FR2555997A1 - MIXTURES OF COLORANTS, PROCESS FOR THEIR PREPARATION AND USE THEREOF FOR DYEING AND PRINTING TEXTILE MATERIALS - Google Patents

Abstract

THE MIXTURES OF AT LEAST TWO DIFFERENT DISPERSIONING COLORANTS RESPONDING TO THE FORMULA: (CF DRAWING IN BOPI) IN WHICH R AND R DESIGNATE INDEPENDENTLY ONE OF THE OTHER A RADICAL ALKYL IN CC, AND R A RADICAL ALKYL IN CC, THE NUMBER OF C ATOMS OF THE R, R AND R ALKYL GROUP, COLLECTIVELY, AT LEAST 7 AND AT MOST 14 PER MOLECULE OF COLORANT, ARE INDICATED BY A GOOD PH RESISTANCE AND A VERY GOOD RISE AND RISE POWER. 'EXHAUSTION. USE OF THESE MIXTURES FOR DYING POLYESTER FIBERS.

Description

Mixtures of dyes, process for their preparation and their use

  The invention relates to novel dye mixtures,

  a process for their preparation as well as their use

  for dyeing and printing textile materials.

  Dyes corresponding to the formula are known:

NO% = N

  wherein Y and X independently of one another are alkyl, and Z is methyl or ethyl). For example, the dye with X = Y = ethyl and z = methyl is a dye which is frequently found in the art but is very quickly destroyed at dye bath pHs greater than 5, and n so it does not matter in exhaustion dyeing. It is

  therefore used almost exclusively in the

  If X and Y are extended to the propyl radical, the dye is depleted, it is still satisfactorily satisfactory and has a good climbing power, but its pH resistance is only insufficiently improved. . It is only with X and Y = butyl that the pH resistance meets the requirements of exhaust dyeing; however, this dye is still poorly

insufficient rise power.

  It has now been found that mixtures of such colors

  mainly dipropyl dye with dibutyl dye surprisingly exhibited both very good pH

  Raising power and a very good power of exhaustion.

  The invention therefore relates to a mixture of dyes containing at least two dyes, which correspond to the formula I ## STR1 ##

\ CN N COR3 2

  in which R1 and R2 denote independently of one another a C3-C8 alkyl radical R3 a radical

  C 1 -C 2 alkyl, the number of alkyl carbon atoms

  than R1 and R2 and R3 per molecule of dye being

  collectively at least 7 and at most 14, in particular

from 7 to 11.

  The preferred dye mixtures contain two dyes of Formula I in the ratio of -70% by weight of the first dye to 70% by weight of the other dye. This is particularly a report

50:50% by weight.

  If R 1 and R 2 independently of one another denote a C 3 -C 8 alkyl, it is an unbranched or branched alkyl, for example n-propyl, isopropyl or n-butyl,

  sec-butyl, i-butyl, n-hexyl, n-octyl and 2-ethylhexyl.

  The two radicals R1 and R2 can here be identical or

different from each other.

  Preferred dye mixtures contain dyes of the formulas 2NO - * - N - * N / 4t 2. = / \ =. / XC.H (n)

CN NCOR3

and / 0 2 / C3H7 (n)

NO.-N = N- * * -N3 7

/ \ C \ H (n) "cN 7

CN N5COR3

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  or dyes corresponding to the formulas. ## EQU1 ## where ## STR2 ## C4 H (n)

\ CN N COR3

and 'Ce- CH7 (n)

NO _e 2-N = N-e, -

and N 2 X "\ / C H (n) 3 7

\ CN NHCOR ^

and

-N = N-. -N 4

N02-,, - - C H (n)

\ CN N COR3

  in which R3 has the specified meaning each time.

  The dye mixtures according to the invention can be prepared according to various possibilities, for example

example

  a) by mixing at least two dyes different from each other corresponding to formula I, or b) by melting together at least two dyes of formula I different from each other, or c) diazotising a diazolizable component corresponding to the formula / 02

NO - '-NH)

* 2

2 \ / 2 (II)

3 =. \ Br / c

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  and by coupling the resulting diazo with a mixture of at least two copulation constituents different from each other corresponding to the formula

\ (III)

NCOR 2

  wherein R 1, R 2 and R 3 have the meaning indicated, and reacting the mixture of coupling products having the formula ## STR1 ##

0 = 0 \ ** / \ R2

  Br / C1 NCOR3 with a metal cynure in polar organic solvents optionally containing water, to give a mixture of the dyes corresponding to formula I. If working according to variant (a) of the process,

  the preparation of the dye mixture according to the invention

  This involves mixing the various dyes of formula I with each other at room temperature, dry or wet. Dispersing agents, mainly of anionic or nonionic nature and water, are advantageously added to this mixture and this mixture is milled using grinding auxiliaries (for example glass beads) to give a dispersion.

ready to use. -

  Anionic dispersing agents which can be envisaged for this purpose are, for example, the condensation products of naphthalenesulphonic acids and of formaldehyde, in particular dinaphthylmethanedisulphonates or

modified lignosulphonates.

  Examples of nonionic dispersing agents

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  known and particularly suitable are adducts of about 3 to 40 moles of ethylene oxide on alkylphenols, fatty alcohols and fatty amines. If the indicated variant b) is used for the preparation of the dye mixture according to the invention, the dyes are melted together in a homogeneous melt and then allowed to cool and, if necessary, ground with anionic dispersing agents. or nonionic and water in the presence of grinding aids; according to this variant also, a dispersion is obtained

ready to use.

  In variant c) of the process, finally, the starting products corresponding to formulas II and III are known and can be prepared by known methods. For example, the constituents of copulation are obtained.

  corresponding to formula III by reacting acetamido

  suitable anilines having the formula 3 - ## STR5 ## with alkyl halides of the formulas R 1 -Hal or R 2 -Hal or with alkyl sulphates having the formulas R 1 -O-SO 3 OH or R 2 O -SO30H in the presence of acid acceptors such as for example

  alkaline carbonates, mainly sodium carbonate.

  The coupling reaction of the mixture of the coupling components of formula III with the diazo component of formula II is carried out by a known technique, and a mixture of the coupling products of formula IV is obtained. This mixture can be isolated. The halogen atom of the diazo component is then replaced by the cyano group in this mixture;

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  this is done by reacting the mixture of coupling products of formula IV with cyanides

  metal. This reaction, which is carried out preferably

  The reaction with copper cyanide is preferably carried out in a polar solvent optionally containing water such as dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone or pyridine-water mixtures at a temperature of about 40 to 150.degree. C, preferably at 130 ° C. By this method, a mixture of dyestuffs corresponding to formula I is obtained. Another analogous possibility of preparing dye mixtures corresponding to formula I is to diazotize a diazo component corresponding to the formula V

/ CN

e-.V

NO2- \ -N2 (V)

  * Me Br / c1 and react with a mixture of coupling components of formula III to give a mixture of coupling products of the formula CN e - e e - eR

- 2N0. -.- N = N-_. /._ (VI)

  ## STR1 ## to exchange the halogen atom in the diazo component with a nitro group by means of a nitrite

alkali and its copper salts. -

  The novel dye mixtures of formula I are used for the dyeing and printing of materials, in particular of textile materials, which

  can be dyed with disperse dyes.

  Before their use, the dye mixtures are

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  advantageously converted into dye preparation, insofar as this has not already been done during their preparation. For this purpose, they can be ground so that their particle sizes are on average between 0.01 and 10 μm. The grinding can be carried out in the presence of dispersing agents. For example, the dried dye mixture is ground with a dispersing agent or kneaded in the form of a paste with a dispersing agent and then dried under vacuum or by spraying. With the preparations thus obtained, it is possible, after addition of water, to dye, pad or print in long baths (bath ratio greater than 1: 5) or in short baths (bath ratio 1: 1 to 1: 5).

  The new dye mixtures are running out of steam

  quently in suspension or aqueous dispersion on bodies

  faked in macromolecular substances

  thematic or semi-synthetic. They are particularly suitable for dyeing, padding or printing fibers, filaments or veils, fabrics or knits,

  aromatic polyesters, as well as in 2 1/2 aces

  cellulose and cellulose triacetate. Similarly, synthetic polyamides, polyolefins,

  polymerization of acrylonitrile and poly-

  Vinyls can be dyed and printed with these.

  Particularly valuable dyes are obtained on

  linear aromatic polyesters. These are in general

  of polycondensation products of terephthalic acid

  and glycols, in particular ethylene glycol, or polycondensation products of terephthalic acid and

  1,4-bis (hydroxymethyl) hexahydro-benzene.

  The polyester fibers are dyed by methods known per se in the presence of vehicles at temperatures

  between 80 and 125 C or in the absence of

  cules under pressure at 100 to 1400C approximately, by the process of exhaustion. We can also embroider or print these

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  fibers with aqueous dispersions of the dye mixtures, and fix the impregnation obtained at about 230 C, for example using water vapor, contact heat or hot air. The 2 1/2 cellulose acetate is preferably dyed between about 65 and 85 C and the cellulose triacetate at temperatures ranging from

up to 115 C.

  Most often, the usual dispersing agents already mentioned, which are preferably anionic or nonionic and can be used also in

mix between them.

  When padding and printing, the usual thickening agents are used, for example modified or unmodified natural products, for example alginates, British gum, gum arabic, gum crystal, carob flour, gum tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides or

polyvinyl alcohols.

  The dyes obtained have good general fastness; special emphasis should be placed on the possibility of mixing them with any dyes, mainly yellow dyes, and that they have no "catalytic weakening" when applied to a textile material, that they exhibit good pH resistance mainly in the process of exhaustion and that their climbing power is very good

and very uniform.

  The following nonlimiting examples are given by way of illustration of the invention; temperatures are given in degrees Celsius; the parts (P) are

  parts by weight, unless otherwise indicated.

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Example 1

  2.5 parts of the dye having the formula No 2 - C 7 (n) NO 1 -N = N * Nb 3 2 · · · / H 7 ·, · CH (n) CN are mixed together.

CN NCOCH3

  and 2.5 parts of the dye having the formula N 2 -N 4 /, -, H (n) NO "-N = N-s, ## STR1 ##

CN NECOCH3

  and grinded with parts of a low-salt dispersant (dinaphthylmethanesulfonic acid type) in parts of water, using 300 parts of

  0.5 mm diameter glass in a microsol mill.

  The resulting dispersion, which contains a mixture of dyes,

  can be used for dyeing polyester materials.

  The dyes corresponding to the above formulas are obtained as follows: 8.6 parts (approximately 0.033 moles) of 3-dibutylaminoacetanilide (prepared by heating for 8 hours at the reflux temperature of 3 aminoacetanilide are dissolved

  with excess butyl bromide, in the presence of carbon

  sodium nitrate) in 300 parts of 50% aqueous acetic acid, and over a period of two hours a solution of diazonium salt prepared from 7.9 parts (0.03 mole) was added dropwise to them. ) of 2,4-dinitro-6-bromaniline with 5.1 parts of 40% nitrosyl sulfuric acid in 12 parts of 96% sulfuric acid. The dye having the formula: ## STR2 ## The precipitated product is filtered off under vacuum, washed with water and then with methanol and dried. 13.7 parts (85.3% of theory) of a deep dark blue powder are obtained

at 195 to 197.

  10.7 parts (0.02 moles) thereof are dissolved in 95 parts of pyridine, 1.9 parts of copper cynaure I and 55 parts of water are added and stirred for 10 hours at 60-70, filtered under vacuum at 50, washed with a pyridine-water mixture at 50 and then with water and dried. We obtain the dye corresponding to the formula

-., / N 4 9

O2N-e \ * -N = N-O ô - / '

CNNCOCH3

  in the form of a greenish brown powder melting at 196 to

  198. Yield 6.6 parts (about 69% of the theory).

  The corresponding dye is obtained in a similar way.

  to the formula: e / 2 -. C H7 e-e C Qg - "<.- NN-4 + .- <3 / \ cN 1, CCHR3 melting at 192-194

Example 2

  The result is a dispersion similar to that described in Example 1, when the two dyes in accordance with Example 1 are melted together in the ratio 1: 1 (point of

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  fusion 172 to 174) and then dispersed.

Example 3

  The dye mixture, containing the dyes corresponding to the formulas: ## STR1 ## ## STR2 ##

2 \ / \ / \ ...

CN N4COCH3

and = / 02 = H / (n)

NO -.- N = N - * \ * 4

  ## STR5 ## is obtained in the ratio of approximately 50:50% by weight by coupling equimolar amounts of the two copulation constituents corresponding to the formulas: ## STR2 ##

* .- .. R (). _ 4

._ v, EA-

  = C 3 H (n) and 1 = C (n) COCH 3 C 3 with a diazotized diazotized component having the formula:

NO 2-,

  Br and reacting the resulting mixture to give the corresponding cyano derivative as described in

Example 1

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Example 4

  If one melts 7 parts of the dye corresponding to the formula NN -2 / -. IC 4H9 (n)

NO2, \ C / H -N =

CN.COCH

  with 3 parts of the dye having the formula -o.-, CH (n) e -... NO O-N = N-. e-N 9 2 / C3H (n)

CN NCOCH3

  a mixture of dyes having a melting point of 183 to 186 is obtained

Example 5

  A mixture of dyes containing the dyes corresponding to the formulas AO2 C H (n) NO * e -N = N-N- -N3 2v _ = / 2A = C H (n) is obtained

'CN NCOCH3

and NO2

2 \ _ / .... \ / - _

* = * = 'CH ,, (n)

\ CN N COCH

and A02 C H (n)

NO H (,,

-, .--. C _ \ _ / (n) Ce

CN N4COCH 3

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  by coupling the acetylaminoanilides obtained by alkylation

  mixed with equimolar amounts of n-bromide

  propyl and n-butyl, with dinitrobromaniline diazotea and transforming the resulting mixture into a mixture of corresponding cyanide derivatives.

Example 6

  One thousand parts of a polyester fabric (Diolen) trademark deposited in 100,000 parts of a dyeing bath containing 192 parts of the dispersion according to Example 1 (corresponding to 9.6 parts of dyestuffs) were dyed at 130 minutes. mixed) and 50 parts of a wetting agent (for example a fatty acid methyltauride) and 50 parts of a dispersant (for example based on dinaphthylmethanesulphonate). A dark blue color is obtained which has a very good fastness to light. The dye bath

is completely exhausted.

  If instead of the dye mixture

  9.6 parts of each of the individual dyes, the

  Bathing is much less good, and in the case of dibutyl dye, the coloring is much less deep.

Example 7

  If dyeing is carried out according to Example 6, but with this difference that the dyes

  are buffered at pH 4, 5, 6, 7 and 8, only

  at pH 6 a slight change in shade, and only at pH 7 a weaker coloration, whereas a comparative dye containing the single dye having the formula has ON02 -. C H

Y N * / - = N_ MI4 2 5

2 \ / \ C

0 = 0 \ __. '' =. N / 2H5

CN NC0CH3

  is significantly lower at pH 5.

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Claims (9)

  1. Mixture of dyes containing at least two dyes, which correspond to the formula I e N2 (I) N02 \ / \ -N = N- \ AT CN N COR3   in which R1 and R2 denote, independently of each other, a C3-C8 alkyl radical, and R3 a C1-C2 alkyl radical, the number of alkyl carbon atoms of R1 and R2 and R3 per molecule dye being   collectively of not less than 7, and not more than 14.   2. Mixture of dyes according to claim 1, characterized in that it contains two dyes corresponding to formula I. 3. Mix of dyes according to claim 2, characterized in that it contains the two dyes in the ratio of 30 70% by weight of a dye at 70-30% by weight weight of the other dye.   4. Mixture of dyes according to claim 3, characterized in that it contains the two dyes in the ratio of 50% by weight of a dye at 50% by weight of the other dye.   5. dye mixture according to claim 2, characterized in that it contains the dyes corresponding to the formulas -'NO2 ()   N2NO 2 - \ / eN N * / - - 4-9 = 0 == 0 CH9 (n) CN NCOR3 and 2555997,   ## EQU1 ## where: ## EQU1 ## n = N-6 t / N 3 7 ZO-e \ / eN-1 \ /, - m \ "\ '=" - 'C3H7 (n) \ CN 14COR3   in which R3 has the meaning indicated in the claim 1.   6. Mixture of dyes according to claim 1, characterized in that it contains the dyes corresponding to the formulas AO2 NO2C4H (n) NO-e1, N = N-, z / 1, -N- NO N\ / \ 2. * = / \ = * 'C4Hl (n) CN N COR3   and '2 9-'. C H (n) NO2 \ - / -: q \\ .- N \ cH n N 2 \ / \ C H () 3 7 -CN.COR3 3 summer-. C.H (n) NO2- -N = N-_.// _ 9, \ 0 = 0 / \ * = * / C3H7 (n) CN N COR   R3 in which R3 has the meaning indicated in the claim 1.   7. Process for the preparation of the dye mixture according to claim 1, characterized in that a) at least two dyes corresponding to formula I are mixed with one another, or   (b) at least two 2555997,   Formula I different from one another, or (c) a diazotable component of formula (2) is 2 X2_./ (I)   Cl and the diazo obtained is copulated on a mixture of coupling components corresponding to the formula '-'._ / 1 (III), _ =. / Rl \ = c R3 "R NCOR3   in which R 1, R 2 and R 3 have the meaning indicated with respect to formula I of claim 1, and the mixture of the coupling products having the formula (IV) ## STR5 ## metal cyanide in polar organic solvents, optionally containing water, to give a mixture of the dye of formula I in accordance with claim 1.   8. Use of the dye mixture according to the claim   1 or the dye mixture obtained according to one of the processes according to claim 6 for dyeing and printing of textile materials.   9; Use according to claim 7 for dyeing and printing polyester materials in the process by exhaustion.   10. Textile materials dyed and printed according to claims 8 and 9.