FR2683822A1 - NEW MIXTURES OF DISPERSION DYES. - Google Patents

Abstract

The subject of the invention is a mixture of dispersion dyes comprising i) from 25 to 85% by weight of a compound of formula I (CF DRAWING IN BOPI) ii) from 5 to 50% by weight of a compound of formula II (CF DRAWING IN BOPI) and iii) from 0 to 35% by weight of a compound of formula III or IV

Description

The present invention aims to

  new dispersion dye mixtures.

  The invention particularly relates to a dispersion dye mixture comprising i) from 25 to 85% by weight of a compound of formula I

CH 3 CN

N O

COO, CH R 2

GOCR 1 O

  wherein R 1 is a C 1 -C 3 (phenyl) -alkyl group or a group of the formula H 5 -C 6 (OCH 2 -CH 2) n wherein the benzene ring is unsubstituted or has one or two substituents selected among chlorine, bromine, C 1 -C 2 alkyl and C 1 -C 6 alkoxy, R 2 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl; C 2 -C 3, (hydroxyalkoxy)

  C 2 -C 6) -C 2 -C 3 alkyl or (C 1 -C 4) alkoxy -

  (C 2 -C 6) alkoxy-C 2 -C 4 alkyl and n is 1, 2 or 3; ii) from 5 to 50% by weight of a compound of formula II R 4 in which R is a group corresponding to one of the following formulas a) to d)

F R N-N

  (a) (b) o Pago N H (C) (d) R 3 and R 4 independently denote a C 1 -C 4 alkyl group and R 5 is a halogen or a C 1 -C 4 alkyl group; and iii) from 0 to 35% by weight of a compound of formula III or IV NC

N (III)

  NC NC (C 2 -C 4 alkylene) -O-R 8 CH 3 CH 3

MC CH 3

-C (IV)

  Wherein R 6 is C 1 -C 6 alkyl or (phenyl) C 1 -C 4 alkyl; R 7 is phenylaminocarbonyl, the phenyl group is phenylaminocarbonyl; is unsubstituted or substituted by 1 or 2 halogens (preferably Cl), benzoyl group substituted with (C 1 -C 4) alkoxycarbonyl or para-cyclohexylphenyl, R 8 has the meaning of R 7 independently of R 7, or signifies a group of formula e -CO- (C 2 -C 4 alkyl) -CO-O (CC-C alkylene) -N (Rit) CH CN CH 3 R 10 denotes an alkyl group in C 1-C 6 or

- (CH 2) 2 _ 3-C 6 H 5 -

  The mixtures of the invention give very bright greenish yellow dyes on fibers and fibrous materials made of

  hydrophobic, synthetic or semi-organic

  synthetic, high molecular weight.

  Preferred mixtures of the invention contain i) from 45 to 75% by weight of a compound of formula I ii) from 15 to 30% by weight of a compound of formula II, and iii) from 0 to 30% by weight ( preferably from 15 to 25% by weight

of a compound of formula III.

  The invention also relates to such mixtures in which component i) comprises two or more compounds of formula I It is preferred that in such a mixture at least one compound of formula I has the group -CO-OR 1 in the ortho position relative to Preferably, all the compounds of formula I of component i) comprise the group

  -CO-O-R 1 in ortho position relative to the azo group.

  Preferably, in such a mixture when R 1 is a benzyl group in a compound of formula I, then in at least 10% by weight of all the compounds of

  Formula I present, R 2 is an alkoxyalkyl group.

  Preferably, in such a mixture when R 1 is phenoxyalkyl in at least 10% by weight of one or more compounds of formula I, the compounds of formula I have the group -CO-O-R 1 located

  in ortho position relative to the azo group.

  The compounds of formula I preferably correspond to formula Ia

COR 1 'CH 3 CN

  Wherein R 1 'is benzyl or phenoxyethyl, R 2' is C 1 -C 4 alkyl or C 1 -C 6 alkoxy C 2 -C alkyl 3 l preferably a group

  n-butyl or (C 2 -C 4) alkoxy-C 2 -C 3 alkyl.

  The individual dispersion dyes of formula I to IV are known or can be prepared

  according to known methods from known compounds.

  The mixtures of the invention can be obtained by simple mixing of the individual dyes in appropriate amounts. The dyes are usually ground very finely and mixed before dispersion.

  prepare the dyeing preparations

  The dye mixtures of the invention can be prepared in dyeing preparations according to known methods, for example by grinding in the presence of a dispersing agent and / or fillers, followed by

  optionally drying under vacuum or by atomisa-

  With these dyeing preparations one can, after addition of a quantity of water more or less important,

  dye, print or pad, in long or short bath.

  The compound or mixture of compounds of formula I can be prepared by diazotating an amine or a mixture of amines of formula V

/ \ NH?

  (V) oo 1 and coupling with one or more compounds of formula VI

CH, CN

o (VI)

OH R 2

  o The symbols are as defined above.

  The compounds of formula V and VI are known or can be prepared according to known methods from known compounds. Diazotation and copulation can be carried out according to known methods. The dye mixtures of the invention are in aqueous suspension on textile materials made of high molecular weight synthetic or semisynthetic hydrophobic organic materials. These mixtures are especially suitable for dyeing or printing textile materials made of polyesters. aromatics as well as cellulose hemipentacetate or cellulose triacetate. The mixtures are suitable for

  dyeing of fibers known as "micro-

  fibers "as well as for transfer printing.

  Dyeing and printing can be performed according to known methods, for example

  as described in French Patent No. 1,445,371.

  The resulting dyes have good to very good general fastnesses, especially to light, heat setting, sublimation and

  Another advantage of color blends

  The ingredients of the invention are their good dyeing power, their high rate and rate of exhaustion or fixation and the fact that a good bath exhaustion is obtained.

  It is also surprising that the fluorescent

  Coumarin dyes of Formula II present in the mixture do not quench when combined with blue dyes of all classes (e.g., azo anthraquinone and methine dyes), which means that the combination of

  resulting green has an extraordinary brilliance.

  The invention also relates to a mixture of dispersion dyes of formula Ic with NXN N-> O (fc) c C Oe, OH (CH 2) m R 2 in which R 1 denotes a benzyl or (phenoxy) C-alkyl group 2-C 4 wherein the benzene ring optionally has one or two substituents selected from chlorine, bromine and C 1 -C 4 alkyl and C 1 -C 4 alkoxy, R 2 denotes a C 1 alkyl group -C 4 or C 1 -C 6 alkoxy and m is 2 or 3, at least 10% by weight of one or more dyes where R 2 is an alkoxy group being present in this dye mixture when R 1 is a benzyl group optionally substituted, while any other dye of formula I may be present in this mixture when it contains at least 10% by weight of a dye o R 1 means a group

  optionally substituted phenoxyalkyl.

  Preferred dye mixtures of formula I are those consisting of compounds of formula I wherein the benzene ring present in R 1 is unsubstituted. The invention also relates to a mixture of dispersion dyes containing from 25 to 85% (preferably from 45 to 75%) by weight of a dye corresponding to the general formula Ic

CH 3 ON

  Wherein R 1 is (C 1 -C 3) -alkyl (phenyl) -alkyl optionally monosubstituted in the benzene ring by chlorine or C 1 -C 2 -alkyl or C 1 -C 2 alkoxy, or a group of the formula H 5 C 6 (-O-CH 2 -CH 2) n, R 2 is hydrogen or C 1 -C 4 alkyl, alkoxy C 1 -C 6 or hydroxy-C 2 -C 3 alkoxy, and m and N, independently of each other, are 1, 2 or 3, 5 to 50% (preferably 15 to 30%). ) by weight of a dye of formula II o R means

N. R 5

N N l 1 1

/ \. 1

  (a) (b) HH (c) (d) R 3 and R 4 each signify a C 1 -C 4 alkyl group, preferably an ethyl group, and R 5 is a halogen or a C 1-4 alkyl group; C 4, preferably chlorine, and from 0 to 35% (preferably from 15 to 25%) by weight of a dye of formula II Ia or I Va

C- = CH N

  CH 3 (alkyl) C 2 -C 3) -O-R 7 CH 3 N H (C 1 -C 3 alkyl)

  means a C 1 -C 6 alkyl group or (phenyl) -

  C 1 -C 2 alkyl, R 6 R 7 denotes a phenylaminocarbonyl group, the phenyl residue of which is optionally substituted by one or two halogen atoms, preferably chlorine; a benzoyl group

  substituted with a (C 1 -C 4) alkoxy group -

  carbonyl; a para-cyclohexylphenyl group or, only in formula II Ia, a group of formula -CO- (C 2 -C 4 alkyl) -CO-O- (C 2 -C 3 alkyl) -N- (alkyl) The especially preferred dyes of formula I which can be used in the mixtures of the invention are those of formula I '.

CH 3 CN

H 3 i -N = N O O

COOR 1 OH R '

  in which the symbols are as defined in

Table 1 below.

BOARD

  Colorant Ri Position of R 2 '#ff substitution 1H 5 C 6 -O-CH 2 CH 2 2' C 4 H / -C 3 H 6 -OC 4 H 9-n (1: 1) 2 H 5 C 6-CH 2 2 '(CH 2) 3-OC 2 Hs 3 H 5 C 6 -O-CH 2 -CH 2 2' C 3 H 7 / C 4 Hg-n / -C 3 H 6 -CO 4 H 9-n

(1: 1: 2)

  4 do 2 C 4 H 9 -N H 5 C 6 -CH 2 2 'do.

6 do 3 'do.

7 H 5 C 6-OC 2 H 4 3 'CH 3

  8 do 3 'C 2 H 5 9 do 3-' -C 3 H 7-n

H 5 C 6 -CO 2 H 4 -O-C 2 H 43 'CH 3

  The especially preferred dyes of formula II which may be used in the mixtures of the invention are those of formula II '(II') N (C Hs 5) 2 in which R 5 is as defined in Table 2 below .

T A B L E A U 2

Colorant v 11 R 5 = 40 ci

12 R 5 = N-N

Se C 8 H 5

13 R 5 =

-Oh

14 R 5 =

X.JL H

  The especially preferred dyes of the formula III which can be used in the mixtures of the invention are those of the formula III 'where the symbols

  are as defined in Table 3 below.

WE R,

ON (-CH 2 CH 2 +) R 7

CH:

T A B L E A U 3

  Colorant R 6 R 7 # -C 4 H 9 -GN ci ci

16 -C 2 H 5 /

17 -CH 2 CH 2 C 6 H 5-ONH CI

c 8

18 -C 2 H 5

/ III '19 do H

C (-CH 2 -O-C-O-C 2 -H 4-N

0 O

CH 3

H = C-CN

CN CH 3

CN N CH 3

\ C = CH /

-CN CH CH 2 CH 20-CO-NHC 6 H 5

  The following examples illustrate the invention without in any way limiting its scope. In these examples, the parts and percentages are by weight and the temperatures are indicated in degrees Celsius. One part by volume corresponds to the volume of one part by weight of The dyestuffs indicated in

  Examples are dyes 1 to 20 defined above.

Example 1

  16.5 parts of dye n 3 with the formula COOC Hac H or Hs Auto are mixed in the form of a filter cake.

OH (O 4) 2 R,

  R 2 "means H / CH 3 / OC 4 Hn (1: 1: 2), 8 parts of the dye n 11 of the formula

N (SH 5)

  and 7.7 parts of the dye No. 15 of the formula ## STR2 ##

  indicated parts corresponding to 100% dye.

  The resulting mixture is subjected to aqueous grinding with

  parts of a lignin-based dispersing agent

  sulfonate, which gives a dye preparation of ultradispersed dyes The average particle size of the mixture is 1 μm and the ratio of

dilution is 3.0: 10.

  At 60, 8.0 parts of this

  dyeing in 2000 parts of water

  mineralized containing 40 parts of ammonium sulphate.

  The pH of the dye bath is adjusted to 5 with 85% formic acid. In this dyeing bath, about 60.100 parts of a polyester fiber-washed fabric are introduced. heated in the space of 40 minutes to 1300 and the dyeing is continued for minutes at this temperature After cooling to, the fabric is removed from the dye bath, rinsed, soaped and purified by reduction.

  according to the usual methods using hydro-

  Sodium sulphite A yellow dye is obtained

  greenish with good general fastness.

Example 2

  By replacing the dye N O 3 of Example 1 with 18 parts of the dye N O 7 of formula

21} N ≤O

  H 5 C "o H 2 cloc 2 OH CH 3 and operating as described in Example 1, a greenish yellow dye with good

general solidities.

  Proceeding as described in the previous examples, equivalent results are obtained by mixing the dyes of types (I ') to (III') of Tables 1, 2 and 3, as indicated in Table 4 below.

T A B L E A U 4

  Ex Colorant I 'Colorant II' Colorant III 'Color of the stain on (no, parts) (no, parts) (no, parts) polyester 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 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 No 11, 6 No 15, 7 No 8, 17 No 11, 6 No 15, 7 No 10, 17 No 11, 6 No 15, No 3, 18 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 # Colorant I 'Color II' Colorant III Nuance of (no, parts) (no, parts) (no., Parts) Polyester dye 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 No 7, 17 5 No 11, 7 0 No 18, 5 5 16 No 3, 18 5 No 11 7 0 No 19, 4 5 17 No 7, 18 5 No, 11, 7 0 No 19 , 4, No. 5, No. 2, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5 21 No 3, 17 0 No 12, 5 No 15, 7 5 22 No 7, 17 0 No 12, 5 No 15, 7 5 23 No 3, 17 0 No 13, 5 No. 15, 7, 5, No. 7, No. 13, No. 15, No. 3, No. 14, No. 15, No. 7, No. 14, 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 Ex # Colorant I 'Color II' Colorant III 'Color of (no, parts) (no, parts) (no, parts) Polyester dye 32 No 7, 20 0 No 13, No. 17, No. 33, No. 7, No. 12, No. 17, No. 34, No. 1, No. 11, No. 15, No. 2, No. 3, No. 0 No 11, 10 0 No 15, 4 0 36 No 7, 16 0 No 11, 10 0 No 15, 4 0

Example 37

  In 70 parts of glacial acetic acid

   26.5 parts of the C-phenoxy ester are dissolved

  ethyl acetate of anthranilic acid (97%) and mixed with 31 parts of hydrochloric acid (36.5%) and 200 parts of ice water; The resulting slurry was diazotized at 0-5 with 7.2 parts of N sodium nitrite. The excess nitrous acid was destroyed with aminosulphonic acid, the solution of the diazonium salt was filtered and added to the solution. With good stirring and 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

CN OH 3 ON

O O

N N

  O (CH 2) 3 CH 3 OH (CH 2) 3-OC 4 -n (37 a) (37 b) in 10 parts of glacial acetic acid and 400 parts of ice water The value of p H is constantly maintained at 4-5 by addition of a solution of caustic soda (at%) The resulting yellow suspension is filtered, washed to neutrality with 1000 parts of water at 50 and the dye is vacuum dried at 40 can be purified

  further the dye mixture by recrystallizing it

  reading, for example in the cellosolve.

  A mixture of dyes of formula 37 c C 2 CH 20 CH 5 (37 c) is thus obtained

CH 3 CN

N O? O

(OH (CH 2) 3 -R 2 "

  o R 2 "" means -CH 3 / OC 4 Hgn (1: 1) It dyes the

  polyester fibers in a greenish yellow hue pre-

  feeling good general solidities.

  Mixtures of dyes of formula I which can be used according to the invention correspond to formula Ia '

6 '5' R 4

OCH 2 CH 20 -

21 3 'R (la') Co CH 3 CN

N-N O

  OH (CH 2) m R 2 in which the symbols are as defined in Table 5 below, where R 5 is hydrogen in all cases, except for the first dye of Example 51, where R 5 means a methyl group in

position 5 '.

  These dye mixtures may be prepared in a manner analogous to that described in Example 1, or also by simple mixing of the

individual components.

T A B L E A U 5

  N Ex R 2 '% R 4 m imax (nm) (DMF) 38' -OC 3 H 7-n 50 H 3 431

-OC 2 H 5 50 H 3

  39 -OC 3 H 7 -n 50 H 3 431 -OC 3 H 7 -i 50 H 3 -OC 4 H -n 50 H 3 431 -OC 4 Hg-i 50 H 3

41 -OC 2 H 5 35 H 3 431

  -OC 3 H 7-n 30 H 3 O 4 H 9 -n 35 H 3 42 -OC 4 H 9 -n 65 H 3 431 -OC 6 H 13-n 35 H 3 NR 2 '% R 4 m Xmax ( nm) Ex (DMF)

43 -0 C 2 H 5 40 H 3 431

-OC 4 Hg-n 40 H 3

-CH 3 20 H 3

  44 -OC 3 H 7-n 50 H 3 431 -OC 4 H 9-n 50 H 3

-OC 2 H 5 40 H 3 431

  -OC 4 H 9-n 40 H 3 -OC 4 H 9 -i 20 H 3

46 -OC 2 H 5 40 H 3 431

  -OC 3 H 7 -n 10 H 3 -OC 4 H 9 -n 40 H 3 -OC 4 H 9 -i 10 H 3

47 -OC 2 H 5 50 H 2 431

-OC 4 H 9-n 50 H 2

48 -OC 2 H 5 30 -CH 3 (4 ') 3,431

-OC 4 Hg-n 70 H 3

49 -OC 2 H 5 30 -C 1 (4 ') 3,431

-OC 4 H 9-n 70 H 3

-OC 2 H 5 30 -OCH 3 (4 ') 3,431

-OC 4 Hg-n 70 H 3

51 -OC 2 H 5 20 -CH 3 (2 ') 3,431

  -OC 4 Hg-n 80 H 3 R 2 '% R 4 m Xmax (nm) Ex (DMF)

52 -OC 2 H 5 25 H 3 431

-OC 4 Hg-n 25 H 3

-CH 3 50 H 3

53 -OC 4 Hg-n 50 H 3 431

-CH 3 50 H 3

54 -OC 4 Hg-n 50 H 2 431

-CH 3 25 H 2

-CH 3 25 H 3

-OC 2 H 5 25 H 3 431

-OC 4 Hg-n 25 H 3

-CH 3 25 H 2

-CH 3 25 H 3

56 -OCH 3 25 H 3 431

-OC 2 H 5 25 H 3

-CH 3 50 H 3

Example 57:

  In 100 parts of glacial acetic acid, 24.8 parts of benzyl ester of anthranilic acid (98%) are dissolved and mixed with 35 parts of hydrochloric acid (36.5%) and 150 parts The resulting suspension is cooled to 0-5 with 7.2 parts of 5 N sodium nitrite. After destroying the excess of nitrous acid with aminosulphonic acid, the solution of the diazonium salt is filtered off. it is added with stirring at pH 4-5 and -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

CH 3 CN

  CNS (57 a) _ON) O OH - (Ct HJ C 2 Hs CH 3 CN (57b) - o 4H

OH (C 2) 3-004.

  in 10 parts of glacial acetic acid and 400 parts of ice water. The pH is constantly maintained at 4-5 by addition of a caustic solution (30%). The resulting yellow suspension is washed, washed at neutrality with 1000 parts of water at 50 and the dye is dried under vacuum at 40 can be purified

  further the dye mixture by recrystallizing it

  reading, for example in the cellosolve.

  A mixture of dyestuffs of formula 57c is thus obtained

: Z O H 5 (57 C)

CO CH 3 CN

b N

OH '(OH 2) 3-R

  o R 2 'means OC 2 H 5 / OC 4 H 9 N (9: 1) It dyes the

  polyester fibers in a greenish yellow hue pre-

  feeling good general solidities.

  Table 6 below shows other mixtures of dyes. They correspond to formula Ia "OCH 24 (la" s) g l

1 2 3

C CH 3 CN

  N OH (CH 2) m -R 2 in which the symbols are indicated in the

next table 6.

  These dye mixtures can be obtained by proceeding as described in Example 37 or by mixing the individual components of formula Ia "

BOARD

N R 2 '% R 4 m Xmax (nm) Ex (DMF)

58 -OC 2 H 5 70 H 3 432

  -OC 4 Hg-n 30 H 3 59 -OC 3 H 7-n 50 H 3 432 -OC 3 H 7 -i 50 H 3 -OC 4 Hg-n 50 H 3 432 -OC 4 Hg-i 50 H 3

61 -OC 2 H 5 35 H 3 432

  -OC 3 H 7-n 25 H 3 OC 4 H 9 -n 40 H 3 62 -OC 4 Hg-n 65 H 3 432 -OC 6 H 13n 35 H 3

63 -OC 2 H 5 40 H 3 432

-OC 4 Hg-n 40 H 3

-CH 3 20 H 3

64 -OC 2 H 5 30 H 3 432

-OC 4 Hg-n 30 H 3

-CH 3 20 H 3

  -C 3 H 7 -n 20 H 3 -OC 2 Hs 40 H 3 432 -OC 4 Hg-i 20 H 3 -OC 4 Hg-n 40 H 3 NR 2 '% R 4 m Xmax (nm) Ex (DMF )

66 -OC 2 H 5 40 H 3 432

* -0 C 3 H 7 -n 10 H 3 -OC 4 Hg-i 40 H 3 -OC 4 Hg-n 10 H 3

67 -OC 2 H 5 50 H 2 432

-OC 4 Hg-n 50 H 2

68 -OC 2 H 5 85 4 '-CH 3 3 432

  -OC 4 Hg-n 15 do 3 69 -OC 2 Hs 85 4 '-CI 3 432 -OC 4 Hg-n 15 do 3

-0 C 2 H 5 90 H 3 432

-OCH 3 10 H 3

71 -OC 2 H 5 50 H 3 432

-CH 3 50 H 3

72 -OC 2 H 5 70 H 3 432

-CH 3 30 H 3

73 -OC 2 H 5 60 H 3 432

-CH 3 20 H 2

-CH 3 20 H 3

74 -OCH 3 50 H 3 432

-OC 2 H 5 50 H 3

-OCH 3 20 H 3 432

-OC 2 H 5 80 H 3

EXAMPLE OF APPLICATION:

  The dye mixture obtained according to Example 1 is converted by grinding in a sand mill in the presence of dispersing agents, for example

  commercial lignin sulphonate, and sub-

  sequential, in an ultra-distal dye preparation

  persian having an average particle size of

  1 pm and a dilution ratio of 3.5: 10.

  12 parts of this preparation are dispersed in 1000 parts of water and introduced at 60 in a circulation bath (13000 parts, containing 30 parts of ammonium sulphate and 0.3 parts of formic acid serving as buffer , and possibly a combination of filler and unison agent). A pre-washed, compressed cross-coil (comprising 1000 parts of polyester yarn on a plastic spool) is introduced, the autoclave is closed and the heat is heated to 1300.degree.

  within 35 minutes After 90 minutes,

  cold to 800, the exhausted bath is evacuated and the dyed substrate is washed thoroughly with cold water and

  purifies by the usual methods by reduction.

  The substrate is then wrung and dried.

gets a solid yellow dye.

  In the application example above, instead of the mixture of Example 1,

  any of the mixtures of Examples 2 to 75.

Claims (4)

  A dispersion dye mixture comprising i) from 25 to 85% by weight of a compound of formula I CH 3 CN N O H OOF 3 CH FN   wherein R 1 is a C 1 -C 3 (phenyl) -alkyl group or a group of the formula H 5 C 6 (OCH 2 -CH 2) n wherein the benzene ring is unsubstituted or has one or two substituents selected from chlorine, bromine and C 1 -C 2 alkyl and C 1 -C 6 alkoxy, R 2 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 2 alkyl -C 3, (hydroxy-alkoxy   C 2 -C 6) -C 2 -C 3 alkyl or (C 1 -C 4) alkoxy -   (C 2 -C 6) alkoxy-C 2 -C 4 alkyl and n is 1, 2 or 3; ii) from 5 to 50% by weight of a compound of formula II O R 4 in which R is a group corresponding to one of the following formulas a) to d) % R 5 N-N (a) (b) WANH (b) A 50 X   H (c) (d) R 3 and R 4 independently represent a C 1 -C 4 alkyl group and R 5 is a halogen or a C 1 -C 4 alkyl group; and iii) from 0 to 35% by weight of a compound of formula III or IV ## STR1 ## CH 3 (II   CH 3 N \ C ao R 6 is C 1 -C 6 alkyl or (phenyl) C 1 -C 4 alkyl, R 7 is phenylaminocarbonyl wherein the phenyl residue is unsubstituted or substituted with 1 or 2 halogen, a benzoyl group substituted with a (alkoxy)   C1-C4) -carbonyl or a para-cyclo group   hexylphenyl, R 8 has the meaning of R 7 independently of R 7, or signifies a group of formula e CN -CO- (C 2 -C 4 alkyl) -CO-O (C 2 -C 3 alkyl) - N (R 1)), CH = CH 2 -C n CH 3 o R 10 denotes a C 1 -C 6 alkyl group or - (CH 2) 2-3-C 6 H 5   A mixture according to claim 1, characterized in that it contains i) from 45 to 75% by weight of a compound of formula I ii) from 15 to 30% by weight of a compound of formula II, and   iii) from 0 to 30% by weight of a compound of formula III.   A mixture according to claim 1, characterized in that the compound of formula I corresponds to formula Ia CO-O-R 1CH 3 N N = N O N \ (la) OH R 2   wherein R 1 'is benzyl or phenoxyethyl, R 2' is C 1 -C 4 alkyl or (alkoxy) C1-C6) -C2-C3alkyl.   4 A mixture of dispersion dyes of formula Ic CH 3 N H N = N O   Wherein R 1 denotes a benzyl or (phenoxy) -alkyl group C 2 -C 4 in which the benzene ring optionally comprises one or two substituents selected from chlorine, bromine and the groups C 1 -C 4 alkyl and C 1 -C 4 alkoxy, R 2 is C 1 -C 4 alkyl or C 1 -C 6 alkoxy and m is 2 or 3, at least 10% by weight one or more dyes wherein R 2 signifies an alkoxy group being present in said dye mixture when R 1 signifies an optionally substituted benzyl group, while any other dye of formula I may be present in said mixture when said it contains at least 10% by weight of a dye o R 1 means a group   optionally substituted phenoxyalkyl.   A mixture of dispersion dyes, characterized in that it contains 25 to 85% by weight of a dye of formula Ic CH 3 N H N = N O   Wherein R 1 is (C 1 -C 3) -alkyl (phenyl) -alkyl optionally monosubstituted in the benzene ring by chlorine or C 1 -C 2 -alkyl; or C 1 -C 2 alkoxy, or a group of the formula H 5 C 6 - (-O-CH 2 -CH 2) n, R 2 is hydrogen or C 1 -C 4 alkyl, alkoxy C 1 -C 6 or hydroxy-C 2 -C 3 alkoxy and m and N, independently of one another, 1, 2 or 3, 5 to 50% by weight of a dye of formula II OR 0, R 4 wherein R signifies a group corresponding to one of the following formulas a) to d) is NN (a) (b) o WINH H, (c) (d) R 3 and R 4 each signify a C 1 -C 4 alkyl group, and R 5 is a halogen or a C 1 -C 4 alkyl group, and O to 35% by weight of a compound of formula II Ia or I Va NC R,   NC (IIIa) CH 3 (al-ky 11 ne in C 2 -C 3) -O-R 7 CH 3 (I Va) / CN N   CH (C 2 -C 3 alkylene) -O-R 7 wherein R 6 is (C 1 -C 6) alkyl or (phenyl) (C 1 -C 2) alkyl, and R 7 is phenylaminocarbonyl wherein The phenyl residue is unsubstituted or substituted by 1 or 2 halogens, benzoyl group optionally substituted with (1-4C) alkoxycarbonyl or para-cyclohexylphenyl or, only in formula IIa, a group of formula -CO- (C 2 -C 4 alkyl) -CO-O- (C 2 -C 3 alkylene) -N- (C 1 -C 6) alkyl CH = C (CN) 2 6 A dyeing process a substrate, characterized in that a mixture is applied to the substrate   according to any one of claims 1 to 5.