DE1911738C3 - Reactive dyes and processes for dyeing cellulosic textile materials - Google Patents

Description

the formula

SO ₃ H

OH

(2)

N = N-C = C

-NH

Ν — R ²
/
C = N

R ¹

OH
SO ₃ HC = CN = NR ²

(3)

N = C

corresponds to where R ^{1 is} CH ₃ , CO ₂ H or CONH ₂ and R ^{2 is} a benzene or naphthalene nucleus which optionally carries 1 to 3 substituents selected from Cl, CH ₃ , OCH ₃ , NHCOCH ₃ , CO ₂ H and SO ₃ H are selected.

These dyes are distinguished by the fact that they are of value in dyeing by exhaust processes, in which process they achieve a high degree of fixation over a wide range of liquor ratios result, which cannot be achieved with the reactive dyes currently available on the market. Simultaneously the new dyes produce color shades with very good lightfastness, whereas the previously known ones Dyes with a similar structure tend to be deficient in this property.

The new reactive dyes can be prepared by using cyanuric chloride in any Order with a molecular fraction of a water-soluble dye of the formula

D - NH ₂ (4)

and reacted with half a molecular fraction of 4,4'-diaminodiphenylurea-2,2'-disulfonic acid. The above process is conveniently carried out by stirring a suspension of the cyanuric chloride in an aqueous medium with the dye of the formula 4 at a temperature of from 0 to 20 ^° C. until one chlorine atom of the cyanuric chloride has been replaced by the radical of the dye , whereupon the diamine is added and the reaction takes place at a slightly higher temperature, usually

Cl
C.

/ V

N N

Il I

NH ₂ -Ar-NH-C C-

\ f

in the range from 30 to 50 ⁰ C, continues until a second halogen atom on the triazine nucleus has reacted with each amino group. Alternatively, the cyanuric chloride can first be reacted with the diamine to form a bis (dichlorotriazine) derivative at the lower temperature and then with the dye at the higher temperature can be implemented. The condensations are preferably carried out at a pH of 4 to 7, an acid-binding agent being added

ίο being set free during the reaction Neutralize hydrochloric acid. When the reaction is over, the new reactive dyes can be used can be isolated by the usual techniques used for the isolation of water-soluble reactive dyes

is known, for example by salting out the reaction mixture in which the dye has been prepared and filtering it off or spray-drying it. Optionally, stabilizers, such as. B. alkali metal hydrogen phosphates, added who the.

Below are some examples of dyes of Formula 4 that are used to make the invention Dyes can be used listed.

l- (2'-5'-dichloro-4'-sulfophenyl) -3-methyl-

4- (3 "-amino-4" -sulfophenylazo) -5-pyrazolone,
1 - (4'-sulfophenyl) -3-carboxy-4- (4 '' -amino-

3 '' -sulfophenylazo) -5-pyrazolone,
l- (2'-methyl-5'-sulfophenyl) -3-methyl-

4- <4 "-amino-3" -sulfophenylazo) -5-py razolon,
1- (2'-sulfophenyl) -3-methyl-4- (3 "-amino-

4 "-sulfophenylazo) -5-pyrazolone,
l- (4 ', 8'-disulfonaphth-2'-yl) -3-methyl-

4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone,
l- (2'-sulfophenyl) -3-carboxy-4- (5 "-amino-

2 "-sulfophenylazo) -5-pyrazolone,
l- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-

4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone,
l- (3'-aminophenyl) -3-methyl-4- (2 ', 5'-disulfo-

phcnylazo) -5-pyrazolone,
l- (3'-aminophenyl) -3-carboxy-4- (2'-carboxy-

4-sulfophenylazo) -5-pyrazolone,
l- (3'-aminophenyl) -3-carboxy-4- [4 "- (2 '", 5'"- di-

sulfophenylazo) -2 "-methoxy-i)" - methyl-

phenylazo] -5-pyrazolone.

The azo dyes of the present invention can also be prepared by a coupling process in many cases will. For example, by condensing cyanuric chloride with half a mole of diaminodiphenylurea disulfonic acid and then a tetrazotizable aromatic diamine with a molecular fraction of an aromatic diamine the general formula

30th

40

NH

/ V

-NH VX

SA

SO ₁ H

CO

(5)

which is tetrazotized and coupled with 2 moles of a corresponding pyrazolone coupling component who-alternatively can the cyanuric chloride with half a mole of diaminodiphenylurea disulfonic acid and then with a molecular fraction of a pyrazolone,

that has an aromatic substituent in the 1-position having, are condensed, this aromatic Substituent contains an acylatable amino group and after a condensation still to one Coupling with a diazonium compound is capable, whereupon the resulting product with 2 mol of a diazotized aromatic amine.

Examples of suitable aromatic compounds suitable for condensation in this regard are are aminophenols, aminonaphthols and aromatic diamines.

The new reactive dyes are valuable for dyeing cellulose textile materials, such as. B. Textile materials, containing natural or regenerated cotton. For coloring such materials the new dyes are preferably obtained by a printing process and especially by a dyeing process on the cellulose fabrics together with a treatment with an acid-binding agent, such as caustified soda, sodium carbonate, sodium phosphate, sodium silicate or sodium bicarbonate, applied, the latter means before, during or after the application of the dye can be applied to the cellulosic textile material. When applied this way, then the new dyes react with the cellulose and produce shades with excellent fastness opposite washing own.

The invention is illustrated in more detail by the following examples. In the examples, all parts are in Expressed weight.

example 1

A solution of 3.7 parts of cyanuric chloride in 30 parts of acetone is dissolved in an ice-cold solution of 11.4 parts of the trihydrate salt of 1 - (4'-sulfophenyl) -3-carboxy - 4 - (2 "- sulfo - 5" - aminoph enylazo) -5-pyrazolone in 200 parts of water. 20 parts of an n-sodium hydroxide solution are then added in order to neutralize the acidity that has developed. A solution of 4.5 parts of the disodium salt of 4,4'-diaminodiphenylurea-2,2'-disulfonic acid in 100 parts of water is added and the mixture is _{heated to 35 ° C. for 1 1/2} hours, during which time 20 parts of a r . Sodium hydroxide solution can be added to keep the solution neutral. 100 parts of potassium chloride are then added and the precipitated solid is filtered off and dried at 50.degree.

The dye obtained in this way is yellow Powder. By analysis it is found that there are 2.08 atoms of the originally bound chlorine in the molecule contains. When applied to cellulosic fabrics in the presence of acid-binding agents then it gives greenish-yellow shades with excellent fastness to light and wet treatments.

The fixing of the above dye was measured at BaurnwoH- and Viskoserayonmaterialien, wherein goods ratios of 5 · 1 and 20 with liquid / 1 was dyed at 8O ⁰ C as follows:

An amount of dye corresponding to 1 mole was 20: 1 dyeing, a piece of material in the other three cases) was added and dyeing at 80 ° C. for 30 minutes. Sodium carbonate was added in an amount of 20 g / l, and dyeing was continued for another hour at 80 ° C. The material was removed from the dye liquor for 30 minutes in water at 8O ⁰ C (20: 1 liquor to goods) washed.
The amounts of dye in the fresh dye liquid and in the exhausted dye liquid and in the wash water were measured at k _max with the aid of an absorption spectrophotometer. The following fixed exposure values were obtained:

60

material Liquid / goods ratio 5: 1 20: 1

cotton
Viscose rayon

76% 91%

75% 87%

Similar colorations in which an amount of dye corresponding to ggg mol and 100 gl salt is used gave the following results:

5: 1 20: 1 cotton 70% 72% ³⁰ viscose rayon 90% 81%

This dye gives an unusual appearance not only in dyeing but also in printing high fixation. For example, fixations of 85% or more are obtained from printing pastes that Contain sodium carbonate, the resulting prints being excellent during washing treatments Have over-dyeing fastness.

The following table gives further dye examples which can be obtained when the 11.4 parts of the trisodium salt of 1- (4'-SuHophenyl) - 3 - carboxy - 4 - (2 "- sulfo - 5" - aminophenylazo) -5-pyrazolone of Example 1 by the equivalent amount of the dye listed in column II of the table be replaced. Column III gives the hues that are obtained when the dye is in the presence an acid binding agent is applied to cellulosic textile materials.

in

Example 2 Example 3

dissolved in water and the solution was diluted to a volume suitable for example 4 for 5: 1 or 20: 1 staining. Salt was added in an amount of 60 g / l, and the solution was heated to 8O ⁰ C. The material (a 5 g strand of cotton in the case of the disodium salt of

l- (2 ', 5'-dichloro-4'-sul-

fophenyl) -4- (5 "-amino-

2 "-sulfophenylazo) -

3-methyl-5-pyrazzo! On

Trisodium salt of

l- (4 ', 8'-disulfonaphth-

2'-yl) -3-methyl-4- (5 "-

amino-2 "-sulfophenyl-

azo) -5-pyrazolone

Trisodium salt of

l- (2'-methyl-3'-amino-

5 '-sulfophenyl) -3-carb-

oxy-4- [2 "-sulfophenyl-

azo] -5-pyrazolone

greenish yellow

yellow

yellow

Example 5

A solution of 3.7 parts of cyanuric chloride in 30 parts of acetone is allowed to run into an ice-cold solution of 4.5 parts of the disodium salt of 4,4'-diaminodiphenylurea-2.2'-disulfonic acid in 100 parts of water. 20 parts of an n-sodium hydroxide solution are then added in order to neutralize the avidity that has arisen. A solution of 4.2 parts of the monosodium salt of 1,3-phenylenediamine-4-sulfonsäurc in 100 parts of water is added and the mixture is stirred for 20 hours and heated to 35 C ^r, during which 20 parts of an n-Nalriumhydroxydlösung be added, to neutralize the avidity that has arisen. The solution is then cooled to 0 ° C. and 25 parts of a 2N hydrochloric acid are added, followed by the addition of 10 parts of a 2N sodium nitrite solution. After 30 minutes, the excess nitrous acid is destroyed by the addition of sulfamic acid, and a A solution of 6.75 parts of the dinatrium salt of 1 - (4 '- sulfophenyl) - 3 - carboxy - pyrazolone in 100 parts of water is added, then sufficient sodium hydroxide solution is added to raise the pH to 7 and after 1 hour 100 parts of potassium chloride were added and the precipitated dye is filtered and dried at 5O ⁰ C.

The yellow powder thus obtained has properties similar to those described in Example 1 bene dye.

Claims (2)

1. Reactive dyes of the formula N
\ D-N-C C-NH I I I! H N N