DE4425222A1 - Reactive mono:azo dyes giving clear strong dyeing with high deg. of fixing - Google Patents

Abstract

N-substd. 4-(o-sulpho-m- or -p-( beta -sulphatoethylsulphonyl)-phenylazo)-anilines (I) of formula (A) and their salts and mixts. are new: R1 = H, Me, or OMe; R2 = NHCONH2, NHCOCH3, Me or H; Z = 2,4-difluoro- or 5-chloro-2,4-difluoropyrimidin-6-yl; the reactive sulphonyl gp. may be in the m- or p-position to the azo gp..

Description

The invention relates to monoazo dyes containing reactive groups, processes for their production and their use as reactive dyes in dyeing and printing processes.

The invention relates to compounds of the formula I.

wherein
R₁ is hydrogen, methyl or methoxy,
R₂ NHCONH₂, NHCOCH₃, CH₃ or H

X is hydrogen or chlorine
and the reactive sulfonic acid residue can be bound in the meta or para position to the azo group, and their salts and mixtures of the compounds of the formula I.

Preferably R₁ R _1a is hydrogen.

R₂ is preferably R₂a as NHCONH₂ or NHCOCH₃.

The reactive sulfonic acid residue is preferably bound in the meta position to the azo group.  

Preferred compounds have the formula Ia

wherein R _2a and X are as defined above.

The invention further includes a process for the preparation of the compound of Formula I or mixtures thereof, which is characterized in that a compound of formula II

with a compound of formula III

implements.

The compounds of formula II are advantageously obtained by one Compound of formula IV

diazotized and on a coupling component of formula V

couples.

The preparation of formulas IV and V is known from the prior art.

The compounds of the formula I can be isolated in a manner known per se; e.g. B. the compounds can be obtained from the salt by conventional salting out with alkali metal salts The reaction mixture is separated, filtered off and (in vacuo) at a slightly elevated temperature be dried. Depending on the reaction and isolation conditions, a Obtaining compound of formula I as a free acid or in salt form or as a mixed salt.

The nature of the cation of the sulfo groups, if they are in salt form, provides is not a critical factor, but can be any in the chemistry of Reactive dyes act usual non-chromophoric cation. The prerequisite is that the corresponding salts meet the condition of water solubility.

Examples of suitable cations are alkali metal ions or unsubstituted or substituted Ammonium ions such as lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.

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

The reactive dyes of the formula (I) are suitable for dyeing and printing the various materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and in particular cellulose-containing fiber materials of all kinds. Such fiber materials are for example the natural cellulose fiber, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The reactive dyes of the formula (I) are also for dyeing or  Suitable for printing fibers containing hydroxyl groups contained in blended fabrics, e.g. B. of mixtures of cotton with polyester fibers or polyamide fibers.

The dyes according to the invention can be applied to the fiber material in various ways apply and fix on the fiber, especially in the form of aqueous dye solutions and printing pastes. They are particularly suitable for the exhaust process but also for dyeing according to the pad dyeing process, after which the goods are mixed with aqueous, optionally saline Dye solutions are impregnated, and the dyes after an alkali treatment or in Presence of alkali, optionally fixed under the action of heat. Farther They are suitable for the so-called cold residence process, after which the dye is combined with the alkali on the foulard. After fixing the stains or prints with cold and hot water, optionally with the addition of a dispersing agent acting and thoroughly rinsing the diffusion of the unfixed components.

The reactive dyes of the formula (I) are notable for high reactivity and very good Fixing ability of generally over 85%. You can therefore after Pull-out dyeing processes are used at low dyeing temperatures and require Pad steam process only short steaming times. The degrees of fixation are high, and they are not fixed portions can be easily washed out, the difference between Degree of exhaustion and degree of fixation remarkably small, d. H. the soap loss is very low. The Reactive dyes of the formula (I) are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. B. of wool, silk or Blended fabrics containing wool.

Draw the dyeings and prints produced with the dyes according to the invention is characterized by clear nuances. In particular, the colors and prints have Cellulose fiber materials a high color strength and a high fiber dye Binding stability, both in the acidic and in the alkaline range, continues to be good Light fastness and very good wet fastness properties, such as washing, water, sea water, Overdye and sweat fastness, as well as good pleating fastness, ironing fastness and Fastness to rubbing.  

The following examples serve to illustrate the invention without restricting it. In the examples, parts mean parts by weight, unless stated otherwise, and Temperatures are given in degrees Celsius.

Example 1 1a) Preparation of 1-aminobenzene-5-β-sulfatoethylsulfone-2-sulfonic acid

In a 500 ml sulfonation flask with KPG stirrer, thermometer, dropping funnel as well Reflux coolers with a drying tube are converted to 125 parts of sulfuric acid (100%, chemically pure) within 30 min 98.45 parts of 1-aminobenzene-3-β- sulfatoethylsulfone entered in portions. To the brown-black, very viscous Solution are then within 5 min 85 parts of oleum with an SO₃ content of 65-66% added dropwise, the temperature rising to about 90 ° C. It is now going on Heated 160 ° C and stirred for 4 hours at this temperature. Then leave on Cool to 60 ° C. and pour the reaction mixture onto 600 parts of ice. By portionwise addition of a total of about 250 parts of soda becomes a pH of 4.5-5 adjusted, precipitated solids are filtered off and the filtrate is mixed with a Mixture of 370 parts of methanol and 4810 parts of acetone. The fancy beige The product is filtered off and dried in a vacuum drying cabinet at 40 ° C. Man receives about 105.5 parts of 1-aminobenzene-5-β-sulfatoethylsulfone-2-sulfonic acid with a Nitrite titer of approx. 60%.

1b) Coupling on m-aminophenylurea

36.2 parts of 1-aminobenzene-5-β- are placed in a 1 liter glass beaker at room temperature. sulfatoethylsulfone-2-sulfonic acid (60%) from 1a) dissolved in 175 parts of water. Man adds 15 parts conc. Hydrochloric acid, cools with an ice / water external cooling as well by adding 200 parts of ice to 0-5 ° C and mixed at this temperature dropwise with a total of 15 parts of a 4N sodium nitrite within 30 minutes Solution. The mixture is left to stir for about 2.5 hours and any nitrite is destroyed Excess by adding about 1.5 parts of a 1N amidosulfonic acid.

To a suspension of 19.8 parts of m-aminophenylurea in 90 parts of water, whose pH value was previously set to 5 and which was cooled to approx. 5 ° C was cooled, the brown diazonium salt solution obtained is now within from 20-30 min. pumped in, with simultaneous addition of 20% soda Solution is always kept at a pH of 5. The mixture is allowed to warm to RT and is allowed to Stir overnight. The dark orange dye solution obtained is at RT 200 parts of sodium chloride are added with stirring and about 10 parts are added a 10% hydrochloric acid adjusted to pH = 3. Approx. 87.7 parts of the dye fall following formula, which are filtered off and processed further moist.

1c) condensation with 5-chloro-2,4,6-trifluoropyrimidine

60 parts of the moist dye from 1b) are at room temperature and pH = 6.5 in 700 parts of water dissolved. You add a drop Nonylphenolpolyglykolether and adds in portions within one hour at RT a total of 7.3 parts of 5-chloro-2,4,6-trifluoropyrimidine, with a pH of 6.5  is maintained by the simultaneous addition of 20% sodium carbonate solution. You still leave Stir for 2 hours at RT and pH = 6.5, add 4 parts of a filter aid and filter from. 160 parts of Kock's salt are added to the filtrate, and the precipitated product is filtered from, dries in vacuo at 50 ° C and receives about 13.5 parts of dye of the following Formula:

The λ _max (H₂O) is 378 nm. This dye dyes cotton in a golden yellow tone with astonishingly high fixation values. The dyeings show good fastness properties and, in particular, good wash-out properties.

Examples 2-16

Analogous to the method described in Example 1 can be used using appropriate Starting materials Examples 2 to 16 are prepared, which are shown in Table 1 below, for which are listed at the beginning of the relevant formula.

The dyes of Examples 2 to 16 also dye cotton in yellow to orange tones remarkably high fixation values. The dyeings show good fastness properties (e.g. Washability, washfastness, lightfastness).

According to the methods described above, the dyes of Examples 1 to 16 obtained as sodium salts. Depending on the chosen implementation, you can and insulation conditions or by subsequent measures in a known manner  Way in the form of the free acid or in another salt form or mixed Salt form can be produced and then, for example, one of the further in the description cations listed.

Possible uses of the dyes described are illustrated below.

Instructions for use A

In a dyebath made up of 0.13 parts of the dye in 100 parts of demineralized water Example 1 and 8 parts of calcined sodium sulfate, 10 parts at 50 ° C. Cotton jersey (bleached) registered. After 25 minutes at 50 ° C at intervals of 10 Min. The addition of a total of 0.4 parts of sodium carbonate calcined to 0.06, 0.12, 0.22 parts, keeping the temperature at 50 ° C for a further 5 minutes. Within 15 minutes is heated to 60 ° C and allowed to continue dyeing at 60 ° C for one hour. Then the colored material is demineralized in flowing hot for 2 min Water (60 ° C ± 10 ° C), then 2 minutes in running hot tap water (50 ° C ± 10 ° C) rinsed. The dyeing is carried out in 500 parts of demineralized water (without Additives) washed boiling. Then rinse again as follows:

• - 2 minutes in flowing hot demineralized water (60 ° C ± 10 ° C)
• - 2 min. In hot tap water (50 ° C ± 10 ° C)
• - 2 min. In cold tap water (15 ° C ± 5 ° C), then centrifuged and dried in an electronically controlled tumbler.

A golden yellow cotton dyeing of good fastness properties is obtained, in particular the good ones Light and wet fastness shows and is stable against oxidative influences and very good Fix values.

Application regulation B

In a dyebath made up of 0.13 parts of the dye in 100 parts of demineralized water Example 1 and 8 parts of calcined sodium sulfate are 10 parts at 50 ° C.  Cotton jersey (bleached) registered. After 25 minutes at 50 ° C at intervals of 10 Min. Or addition of a total of 0.5 parts of sodium carbonate and 0.3 parts of NaOH 32% to 0.08, 0.16, 0.26 parts sodium carbonate or 0.05, 0.1, 0.15 parts NaOH 32%, the temperature being held at 50 ° C. for a further 5 minutes. Within 15 minutes heated to 60 ° C and allowed to continue dyeing at 60 ° C for one hour. Subsequently the dyed material is soaked in flowing hot, demineralized water from 60 ° C ± 10 ° C, then rinsed for 2 minutes in hot tap water at 50 ° C ± 10 ° C. The dyeing is carried out in 500 parts of demineralized water (without additives) for 20 minutes. washed at the boil. Then rinse again as follows:

• - 2 minutes in flowing hot demineralized water (60 ° C ± 10 ° C)
• - 2 min. In hot tap water (50 ° C ± 10 ° C)
• - 2 min. In running cold tap water (15 ° C ± 5 ° C), then centrifuged and dried in an electronically controlled tumbler.

After rinsing and drying, a golden yellow cotton color is obtained, which the for the coloring according to regulation A has properties. In an analogous way as described in regulations A and B, the dyes can also be used according to the others Examples or dye mixtures thereof can be used for dyeing. The received Dyes have good fastness properties and very good fixing values.

Instructions for use C

A printing paste with the ingredients

40 parts of the dye from Example 1
100 parts of urea
350 parts of water
500 parts of a 4% sodium alginate thickener
10 parts of sodium bicarbonate
1000 pieces in total

is applied to cotton material using the usual printing processes.  

The printed material is steamed for 4-8 minutes at 102 ° -104 ° and then cold and hot rinsed. The fixed cotton material is then washed to boil (analog Regulation A) and dried. The golden yellow print obtained shows good general fastness properties.

Analogous to regulation C, the dyes of the other examples or Dye mixtures from Examples 1-8 used for printing cotton will. In all cases, prints with good fastness properties and very good Get fixation values.

Claims (9)

1. Compounds of formula I. wherein
R₁ is hydrogen, methyl or methoxy,
R₂ NHCONH₂, NHCOCH₃, CH₃ or H X is hydrogen or chlorine,
and the reactive sulfonic acid residue can be bound in the meta or para position to the azo group, and their salts and mixtures of the compounds of the formula I. 2. Compounds according to claim 1, wherein R₁ R _1a is hydrogen. 3. Compounds according to claim 1 or claim 2, wherein R₂ R _2a as NHCONH₂ or NHCOCH₃. 4. Compounds according to any one of the preceding claims, wherein the reactive Sulfonic acid residue is bound in the meta position to the azo group.   5. Compounds of formula Ia wherein R₂a and X are as defined in claims 1 and 3. 6. A process for the preparation of a compound of formula I, characterized in that a compound of formula II with a compound of formula III implements. 7. Use of a compound of formula I according to claim 1 or mixtures thereof for dyeing or printing substrates containing hydroxyl groups or nitrogen.   8. Use according to claim 7 for dyeing or printing leather or of Fiber materials made of natural or regenerated cotton or these contain. 9. Use according to claim 8, for dyeing or printing textile material, which Cotton exists or contains it.