EP0793692A1

EP0793692A1 - Mixtures of azo dyes for black hues

Info

Publication number: EP0793692A1
Application number: EP95937884A
Authority: EP
Inventors: Uwe Nahr
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1994-11-21
Filing date: 1995-11-09
Publication date: 1997-09-10
Also published as: DE4441369A1; JPH10508896A; WO1996016129A1

Abstract

Disclosed are dye mixtures containing a) an azo dye of formula (I) in which Hal is chlorine or bromine, b) the azo dye of formula (II) wherein L is allyl or optionally hydrogen, c) an azo dye of formula (III) and/or (IV) wherein the specified radicals are as indicated in the description and d) optionally an azo dye of formula (V) wherein Z1 is chlorine or bromine and Z2 is hydrogen or methoxy, dye preparations containing the new dye mixtures, the use of the new dye mixtures for dying polyesters in textile form and a process for dying poyesters in textile form.

Description

Mixtures of azo dyes for black shades

description

The present invention relates to new dye mixtures containing, based in each case on the total weight of the dyes,

a) 10 to 20 wt .-% of at least one azo dye of the formula I.

where shark means chlorine or bromine

b) 30 to 80 wt .-% of the azo dye of the formula Ha

and optionally the dye of the formula Ilb

wherein the proportion of dye Ha is 50 to 100% by weight and of dye Ilb is 0 to 50% by weight, based in each case on the weight of dye Ha and Ilb, 25 to 50% by weight of at least one azo dye of the formula III or IV

wherein

R ¹ nitro or -CC -Al ylsulfonyl, which is optionally substituted by hydroxy,

R ² and R ³ are each independently hydrogen or chlorine or R ² bromine and R ³ hydrogen or bromine,

R ⁴ and R ⁵ are each independently hydrogen or chlorine,

R ⁶ and R ⁷ each independently of one another are hydrogen, phenyl or C 1 -C ₄ -alkyl, which is optionally substituted by hydroxy, phenoxy, 2-cyanoethoxy, acetyloxy, phenoxyacetyloxy, benzoyloxy, methoxycarbonyloxy or phenylaminocarbonyloxy, or when R ² and R ³ each represent hydrogen or chlorine, including C 1 -C ₄ cyanoal yl,

X ^{1 is} hydrogen, hydroxy, methoxy, acetylamino or nitro,

X ² , X ³ , X ⁴ and X ⁵ are each independently hydrogen, methyl or methoxy and

X ^{6 is} hydroxy, 2-hydroxyethoxy, formyl or methoxycarbonylamino, and d) 0 to 5% by weight of at least one azo dye of the formula V.

in the

Z ¹ chlorine or bromine and

Z ^{2 is} hydrogen or methoxy,

with the proviso that the sum of the dyes mentioned under a), b), c) and d) is 100% by weight,

Dye preparations containing the new dye mixtures, the use of the new dye mixtures for dyeing polyester in textile form and a process for dyeing polyester in textile form.

From JP-A-26060/1985 and US-A-4405330 dye mixtures are known, which among other things. contain the dyes of the above formula I and Ha. Furthermore describes the

DE-A-2 818653 dye mixtures which have a dye of the formula I as mixing partner. However, it has been shown that these dye mixtures still have defects when used.

Finally, dye mixtures are known from EP-A 590438 which contain the dyes of the formulas I, Ha, III, IV and, if appropriate, IIb. However, textiles dyed with these dye mixtures show a different shade under different types of light, this effect being further enhanced by the aftertreatment with an finishing agent (silicone oil based on an amino-functional polysiloxane).

The object of the present invention was to provide new dye mixtures which also contain the dyes of the formula I, Ha, III, IV and, if appropriate, Ilb. When used, the new hybrids should produce black shades and should have good application properties, in particular an unchanged neutral evening color. 'Neutral evening color' means that a color in daylight and incandescent light looks the same. This behavior can be determined colorimetrically according to ISO 7724-3-1984. This neutral evening color should also remain unchanged in the aftertreatment of the dyed textile goods with finishing agents known per se, for example silicone oils, such as amino-functional polysiloxanes.

We have found that this object is achieved by the dye mixtures specified at the outset.

All alkyl groups occurring in the formulas III and IV can be either straight-chain or branched.

R ¹ radicals are, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl or 2-hydroxyethylsulfonyl.

R ⁶ and R ⁷ are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 2-phenoxyethyl, 2- or 3 -Phenoxypropyl, 2- (2-cyanoethoxy) ethyl, 2-acetyloxyethyl, 2-phenoxyacetyloxyethyl, 2-benzoyloxyethyl, 2-methoxycarbonyloxyethyl, 2-phenylaminocarbonyloxyethyl or 2-cyanoethyl.

Preferred are dye mixtures containing at least one azo dye of the formula III or IV, in which

R ¹ nitro,

R ² and R ^{3 are} each hydrogen or chlorine,

R ^{4 is} hydrogen or chlorine,

R ^{5 is} hydrogen and

R ⁶ and R ⁷ independently of one another hydrogen, phenyl, C 1 -C ₄ -alkyl or ethyl substituted by hydroxy, phenoxy, 2-cyanoethoxy, acetyloxy, phenoxyacetyloxy, benzoyloxy, methoxycarbonyloxy, phenylaminocarbonyloxy or cyano

mean and X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each have the abovementioned meaning.

Dye preparations containing up to 5% by weight, preferably up to 3% by weight and in particular 1 to 3% by weight, based in each case on the total weight of the dyes, of at least one azo dye of the formula V, in which Z ¹ especially chlorine. Mixtures containing at least one azo dye of the formula III and / or IV and V are to be emphasized, these azo dyes having the following substituent pattern.

Dyes of the formula III:

Dyes of the formula IV:

Dyes of the formula V:

00

Particularly noteworthy are mixtures containing at least one azo dye of the formula Illd, Ulk and / or IVb and Vb.

Advantageous dye mixtures are those that are 70 to

90% by weight of the dye of the formula Ha and 10 to 30% by weight of the dye of the formula Ilb, in each case based on the weight of dye Ha and Ilb.

The new dye mixtures each contain, based on the total weight of the dyes, a) 10 to 20% by weight, preferably 12 to 17% by weight, of at least one azo dye of the formula I, b) 30 to 80% by weight, preferably 30 to 55% by weight of the azo dye of the formula Ha and optionally of the formula IIb, c) 25 to 50% by weight, preferably 30 to 50% by weight, of at least one azo dye of the formula III and / or IV and d) 0 to 5% by weight, preferably 1 to 3% by weight, of at least one azo dye of the formula V, with the proviso that the sum of the dyes mentioned under a), b), c) and d) is 100 Wt .-% results.

The dyes of the formula I, Ha, Ilb, III, IV and V are generally known dyes. They are e.g. from DE-A-2 818 653, DE-A-3 112 427, EP-A-64 221, US-A 5 283 326 or from K. Venkataraman "The Chemistry of Synthetic Dyes', Vol. III, pages 444 to 447, Academic Press, New York, London, 1970, or can be obtained by the methods mentioned there.

The dye mixtures according to the invention are prepared in a manner known per se, e.g. by mixing the respective partners in the weight ratio mentioned. If necessary, further components, e.g. Dispersants, such as lignin sulfonates or sulfonation products of the reaction product of formaldehyde with aromatics, or other auxiliaries, can be added. It is also possible to see already finished dye preparations from the respective partners or finished dye preparations with pure dyes.

Accordingly, the present invention further relates to dye preparations containing 15 to 60% by weight, based on the weight of the dye preparation, of a dye mixture described in more detail at the outset, and 40 to 85% by weight, based on the weight of the dye preparation, of dispersant .

The new dye mixtures are suitable for dyeing polyester in textile form. According to the invention, these include textile forms, such as fibers, threads, threads, knitted fabrics, woven goods or Non-wovens, polyester or blended polyester with cotton, wool, cellulose acetate or triacetate. Colorings are obtained in black shades. The dyeing processes are known per se. Further details can also be found in the examples.

Another object of the present application is a process for dyeing polyester in textile form, which is characterized in that polyester is dyed in an aqueous liquor with the dye mixture specified in more detail above, and the dyed polyester is then, optionally after a reductive post-cleaning, treated with a silicone oil.

The coloring is usually carried out at a temperature of 90 to 15 140 ° C, with 120 to 135 ° C being particularly mentioned. The pH is generally 2 to 7, preferably 3 to 5.

During dyeing, 20 dyeing auxiliaries known per se may be present in the dye bath, e.g. Dispersant based on lignin sulfonates or condensation products of naphthalene sulfonic acid with formaldehyde.

The material to be dyed is then removed, washed, optionally subjected to a reductive aftertreatment known per se (e.g. with sodium dithionite) at 60 to 80 ° C. and drying, and then treated with a silicone oil. In this treatment, the material to be dyed is padded in an aqueous liquor at about 20 to 30 ° C with a commercially available silicone oil, e.g. based on amino-30 alkylm-modified polysiloxanes, with a liquor absorption of 50 to 100%. This is followed by drying at 100 to 130 ° C and finally fixing at 160 to 260 ° C.

The dye mixtures according to the invention result in a strong coloration of 35 dyeings and have a neutral evening color. They also have excellent production properties. When carrying out the method according to the invention, i.e. aftertreatment of the polyesters dyed with the dye mixtures according to the invention in textile form with finishing agents based on silicone oils results in an increase in the color strength, which can be 20 to 40% depending on the quality of the polyester used. In addition, the textile goods treated in this way have the desired neutral evening color unchanged.

45 The following examples are intended to explain the invention in more detail.

Dyeing instruction

5 10 g of polyester fabric are placed at a temperature of 50 ° C. in 200 ml of a dyeing liquor which contains X% by weight, based on the polyester fabric, of a dye preparation and whose pH is adjusted to 4.5 using acetic acid. The treatment is carried out at 50 ° C. for 5 minutes, the temperature of the liquor is then raised to 130 ° C. within 30 minutes, the temperature is maintained for 60 minutes and the mixture is then allowed to cool to 60 ° C. within 20 minutes.

The dyed polyester fabric is then reductively cleaned by placing it in 200 ml of a liquor containing 5 ml / l for 15 minutes

15 32 wt .-% sodium hydroxide solution, 3 g / 1 sodium dithionite and 1 g / 1 of an adduct of 48 mol of ethylene oxide with 1 mol of castor oil, treated at 65 ° C. Finally, the tissue is rinsed, neutralized with dilute acetic acid, rinsed again and dried.

20th

The polyester fabric is then padded with 40 g / l of a commercially available silicone oil based on an aminoalkyl-modified polysiloxane at a pH of 5 to 6. The liquor absorption is 100%. It is dried for 3 minutes at 120 ° C. and treated

25 1 minute at 180 ° C.

The dye preparation mentioned above each contained 40% by weight of dye mixture and 60% by weight of a dispersant based on lignin sulfonate, in each case based on the weight of the preparation.

The dye mixture was composed as indicated in the following table, the following dyes being used.

35

Dye 1

45 12

Dye 2

₂₂

Dye 3

₂₂

Dye 4

Dye 5

Dye 6

Dye 7

Dye 8

NHCOCH ₃

The mixtures of Examples 1 to 6 each gave strong black colorations which, even after treatment with a silicone oil for color enhancement, still have an unchanged evening color.

Claims

claims

1. dye mixtures containing, in each case based on the total weight of the dyes,

a) 10 to 20 wt .-% of at least one azo dye of the formula I.

where shark means chlorine or bromine

30 to 80 wt .-% of the azo dye of the formula Ila

and optionally the dye of the formula Ilb

wherein the proportion of dye Ila is 50 to 100% by weight and of dye Ilb is 0 to 50% by weight, based in each case on the weight of dye Ila and Ilb, 25 to 50% by weight of at least one azo dye of the formula III and / or IV

wherein

R ¹ nitro or -CC ₄ alkylsulfonyl, which is optionally substituted by hydroxy,

R ⁴ and R ⁵ are each independently hydrogen or chlorine,

R ⁶ and R ⁷ each independently of one another are hydrogen, phenyl or C 1 -C ₄ -alkyl, which is optionally substituted by hydroxy, phenoxy, 2-cyanoethoxy, acetyloxy, phenoxy-acetyloxy, benzoyloxy, methoxycarbonyloxy or phenylaminocarbonyloxy, or if R ² and R ³ each represent hydrogen or chlorine, including C 1 -C ₄ cyanoalkyl,

X ^{1 is} hydrogen, hydroxy, methoxy, acetylamino or nitro,

X ² , X ³ , X ⁴ and X ⁵ each independently of one another are hydrogen, methyl or methoxy and

X ^{6 is} hydroxy, 2-hydroxyethoxy, Fonr l or methox - carbonyla ino, and d) 0 to 5% by weight of at least one azo dye of the formula V.

in the

Z ¹ chlorine or bromine and

Z ^{2 is} hydrogen or methoxy,

with the proviso that the sum of the dyes mentioned under a), b), c) and d) is 100% by weight.

2. dye mixtures according to claim 1, containing at least one azo dye of the formula III and / or IV, wherein

R ¹ nitro,

R ² and R ^{3 are} each hydrogen or chlorine,

R ^{4 is} hydrogen or chlorine,

R ^{5 is} hydrogen and

R ⁶ and R ⁷ independently of one another are hydrogen, phenyl,

Cι-C ₄ alkyl or substituted by hydroxy, phenoxy, 2-cyanoethoxy, acetyloxy, phenoxyacetyloxy, benzoyloxy, methoxycarbonyloxy, phenylaminocarbonyloxy or cyano

mean and X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each have the meaning given in claim 1.

3. dye preparations according to claim 1, containing up to 5 wt .-%, based on the total weight of the dyes, of at least one azo dye of the formula V.

4. dye mixtures according to claim 1, containing up to 3 wt .-%, based on the total weight of the dyes of at least one azo dye of the formula V in which Z ^{1 is} chlorine.

5. dye preparations containing 15 to 60 wt .-%, based on the weight of the dye preparation, a dye mixture according to claim 1 and 40 to 85 wt .-%, based on the weight of the dye preparations, dispersant.

6. Use of the dye mixtures according to claim 1 for dyeing polyester in textile form.

7. A process for dyeing polyester in textile form, characterized in that polyester is dyed in an aqueous liquor with a dye mixture according to claim 1 and the dyed polyester is then treated with a silicone oil, if appropriate after a reductive aftertreatment.