DE1619509B2 - Color preparations and their uses - Google Patents

Description

The invention relates to cold-soluble dye preparations consisting of (a) one of reactive groups free 1: 2 chromium or cobalt complex azo dye, which has at least one optionally N-monosubstituted or -acylated sulfonamide group, (b) an alkali-releasing inorganic compound and optionally (c) an anionic dispersant and (d) an adjusting agent. The invention relates to also the use of these dye preparations for dyeing and printing natural or synthetic Polyamide fibers.

Metal complex azo dyes containing sulfonamide groups which are used in the dye preparations according to the invention present are known in large numbers from the literature, for example from German patents 870 305, 937 367, 940 483, 945 342, 953 827, 340, 1072 338, 1049 021, the French Patents 1353 364, 1380 632, 1433 756, den British patents 741602, 988 829, 995 361 and Belgian patents 553 658, 566 180, 394, 638 213, 643 959, 644 415, 534 106, 531 678, 094 and 537 533. Generally they are in the case of the 2: 1 chromium or cobalt complex azo dyes around the metal complexes of mono- or disazo dyes, as metal complex-forming groups (before metallization) ο, ο'-dioxy, o-oxy-o'-amino, o-oxy-o'-alkoxy, o'-carboxy-o'-oxy or o-alkoxy-o'-aminoazo groups exhibit. By definition, the dyes should not contain any reactive groups.

Suitable alkali-releasing inorganic compounds, which are contained in the dye preparations, such can be considered that are capable, in aqueous solution at temperatures ranging from 1O ⁰ C and ίο higher the sulfonamide groups contained in the metal complex dyes in the corresponding sulfonamide salts of the general formula

- SO, - N — RMe © or —SO ₂ -N

Me \

where R is H or a substituent such as an alkyl or aryl group, or an acyl group and Me

oo stands for an alkali atom. For this are inorganic alkali compounds with an alkaline effect in aqueous solution are suitable, such as alkali hydroxides, z. B. lithium, sodium and potassium hydroxide, alkali carbonates, e.g. B. sodium or potassium carbonate, secondary or tertiary alkali phosphates, e.g. B. disodium hydrogen phosphate, trisodium orthophosphate, tetrasodium pyrophosphate, Dipotassium hydrogen phosphate, tripotassium orthophosphate and tetrapotassium pyrophosphate.

The dye preparations contain the alkali-releasing inorganic compounds in quantities sufficient to bring about partial or complete salt formation of the sulfonamide groups contained in the metal complex ^{dyes in aqueous solutions of 10 ° C. and higher.} It is preferred to use 20 to 200 parts by weight of alkali-releasing inorganic compounds per 100 parts by weight of metal complex azo dye.

If the dye preparations are to be adjusted to a specific strength, customary adjusting agents can be added which do not interfere with the subsequent dyeing process, such as dextrin, sodium chloride or sodium sulfate.
Anionic dispersants can be present in the dye preparations according to the invention. Preferred anionic dispersants here are naphthalene sulfonic acid, alkylnaphthalene sulfonic acids, condensation products of naphthalene or naphtholsulfonic acids with formaldehyde or naphthalene or naphtholsulfonic acids and phenols, e.g. B. m-cresol with formaldehyde or reaction products of lignosulfonic acids with aromatic amines, e.g. B. aniline, for use. Preferably, 5 to 300 parts of the anionic dispersant are used per 100 parts of metal complex azo dye.

The dye preparations according to the invention have

preferably a pH between 8.6 and 11.0.

The dye preparations according to the invention offer the particular application advantage that 1: 2 chromium and cobalt complex azo dyes which contain at least one optionally mono-alkylated or mono-acylated sulfonamide group can easily be dissolved without heating. The achievable dye concentrations are higher in some cases, as they, ie, by dissolving the metal complex dyes at elevated temperatures up to 100 ⁰ C can be obtained by the normal method. in the

3 4

Compared to the dyestuff prepa sulfonylamino-7-naphthol known from the literature, 25 parts of tri-

rates in which sulfonamide-containing metal sodium phosphate and 5 parts of di-butylnaphthalene

complex azo dyes mixed in a neutral aqueous solution in sulfonate. 60 parts of the preparation dissolve

The form of their poorly soluble at 10 to 30 ⁰ C sodium in 1000 parts of water of 25 °.

salts of the dye complex acids are present, which for the 5th

Dyeing first dissolved in water at 80 to 100 ° C and Example 3

are then added to the dye liquor, the inventively 50 parts of the chromium 1: 2 complex of the monoazo

dye preparations according to the invention have the advantage of. dyes 2-aminophenol-4-sulfonamide -> 1- (2,5'-Di-

chlorophenyl) -3-methyl-5-pyrazolone with 20 parts are very easy even at temperatures of 10 to 20 ° C

in partly higher dye concentrations in io len tripotassium phosphate and 2 parts of di-butylnaphtha-

To dissolve water and, technically speaking, linsulfonate is mixed with it. Loosen 60 parts of the preparation

considerably easier to use. in 1000 parts of water at 25 °.

Compared to that from the British patent specification. .
906 807 known dye preparations require the 13 e ι s ρ ι e 1 4
preparations according to the invention no non-ionic 15 50 parts of the cobalt 1: 2 complex of the monoazo dispersant; so they show no delay dyes 2-aminophenol-4-sulfonamide - * ■ 2-naph the drawability on the substrate, furthermore, thol, 30 parts of potassium carbonate and 5 parts of an economic advantage that the additions of suidation products from 2-naphthol 6-sulfonic acid and fanilic acid derivatives can be dispensed with. Formaldehyde are mixed. 60 parts of the prepa-

The dyeing preparations according to the invention can ao rates dissolve in 1000 parts of water at 25 °.

obtained by simply mixing the components. . .

will. The example from British Patent Specification 906 807

known preparations, however, have to dissolve 50 parts of the chromium 1: 2 complex of the monoazo

the components in water and then dyes 2-aminophenol-5-sulfonamide -> 1- (3'-Ni

Evaporation of the water can be produced. as trophenyl) -3-methyl-5-pyrazolone, 5 parts sodium hy-

The claimed dye preparations are mainly powdered hydroxide, 5 parts of dinaphthyl methanesulfonate

for dyeing nitrogenous materials such as and 10 parts of dextrin are mixed. 40 parts of the

Leather and silk, but especially wool and synthetic preparations, dissolve in 1000 parts of water at 25 °. table super polyamide materials.

The dyeing is carried out according to the 30 examples for these materials
usual procedures. Dissolve the claimed 50 parts of the chromium 1: 2 complex of the monoazo dye preparations z. B. in water from 10 to 30 ° C on dyes 4 - chlorine - 2 - aminophenol - »1 - (3 '- sulf one and gives the alkaline dye solution in amidophenyl) -3-methyl-5-pyrazolone with 25 The dye liquor, which appropriately mixes the trisodium phosphate for neutralization. 40 parts of the pre-required amount of organic acids, e.g. B. 35 parates dissolve in 1000 parts of water at 25 °.
Acetic or formic acid or mineral acid, such as hydrochloric acid. .
or sulfuric acid. Example 7

Because of the risk of damage to the wool, 50 parts of the cobalt 1: 2 complex of Monoazoder Praxis are generally more alkaline setting dye 4-methoxy-2-aminophenol-5-sulfonamide - »lungs of wool dyes, including chromium-40 l-carbomethoxyamino-7-naphthol, 25 parts sodium and cobalt complex azo dyes avoided. It has carbonate, 5 parts of dibutylnaphthalenesulfonate and lOTeisich therefore apparently also with the dye-producing dextrin are mixed. 40 parts of the preparation established the view that alkaline dissolve in 1000 parts of water at 25 °.
Settings of wool dyes in practice are not. .
can be offered. Consequential are 45 examples
only neutral or weakly alkaline dye constituents 31 parts of the 1: 2 chromium complex of the dye positions (pH 7.5 to 8) have been customary in practice. With 6-nitro-4-chloro-2-aminophenol - »■ l- (2 ', 6'-dimethyl application of the dye preparation according to the invention 3-sulfonamidophenyl) -3-methyl-5-pyrazolone, 30 parts rate is now in spite of the alkaline setting no tetrasodium pyrophosphate and 36 parts of a Kon-Risk of wool damage, since the dye solution in 50 densationsproduktes of ligninsulphonic acid and aniline acid dye liquor are quickly mixed at low temperatures. 50 parts of the preparation dissolve in being neutralized. 1000 parts of water at 25 °.

In the following examples, parts represent Ge. .

important parts, the temperature data are degrees Celsius. example

". . . 55 50 parts of the cobalt 1: 2 complex of the monoazo

Example 1 dyes 2 - aminophenol - 4 - phenylsulfonamide ->

50 parts of the cobalt 1: 2 complex of monoazo-2-naphthol are mixed with 25 parts of tripotassium phosphate, dyes 2-aminophenol-4-sulfonamide - »■ 1- (2 ', 5'-di- 5 parts of di-butylnaphthalene sulfonate and 30 parts of chlorophenyl) -3-methyl-5-pyrazolone are mixed with 25 parts of a condensation product of naphthalene-sulphate trisodium phosphate and 10 parts of a condensate acid and formaldehyde. 35 parts of the sation product from 2-naphthol-6-sulfonic acid and preparation dissolve in 1000 parts of water at 25 °. Formaldehyde mixed. Loosen 40 parts of the preparation.
in 1000 parts of water at 25 °. B e 1 s ρ 1 e 1 10

_. . . . Used to dye 5000 parts of woolen yarn

B e 1 s ρ 1 e 1 2 g _{5 60 parts of the} preparation described in Example ι,

50 parts of the chromium 1: 2 mixed complex of the mono- containing the cobalt 1: 2 complex of the monoazo-

azo dyes 2 - aminophenol - 4 - sulfonamide -> dye 2-aminophenol-4-sulfonamide -> 1- (2 ', 5'-di-

2-naphthol and 4-nitr.o-2-aminophenol -> 1-methyl-chlorophenyl) -3-methyl-5-pyrazolone, in 2000 parts

5 6

Dissolved water at 25 °. This solution is an example 15
Dyebath added containing 50 parts of acetic acid (60%)

and 100 parts of a condensation product of 20 parts of the chromium 1: 2 complex 2-amino-5-sul-

Contains naphthalene-2-sulfonic acid and formaldehyde. fonamidobenzoic acid -> ■ 1-phenyl-3-methyl-5-pyr-

The dye liquor prepared in this way will be about 5 azolone at 40 to 50 ° with 20 parts of trisodium phosphate

Pumped through the dyed material for 10 minutes before the (-6-hydrate) and 60 parts of dextrin are mixed. 50 parts

When the temperature of the dyebath is raised to the boiling point, the preparation dissolves in 1000 parts of water

will. After a cooking time of about 45 minutes it is 20 to 25 °.

the coloring completed. A coloration is obtained. -I ₁ /:

which are absolutely impeccable in their authenticity properties

is free and corresponds to a color that results, 20 parts of the chromium 1: 2 complex 2-anainobenzoe-

if the amount of the same used for dyeing acid -> l- (3'-sulfonamidophenyl) -3-methyl-5-pyr-

Dye is dissolved in hot water. azolon are mixed with 10 parts of tripotassium phosphate

. -I ₁₁ mixes. 40 parts of the dye preparation dissolve in

ti e ι s ρ ι e 1 II _{lg 1000 parts of water from} 20 to 25 °.

A color paste according to the following example 17 is used to dye tops of wool according to the pad-steam process
Recipe scheduled:

15 parts of the preparation described in Example 3 20 parts of the chromium 1: 2 mixed complex 2-amino

are dissolved in 500 parts of water at 25 °. To this »o phenol-4-sulfonamide -> 1-phenyl-3-methyl-5-pyr-

Solution gives the solution of 10 parts of an azolone with 20 parts of trisodium phosphate,

Thickening agent based on locust bean gum in 5 parts of benzamide and 3 parts of dibutylnaphthalene sulfonate

300 parts of water and stir well again. Then and 10 parts of a condensation product

20 parts of a coacervate-forming lignosulfonic acid and aniline are ground with stirring. 50 parts of the

the auxiliaries (e.g. laurylic acid diethanolamide) »s preparation dissolve in 1000 parts of water from 20 to

and 25 parts of 60% acetic acid were added. Then 25 °.

you fill the paste with 140 parts of water to ins-. .

a total of 1000 parts. With this paste, B e ι s ρ ι e 1 18

1000 parts of woolen sliver on a padding impregnated 20 parts of the cobalt 1: 2 complex 2-aminophenol

gnared and then steamed. After the Aus 30 4-sulfonamide -> ω -Cyan -acetophenon, 40 parts of tri-

washing results in a dyeing with the fastness sodium phosphate and 15 parts of dextrin are mixed

properties of a coloring obtained when mixing. 50 parts of the preparation dissolve in 1000 parts

When preparing the paste, add the appropriate amount of water from 20 to 25 °.

of the same dye is dissolved in hot water. _,. . , ^ _n

^e ₃₅ Example 19

B e i s ρ i e 1 12 72 parts of the cobalt 1: 2 complex 2-aminophenol

4-methylsulfonamide -> 2-naphthol are made up of 12 parts

For dyeing 750 parts of synthetic supersodium trisodium phosphate, 12 parts of a condenser polyamide yarn 60 parts of the bation product in Example 2 from ligninsulphonic acid and aniline Written preparation in 1000 parts of water at 25 ° 40 and 5 parts of benzamide. 50 parts of the color dissolved. This solution is added to a dyebath, fabric preparations dissolve in 1000 parts of water which contains 15 parts of 60% acetic acid. After a short 20 °.

Circulation of the dye liquor through the material to be dyed. .

heated to boiling point and cooked for about 20 minutes. Example 20

To exhaust the liquor, 16 parts 45 50 parts of the cobalt 1: 2 complex 2-aminophenol

60% acetic acid added, whereupon again 4-sulfonamide -> 5,8-dichloro-l-naphthol are with

Is cooked for 20 minutes. The black obtained 20 parts of trisodium phosphate and 25 parts of saccha

The fastness of the dyeing corresponds to a dyeing, mixed rose. Dissolve 45 parts of the dye preparation

which results when the amount used for dyeing is 1000 parts of water at 25 °.

of the same dye is dissolved in hot water. 50 _, .., ..

Example 21

B is ρ ie 1 13 _{20 Tdle deg} Q _1101n .! . 2-complex 2-aminophe-

18 parts of the 1: 2 chromium mixed complex of 4-ninol-4-sulfonamide - »1,3-dihydroxy-iso-quinoline are

tro-2-aminophenol - »1-methylsulfonylamino-7-naphdene mixed with 15 parts of tripotassium phosphate,

thol and 2-aminophenol-4-sulfonamide -> Acetoacet- 55 50 parts of the preparation dissolve in 1000 parts of water

aniline, 50 parts trisodium phosphate, 12-hydrate, 29 parts from 20 to 25 °.

len of a condensation product from lignosulfone ". .

acid and aniline and 3 parts of di-butylnaphthalenesul- 13 e 1 s ρ 1 e 1 22

f onat are mixed. 50 parts of the mixture dissolve 50 parts of the chromium 1: 2 complex 2-aminophenol

in 1000 parts of water at 25 °. 60 3,5-bis-methylsulfonamide -> l-phenyl-3-methyl-pyr-

t> ■ ■ λ ι * azolon-5, 20 parts tripotassium phosphate and 5 parts

Example 14 Benzamide are mixed. 45 parts of the preparation

20 parts of the dye 2-aminophenol-4-sulfonamide dissolve in 1000 parts of water at 20 °.

- »Acetoacet-2-ethyl-hexylamide, cobalt-1: 2 complex,. .

19 parts trisodium phosphate and 2 parts dibutyl 65 B e 1 s ρ 1 e 1 23

naphthalene sulfonate are mixed. 50 parts of the 100 parts of the cobalt 1: 2 complex 4-chloro-2-ami-

Dye preparations dissolve in 1000 parts of water nophenol -> 6- (Hydroxyethylsulfonamido) -2-naphthol

from 20 to 25 °. are made with 10 parts of trisodium phosphate and 35 parts

7 8

grind len sucrose. 50 parts of the preparation B is ρ ie 1 27
dissolve in 1000 parts of water from 20 to 25 °.

. . 60 parts of the cobalt 1: 2 complex 5-nitro-2-amino-

Example 24 phenol -> 6-sulfonamido-2-naphthylamine are used with

40 parts of the cobalt 1: 2 complex 4-chloro-5-sulfone-5 19 parts tripotassium phosphate mixed. 45 parts of the

amido - 2 - aminophenol -> 3 - hydroxythionaphthene preparations dissolve in 1000 parts of water at 20 °.

are mixed with 20 parts of trisodium phosphate (-6 hydrate)

mixed. 45 parts of the preparation dissolve in B ice ρ ie 1 28
1000 parts of water from 20 to 25 °.

. . ίο 75 parts of a dye made by mixing

Example 25 chroming of equal parts of 2-aminophenol

50 parts of the chromium 1: 2 complex 4-chloro-2-amino-4-sulfonamide -> ■ 2-naphthol, 4-nitro-2-aminophenol

phenol - »3-sulfonamido-S-acetylamino-l-naphthol -> S-acetylamino ^ -naphthol and 2-aminophenol-

are with 12 parts tripotassium phosphate, 10 parts 4-sulfonamide - »l-naphthol-3-sulfonmethylene-4-ether

a condensation product of ligninsulfonic acid 15 with 15 parts of trisodium phosphate and 10 parts

mixed with aniline and 3 parts of di-n-butylnaphthalenesulfonate len sucrose. 50 parts of the preparation

mixed. 50 parts of the preparation dissolve in water dissolve in water at 20 to 25 °.

from 20 to 25 °. _ß . . , _o .

B e 1 s ρ 1 e 1 29

Example 26 _ao 72T _e iledesChrom-1: 2-complexes2-aminophenol-

40 parts of the chromium-1: 2-complex 4-chloro-5-nitro-4 - ethylsulfon -> 8 - methylsulfonylamino - 2 - naphthol

2 - aminophenol -> ■ 3,6 -Bis - sulfonamido -1-naphthol with 13 parts of trisodium phosphate, 12 parts

with 15 parts of trisodium phosphate and 20 parts of benzamide and 1 part of di-n-butylnaphthalene sulfonate

len sucrose mixed. 50 parts of the preparation mixed. 40 parts of the preparation dissolve in

dissolve in 1000 parts of water from 20 to 25 °. 25 1000 parts of water at 20 °.

Claims (5)

Patent claims: 1.Cold-soluble dye preparation, consisting of (a) a 1: 2 chromium free from reactive groups or cobalt complex azo dye which is at least one optionally N-monosubstituted or acylated Sulfonamide group, (b) an alkali-releasing inorganic compound and optionally (c) an anionic dispersant and (d) an adjusting agent. 2. Cold-soluble dye preparation according to claim 1, characterized in that it has 100 parts by weight of a 1: 2 chromium or cobalt complex azo dye free of reactive groups, which has at least one optionally alkyl- or aryl-substituted sulfonamide group, 20 up to 200 parts by weight of a tertiary alkali phosphate and 5 to 300 parts by weight of an anionic one Contains dispersant. 3. Cold-soluble dye preparations according to Claims 1 and 2, characterized by a content to trisodium phosphate or tripotassium phosphate as an alkali-releasing inorganic compound and a condensation product of hydroxynaphthalenesulfonic acid and formaldehyde as an anionic dispersant. 4. Cold-soluble dye preparations according to Claims 1 and 2, characterized by a content on trisodium phosphate, tetrasodium phosphate or tripotassium phosphate as alkali inorganic compound and a condensation product of lignosulfonic acid and aniline as an anionic dispersant. 5. Use of cold-soluble dye preparations according to Claims 1 to 4 for dyeing and printing on natural or synthetic polyamide fiber materials.