CH654845A5 - ANIONIC MONOAZO COMPOUNDS, METHOD FOR THE PRODUCTION AND THEIR USE IN COLORING AND PRINTING METHODS. - Google Patents

Description

The present invention relates to a single sulfo group-containing monoazo compounds and their salts, 45 processes for the preparation and use of these compounds in processes for dyeing and printing.

In the narrower sense, the invention encompasses compounds which are in the form of the free acid of the formula I.

correspond to what

Ri

65 R2

n

R3

(1-6C) alkyl or (3-6C) alkyl monosubstituted by hydroxy, chlorine or cyano,

Hydrogen or (1-4C) alkyl,

I or 2 and independently of one another are hydrogen or methyl,

3rd

654 845

15

the condition for the substituents on the sulfonamide nitrogen being that the radical R 1 and the optionally alkyl-substituted phenyl radical together have 9 to 15 carbon atoms,

Rj represents hydrogen, halogen, (1-4C) alkyl or (1-4C) alkoxy 5

and

Ri represents hydrogen or (1 -4C) alkyi, and their salts.

The total number of carbon atoms for R 1 and the optionally alkyl-substituted phenyl radical on the sulfonamide nitrogen is preferably 9-12, more preferably 9 or 10 and particularly preferably 10 carbon atoms.

Ri as unsubstituted alkyl can be straight-chain or branched and is preferably (1-4C) alkyl; more preferably it is methyl, ethyl or straight-chain or branched butyl; it is particularly preferably the n-butyl radical.

Ri as substituted alkyl can be straight-chain or branched and contains the substituent on a atom other than the Ci atom; it preferably contains 3 or 4 carbon atoms. It is more preferably hydroxy-substituted and means 2-or 3-hydroxypropyl or 2-, 3- or 4-hydroxybutyl,

the propyl and butyl groups can be linear or branched; particularly preferably it means straight-chain 2-hydroxypropyl or 2-hydroxybutyl; it very particularly preferably means straight-chain 2-hydroxybutyl.

R 1 preferably denotes R 1 a as linear or branched (1-4C) alkyl or linear, branched (3 or 4C) alkyl monosubstituted by hydroxy, chlorine or cyano,

wherein the substituent is on a atom other than the Ci atom; more preferably R | b as methyl, ethyl, straight-chain or branched butyl; straight-chain or branched 2- or 3-hydroxypropyl or 2-, 3- or 4-hydroxybutyl; more preferably R] c as methyl, ethyl, n-butyl, 2-hydroxypropyl- (n) or 2-hydroxybutyl- (n); in particular Ri represents Ru as n-butyl or 2-hydroxy-butyl- (n); Ri very particularly preferably represents n-butyl.

R2 as alkyl is preferably methyl or ethyl, especially methyl.

R2 preferably represents R2a as hydrogen, methyl or ethyl; especially for R2b as hydrogen or methyl.

If the phenyl radical on the sulfonamide nitrogen is monosubstituted, all free positions are equally preferred. If the phenyl radical is disubstituted, the two substituents are preferably in the 2,4-, 2,5- or 3,5-position, in particular in the 2,4- or 2,5-position. If the phenyl radical is trisubstituted, the three substituents are preferably in the 2,4,6-position.

R4 as halogen preferably denotes chlorine or bromine, in particular chlorine. R4 as alkyl or alkoxy preferably contains m 1 or 2 carbon atoms and in particular represents methyl or methoxy.

The substituent R4 is preferably in the 4-, 5- or 6-position of the phenyl radical; especially in 4- or 5-position. 53

R4 preferably represents R4a as hydrogen, chlorine, methyl or methoxy; more preferably for R4b as hydrogen or methyl; in particular R4 stands for hydrogen.

Rs as alkyl preferably means methyl.

Rs preferably represents RSa as hydrogen or methyl; in particular Rs means hydrogen.

Compounds which are in the form of the free acid of the formula Ia are preferred

Yes

'za (R3> n and their salts, in which R, c and the optionally alkyl-substituted phenyl radical on the sulfonamide nitrogen together have a total of 10 carbon atoms; the radical R4a is in the 4-, 5- or 6-position; and in which,

if the N-phenyl radical carries two substituents, these are in positions 2,4-, 2,5- or 3,5, and if the 20 N-phenyl radical carries three substituents, these are in positions 2,4,6 are located.

Those compounds of the formula Ia in which

(1) R4 is R4;

25 (2) R | C represents Rid;

(3) Ria is R2b;

(4) those of (2) or (3), wherein R4a is hydrogen;

(5) the compound of group (4), in which R | C is n-butyl and R2a and R3 are hydrogen.

30 The nature of the cation of the sulfo group in a compound of formula I, if it is in salt form,

is not a critical factor, but can be any non-chromophoric cation common in the chemistry of anionic dyes, for example an alkali metal ion or unsubstituted or substituted ammonium ion. Examples of suitable cations are lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.

* 0 Preferred cations are the alkali metal ions and ammonium, of which sodium is particularly preferred.

The compounds of formula I are prepared by the diazonium compound of an amine of formula II

II

with a compound which is in the form of the free acid of the formula III

NHR,

III

corresponds, or couples a salt thereof in acidic to neutral medium.

654 845

4th

Diazotization and coupling are carried out according to conventional methods. The coupling reaction is advantageously carried out in an acidic environment, preferably at pH 3 to 4.5, in water or in a mixture of water and a water-miscible organic solvent; preferably the reaction temperature is between 0 and 30 ° C, especially when using water as reaction medium between 0 and 10 ° C, when using water in a mixture with an organic solvent, e.g. Water / ethanol, especially between 0 and 20 ° C.

The process mentioned gives the monoazo compounds of the formula I in the form of the salts and, as such, can be isolated from the reaction mixture by methods known per se. The monoazo compounds are advantageously isolated by salting out, filtering, washing and then drying in vacuo.

Depending on the reaction and isolation conditions, the compounds of the formula I are obtained in the form of the free acid or preferably in the salt form or in the mixed salt form. By subsequent, known per se salting, the compounds of formula I can also be converted into another salt form or into mixed salts and then contain, for example, one or more of the cations listed above.

The starting compounds of the formulas II and III are known or can be prepared analogously to processes known per se.

The compounds of the formula I, in particular in salt form, are anionic dyes and can be used for dyeing and printing any organic textile or non-textile substrates that can be dyed with anionic dyes. Suitable substrates are leather and textile material which consists of or contains natural or synthetic polyamides, polyurethanes or base-modified polyolefins. However, the dyes are used with particular advantage for dyeing and printing textile material which consists of or contains natural and synthetic polyamide fibers such as wool, silk and in particular nylon such as nylon 6 or nylon 66, and also particularly advantageously with carpet printing .

The compounds of the formula I can be used as such or in the form of liquid or solid preparations, as are usually used for anionic monoazo dyes. Processing into stable liquid, for example concentrated aqueous or solid coloring preparations can be carried out in a generally known manner, e.g. by dissolving in suitable solvents such as water, optionally with the addition of a conventional auxiliary such as urea as a solubilizer; or then by grinding or granulating.

It is also possible to use the compounds in the form of cold-dispersible preparations. For this purpose, the dyes are subjected to mechanical comminution in the presence of one or more customary anionic dispersants and, if appropriate, further auxiliaries by dry or wet grinding with the dispersion medium water and, if appropriate, subsequently dried by atomization. These preparations are dispersed again in finely dispersed form when introduced into cold water.

Dyeing and printing processes can be carried out according to methods known per se. For example, dyeing can be carried out using the pad or exhaust dyeing method, the latter being preferred, since the compounds of the formula I are drawn up from an essentially neutral, aqueous dye bath, such as weakly alkaline to weakly acidic, aqueous dye bath. The space-dyeing process can also be used. Furthermore, the dyes according to the invention are suitable for the use of rubber displacement technology in carpet dyeing in order to achieve certain pattern effects.

The dyes of the formula I are distinguished in particular by the fact that, with good neutrality, they have high migrability combined with very good leveling properties. In particular, on nylon, which tends to streak when dyed, balanced streak-free dyeings are obtained. In addition, the dyes have good solubility and good build-up. The dyeings obtained with the dyes of the formula I show remarkable light fastness and other good general fastness properties such as good wet fastness properties, in particular wash, (cold) water, walk and sweat fastness, and other fastness properties such as good rub fastness (dry and wet). and good ozone fastness. In addition, the dyes are very strong in color.

The dyes of the formula I according to the invention are easy to combine with known dyes of the same category, especially in important trichromes, resulting in tone-in-20 tone colorations; the good properties of the dyeings, in particular the good lightfastness and level character, are retained; the combination stains also show no catalytic fading.

In the following examples, parts are 25 parts by weight and percentages are by weight; the temperatures are given in degrees Celsius.

example 1

30.4 parts of 2-amino-N-n-butyl-N-phenyl-benzenesulfone-30 acid amide are dissolved in 80 parts of ethyl alcohol with 56 parts of 30% hydrochloric acid at 45 ° and then cooled to -5 ° with an ice bath. A solution of 7.0 parts of sodium nitrite in 25 parts of water is added dropwise over a period of 20 minutes at a temperature of -5 ° to 0 °. After stirring for 30 minutes, the diazotization is complete; a small excess of nitrite is destroyed by adding a little amidosulfonic acid. 23.9 parts of 2-amino-8-hydroxynaphthalene-6-sulphonic acid are dissolved in 150 parts of water by adding 12 parts of a 30% strength sodium hydroxide solution; the result is a pH of about 8. This solution is slowly added dropwise to the diazo solution prepared above over a period of 1 hour, the pH being kept between 3 and 3.5 by adding a 50% sodium acetate solution. After stirring for 2 1/2 hours, the coupling is complete. 45 The pH is adjusted to 9 by adding 30% sodium hydroxide solution; the precipitated dye is filtered off and the residue is washed with 200 parts of a 10% sodium chloride solution. The dye obtained, which is dried in vacuo at 100 °, corresponds in the form of the acid thus free to the formula ch2ch2ch2ch3

and is isolated as the sodium salt. It dyes natural and synthetic polyamide fibers in bluish red tones. The dyeings show good light fastness and have good wet fastness properties.

The dye is a very suitable trichromatic element.

5

65-: ..545

Examples 2-47

Analogously to Example 1 above, starting from the corresponding starting materials, further dyes can be prepared in the form of the free acid of the formula

NHRg and for which the variables and the necessary position information are listed in the following table.

Example No.

R1

R2

r3

r6

* 4

%

32

c4H9 (n)

2-CK3

4-ch3

H '

H

H

33

do.

do.

do.

H

5-CK3

H

34

do.

H

H

H

4-C1

ch3

35

-CH2CH2CH20H

h h

H

H

H

36

do.

2-CH3

h h

H

H

OH

1

37

-ch2chch3

do.

h h

h h

38

do.

do.

h h

h ch3

39

do.

h h

H

4-CH3

H

40

do.

h h

h do.

ch3

41

-ch2ch2ch2ch2oh h

h h

h h

42

do.

h h

h h

ch3

Oh

1

43

-ck2chch2ch3

h h

h h

H

44

do.

k h

h h

ch3

45

do.

h h

H

6-OCH3

H

46

do.

H

H

H

5-CH3

H

47

do.

3-ck3

H

H

H

H

table

Example No.

ri

R2

* 3

r6

r4

rs

2nd

C2 "5

2-CH3

4-CH3

H

H

H

3rd

do.

do.

do.

H

H

CH3

4th

do.

do.

do.

H

5-CH3

H

5

do.

do.

"do.

'h do.

ch3

6

do.

do.

5-CH3

h h

H

7

do.

do.

do.

H

6-OCH3

H

8th

do.

do.

do.

H

4-ch3

H

9

do.

2-c2h5

h h

do.

H .

10th

do.

do.

h h

h h

11

ck3

2-CH3

4-CH3

6-CH3

h h

12

do. .

do.

5-CH3

H

4-ch3

K

13

do.

2-c2h5

H

H

H

H

14

<ïo.

3-C2H5

K

H

5-CH3

H

15

do. •

2-CH3

4-ch3

6-CH3

H

ch3

16

-ch2chch3

H

H

11

H

K

ch3

17th

do.

H

H

H

5-CH3

H

18th

c3h7 (n)

3-CH3

H

H

H

H

19th

do.

do.

H

H

4-c1

H

20th

do.

do.

H

H

5-CH3

H

21st

do.

2-CÜ3

5-CH3

H

H

ch3

22

C3H7O)

4-CH3

H

H

h h

23

£ 4 ^ 9 (0)

h h

H

H

ch3

24th

do.

2-ch3

H

H

H

H

25th

do."

2-c2h5

h h

H

H

25th

do.

h h

H

4-c1

H

27th

do.

h h

H

6-0CH3

H

23

do.

h h

H

4-Ch'3

H

23

do.

H

H.

H

5-CH3

H

30th

do.

H

H

H

do.

CH3

31

do.

H

H

II

6-OCH3

do.

The dyes of Examples 2 to 47 dye natural and synthetic polyamide fibers in bluish red tones. These colors show good light and wet fastness properties. 3o According to the reaction and isolation conditions described, the dyes of Examples 2-47 are obtained as sodium salts. However, they can also be converted into another or mixed salt form by salting using methods which are conventional per se and then contain, for example, one or more of the cations listed further in the description.

Possible uses of the dyes according to the invention are illustrated below:

40 Application example A (pull-out dyeing on polyamide fabric)

100 parts of pre-wetted synthetic polyamide fabric, e.g. Nylon 66 are placed in a dye bath of 40 °, which has the following composition:

45 2 parts of the dye from Example 1 10 parts of anhydrous sodium sulfate 4000 parts of water

The dye liquor is heated to boiling over the course of 30 minutes and held at the boiling temperature for one hour. 50 Then 4 parts of glacial acetic acid are added and the dyeing is ended by heating to boiling temperature for a further 30 minutes. The evaporated water is continuously replaced during dyeing. The bluish red colored nylon cloth is removed from the liquor, rinsed with water 55 and dried. Wool can also be dyed using the same procedure.

Application example 8 (pull-out dyeing on nylon yarn)

100 parts of pre-wetted nylon 66 yarn are added to a dyeing bath at 26-27 ° of the following composition:

1 part of the dye from Example 1 1-2 parts of oleylamine (leveling agent)

1 part monosodium phosphate 3000 parts water

The dyebath is heated to boiling temperature, then 1 part glacial acetic acid is added and kept at boiling temperature for 45 minutes. Water that

654 845

6

Process evaporates, is continuously replaced. The bluish red colored nylon 66 yarn is removed from the liquor, rinsed with warm water and dried.

The dyes of Examples 2-47 or a mixture consisting of two or more dyes of Examples 1-47 can also be used for dyeing polyamide in an analogous manner to that indicated in Application Examples A and B.

The dyeings obtained show good light and wet fastness properties.

Application example C (printing instruction for polyamide fabric)

Polyamide is printed with a printing paste of the following composition:

30 parts of the dye from Example 1 50 parts of urea

50 parts of solubilizer (e.g. thiodiethylene glycol) 290 parts of water

500 parts of a suitable thickener (e.g. based on locust bean gum)

20 parts of an acid donor (e.g. ammonium tartrate) 60 parts of thiourea

The printed textile is steamed for 40 minutes at 102 ° (saturated steam, then rinsed cold, then washed at 60 ° for 5 minutes with a dilute solution of a commercially available detergent and rinsed again cold. A bluish red print with good light and wet fastness results .

Printing pastes can be prepared in an analogous manner which contain as a constituent a dye from Examples 2-47 or a mixture of two or more dyes from Examples 1-47. These pastes can be used for printing analogously to the above-mentioned regulation.

Application example D (continuous dyeing of polyamide carpet)

Carpet made of polyamide (e.g. from ordinary nylon 6 or nylon 66) is wetted and squeezed with a preparation consisting of 1-2 parts of decyl alcohol, which has been ethoxylated with 4 moles of ethylene oxide per mole of alcohol, or a similar surface-active agent and 998-999 parts of water to achieve an impregnation and total absorption of wetting agent of 80-100 ° o.

The carpet material pretreated in this way is treated with a dye liquor from the constituents 5 0.5-5 parts of the dye from Example 1

1 -2 parts of a guar resin-based thickener

(like Celca Gum D-49-D)

1-2 parts of decyl alcohol that has been ethoxylated with 4 moles of ethylene oxide per mole of alcohol (or a similar surfactant)

91-97.5 parts of water and a sufficient amount of trisodium phosphate or acetic acid to adjust the pH to 5 (for example for nylon 6 and for nylon 66) on a continuous system (for example i5 Kuesters) colored to achieve a liquor intake of 300-600 %. The bluish red colored polyamide carpet material is then steamed in a vertical or horizontal steam generator for 4-10 minutes, rinsed with warm water and dried.

20th

Application example E (continuous dyeing of polyamide carpet with rubber displacement)

On polyamide carpet material (e.g. ordinary nylon 6 or nylon 66), which has been wetted and squeezed off as described in application example D 25, a rubber layer consisting of:

10 parts of guar resin-based thickener (e.g.

Celca Gum D-49-D)

0.25 parts of glacial acetic acid and 3o 989.75 parts of water are applied.

The pretreated polyamide carpet is dyed on a continuous system (e.g. Kuesters) with a dyeing liquor as described in application example D, 35 a liquor absorption of 300-600% being achieved. The bluish red colored polyamide carpet is steamed in a vertical or horizontal steam generator for 4-10 minutes, rinsed in warm water and dried.

In an analogous manner to that described in application examples D-so and E, dyeing liquors containing a dye from Examples 2-47 or a mixture of two or more dyes from Examples 1-47 can also be used for dyeing.

Claims (2)

654 845 PATENT CLAIMS 2,4,6, and their salts. 1 or 2 and independently of one another denote hydrogen or methyl, the condition for the substituents on the sulfonamide nitrogen being that the radical R 1 and the optionally alkyl-substituted phenyl radical together have 9 to 15 carbon atoms, R4 represents hydrogen, halogen, (I -4C) alkyl or (1 -4C) alkoxy and Rs represent hydrogen or (1-4C) alkyl, and their salts. 2. Compounds according to claim 1, wherein R 1 and the optionally alkyl-substituted phenyl radical have a total of 9 to 12 carbon atoms as substituents on the sulfonamide nitrogen. 3. Compounds according to claim 2, wherein said number of carbon atoms is 10. 4. Compounds according to claim 3, wherein Ri is n-butyl and R2 and R3 are hydrogen. 5. Compounds according to claim 1, which are in the form of the free acid of the formula Ia II with a compound which is in the form of the free acid of the formula III III corresponds, or couples a salt thereof in acidic to neutral medium. 9. A process for dyeing or printing organic, non-textile substrates which can be dyed with anioni-35 dyes, characterized in that dyeing or printing is carried out with a compound of the formula I defined in Claim I or a mixture thereof. 40 Ia match where R4a is hydrogen, chlorine, methyl or methoxy in position 4, 5 or 6 means Ric for methyl, ethyl, n-butyl, 2-hydroxypropyl- (n) or 1. Compounds in the form of the free acid of formula 1 6. Compounds according to claim 5, wherein R4a is hydrogen. 7. A compound according to claim 6, wherein Ric n-butyl and 5 R2a and R3 are hydrogen. 8. A process for the preparation of compounds of the formula I defined in claim 1, characterized in that the diazonium compound of an amine of the formula II correspond to what Ri (1-6C) alkyl or (3-6C) alkyl monosubstituted by hydroxy, chlorine or cyano, Rz is hydrogen or (1-4C) alkyl, 2-hydroxybutyl- (n), Ria represent hydrogen, methyl or ethyl, R3 and n are as defined in claim 1, Ricund and the optionally alkyl-substituted phenyl radical on the sulfonamide nitrogen together have a total of 10 carbon atoms; and wherein, when the N-phenyl group is disubstituted, the two substituents are in the 2,4-, 2,5- or 3,5-position, and when this group is trisubstituted, the three substituents are in