GB2261439A

GB2261439A - Mixtures of disperse dyes

Info

Publication number: GB2261439A
Application number: GB9223700A
Authority: GB
Inventors: Beat Henzi
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1991-11-16
Filing date: 1992-11-12
Publication date: 1993-05-19
Anticipated expiration: 2012-11-12
Also published as: GB9223700D0; JPH06100793A; GB2261439B; FR2683822A1; IT1263025B; FR2683822B1; ITRM920823A1; ES2065237A1; DE4238231A1; ES2065237B1; CH684597A5; ITRM920823A0

Abstract

1. A mixture of disperse dyes comprising i) 25-85% by weight of a compound of formula I <IMAGE> in which R1 is phenyl-C1-3 alkyl or a group of formula H5C5-(OCH2CH2)n-, the phenyl nucleus unsubstituted or substituted by one or two groups selected from chloro, bromo, C1-2 alkyl and C1-6 alkoxy; R2 is C1-6 alkyl, C1-5 alkoxy-C2-3 alkyl hydroxy-C2-6 alkoxy-C2-3 alkyl or C1-4 alkoxy-C2-5 alkoxy-C2-4 alkyl and n is 1, 2 or 3; ii) 5 to 50% by weight of a compound of formula II <IMAGE> in which R is a group of formula a; to d> <IMAGE> in which R3 and R4 independently are C1-4alkyl; and R5 is C1-4alkyl or halogen; and iii) 0 to 35% by weight of a compound of formula III or IV <IMAGE> in which R6 is C1-6alkyl or phenyl C1-4alkyl R7 is phenylaminocarbonyl, the phenyl group of which is unsubstituted or substituted by 1 or 2 halogen groups (preferably CI), benzoyl substituted by C1-4 alkoxycarbonyl or para-cyclohexylphenyl; R8 has a significance of R7 independently of R7 or is a group of formula e <IMAGE> where R10 is C1-6alkyl or -(CH2)2-3-C6H5.u

Description

1 MIXTURES OF DISPERSE DYES The invention relates to mixtures of disperse

dyes.

According to the invention there is provided a mixture of disperse dyes comprising i) 25-85% by weight of a compound of formula 1 CH,1 M N 0 C", 01 R2 in which R, is phenyl-Cl-3 alkyl or a group of formula H5C6-(OCH2CH2)n-l the phenyl nucleus unsubstituted or substituted by one or two groups selected from chloro, bromo, Cl-2alkyl and C,-6alkoxy; R2 is C,6alkyl, Cl,',alkoxy-C2-3alkyl, hydroXY-C2-6alkoXY-C2-3alkyi or Cl4alkoxyC2-6alkoXY-C2-4alkyl and n is 1, 2 or 3; ii) 5 to 50% by weight of a compound of formula 11 R R3'N"1:a 0 k in which R is a groups of formula a) to d) R5 N- i N (a) (b) 2 - 1 -11 elo 1 H (c) 0 W).-NH (d) in which R3and R4 independently areCl-4alkyl; and R5 'S Cl-4alkyl or halogen; and iii) 0 to 35% by weight of a compound of formula Ill or W C C= Cl N NC \ (C,2-4alkylene)-0-% CH3 C CH3 CH3 CH3 / C= CH- N NC - \ ((:-,aikyleneyO-R7 CH3 (111) (IV) in which R. is C1,.alkyl or pheny1C1-4alkyl; R7 is phenylaminocarbonyl, the phenyl group of which is unsubstituted or substituted by 1 or 2 halogen groups (preferably Cl), benzoyl substituted by Cl-4alkoxycarbonyl or para-cyclohexylphenyl; R. has a significance of R7 independently of R7 or is a group of formula e -WCt-4ai"ne-CCK)r,2-3alkylene-N(Rjo CF+= ( r-Q- M CH3 1 3 where R10 'S Cl-6alkyl or -(CH2)2-,-C,H,.

The mixtures according to the invention have been found to produce very strong brilliant greenish-yellow dyeings on fibers and fibrous material of synthetic and semisynthetic high molecular hydrophobic organic compounds.

Preferably in a mixture according to the invention i) 45-75% by weight of a compound of formula 1 ii) 15-30% by weight of a compound of formula 11, and iii) 0-30% (preferably 15-25%) by weight of a compound formula Ill are present.

Further according to the invention there is provided a mixture in which component i) comprises two or more compounds of formula 1.

Preferably, in such a mixture in at least one compound of formula 1, the CO-O-Rl group is ortho to the azo group.

Preferably in component i) in all compounds of formula 1 the group -CO-ORl is ortho to the azo group.

Preferably in such a mixture if in one compound of formula 1, R, is a benzyi group then in at least 10% by weight of all compounds of formula 1 present R2 is alkoxyalkyi.

Preferably in such a mixture if in 10% by weight of one or more compounds of formula in the ortho 1 R, is phenoxyalky], the compounds of formula 1 have the group -CO-O-R, position to the azo group.

Preferably a compound of formula 1 is of formula la 4 0 CH (1 a) in which R,' is benzyl or phenoxyethyl; R2' is Cl-,alkyl or Cl-6alkoXY-C2-3alkyl (preferably n.butyl or C2-4alkoXY-C2-3alkyl).

The individual disperse dyes of formula I to IV are known or can be prepared from known compounds by known methods. Preparation of the mixtures according to the invention is carded our by mixing the individual dyes in the appropriate amounts. The dyes are usually ground very finely and mixed prior to dispersing. Usually dispersing agents can be used to prepare the dyestuff preparations. The working up of the dyestuff mixtures according to the invention into dyeing preparations can be carried out by known methods, for example by milling in the presence of dispersing agent or filler. The preparations can be dried under vacuum or in an atomizer. They may be used, when water is added,to dye, print or pad using long or short bath.

The compound or mixture of compounds of formula 1 can be prepared by i) diazotising an amine or mixture of amines of formula V - NH2 1 (V) ii) coupling the diazotized amine or amines of formula V with a compound or compounds of formula V1 i 3 M 1\ 0 CH R2 (V1) where the symbols are as defined above. Compounds of formula V and V] are known or may be made from known compounds by known methods. Diazotization and coupling can be carried out by know methods.

T 1 he dye mixtures according to the invention exhaust excellently from aqueous suspension onto textile material of synthetic or semisynthetic hydroplastic high molecular weight organic material. These mixtures are especially useful for-dying or printing textile material of linear, aromatic polyester, such as cellulose 2-1/2 acetate and cellulose triacetate. The mixtures are good for dyeing what is known as "micro fibers" as well as for thermotransfer printing.

Dyeing and printing can be carded out by known methods (e.g. according to British Patent 1,114,433 [=FP 1,445,371]).

The resulting dyeings have good to very good properties generally especially good light fastness, good thermofixation fastness, good sublimation fastness and good blistering fastness. A further advantage of the dyestuff mixtures is in their good build-up, high exhaustion and good rate of fixation and that a good spent liquor results.

It is also surprising that the fluorescence in the mixture of the cournarin dyestuffs of formula 11 is not extinguished when combined with all classes of blue dyestuff (e.g. azo anthraquinone and methine). This means that the resulting green combination show extraordinary brilliance.

6 Further according to the invention there is provided a mixture of disperse dyes of formula IC CH3 M H- N-N- 0 COM, OH (CH2)^ (1c) wherein R, signifies a benzyl or phenoXY-C2-4alkyi group which optionally bears on the benzene nucleus up to two substituents from Cl,alkyl, Cl-4alkoxy, chlorine or bromine, R2signifiesCl-4alkyl or Cl_.alkoxy., and m signifies 2 or 3, whereby in the mixture of dyestuffs in which R, is only optionally substituted benzyi, at least 10 percent by weight of one or several dyestuffs wherein R2 signifies alkoxy are present, while in the mixture with at least 10 percent by weight of a dyestuff wherein R, is optionally substituted phenoxyalkyl, any other dyestuffs of formula 1 may be present.

Preference is given to the dyestuff mixtures of formula 1, in which the benzene nucleus in R, is unsubstituted.

Still further according to the invention there is provided a disperse dyestuff mxiture, containing 25 to 85%, preferably 45 to 75% by weight of a dyestuff of the general formula IC wherein CH3 M - N-11--- >\ 0 N COOR, CH\ (CH2)A (lc) 7 R, signifies phenyl-Cl-3alkyl which is optionally substituted once in the nucleus by chlorine, Cl-2alkyl orCl-2alkoxy; or a group of formula H5C6-(- O-CH2-CHI, R2 signifies hydrogen, Cl-4alkyl, Cl-6alkoxy, hydroXY-C2- 3alkoxy orCl-4alkoxy, and m and n, independently of one another, signify 1, 2 or 3, 50 to 50% preferably 15 to 30% by weight of a dyestuff of formula 11 R F'N"' 0 k wherein R signifies R5 1 (a) 1 X0 1 (c) 0 W)-- NH N-N (b) (d) R4signifyCl-4alkyl, preferably ethyl and R. signifiesCl-4alkyl or a halogen atom, preferably a chlorine atom, and 0 to 35%, preferably 15 to 25% by weight of a dyestuff of formula Ilia or 1Va 8 NC C==CH- N NC (C,-,alkylene)4>R7 CH3 CH3 CH3 N CH3 C=CH N - X (q M 12 CH3 wherein (Ct-,aikMna)-C)-R, R. signifies Cl-6alkyl or phenyl-Cl-2a[kyi, (]]]a) ([Va) R7signifies phenylaminocarbonyl which is optionally substituted in the nucleus by one or two halogen atoms, preferably chlorine; benzoyl which is optionally substituted by C, alkoxycarbonyl; paracyclohexylphenyl, or only in formula Ill a group of formula -CO-C2-4alkylene-CO-O-C2-3alkylene-N(C1-6alkyi) CH--CM CH3 Especially preferred dyes of formula 1 that can be used in mixtures according to the invention are of formula 1' 3 M 11-9 N--N- \ N 0 MOR, CH R2' in which the symbols are defined in Table 1 below.

9 TABLE 1

Dye # R, Substitution R2' position 1 H.C.-O-CH2CH2- 2'-C4Hd-C3H,-0-C4H,-n (11:1) 2 HA-CH12- Z- -(CHI-OC2H.

3 HA-0-CH12-CH2- Z- -C,,H7/C4H,-n/-C,H6-OC4H,-n (11:12) 4 do. Z- -C41H.-n HA-CH2- Z- do.

6 do. 3'- do.

7 H5C6-OCA- 3'- -CHl 8 do. 3'- -C21HI r> 9 do. 3-' -C,1H17-n H.C6-OC2H14"O-C2H14- X- -CH1,1 Especially preferred dyes of formula 11 that can be used in mixtures according to the invention are of formula H' F /a 0 N(C.2H5 in which R5 is as defined in Table 2 below.

(1 r) TABLE 2

Dye # 11 R5 C, 12 R5= N-N C8 H.5 13 R5 o 14 R5 0 M-kNH Especially preferred dyes of formula llIthat can be used in mixtures according to the invention are of formula Ill' in which the symbols are as defined in Table 3 below in dyes 15-19 11 N CI+ % C= N 1 \ CH2CH2)"0"R7 M CH3 Dye 20 is a preferred compound of formula IV.

TABLE 3

Dye # R6 R7 -C41-19 -C-N cl 11 0 cl 16 -C5,Hs COCCH3 0 17 -CH2CH2C61-15 -C-NH-QC1 11 0 cl 18 -C21-15 1 1 12 19 do. p--0C -- K- C.2H, tH4 - Cr (-CHA4 11 0 0 O-CH3 CHT- M M do. CH3 CH, 3 CH3 M CH2CH20mWNHr-tH, CH3 In the following Examples all parts and percentages are by weight, all temperatures are in C. Any part by volume is based on the volume of one part by weight of water. The dyes referred to in the Examples are dyes 120 defined above Example 1

16.5 parts of dyestuff no. 3 of formula 000CH20H2CCiHS CH3 M - -U-N-\ N 0 CH \ (CH2-R2' where R2"where RJ is H/CH3/OC4H. n(1:1:2) 5.8 parts of dyestuff no. 11 of formula 13 0 1 0 N(CH,)2 cl and 7.7 parts of dyestuff no. 15 of formula CN, O.C AH9 N M CH3 cl CH2CH2O.CX>NH---- Cl are mixed mechanically in presscake form (100% dyestuff base). From the resultant mxiture, an ultra-disperse dyestuff misture is produced inventionally, by means of aqueous grinding with 70 parts of a dispersing agent based on lignin sulphonate. The mixture has an average particle size of lim and a dilution ration of 3.0:10.

8.0 parts of this dye preparation are introduced to 2000 parts of dimineralized water at WC, containing 40 parts of ammonium sulphate. The pH value of the dye bath is adjusted to 5 with 85% formic acid. 100 parts of cleaned polyester fiber favric are placed in this dye bath at ca. WC, the equipment is closed, heated over 40 minutes to 130', and dyeing continues for 60 minutes at this temperature. After cooling to 40'C, the polymester fiber fabric is removed from the dye bath, rinsed soaped and purified by reduction in the usual way using sodium hydrosulphite. A clear greenish-yellow dyeing with very good all-round fastness is obtained.

Example 2

By replacing dyestuff no. 3 in Example 1 with 18 parts of dyestuff no. 7 of formula 14 3 M 0-N-N- \ 0 m H5CCCH2CH20M CH CH3 and otherwise operating as described in Example 1, a clear greenish- yellow dyeing with very good all-round fastness is similarly obtained.

Equally good results can be obtained by mixing the dyestuffs of types (P) to (HP) of 1 ables 1, 2 and 3, as listed in the following Table 4, analogously to the preceding Examples.

TABLE 4

Ex. # Dye l' Dye If' Dye 111' Nuance of (no., parts) (no., parts) (no., parts) PES dyeing 3 No. 3, 19.5 No. 11, 7.5 No. 15, 3.0 greenish-yellow 4 No. 1, 17.0 No. 11, 6.0 No. 15, 7.0 91 No. 2, 16.0 No. 11, 6.5 No. 15, 7.5 6 No. 6, 16.5 No. 11, 6.0 No. 15, 7.5 7 No. 8, 16.5 No. 11, 6.0 No. 15, 7.5 8 No. 9, 17.0 No. 11, 6.0 No. 15, 7.0 9 No. 10, 17.5 No. 11, 6.5 No. 15, 6.0 No. 3, 18.5 No. 11, 7.0 No. 16 4.5 11 No. 7, 18.5 No. 11, 7.0 No. 16,4.5 12 No. 3, 18.5 No. 11, 7.0 No. 17,4.5 Ex. # Dye 1' Dye W Dye Ill' Nuance of (no., parts) (no., parts) (no., parts) PES dyeing 13 No. 7, 18.5 No. 11, 7.0 No. 17, 4.5 greenish-yellow 14 No. 3, 17.5 No. 11, 7.0 No. 18, 5.5 If No. 7, 17.5 No. 11, 7.0 No. 18, 5.5 91 16 No. 3, 18.5 No. 11 7.0 No. 19, 4.5 If 17 No. 7, 18.5 No., 11, 7.0 No. 19, 4.5 11 18 No. 3, 17.0 No. 11, 6.5 No. 20, 6.5 fe 19 No. 7, 17.0 No. 11, 6.5 No. 20, 6.5 If No. 7, 18.5 No. 11, 7.0 No. 21, 4.5 If 21 No. 3, 17.0 No. 12, 5.5 No. 15: 7.5 If 22 No. 7, 17.0 No. 12, 5.5 No. 15, 7.5 23 No. 3, 17,0 No. 13, 5.5 No. 15, 7.5 24 No. 7, 17.0 No. 13, 5.5 No. 15, 7.5 No. 3, 17.0 No. 14, 5.5 No. 15, 7.5 26 No. 7, 17.0 No. 14, 5.5 No. 15, 7.5 27 No. 3, 22.5 No. 11, 7.5 28 No. 3, 24.0 No. 11, 6.0 29 No. 7, 24.0 No. 11, 6.0 No. 7, 24.0 No. 11, 6.0 31 No. 7, 12.0 No. 11, 6.0 No. 3, 12.0 16 Ex. # Dye l' Dye ll' Dye Ill' Nuance of (no., parts) (no., parts) (no., parts) PES dyeing 32 No. 7, 20.0 No. 13, 5.0 No. 17, 5.0 91 33 No. 7, 20.0 No. 12, 5.0 No. 17, 5.0 99 34 No. 1, 9.0 No. 11, 6.5 No. 15, 5.0 1% No. 2, 9.0 No. 3, 16.0 No. 11, 10.0 No. 15, 4.0 It 36 No. 7, 16.0 No. 11, 10.0 No. 15, 4.0 91 Example 37

26.5 parts of anthranilic acid- P-phenoxyethyl ester (97%) are dissolved clearly in 70 parts of glacial acetic acid of 45', and mixed with 31 parts of hydrochloric acid (36.5%) and 200 parts of ice water; the resulting suspension is diazotised as usual at 0-5 with 7.2 parts of 5N sodium nitrite. After breaking down the excess nitrous acid with aminosulphonic acid, the filtered diazonium salt solution is added at 5- 10 with good stirring at pH 4-5 to a solution containing 11.0 parts of the coupling component of formula 37a and 13.9 parts of the coupling component of formula 37b 3 M 0 N OH \ (CH2)3-CM3 (37a) CH. M 0 N 0H \ (CHI-GC4H.-n (37b) parts of glacial acetic acid and 400 parts of ice water. The pH value is maintained constantly in the range 4-5 by adding caustic soda solution (30%). The resultant yellow 17 suspension is filtered off, washed until free from acid with 1000 parts of water of 50', and the dyestuff is vacuum-dried at 40. The dyestuff mixture may be further purified by recrystallization e.g. from cellosolve as the solvent.

In this way, a dyestuff mixture of formula 37c OCH2CH2O.C.H.

m CH3 CN 1 0\- N"- >\ 0 N 0H \ ((H2)3-R2"1 (37c) where R2"' is -CH3/oC,Hgn (-1:1) is obtained. It dyes polyester fibres in a greenish-yellow shade with very good all-round fastness.

Mixtures of dyes of formula 1 that can be used in the invention are of formula Ia' 1 1 6 5 % 4 rr,H2C>4' ' 31 RS qH3 M =0 N \ _R, CH \ (CH2)n'r% (]a') 18 in which the symbols are defined in Table 5 below, wherein R. signifies hydrogen in all cases, with the exception of the l st dyestuff of example 51, in which R5 is methyl in 5'-position.

These dyestuff mixtures may be produced analogously to the method given in example 1, but may also be produced equally well by subsequently mixing the individual components instead of using a mixed coupling process.

TABLE 5

Ex. No. 192' % R4 m)'max. (nm) (DMF) 38 -OC3H7-n 50 H 3 431 -OC2H5 50 H 3 39 -OC3H7-n 50 H 3 431 -OC3H7-i 50 H 3 -OC4H.-n 50 H 3 431 -OC4H9-i 50 H 3 41 -OC2H5 35 H 3 431 -OC3H7-n 30 H 3 OC4H.-n 35 H 3 42 -OC,Hg-n 65 H 3 431 -OC,H13-n 35 H 3 19 Ex. No. R2' % R4 m (n m) (DMF) 43 -OC2H5 40 H 3 431 -OC4H9-n 40 H 3 -CH3 20 H 3 44 -OC3H7-n 50 H 3 431 -OC4H.-n 50 H 3 -OC2H5 40 H 3 431 -OC4H.-n 40 H 3 -OC4H9-i 20 H 3 46 -OC2H5 40 H 3 431 -OC3H7-n 10 H 3 -OC4H.-n 40 H 3 -OC4H9-i 10 H 3 47 -OC2H5 50 H 2 431 -OC4H.-n 50 H 2 48 -OC2H5 30 -CH3(4') 3 431 -OC4H.-n 70 H 3 49 -OC2H5 30 -CI(4') 3 431 -Oc4H.-n 70 H 3 -OC2H5 30 -OCH3(4') 3 431 -OC4H.-n 70 H 3 -OC2H5 20 -CH3(2') 3 431 -OC4H.-n 80 H 3 Ex. No. R2' % R4 m;ma, (n m) (DMF) 52 -OC2H5 25 H 3 431 -OC,H,-n 25 H 3 -CH3 50 H 3 53 -OC4H9-n 50 H 3 431 -CH3 50 H 3 54 -OC4H9-n 50 H 2 431 -CH3 25 H 2 -CH3 25 H 3 'OC2H5 25 H 3 431 -OC,H.-n 25 H 3 -CH3 25 H 2 -CH3 25 H 3 56 -OCH3 25 H 3 431 -OC2H5 25 H 3 -CH3 50 H 3 Example 57

24.8 parts of anthranilic acid benzyiester (98%) are dissolved clearly in 100 parts of glacial acetic acid of 45, and mixed with 35 parts of hydrochloric acid (36.5%) and 150 parts of ice water. The resultant suspension is diazotised at 0-5 with 7.2 parts of 5N sodium nitrite. After breaking down the excess nitrous acid with arninosulphonic acid, the filtered diazonium salt solution is added with stirring at pH 4-5 at 5-10 to a solution containing 22.5 parts of the coupling component of formula 57a and 2.8 parts of the coupling component of formula 57b 21 (57a) CH3 M 0 N OH \ (CH2-OCHS CH3 M 0 N CH \ (CH2)3'0P4H9 (57b) parts of glacial acetic acid and 400 parts of ice water. The pH is maintained constantly in the range 4-5 by adding caustic soda solution (30%). The resultant yellow suspension is filtered off, washed until free from acid with 1000 parts of water of 50', and the dyestuff is vacuum-dried at 40'. The dyestuff mixture may be further purified by recrystallization e.g. from cellosolve as the solvent.

In this way, a dyestuff mixture of formula 57c OCH (:Hs co CHS M C5-N-11 0 N OH (CH2)3"R2 (57c) 22 (where R2' is OC,H5/OC4H,n -9:1) is obtained. It dyes polyester fibres in a greenish-yellow shade with very good all-round fastness.

The following Table 6 gives further dyestuff mixtures. They correspond to formula Ia", 8 5 F OCH2-Q41 2 3 CH3. M N-N 0 N OH (CH.)m-R2 the variables of which are listed in Table 6.

(1a") Dyestuff mixtures may be produced, analogously to the method given in Example 37, by subsequently mixing well the individual components of formula W' 23 TABLE6

Ex. No. R2' % R4 m kmax (nm) (DMF) 58 -OC2H5 70 H 3 432 -OC,H.-n 30 H 3 59 -OC,H7-n 50 H 3 432 -OC3H7-i 50 H 3 -0^ k4H.-n 50 H 3 432 -OC4H9-i 50 H 3 61 -OC2H5 35 H 3 432 -OC3H7-n 25 H 3 OC4H9-n 40 H 3 62 -OC4Hqwn 65 H 3 432 -OC6Hl3-n 35 H 3 63 -OC2Hs 40 H 3 432 -OC4H.-n 40 H 3 -CH3 20 H 3 64-OC2H5 30 H 3 432 -OC4H.-n 30 H 3 -CH3 20 H 3 -C3H7-n 20 H 3 -OC2H5 40 H 3 432 -OC4H9-i 20 H 3 -OC4H9-n 40 H 3 24 Ex. No. R2' % R4 m,a,. (nrn) (DMF) 66 -OC2H5 40 H 3 432 -OC,H7-n 10 H 3 -OC4H9-i 40 H 3 -OC4H.-n 10 H 3 67 -OC2H5 50 H 2 432 -OC,Hg-n 50 H 2 68 -OC2H5 85 4'-CH3 3 432 -OC4H9-n 15 do. 3 69 -OC2H5 85 4'-Cl 3 432 -OC,Hg-n 15 do. 3 -OC2H5 90 H 3 432 -OCH3 10 H 3 71 50 H 3 432 -CH3 50 H 3 72 -OC2H.5 70 H 3 432 -CH3 30 H 3 73 -OC2H.5 60 H 3 432 -CH3 20 H 2 -CH3 20 H 3 74 -OCH3 50 H 3 432 -OC2H5 50 H 3 20 H 3 432 -OC2H5 80 H 3 1 1 1 APPLICATI1ON EXAMPLE The dyestuff mixture obtained according to example 1 is converted by sand- grinding in the presence of dispersing agents, e.g. commercial lignin sulphonate, and subsequent pulverization, into an ultra-disperse dye preparation with an average particle size of 1 ptm and a dilution ratio of 3.5:10.

12 parts of this preparation are dispersed with 1000 parts of water and added at 60' to the circulating bath (13,000 parts, containing 30 parts of ammonium sulphate and 0.3 parts of formic acid as a buffer and optionally a carrier/levelling agent combination). The pre-cleaned, compressed cross-wound spool (1000 parts of polyester yarn on a plastic sleeve) is introduced, the dyeing autoclave is closed and heated to 130 in 35 minutes. After 90 minutes, there is cooling to W, the exhausted liquor is drained and the dyed substrate is washed thoroughly with cold water and purified in the usual way by reduction. The substrate is then centrifuged and dried. A level, clear greenish-yellow dyeing is obtained.

The application example can be repeated, using instead of the mixture of Example 1 any one of the mixtures of Examples 2 to 75.

26

Claims

1 A mixture of disperse dyes comprising i) 25-85% by weight of a compound of formula 1 (M3 M F[- N-N-- >\0 N COOR, OH R2 in which (1) R, is phenyl-Cl_3alkyl or a group of formula H5C6-(OCH2CHI-1 the phenyl nucleus unsubstituted or substituted by one or two groups selected from chloro, bromo, Cl-2alkyl and Cl_.alkoxy; R2'S C,,,alky], Cl-6alkoXY-C2-3alky], hydroXY-C2-6a[koXY-C2-3alkyl orCl- 4alkoxyC2-6alkoXY-C2-4alkyl and n is 1,

2 or 3; ii) 5 to 50% by weight of a compound of formula 11 R3,r,,,Cl R 0 1 R4 in which R is a groups of formula a) to d) R5 N-N (a) ",i 1 1-ZZ ""b 1 (b) 27 1 A 0 4 (c) 0 W).'NH 1-6 in which R 3and R4 independently areCl-4alkyl; and R, 'S Cl-4alkyl or halogen; and iii) 0 to 35% by weight of a compound of formula Ill or IV C 1% C= CH- N Nd \ (C2-4alkylene)-0-1% CH3 CH3 CH3 C CH3 C= C14 N 1 - \ (q NC (C,2-,aikylene7 CH3 (1v) in which R6 'S C1-6alkyl or pheny1C1-4alkyl R7is phenylaminocarbonyl, the phenyl group of which is unsubstituted or substituted by 1 or 2 halogen groups, benzoyl substituted by Cl-4alkoxycarbonyl or paracyclohexylphenyl; R. has a significance of R7 independently of R7or is a group of formula e 28 -X)-C.2-4ai"ne-(nADC-3a]kylens-N(R,. I-Q- CH-- ( CH3 where R10 is Cl_.alkyl or -(CH2)2-3-C6H,, 2. A mixture according to Claim 1 in which i) 45-75% by weight of a compound of formula 1 ii) 15-30% by weight of a compound of formula 11, and iii) 0-30% by weight of a compound formula Ill are present.

3.

M (e) A mixture according to Claim 1 or Claim 2 in which the compound of formula 1 is of formula la in which CGO-Rl CH3 M C: - bt---N- \O N OH F' R, is benzy] or phenoxyethy]; R2' is Cl-,alkyl orCl-6alkoXY-C2-3alkyl

4. A mixture of dyes of formula lc CH3 M H- N 0 N 0DOR, \ (CH2)M5R2 wherein (1a) 00 R, signifies a benzyl or phenoXY-C2-4alkyl group which optionally bears on the benzene 1 29 nucleus up to two substituents from R2signifiesCl-4alkyl orCl-6alkoxy, m signifies 2 or 3, whereby in the mixture of dyestuffs in which R, is only optionally substituted benzyi, at least 10 percent by weight of one or several dyestuffs wherein R 2signifies alkoxy are present, while in the mixture with at least 10 percent by weight of a dyestuff wherein R, is optionally substituted phenoxyalkyl, any other dyestuffs of formula 1 may be present.

Cl-4alkyl, c -4aikoxy, chlorine or bromine,

5. A disperse dyestuff mixture containing 25 to 85% by weight of a dyestuff of the general formula]c CH3 M H- N N 0 N OOCR, OH (CH,,)^ wherein R, signifies phenyl-Cl-3alkyl which is optionally substituted once in the nucleus by chlorine, Cl-2alkyl orCl-2alkoxy; or a groups of formula H5C6+0-CH2-CHI, R2 signifies hydrogen, C,,alkyl, C1.6alkoxy, hydroXY-C2-3alkoxy orCl-4alkoxy, and m and n, independently of one another, signify 1, 2 or 3, 50 to 50% by weight of a dyestuff of formula 11 R 0 wherein R signifies R5 N-N "A i 1-Z S,o i 11:; (a) 1 0 1 H (c) (b) 0 W).-NH 1'

6 (d) R4signifyCl-4alkyl, preferably ethyl and R. signifiesCl-4alkyl or a halogen atom, preferably a chlorine atom, and 0 to 35% by weight of a dyestuff of formula Ilia or 1Va C cc NC \ (C-4alkylene)-0-% W3 CH3 3 CN CH3 C=CFt N M (C,2-,alkylenla)'GR7 wherein R. signifies C,-.alkyl or phenyl-Cl-2alkyl, R7 signifies phenylaminocarbonyl which is optionally substituted in the nucleus by one or two halogen atoms, preferably chlorine; benzoyl which is optionally substituted by C1-4 alkoxycarbonyl; paracyclohexylphenyl, or only in formula Ill a group of formula (Ilia) (lVa) 31 -CO-C2-4alkylene-CO-O-C2-3alkyiene-N(C1-6alkyi) CWC(M)2 6. A disperse dye mixture substantially as herein described with reference to any one of the Example5.

7.

A process for dyeing a substrate comprising applying to the substrate a mixture according to any one of Claims 1 to 6.

8. A substrate to which a mixture according to any one Claimsl to 6 has been applied.

9. A process substantially as herein described with reference to the Application Example.