DE3326954A1 - Anionic monoazo compounds, process for their preparation and their use in dyeing and printing processes - Google Patents

Abstract

Novel anionic monoazo compounds correspond to the formula I <IMAGE> in which R1 denotes (1-6C)-alkyl or (3-6C)-alkyl monosubstituted by hydroxyl, chlorine or cyano, R2 denotes hydrogen or (1-4C)-alkyl, R3 denotes hydrogen or methyl, n denotes 1 or 2 and R1 and the optionally alkyl-substituted phenyl radical on the sulphonamide nitrogen together contain a total of 9-15 C atoms, R4 represents hydrogen, halogen, (1-4C)-alkyl or (1-4C)-alkoxy and R5 represents hydrogen or (1-4C)-alkyl. They are prepared by a customary diazotisation and coupling reaction. The compounds are used as dyes for the dyeing or printing of organic substrates which can be dyed using anionic dyes, such as leather or textile material which consists of natural or synthetic polyamides, polyurethanes or basically modified polyolefins or contains these; the preferred substrate in this case is synthetic polyamide.

Description

ANIONIC MONOAZO COMPOUNDS, METHOD OF MANUFACTURING AND THEIR

USE IN INKING AND PRINTING METHODS The present invention relates to a single sulfo group containing monoazo compounds and their salts, Process for the preparation and use of these compounds in processes for dyeing and printing.

In the narrower sense, the invention encompasses compounds which, in the form of the free acid of the formula I correspond, where R1 is (1-6C) hikyl or monosubstituted by hydroxy, chlorine or cyano (3-6C) alkyl, R2 is hydrogen or (1-4C) alkyl, n is 1 or 2 and R3 is independently hydrogen or methyl, where for the substituents on the sulfonamide nitrogen, the condition applies that the radical R1 and the optionally alkyl-substituted phenyl radical together have 9 to 15 carbon atoms, R4 for hydrogen, halogen, (1-4C) alkyl or (1-4C) alkoxy and R5 for hydrogen or! l -4C) alkyl, and their salts.

The total number of carbon atoms for R1 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.

As unsubstituted alkyl, R1 can be straight-chain or branched and preferably represents (1-4C) alkyl; more preferably it stands for methyl, Ethyl or straight-chain or branched butyl; it is particularly preferred for the n-butyl radical.

Substituted alkyl R1 can be straight-chain or branched and contains the substituent on a atom other than Cl; preferably it contains 3 or 4 carbon atoms. It is more preferably hydroxy-substituted and here means 2- or 3-Ilydroxypropyl or 2-, 3- or 4-Hydroxybutyl, whereby the Propyl- and Butyl groups can be linear or branched; particularly preferred means it is straight-chain 2-hydroxypropyl or 2-hydroxybutyl; very particularly preferred means it is straight-chain 2-hydroxybutyl.

preferably means Rla as linear or branched (1-4C) alkyl or Monosubstituted, linear or branched (3 or 4C) alkyl, where the substituent is on a atom other than the Cl atom; more preferably Rlb as methyl, ethyl, straight-chain or branched butyl; straight chain or branched 2- or 3-hydroxypropyl or 2-, 3- or 4-hydroxybutyl; Further preferably Rlc as methyl, ethyl, n-butyl, 2-hydroxypropyl- (n) or 2-hydroxybutyl- (n); in particular R1 stands for Rid as n-butyl or 2-hydroxybutyl- (n); most notably R1 is preferably n-butyl.

As alkyl, R2 preferably represents methyl or ethyl, in particular for methyl.

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

If the phenyl radical is monosubstituted on the sulfonamide nitrogen, then are all free positions equally preferred. If the phenyl radical is disubstituted, so the two substituents are preferably in 2,4; 2.5 or 3.5 position, especially in the 2,4- or 2,5-position.

If the phenyl radical is trisubstituted, there are three substituents 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 1 or 2 carbon atoms and stands especially for methyl or methoxy.

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

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

R5 as alkyl is preferably methyl.

R5 preferably represents R5a as hydrogen or methyl; in particular R5 means hydrogen.

Preference is given to compounds which, in the form of the free acid of the formula la and their salts, in which R1c and the optionally alkyl-substituted phenyl radical on the sulfonamide nitrogen 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 bears two substituents, these are in the positions 2,4; 2.5 or 3.5 are, and if the N-phenyl radical has three substituents, these are in the positions 2,4,6.

Further preferred are those compounds of the formula Ia in which (1) R4a represents R4b; (2) R1c is Rld; (3) R2a is R2b; (4) those of (2) or (3), in which R4a is hydrogen; (5) the compound of group (4), where Rlc is n-butyl and R2a and R3 are hydrogen.

The nature of the cation of the sulfo group in a compound of the formula I, if this is in salt form, is not a critical factor but it can be anything in the chemistry of anionic dyes act common nonchromophores cation, for example an alkali metal ion or unsubstituted or substituted ammonium ion. Examples of suitable cations are lithium, sodium, potassium, mimonium, mono-, di-. Tri- and tetramethylammonium, Triethylammonium and mono-, di- and triethanolamnionium.

Preferred cations are the alkali metal ions and ammonium, thereof sodium is particularly preferred.

The compounds of the formula I are prepared by the diazonium compound of an amine of the formula II with a compound which corresponds to the formula III in the form of the free acid, or a salt in front of it couples in acidic to neutral medium.

Diazotization and coupling are durchge according to conventional methods leads. The coupling reaction is advantageous in an acidic medium, preferably at pH 3 to 4.5, in water or in a mixture of water and one miscible with water Made organic solvent, preferably the reaction temperature is between 0 ° and 30 "C, when using water as the reaction medium especially between 0 ° and 100C, when using water mixed with an organic solvent, e.g. water / ethanol, especially between 0 ° and 20 "C.

The process mentioned produces the monoazo compounds of Formula I in the form of the salts and can be used as such by methods known per se be isolated from the reaction mixture. The isolation of the Monoazo compounds by salting out, filtering, washing and then drying in a vacuum.

Depending on the reaction and isolation conditions the compounds of formula 1 in the form of the free acid or preferably in salt form or obtained in mixed salt form. By subsequent salination known per se the compounds of the formula I can also be used in another salt form or in mixed form Salts are converted 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, especially in salt form, are anionic Dyes represent, they can be used for dyeing and printing of any with anionic Dyes, dyeable organic substrates can be used. Suitable substrates are leather and textile material made from natural or synthetic polyamides, Polyurethanes or base-modified polyolefins or contains them. However, the dyes are particularly advantageously used for dyeing and printing of textile material, which is made from natural and synthetic polyamide fibers such as Wool, silk and especially nylon, such as nylon 5 or nylon 66, consists or these contains, as well as particularly advantageously used in 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 are used. Processing to stable liquid, for example concentrated aqueous, or solid coloring preparations can be based on well-known Manner, e.g. by dissolving in suitable solvents such as water, if necessary with the addition of a customary auxiliary such as urea as a solubilizer; or then also by grinding or granulating.

It is also possible to use the compounds in the form of cold-dispersible compounds To use preparations. For this purpose, the dyes ground in the presence of one or more Customary anionic dispersants and optionally other auxiliaries on the A mechanical method of dry or wet grinding with the dispersion medium water Subjected to comminution and, if appropriate, then dried by atomization.

These preparations spread out when placed in cold water again in finely dispersed form.

Dyeing and printing processes can be carried out according to methods known per se will. For example, the padding or exhaust dyeing process can be used to dye the latter being preferred, since the compounds of the formula I essentially consist of neutral, aqueous dyebath, such as weakly alkaline to weakly acidic, aqueous Draw up the dye bath. The "space dyeing" process can also be used. Farther the dyes according to the invention are suitable for the application of the rubber displacement technique in carpet dyeing to achieve certain pattern effects.

The dyes of the formula I are distinguished in particular by that with good neutral drawability they have a high ability to migrate combined with a very high degree of migration have good equalization properties. In particular, you get on nylon, the Dyeing tends to be streaky, balanced streak-free dyeings. Also own the dyes have good solubility and good build-up capacity. The one with the dyes The dyeings obtained of the formula I show remarkable lightfastness and others good general fastness properties such as good wet fastness properties, especially washing, (cold) water, Walk and perspiration 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 can be combined easily with known dyes of the same category, especially in important trichromes, resulting in tone-on-tone colorations, while retaining the good properties of the Dyeings, especially good lightfastness and level character, are preserved; the combination dyeings also show no catalytic fading.

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

Example 1 30.4 parts of 2-amino-Nn-butyl -N-phenylbenzene sul fonsäureaini d are dissolved in 80 parts of ethyl alcohol with 56 parts of 30% hydrochloric acid at 450 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 the course of 20 minutes at a temperature of -5 "to 0 °. The diazotization is complete after stirring for 30 minutes; a slight excess of nitrite is destroyed by adding a little sulfamic acid. 23.9 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved in 150 parts of water by adding 12 parts of a 30% sodium hydroxide solution; the result is a pH of approx 1 hour slowly added dropwise to the diazo solution prepared above, the pH is kept between 3 and 3.5 by adding a 50% sodium acetate solution. After 2 1/2 hours of stirring, the coupling is ended the pH is adjusted to 9, the dyestuff which has precipitated out is filtered off and the residue is washed with 200 parts of a 10% strength sodium chloride solution correct in the form of the free acid of the formula 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.

Example 1 e 2 - 47 Analogously to the above Example 1, starting from the corresponding starting materials, further dyes can be prepared which are in the form of the free acid of the formula and for which the following table lists the variables and the necessary position information. Tabel Example No. R1 R2 R3 R6 R4 R5 2 C2H5 2-CH3 4-CH3 HHH 3 do. do. do. HH CH3 4 do. do. do. H 5-CH3 H 5 do. do. do. H do. CH3 6 do. do. 5-CH3 HHH 7 do. do. do. H 6-OCH3 H 8 do. do. do. H 4-CH 3 H 9 do. 2-C2H5 HH do. H 10 do. do. HHHH 11 CH3 2-CH3 4-CH3 6-CH3 HH 12 do. do. 5-CH3 H 4-CH3 H 13 th. 2-C2H5 HHHH 14 do. 3-C2H5 HH 5-CH3 H 15 do. 2-CH3 4-CH3 6-CH3 H CH3 16 -CH2CHCH3 HHHHH CH3 17 th. HHH 5-CH3 H 18 C3H7 (n) 3-CH3 HHHH 19 do. do. HH 4-Cl H 20 do. do. HH 5-CH3 H 21 do. 2-CH3 5-CH3 HH CH3 22 C3H7 (i) 4-CH3 HHH 23 C4H9 (n) HHHH CH3 24 th. 2-CH3 HHHH 25 do. 2-C2H5 F. HHH 26 th. HHH 4-Cl H 27 th. HHH 6-OCH3 H 28 do. HHH 4-CH3 H 29 do. HHH 5-CH3 H 30 do. H | 6 H do. CH3 31 th. HHH 6-OCH3 do.

Table (continued) Example No. R1 R2 R3 R6 | R4 R4 R5 32 C4H9 (n) 2-CH3 4-CH3 HHH 33 do. do. do. H 5-CH3 H 34 do. HHH 4-Cl CH3 35 -CH2CH2CH2OH HHHHH 36 do. 2-CH3 HHHH OH 37 -CH2CHCH3 do. HHHH 38 do. do. HHH CH3 39 do. HHH 4-CH3 H 40 do. HHH do. CH3 41 -CH2CH2CH2CH20H HH HH H 42 do. HHHH CH3 OH 43 -CH2CHCH2CH3 HHHH 44 do. HHHH CH3 45 do. HHH 6-OCH3 H 46 do. HHH 5-CH3 H 47 do. 3-CH3 HHHH The dyes of Examples 2 to 47 dye natural and synthetic polyamide fibers in bluish red shades. These dyeings show good light and wet fastness properties.

According to the implementation and isolation conditions described obtained the dyes of Examples 2-47 as sodium salts. However, you can too by salination according to methods customary per se into another or mixed Salt form are converted and then, for example, one or more of the in the Description contain cations listed further.

The following are possible uses of the dyes according to the invention illustrated-t: APPLICATION EXAMPLE A (exhaust dye on polyamide glue) 100 parts pre-wetted synthetic polyamide fabric, e.g. nylon 66, is placed in a dye bath given by 40 °, which has the following composition: 2 parts of the dye from example 1 10 parts of anhydrous sodium sulfate 4000 parts of water.

The dye liquor is heated to the boil in the course of 30 minutes and kept at boiling temperature for one hour. Then 4 parts of glacial acetic acid are added and the dyeing is ended by heating at the boiling point for a further 30 minutes. During the dyeing, the evaporated water is continuously replaced. That bluish The red-colored nylon cloth is taken out of the liquor, rinsed with water and dried. Wool can also be dyed using the same procedure.

APPLICATION EXAMPLE B (exhaust dyeing on nylon yarn) 100 parts pre-wetted Nylon 66 yarn is added to a dye bath of 26-27 ° of the following composition: 1 part of the dye from Example 1 1-2 parts oleylamine (leveling agent) 1 part Monosodium phosphate 3000 parts of water.

The dyebath is heated to boiling temperature, then 1 part Glacial acetic acid was added and kept at the boiling temperature for 45 minutes.

Water that evaporates during the dyeing process becomes continuous replaced. The blue-tinged red nylon 66 yarn is removed from the liquor. rinsed with warm water and dried.

In a manner analogous to that given in application examples A and B. The dyes of Examples 2-47 or a mixture consisting of two can also be used or more dyes of Examples 1-47 are used for dyeing polyamide, The dyeings obtained show good light and wet fastness properties.

APPLICATION EXAMPLE C (Printing specification for polyamide fabrics) 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 Carob gum) 20 parts of an acid donor (e.g. amnionium tartrate) 60 parts Thiourea.

The printed textile material is heated for 40 minutes at 102 ° (saturated steam) steamed, then rinsed cold, then at 600 for 5 minutes with a diluted Washed solution of a commercially available detergent and rinsed again with cold water. Man receives a bluish red print with good light and wet fastness properties.

In an analogous manner, printing pastes can be produced that are used as a component a dye of Examples 2-47 or a mixture of two or more dyes of Examples 1-47. These pastes can be used analogously to the regulation given above can be used with the printer.

APPLICATION EXAMPLE D (Continuous dyeing of polyamide carpets) Carpet goods polyamide (e.g. from ordinary nylon 6 or nylon 66) is combined with a preparation Consists of 1-2 parts of decyl alcohol with 4 moles of ethylene oxide per mole of alcohol ethoxylated, or similar surfactant and 998-999 parts Water wetted and squeezed off to impregnate and absorb total wetting agent of 80-100% can be achieved.

The carpet material pretreated in this way is made with a dye liquor the constituents 0.5-5 parts of the dye from Example 1 1-2 parts of a thickener based on guar resin (such as Celca Gum D-49-D) 1-2 parts of decyl alcohol, which contains 4 mol Ethylene oxide has been ethoxylated per mole of alcohol (or a similar surface-active substance Mean) 91-97.5 parts of water and a sufficient amount of trisodium phosphate or acetic acid to adjust the p to 5 (e.g. for nylon 6 and for Nylon 66) on a continuous system (e.g. Kuesters) colored under Achievement of a liquor pick-up of 300-600%. The bluish red colored polyamide carpet material is then in a vertical or horizontal steam generator for 4-10 minutes steamed for a long time, rinsed with warm water and dried.

APPLIKATIOD'S EXAMPLE E (Continuous dyeing of polyamide carpet with Rubber displacement) On polyamide carpet material (e.g. ordinary nylon 6 or Nylon 66), which wets and squeezes off analogously as described in Application Example D. a rubber layer consisting of: 10 parts of a guar resin-based thickener (e.g. Celca Gum D-49-D) 0.25 parts of glacial acetic acid and 989.75 parts of water are applied.

The polyamide carpet pretreated in this way is made on a continuous system (e.g. Kuesters) with a dye liquor as described in application example D. colored, with a liquor uptake of 300-600 rxW is achieved. The bluish tint red colored polyamide carpet is used in a vertical or horizontal steam generator Steamed for 4--10 minutes, rinsed in warm water and dried.

In the same way as described in application examples D and E. can also with dye liquors containing a dye of Examples 2-47 or a Mixture of two or more dyes of Examples 1-47 are colored.

Claims (16)

Claims 1. Compounds in the form of the free acid of the formula I correspond, in which R1 is (1-6C) alkyl or (3-6C) alkyl monosubstituted by hydroxy, chlorine or cyano, R2 is hydrogen or (1-4C) alkyl, n is 1 or 2 and R3 is independently hydrogen or methyl, where for the substituents on the sulfonamide nitrogen the condition applies that the radical R1 and the optionally alkyl-substituted phenyl radical together have 9 to 15 carbon atoms, R4 for hydrogen, halogen, (1-4C) alkyl or (1-4C) alkoxy and R5 for hydrogen or (l -4C) alkyl, and their salts. 2. Compounds according to claim 1, wherein R1 and optionally alkyl-substituted phenyl radical as substituents on the sulfonamide nitrogen have a total of 9 to 12 carbon atoms. 3. Compounds according to claim 2, wherein said number of carbon atoms 10 is. 4. Compounds according to any one of claims 1-3, wherein R1 is methyl, Ethyl, n-butyl, 2-hydroxypropyl- (n) or 2-hydroxybutyl- (n). 5. Compounds according to any one of claims 1-4, wherein R2 is hydrogen, Means methyl or ethyl. 6. Compounds according to claim 3, wherein R1 is n-butyl and R2 and R3 stand for hydrogen. 7. Compounds according to any one of claims 1-6, wherein R4 is hydrogen, Is chlorine, methyl or methoxy. 8. Compounds according to any one of claims 1-7, wherein R5 is hydrogen or methyl. 9. Compounds according to claim 1, which are in the form of the free acid of the formula Ia correspond, where R4a is hydrogen, chlorine, methyl or methoxy in position 4, 5 or 6, Rlc for methyl, ethyl, n-butyl, 2-hydroxypropyl- (n) or 2-hydroxybutyl- (n), R2a for hydrogen, Methyl or ethyl, R3 and n are as defined in claim 1, Rlc and the optionally alkyl-substituted phenyl radical on the sulfonamide nitrogen together have a total of 10 carbon atoms; and in which, if the N-phenyl radical is disubstituted, the two substituents are in the 2,4-, 2,5- or 3,5-position, and if this radical is trisubstituted, the three substituents are in the positions 2,4, 6 and their salts. 10. Compounds according to claim 9, wherein R4a is hydrogen. 11. Compounds according to claim 9 or 10, wherein R2a is hydrogen or methyl. 12. A compound according to claim 10, wherein R1c is n-butyl and R2a and R3 Mean hydrogen. 13. 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 with a compound which is in the form of the free acid of the formula III or a salt thereof in an acidic to neutral medium. 14. Process for dyeing or printing with anionic dyes dyeable organic substrates, characterized in that one with a compound of formula I defined in claim 1 or a mixture thereof, dyes or prints. 15. The method according to claim 14 for dyeing or printing textile materials, which consist of or contain natural or synthetic polyamides. 16. The or colored by the method according to claim 14 or 15 printed materials.