DE3443621A1 - Dyestuff mixtures - Google Patents

Abstract

Mixtures of at least two different disperse dyestuffs of the formula <IMAGE> in which R1 and R2 independently of one another denote a C3-C8-alkyl radical and R3 denotes a C1-C2-alkyl radical, where the number of alkyl C atoms of R1, R2 and R3 together is at least 7 and at most 14 per dyestuff molecule, are distinguished by a good pH resistance and a very good add-on ability and affinity; they are particularly suitable for the dyeing of polyester fibres.

Description

'""■' ■ '■ \ - ^s ' \ 1 -; ^: vi-

Dr. F. Imstefrisen. - D>: E. Earsrnarm Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun.

PATENT LAWYERS

APPROVED REPRESENTATIVES. M ^ U R O P A. I S C H B N P A T E N T A M T REPRESENTATIVE BEFORE THE EUROPEAN PATENT OFF. C E

CIBA-GEIGYAG 1-14677 / =

Basel, Switzerland)

DYE MIXTURES

The invention relates to new dye mixtures, processes for their Manufacture and their use for dyeing and printing textile materials.

Dyes of the formula

/ ⁰ I.

CN

w * -w

N ^ COZ

(with X and Y independently of one another alkyl and Z methyl or ethyl), are known. For example, the dye with X ■ Y «ethyl and Z» Methyl is a dye that is often found in practice, but which is destroyed very quickly at pH values of the dyebath above 5 and therefore has no meaning in exhaust dyeing. It is therefore used almost exclusively in continuous dyeing. If you extend X and Y to propyl, the dye still pulls out well and shows a good build-up capacity, but its pH stability is insufficient improved. Only with X and Y ■ butyl is the pH resistance sufficient the requirements of exhaust dyeing; however, this dye is poorly absorbed and has an inadequate build-up capacity.

It has now been found that mixtures of such dyes, especially the dipropyl dye with the dibutyl dye, surprisingly both very good pH stability and very good

have good build-up capacity and very good drawability.

The invention accordingly relates to a dye mixture containing at least two dyes, which of the formula I.

^N0 2 \ / " ^N " ^N "\ / \ ^(I)

^X CN NiICOR ₃ ²

correspond to, where mean:

R and R "independently of one another a C -C -alkyl radical and R a C ~ C alkyl radical, where the number of alkyl C atoms of R and R_ and R- per dye molecule together is at least 7 and at most 14, in particular 7 to 11.

Preferred dye mixtures contain two dyes of the formula I in a ratio of 30-70% by weight of one dye 70-30% by weight of the other dye; in particular, it is a 50:50% by weight ratio.

If R. and R_ are, independently of one another, C - C -alkyl, this is the case unbranched or branched alkyl, for example n-propyl, iso-propyl, η-butyl, sec-butyl, i-butyl, n-hexyl, n-octyl and 2-ethylhexyl. Both radicals R and R_ can be identical or be different from each other.

Preferred dye mixtures contain the dyes of the formulas / O ₂

/ ~ \ / '\ A ^H 9 ^(n)
N0 -> - ( Vn »n—; V ¹ V

^X CN NilCOR ^{4 9}

_N0 - / W _n -ZA- / ³ * ^

^Χ = ( yS \ η (n)

CN NHCOR ₃ '

or the dyes of the formulas

N0 ₂ - <> -N = N- <><

- \ / ⁼ • ^C 4 ^H 9 ⁽ⁿ⁾ CN NHCOR ₃

/ O ₂

^No 2 "* () - ^{n = n} - ( y- \"'

^{2 V y V y} Vh An)

> - ^C 3 ^H 7 CN NHCOR

/ 0

\ n

· C H

CN NHCOR ₃ "* '

where R_ in each case has the meaning given.

The inventive dye mixtures can according to various Possibilities are established, e.g. in such a way that one can:

a) two or more different dyes of the formula I are mixed with one another, or

b) two or more different dyes of the formula I are fused with one another, or

c) a diazo component of the formula

^N0 2 "* \

diazotized and based on a mixture of two or more of each other different coupling components of the formula

wherein R., R. and R have the meaning given, coupling, and the Mixture of the coupling products of the formula

\ t / Cl NiICOR ₃ ²

with metal cyanide in polar, optionally hydrous organic ones Solvents to form a mixture of the dyes of the formula I.

If you work according to process variant a), there is production the inventive dye mixture in that one the individual dyes of the formula I are mixed dry or wet with one another at room temperature. It is advantageous to use this mixture nor dispersants, especially of an anionic or nonionic nature, and water, and grinds this mixture with the aid of grinding aids (e.g. glass balls) to a ready-to-use dispersion.

Anionic dispersants which are suitable for this purpose are, for example Condensation products from naphthalenesulfonic acids and

"Ζ"

Formaldehyde, especially dinaphthylmethane disulphonate or modified ones Lignosulfonates.

Examples of known and particularly suitable nonionic dispersants are addition products of about 3 to 40 mol of ethylene oxide with alkylphenols, fatty alcohols or fatty amines.

Is used for the preparation of the dye mixture according to the invention the variant b) mentioned here the dyes are melted together to form a homogeneous melt, and then cooled left and optionally with anionic or nonionic dispersant and water in the presence of grinding aids marry; even after this variant you get a ready-to-use one Dispersion.

In process variant c), finally, are the starting products of the formulas II and III are known and can be prepared by known methods. This is how you get the clutch components, for example of the formula III in such a way that the corresponding acetamidoanilines of the formula

NilCOIL
with alkyl halides of the formula

R ₁ -HaI or

or alkyl sulfates of the formula

RO-SO ₃ OH or RO-SO OH

in the presence of acid acceptors, such as alkali carbonates, especially sodium carbonate.

The coupling reaction of the mixture of coupling components of the
Formula III with the diazo component of the formula II takes place according to
known manner, a mixture of the coupling products of the formula IV being obtained. This mixture can be isolated. The halogen atom in the diazo component is then replaced by the cyano group in this mixture; this is done in such a way that one
the mixture of the coupling products of the formula IV with metal cyanides
implements. This reaction, which is preferably carried out with copper cyanide, is preferably carried out in a polar, optionally water-containing solvent such as dimethyl sulfoxide, dimethylformamide,
N-methylpyrrolidone or pyridine-water mixtures at a temperature of about 40 to 150 ^° C., preferably 80 to 130 ^° C. According to this method, a mixture of dyes of the formula I is obtained.
Another analogous possibility for the preparation of dye mixtures of the formula I is that a diazo component of the formula V

^N V \ / ^# " ^NH 2 ^(V)

• -ν

ßr / ci

diazotized and with a mixture of coupling components of the
Formula III to a coupling product mixture of the formula

converts and the halogen atom in the diazo component by a nitro group by means of alkali metal nitrite and copper salts.

The new dye mixtures of the formula I are used for dyeing and printing of materials, in particular textile materials, which can be dyed with disperse dyes. Before using them the dye mixtures are advantageously converted into dye preparations if this has not already happened during production. To do this, they can be comminuted so that their average particle size is between 0.01 and 10 ^ m. Crushing can be done in The presence of dispersants. For example, the dried dye mixture is ground with a dispersant or kneaded in paste form with a dispersant and then added dried in vacuo or by atomization. The preparations obtained in this way can, after adding water, be used in a long liquor (Liquor ratio greater than 1: 5) or short liquor (liquor ratio 1: 1 to 1: 5) dye, pad or print.

The new dye mixtures draw from aqueous suspension or Dispersion works excellently on moldings made from fully synthetic or semi-synthetic high molecular substances. Are particularly suitable they are used for dyeing, padding or printing fibers, threads or fleeces, woven or knitted fabrics made from linear, aromatic polyesters as well from cellulose-2 1/2 acetate and cellulose triacetate. Synthetic too Polyamides, polyolefins, acrylonitrile polymerization products and polyvinyl compounds can be colored and printed with them. Particularly valuable dyeings are obtained on linear, aromatic polyesters. These are generally polycondensation products from terephthalic acid and glycols, especially ethylene glycol, or polycondensation products from terephthalic acid and 1,4-bis (hydroxymethyl) hexahydrobenzene.

The polyester fibers are dyed by processes known per se in the presence of carriers at temperatures between about 80 and 125 ^° C. or in the absence of carriers under pressure at about 100 to 140 ^° C. by the exhaust process. Furthermore, these fibers can be padded with the aqueous dispersions of the dye mixtures or

print and fix the impregnation obtained at about 140 ° to 230 ° C., for example with the help of steam, contact heat or hot air. Cellulose 2 1/2 acetate is dyed preferably between about 65 to 85 ^° C. and cellulose triacetate at temperatures up to 115 ^° C.

Usually the usual dispersants already mentioned are added, which are preferably anionic or nonionic and can also be used in a mixture with one another.

The usual thickening agents are used in padding and printing use, e.g. modified or unmodified natural products, e.g. alginates, British gum, gum arabic, crystal gum, locust bean gum, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic Products, for example polyacrylamides or polyvinyl alcohols.

The dyeings obtained have good all-round fastness properties; Particularly noteworthy is her ability with any, above all Yellow dyes mixed and applied to textile material to show no "catalytic fading", especially one in the exhaust process have good pH stability and their very good and level absorption capacity.

The following examples illustrate the invention without restricting it thereto; Temperatures are given in degrees Celsius; Unless stated otherwise, parts (T) are parts by weight.

Example 1; 2.5 parts of the dye of the formula

_A - </ · -% .CH ₇ (η) y ^ ν \ / 3 7

NO - ^ j; »- N = N- ^ ^Χ · -Ν

and 2.5 parts of the dye of the formula

f \ '/ ~ \ / ^C 4 ^H 9 ⁽ⁿ⁾

² = <= 'C. H _Q (η)

\ / 4 9

CN NHCOCH ₃

are mixed and mixed with 10 parts of a low-salt dispersant (dinaphthylmethanesulfonic acid type) in 85 parts of water with the aid of 300 parts of glass spheres of 0.5 mm diameter in a microsol mill ground. The dispersion obtained, which contains a dye mixture, can be used for dyeing polyester materials will.

The dyes of the above formulas are obtained as follows:

8.6 parts (about 0.033 mole) 3-dibutylaminoacetanilide, (manufactured by refluxing 3-aminoacetanilide for 8 hours with excess butyl bromide in the presence of sodium carbonate) are dissolved in 300 parts of 50% aqueous acetic acid and within 2 hours with a 5.1 part dropwise 40% nitrosylsulfuric acid in 12 parts of 96% sulfuric acid diazonium salt solution prepared from 7.9 parts (0.03 mol) of 2,4-dinitro-6-bromaniline. The unusual dye of the formula

\ r NilCOCH ^{4 9}

is suction filtered, washed with water, then with methanol and dried. 13.7 parts (85.3% of theory) of dark blue powder with a melting point of 195 ° to 197 ° are obtained.

- χτ- '

10.7 parts (0.02 mol) thereof are dissolved in 95 parts of pyridine, 1.9 parts of copper (I) cyanide and 55 parts of water are added and Stirred for 10 hours at 60-70 °, suction filtered at 50 °, washed with a pyridine-water mixture at 50 °, then washed with water and dried. The dye of the formula is obtained

0 Ν-

Ζ—

CN NHCOCH ₃

as a green-brown powder with a melting point of 196 to 198 °. Yield 6.6 parts (^ 69% of theory).

The dye of the formula is obtained in an analogous manner:

from melting point 192-194 °.

Example 2: A dispersion similar to that described in Example 1 is obtained if the two dyes according to Example 1 are melted together in a ratio of 1: 1 (melting point 172 to 174 °) and then dispersed.

Example 3: The dye mixture containing the dyes of the formulas

• * "~ * \ / i * ~ * K _X C_H (n)

CN

CN NHCOCH

A ⁽ⁿ⁾

/ 2
NO - () .- N = N -. (W

CN NHCOCH ₃

in a ratio of approx. 50:50% by weight is obtained by equimolar amounts of the two coupling components of the formulas

- CH (n) .-. ' ^N CH (n)

NHCOCH ₃ NHCOCH

with a diazotized diazo component of the formula

couples and the mixture obtained converts to the corresponding cyan derivative as described in Example 1.

Example 4r 7 parts of the dye of the formula are melted

CN NHCOCH with 3 parts of the dye of the formula

^X CN NIiCOCH ^{3 7}

a dye mixture with a melting point of 183 ° to 186 ° is obtained in this way.

-vt- lh

Example 5: A dye mixture containing the dyes of the formulas

/ 2

/ -% / "% / ^C 3 ^H 7 ⁽ⁿ⁾

² \. '\ = / ^N CH (n)

CN NHCOCH and

-W

CN NHCOCH _n ^{4 9}

f \ /% / ^C 3 ^H 7 ⁽ⁿ⁾
NO - <; .- N = N- (> n (

CN NHCOCH ₃ .

is obtained by the mixed alkylation with equimolar Amounts of n-propyl and n-butyl bromide obtained acetylaminoanilides coupled with diazotized dinitrobromaniline and the resulting mixture in a mixture with the corresponding cyano compounds convicted.

Example 6; 4000 parts of polyester fabric (diols) are in 100,000 parts of a dyebath containing 192 parts of the dispersion according to Example 1 (corresponding to 9.6 parts of mixed dye) and 50 parts each of a wetting agent (e.g. fatty acid methyl tauride) and a dispersant (e.g. dinaphthyl methanesulphonate) , stained for one hour at 130 °.

A strong blue coloration with very good lightfastness is obtained. The dye bath is completely drawn out.

If 9.6 parts of each are used instead of the dye mixture Individual dyes, the bath extract is significantly worse and the dibuty compound is less deeply colored.

Example 7; If dyeings are carried out according to Example 6, but with the difference that the dyeings are buffered at pH 4, 5, 6, 7 and 8, a slight change in shade is only found at pH 6 and a weaker coloration only at pH 7, while a comparative dyeing containing the single dye of the formula

0J- \ \ N «

2 \ / N / N

· = ·, · = · C "H _P

CN

already becomes significantly weaker from pH 5.

Claims (10)

Claims; 1. Dye mixture containing at least two dyes, which of formula I. (D correspond to, where mean: R and R independently of one another are a C -C -alkyl radical and R _{0 is} a 12 Jo S C -C -alkyl radical, the number of alkyl C atoms of R. and R ₉ and R.sup.1 per dye molecule together being at least 7 and at most 14. 2. Dyestuff mixture according to claim 1, characterized in that that it contains two dyes of the formula I. 3. Dyestuff mixture according to claim 2, characterized in that it contains the two dyestuffs in a ratio of 30-70% by weight of the Contains one dye to 70-30% by weight of the other dye. 4. Dye mixture according to claim 3, characterized in that that it contains the two dyes in a ratio of 50% by weight of one dye to 50% by weight of the other dye. 5. Dyestuff mixture according to claim 2, characterized in that it contains the dyestuffs of the formulas / Ο /% / \ AV ⁿ⁾ , CN NHCOR, and 3 - Mr- I / ° 2 /, κ α — κ / CH (η) NO- / WW ³ · = ·. = · C ₃ H ₇ Cn) CN. NHCOR wherein R- has the meaning given in claim 1, contains. 6. dye mixture according to claim 1, characterized in that that they are the dyes of the formulas · - ·. •• - • v £, H "(n) CN NiICOR ₃ ^{k 9} and f Vn , · = ·· "C ₀ H, (n)" CN NilC0R _fl ^{3 7} / O ₂ NO- /> -N = N-.f W ⁴ CN NHCOR ₃ wherein R_ has the meaning given in claim 1, contains. 7. Process for the preparation of the dye mixture according to claim 1, characterized by: a) two or more different dyes of the formula I are mixed with one another, or b) two or more different dyes of the formula I merged with each other, or c) a diazo component of the formula , NO, ₂ ^ y2 \ r / Cl diazotized and based on a mixture of coupling components of the formula NH CO R ₃ where R., R _? and R- have the meaning given under formula I in claim 1, couples, and the mixture of coupling products of the formula ^N ° ² ~ "w" ^{N = N} "\ ./ \ ^ r / Cl NilCOR- with metal cyanide in polar, optionally hydrous organic ones Solvents to form a mixture of the dye of the formula I according to claim 1. 8. Use of the dye mixture according to claim 1 or according to one of the methods according to claim 6 obtained dye mixture for dyeing and printing textile materials. 3U3621 9. Use according to claim 7 for dyeing and printing polyester materials in the exhaust process. 10. The textile material dyed and printed according to claims 8 and 9 ien. FO 7.1 / DOE / jtVhc *