 and 117.9 parts 2-bromo-4,6-dinitroaniline are added thereto. Diazotization is complete after 3 hours. The diazonium solution is added to a mixture of all the coupling component obtained above, 450 parts glacial acetic acid, 3000 parts ice and 9 parts aminosulphonic acid at -5 to +20 over a period of 30 to 40 minutes. The dyestuff precipitates quickly and the solution is stirred at 0 to 2"C until no further diazo compound is detectable. The dye suspension is adjusted to pH 6 to 7 by the addition of 30% sodium hydroxide solution.Then the solution is heated to 85" over a period of an hour and is kept at this temperature for an hour followed by heating to 90" and stirred for a further hour whereby the dyestuff components convert to the thermostable form. The dye is then filtered, washed with 5000 parts hot water and dried in vacuo at 80 .

D Preparation ofDispersion In a flask, 78 parts of the dye mixture of Example 8 and 222 parts commercially available ligninsulphonate dispersing agent in 100 to 150 parts water are ground with 800 parts by volume silicia quartz beads for 6 hours (2000-2500 R.p.m.). The whole is diluted with 300 parts water and suction filtered. Any dyestuff and/or dispersing agent remaining on the beads is rinsed into the flask with a little water. The dispersion is adjusted to pH 6 to 6.5 with phosphoric acid and spray-dried (hot air 1300).

Example 9 Preparation of Dye A 232 Parts N-(2'-acetoxyethyl)-N-(2'-cyanoethyl)-aminobenzene and 200 parts acetic acid were poured into the diazonium salt solution produced as described in Example 6 at 0 to 5". The precipitated dye is filtered washed free of acid and dried.

Preparation ofDye B The diazonium salt solution of Example 6 is coupled with 246 parts N-(2'-acetoxypropyl)-N-(2'cyanoethyl)aminobenzene in 200 parts acetic acid. The dye is filtered, washed and dried.

Preparation ofDyeing Formulation 22.2 Parts dye A and 70.8 parts dye B are ground and dried with 207 ligninsulphonate as described above under D. The powdered product obtained has notable dispersion stability.

The mixtures given in the following Table may be prepared in accordance with the procedures of the foregoing Examples.

T A B L E

gx.

General Niol % a 1st Conponent 2nd Component 3rd Ca-p formula 2 Hol X : Elol Z j Pal 10 N - NgNliQHQH2COCHfCH2OCB3 X - H a 50 Br i.llCOCilj 50 2 .222 '3,3 X O na'ry-bloe Br '0IC0c'd3 Cl 2.10 1 I 'aOCOCE(3 st l X1- I I 11 !o2SX i H NSNzQd2CiiOCOCH3 :era.25 a(3:ea. 25 1 'Ca. brown l2'O: 0 2 3 3 '3,0'3,'3, 3'2 - H r 22 - 013 i 3 3 - 2, 3 I xc I 2 I I - I nor CHCEI'3'3 2 - H : 40 2 - 013 I 60 12 i32- 0101001 2 2 2 3 X ~ d 1 40 X - 3 1 60 i blue 01 QH3 CH2QiOCOQH3 2 l 3 ll I I I I I 13 lo SbX - N4Nz C3'2IH2C'S 2 2 H , l 1 50 2 - '3,3 50 i orange j 2 CH2CileCOCH2O G 5 I 1 3 1 3 . I . I 14 111. ,,17A31H313 3 { X - H , 30 3 - '3, . .',llr'-broo j 2 Cl C:'.2C:iOCO-C6H5 E .

Cl I I 33 - S4SdCH2C'dCOCH2QH20CH3 - QH3 | 45 W - bloa 15 1 2. 1 1 3 Ir 321010 3 3 I I .1 I I cU Cd Cd2COOCH3 S2 U H o',.35 2 3, X1 CH3 1 50 scarler Xz 2)1jT CHZCDOCH3 2 - H 33 - 31 - H 1i:-3100131 x H 50 1" 50 X -: 50 X PCI: 50 orange 17 33 N - 3k%3 0"3 - l l "3' C1 fl II 30 11 " 3' - H' 3'1 - 3'1 - H 25 033/N - 1W2c-'-!030103 ca.Z5 Xl CH31 1 Ica.50 yelloi-Srown c L 2-HI xz H , i , 2 .3.

"2 f . Nb /Ci2CHOCOCdzCd3 X - H : 1 103,1,35 3'i P H yellow-brown 171 o-/ai,cicacacii,Ca X.H : 25 I . CH3 Sa. 2j '3, 3 10 '2' '2 3 1 ,oa.25 XCizC:aCOCi2CY.3 X2 - H X2 ClI3, X2 3 tl C92Fii03CiilC7i3 0 303 " 0 3 - H 3'l - CO 7 - H 21 , CRC: ncocü3 1 X w Cü ' X1 - H,. 25 25 3'3, | 02NtS = Sg sca. 25 ta. 25 ,ca.5 riavy-blue Br S:oCOCi.3 2 " 3 2 | '2.' 3: 3' '0 IY\- , .

13 1031.A011103 - NiNzCHzC:iOCOaH3 H red - 103' 3'1 - H X 2 03H3 17A31,:1101H3 2 1 H ra. 25 3'3 - 1313 pa. 25 3 - CH3, red 2 3 '2 xl . ' 32 li Ofe.4N - N N-ON33 X - H i X1 "oa.25 ra,53 2'' soarlet XCR2CdOCOCH X - H 3' - CH, X " CH N5C0-16H5 5 X1 3 2 i 2 3, '2 3, 3'2 '3, N2CliOCCa3 X1 " I .

23 25 03300 NQN 25 1 Icy. 25 1 red 35 1O31,O0,1,0aI3 33 - H 33 - CII 3'3 - CH3' 3: 3 '10 .3

0 ( Ie lSt nd 2Did Component 3 Component No.l GEncrl Formul ~ I Hol Z Inol z ::1 Poiyssrer 24 1 fNgN X zCEfH2CN X - R | 2 z 131 d \OIZrJIOMC I -R ! M3i 55 i- red "(M3)2 i 1 r 23 - H0131310210131 X - R 1 50 X - CE3 50 | ~ red 02? 3 107103 (",-:oM20-CsRs 2 1 1 . I ~t sCE CC':OCOCE O-C 2 - H 50 2 - : - raby 0131313 ] I 10131 I ' I 0"- : Oy-S.---IFCYZCHZFI '3p 30 271 2' - H3 2 i 30 2 a G31 70 ri red he 'I 20 , I Cl I 27 I 'c,10 26 .a248 - 2 - H 55 2 - 131 I 5 - red ::hl 01S '3'1CIIO1SlH 131 CIn A 3, 223 I ,50 3' - 10 50 2S O N g;N x -x 23 X ~ : 50 X 1 G | 50 s~ reddish 02:: ,2CBOEOCI?2CRZCHfl: 3c, r"-OC IP 1011 S'.nCOC3 CdzC, ioXC,0 > 2CR2CHzCi 3 ' 2 2 3 30 I .0 2 2 1 30 ifCd210010103 X ~ ics.U : 2 - :cI5 X1-H: ca.50 NON. ,ea.25 1 r,a.50 bin,, 10 '3,01010 X - G t X2 - 10' 10, 2, 3 z 2 3 2 3 Cl 2 H I 10310010103 I 31 ltl 2 - 1313 :50 i sratiet 10 '3, Q Q' X - E 'Cig i 10 22 1 1 30 1 131 1 ' I X10, . i 0730 H - oa.25 1 taiG red 32 1 2 ; X e 'ta.25 zCrOCOCd2Cü3 2 Ci!zC4OCO d2CH3 22 w H X2 - OB3 1 10 2 3' 0 ICl 1 3' - H 2 - 131 2 - H 0 ;; g N e S$ S < Cd2r COCIt 3 R ' X - G X 1 i r 5C ! pail; n,,l',,, Fx C2CrOCOCH Z2 | 37 ~ Cl3 | X2 ' Ci3 1 brown Cl 34 O3HH - N f Nw Z 2 > | 2 - ü 50 X - Q3 i 50 - red I 102132?.6H5 103 30 '3, 3 '3 CS N - H 0 N/10?H010103 21 - H . 2 - ll rubg ra.25 N 3 N f no 1,a.23 . 1 3 ice.25 raby CI110103 3 X2 R 2 Xz - G3 Xz 2, 2 - I 2 2 103 3 3 0 807 OIH 36 1 02S4S ~ NgSHC;SCH2COOCH2aH3 X w E f 50 . ~ Dady sh 3.

iotlCOCH3 i E-| s blue 2 1 ISa,, 2 I 33 - - I , 33 ' aS soatlet 2 - H HQN/,,,CH71001C}CH210 2 - H 1 2 - 10 ca.25 103 10'10010103103 23 X2~ 1313 I I XZ-CH3 22 1 3E j O S 07H0H e HCH 2 2 X - H ' 70 X - CH3 : 30 I red I r o I

i General Forrula S't lanpanent 2nd Canpenet |3rd (3rd de on Hal 2' Piol Z . Nol Z | $ :'SaS 2 Polyester : 1. I 13' 3S 023 0 N - X - E z 55 X - 53 3' - 10 aOse 45 2 II8'JC."'9'3, 10 10 2Cdz 10 7 - 2 ; 3 x2 I I I I Ii 40 i ~ N.J H - N(ni2CB) X ~ H 1 60 X - aH3 9 40 1 ~ brown -. :60 I -j: 2 %1 2- 6 5 ,l . g xo 10 13' 1 1 41 | 02S&commat;s = No;:10201 3' - H 50 2 - aH3 50 i led b-dCOO 3 7, 2 18710710 3' X bSz H 2 X ~ R | 25 X - 131 75 31 02lts- -tp/CHIC"2 -. :IS i - I ~ / Irerlet icHzaluconr3 I 5101 H Z a 3 l l I 73 I( 3' 1 43 QS3-Q-bhfi/ C2ni3tOM3 | 2 - H z 50 x - aH3 50 . - scarlet b-d C0033 2 7 7 3 1 I 11 0103 10 I 2 - B JOCH31I:ZCEOCOiB XI-B25 44 02H0H - NXCR3 < 02C-OCOCH3 s X 'S ' 1 2911.25 s 911.50 ravy-blue 2 NSC0:32cH2cl 2 "2. ' 2 - t 2 10 2 - 10 2 gC02CH2C1 2' 7 3 I 2 I I 7 1 I 2 I 10 010 10 0103 1 3'i - H ' 3'i - :' 3'i - H 45 - ~ 2 2 a -10010131 25 ea.25 I. so SnowS 7 ea.25 3 i 25 S 2 107Ch,'0101313 27 ^ X2 - CH31 X2 - 102 I X2 22 I I Cl I 46 '3700 X R I h.CCE2alZCI X-8!XI X - are 70 i red j CH20I710,0I01313 I '.7 3' C1 ll i e N4Y - DI4N= 2 3 | X - H | 5 2 -- 15 - bna,,n I' I ::CCYJ I , 48 0756 - Nb zCllzCH2CS , 70 2=10 80 I - serle IHIOCH 19 " 3 ll 10010I5I I 3 2 '7, 3 I I I I I 2 2 3' - H I 65 2 - 10 35 40 1 OzS4N ? + I.ni X ~ H g 65 X ~ 10 3 35 t , yelia' I \""1FHococH,ac, , I beaI,S I I 3' 1 90 010 10 73 I 50 2 %''= 101010710 10 3' - I..H : 35 -Mg I 50 1 OzNA S K /2 .3:CdzC;;COCd2ad2CH3 2 3 N | 35 X aN3 55 .

1 1 N:!COOH3 2 o I - I I r"Oz 01113 I I - seny-bine 51 1 02N40N - NSh-OH2Cl!COCH3 x R H 50 2 CH3 - 103 | 5 02CH3 rtrCOol) l I '3 Cl I I H 10 10 I I /22 sz! c CH7I,60OCH(103)7 3' - 'S I 75 2 Z 103 | 85 a | - yellow Br sCH2Ci!OCOCRt I 2 l l ll brawls 20 I 2 I 80 2 ii H - 102 I-CRJ 1 20 - raby 2-H I tH2PIOCDCHZCH20CI!2-CI ilcocg IIi0Ip1H2C0201II7 t 20 1

ED. 1 central Par-si. I.e Coagponst Znd Co-pS.nt 3rd Capan.S ibid. an Nn. t 2 Cü2Cb Mol le : Howl Hol Z 'Sal 2 r.?l 2 polyester (CHiN0 O'1x -Cllj - 20 o:tnOf I I 5 (CH3)fiS 2 f X - H 60 X - 013 0 - ,11,,' 2 pcisnl- 3 5 2 2/513121alIH2 . I 55 OzXWN ~ N&commat;Z S > z-Ql'Ql X - H 50 xCH3! 50 B 50 a-sy-blue 3 Br 1 2 Cl 131 C'B1'I0C,' 1 a B X1- : 2 - H 56 i2CHOCOCE3 X R :ca.2S , ea.2S ca.5O I ruby 56 02B B - B I ; NHCOCH2Cü3 2w H Xz j E C X ~ 3' | X CR 'SNIOlS IN 2 2 2 3 a 2 3 I 5 Br - 1312112IN 57 oRO H - H N"" 3' - H t 75 X - 131 | 25 f I-I 2 CB2IS'01CC6B5 i 3 Application Example A Dyeing Preparation 11 93 Parts of Dyestuff A above are ground with 207 parts ligninsulphonate as described above under D.

j Dyeing Preparation 111 93 Parts dyestuff B above are ground with 207 parts ligninsulphonate as described above under D.

1000 Parts polyester material are pre-wetted for 5 minutes at 60 with 30 parts ammonium sulphate dissolved in 14 litres water and adjusted to pH5 with 85% formic acid. 31.6 Parts of dyeing preparation II and 8.4 parts dyeing preparation III dispersed in 1 litre water are added thereto. The dyebath is heated over 30 ) minutes to 1300 and dyeing is conducted for 60 minutes. The dyebath is cooled to 80 , the dyed substrate removed, rinsed and dried. A even, rubbing-fast yellow-brown dyeing is obtained.

Application Example B 3 Parts of the preparation D above are stirred in 4000 parts water at 60". With this dyebath 100 parts polyester fibre is dyed with the addition of 20 parts ortho-phenylphenol for 1 hour at 98". After cooling, rinsing, soaping and drying a navy-blue dyeing with good fastnesses is obtained.

Application Example C 7 Parts of the mixture of Example 1 are ground to a fine powder with 4 parts sodiumdinaphthylmethane sulphonate, 4 parts sodiumcetylsulphate and 5 parts anhydrous sodium sulphate in a ball mill for 48 hours.

1 Part of this dyeing preparation is pasted with a little water and the suspension is added to a dyebath containing 3 parts sodiumlaurylsulphate in 4000 parts water. 100 Parts scoured polyester (liquor to goods ratio 40:1) are added to the bath at 40 to 50 , 20 parts of a chlorobenzene are added, the bath is slowly heated to 100" and dyeing is carried out for 1 to 2 hours at 95-100". The even red dyeing which is washed, soaped, washed again and dried has good fastnesses.

In analogy to the above procedures the dyestuff mixtures of Examples 2 to 57 may be used to dye polyester fibres.

Claims

1. A mixture of disperse dyestuffs containing at least one compound of formula I,

and at least one compound of formula II

in which D, is a disperse dye diazo component radical, R1, is hydrogen, alkyl, alkoxy or acylamino, R2, is hydrogen, alkyl or alkoxy which is optionally mono-substituted by a substituent selected from halogen, cyano, acyl, acyloxy, hydroxyl, alkoxy, phenyl and phenoxy, F3, is hydrogen, alkenyl, chloro- or bromo-alkenyl, linear alkyl which is optionally substituted by up to two substituted selected from halogen, acyloxy, hydroxyl, and alkoxy or mono-substituted by a cyano, acyl, phenyl or phenoxy group, F3,, is hydrogen, alkenyl, chloro- or bromo alkenyl, linear or branched alkyl, which is optionally substituted by up to two substituents selected from halogen, acyloxy, hydroxyl, and alkoxy or mono-substituted by a cyano, acyl, phenyl or phenoxy group, R4, is a sulphur-free acyloxy or alkoxycarbonyl radical, one of F5 is R5' is hydrogen and the other is methyl, the D's R1's R2,s and F4,s being identical, any alkyl groups or moieties and any alkoxy groups in such dyestuffs contain 1 to 8 carbon atoms, any alkenyl groups 2 to 4 carbon atoms, and said mixture contains 15 to 85% compound of formula I and 85 to 15% compound of formula II.

2. A mixture according to Claim 1, in which D is a radical of the benzene series, benzothiazolyl, thiazolyl or thiophene series.

3. A mixture according to Claim 1 or Claim 2, in which D is thiophene-2-substituted by up to two nitro groups; benzothiazolyl-2 in which the benzene nucleus is substituted by up to two substituents selected from chlorine and nitro; or phenyl substituted in the para-position by nitro, alkylsulphonyl, aminosulphonyl, mono- or dialkyl-aminosulphonyl or phenylazo (which phenylazo is optionally substituted by up to three substituents selected from methyl, methoxy, chlorine, bromine and nitro) and optionally bearing up to two further substituents selected from halogen, nitro, cyano or alkylsulphonyl, any alkyl and alkoxy groups in said dyestuffs contain 1 to 4 carbon atoms.

4. A mixture according to any one of Claims 1 to 3, containing at least one compound of formula la

and at least one compound of formula Ila

in which D' is a radical of formula (a), (b), (c) or (d)

wnerein F6 is hydrogen, chlorine, bromine, iodine, nitro or cyano, F7 is nitro (C1 ,2)alkylsulphonyl, aminosulphonyl, mono- or di(C1.2)alkylaminosulphonyl or phenylazo in which the benzene ring is optionally substituted by up to three substituents selected from methyl methoxy, chlorine, bromine and nitro, F8 is hydrogen, chlorine or bromine, R9 is hydrogen, chlorine, bromine, lodine, cyano or (C1-2) alkylsulphonyl, with the proviso that one of R8 and R9 is hydrogen, R11 is hydrogen, methyl, methoxy, ethoxy, formylamino, alkyl (C1.4)carbonylamino, alkyl (C1.

2)carbonylamino monosubstituted by hydroxyl, chlorine, bromine, cyano, phenyl, (C1.3)alkoxy or phenoxy, alkoxy-(C1.4)carbonylamino, ethoxycarbonylamino monosubstituted by hydroxy, (C1.

3)alkoxy or (C12) alkoxyethoxy, benzoylamino or (C1.2)alkylsulphonylamino, R12 is hydrogen, methyl (C1 2)alkoxy, (C1.2)-alkoxyethoxy or (C1.2) alkoxy monosubstituted by chlorine, bromine, cyano or phenyl, R13 is hydrogen, linear (C1-4)alkyl, (C2-3)-alkenyl, linear (C2-3)alkyl mono-substituted by (C1-2)alkoxy, cyano, formyloxy, alkyl (C1-4) carbonyloxy, alkoxy(C1-3)carbonyl, benzoyloxy or alkoxy (C1-3)carbonyloxy, R13' has one of the significances of R13 but where the alkyl and substituted alkyl radicals are linear or branched, R14 is formyloxy, alkyl (C1.4)carbonyloxy, benzoyloxy, phenoxyacetoxy, alkoxy (C1-4)-carbonyloxy, alkoxy(C1-4)carbonyl, alkoxy (C1-2) ethoxycarbonyl, alkoxy (C1-2)ethoxycarbonyloxy, alkoxy-(C1 2)alkyl(C1.2) carbonyloxy, mono- or di (C1.4alkyl) aminocarbonyloxy or phenyl aminocarbonyloxy wherein the benzene nucleus is optionally substituted by up to two substituents selected from chlorine, bromine, methyl and methoxy, whereby in such mixture D', R11, R12, and R14 in the compound of formula la is identical with that of the compound of formula Ila.

5. A mixture according to Claim 4, in which D' is a group of formula (d).

6. A mixture according to Claim 4 or CLAIM 5/8, IN WHICH R6 is F6, where R6' is hydrogen, chlorine, bromine or nitro, R7 is nitro, F8 is hydrogen and R9 is R9' where R9'is hydrogen, chlorine, bromine, cyano or methylsulphonyl.

7. A mixture according to any one of Claims 4to 6, in which R11 is R11', where R11' is hydrogen, methyl, alkyl (C1-2) carbonylamino, chloro- or bromoalkyl-(C1-2)carbonylamino, alkoxy (C1-2) carbonylamino or alkoxy-(C1-2) ethoxycarbonylamino, R12 is R12, where R,2, where F12 is hydrogen, methoxy or ethoxy, F13 is R13a, wherein R13a is linear (C2-3) alkyl, allyl or linear (C2-3) alkyl monosubstituted by cyano, alkyl (C1-2) carbonyloxy, alkoxy (C1-2)-carbonyl or alkoxy (C1-2) carbonyloxy, R,3 has one of the significances of R13a but where the optionally substituted (C2-3) alkyl may be linear or branched and F14 is alkyl-(C1-2) carbonyloxy or alkoxy (C1-2) carbonyloxy.

8. A mixture according to any one of Claims 1 to 6, in which R5 is hydrogen and F5 is methyl, R1 is R11 R2 is R,2, R3 is R,3, R3' is 13' all as defined in Claim 4 and F4 is acyloxy.

9. A mixture according to Claim 8, in which F4 is alkyl (C1-2) carbonyloxy or alkoxy (C1-2) carbonyloxy.

10. A mixture according to Claim 8 or Claim 9 in which R11, R12, R13 and R,3 are as defined in Claim 7.

11. A mixture according to Claim 4, where D' is a radical (d) wherein F8 is chlorine or bromine, R7 is nitro, R8, R9, R11 and R12 are hydrogen, R13 and R13' are cyanoethyl, R14 is alkyl (C1-2) carbonyloxy, R5 is methyl and R; is hydrogen;

12. A mixture according to Claim 4, where D' is a radical (d) wherein R6, RB, F11 and R12 are hydrogen, R7 is nitro, R9 is cyano, R13 and R13' are cyanoethyl, R14 is alkyl (C1-2) carbonyloxy, R5 is methyl and R5' is hydrogen;

13. A mixture according to Claim 4, wherein D' is a radical (d) wherein F6 and R9, independently, are chlorine, or bromine, R7 is nitro, R8, F11 and R12 are hydrogen, R13 and R,3 are cyanoethyl, R14 is alkyl (C1.2) - carbonyloxy, Fs is methyl and F5 is hydrogen;

14. A mixture according to Claim 4, comprising the following three dyestuffs

in which each Rg is chlorine, bromine or iodine, especially bromine, each R11 is alkyl (C1.2)-carbonylamino, each R12 is (C1-2) alkoxy, and each R15 is (C1-2) alkyl.

15. A mixture containing 15 to 85% dyestuff of formula

and 85% to 15% dyestuff of formula

16. A mixture containing 15% to 85% dyestuff of formula

and 85 to 15% dyestuff of formula

17. A mixture containing 15 to 85% dyestuff of formula

and 85 to 15% dyestuff of formula

18. A mixture containing 15 to 85% dyestuff of formula

and 85to 15% dyestuff of formula

19. A mixture containing approximately 25% dyestuff of formula

approximately 50% dyestuff of formula

and approximately 25% dyestuff of formula

20.A process for the preparation of a mixture according to Claim 1, comprising, coupling a diazotized I amine with at least one compound of formula IV and at least one compound of formula V,

21. A process for the preparation of a mixture according to Claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 57.

22. A mixture of disperse dyestuffs whenever obtained by a process according to Claim 20 or Claim 21.

23. A process for dyeing or printing synthetic or semi-synthetic, hydrophobic, high-molecular weight organic textile substrates from aqueous suspension comprising employing a mixture according to any one of Claim 1 to 19 or 22 as dyeing agent.

24. A process for dyeing or printing synthetic or semi-synthetic, hydrophobic, high-molecular weight organic textile substrates substantially as hereinbefore described with reference to any one of Examples A to C.

25. Dyed or printed substrates whenever obtained by a process according to Claim 23 or 24.