DE3021555C2 - - Google Patents

Description

The subject of claim 1 is the disperse dye of the formula I.

which can exist in four crystal modifications, two ( α , β ) of which are unstable under staining conditions above 100 ° C and two ( γ , δ ) as stable under all staining conditions.

Disperse dyes are generally mainly after the so-called "Exhaust method" applied. This is the substrate to be colored treated in a dye liquor at temperatures between approx. 70 and 130 ° C, which in addition to dispersing agents, inorganic or organic salts and / or organic acids (to adjust the optimal pH) contains water-soluble dye in finely divided form. Unstable dyes are stored in such a dye liquor when the Temperature their crystal modification around, causing the dispersion to form relatively large crystals that are difficult to use for coloring are collapsing.

The result of such "coloring" is a weaker and / or uneven stained substrate with superficial deposits of not fixed dye, which in addition to mostly reduced light, washing, welding and fastness to rubbing means an economic loss.

The two crystal forms of the dye of the formula I, which are called α - and β- modification and are unstable when dyeing above 100 ° C., arise: the α -modification in the conventional preparation according to the invention by known methods by coupling diazotized para-aminobenzoate with 1- n-Butyl-3-cyan-4-methyl-6-hydroxypyridon-2, preferably in aqueous solution, at pH 3-6 and 0-10 ° C, the β form can be obtained by recrystallizing the dried α- modification from 2- Aethoxyethanol can be obtained.

The δ form is the most stable of the four existing crystal modifications of the dye according to the invention. All crystal modifications are finally converted into the δ crystal modification by heat treatment.

Suitable methods for producing the γ modification are heating the crystal slurry obtained after the coupling for one to five hours, in an aqueous suspension adjusted to a pH between 2 and 4, at temperatures between 80 and 100 ° C., preferably the cold suspension is adjusted to pH 3 and heated in the presence of a surfactant to temperatures between 90 and 95 ° C for about 2 hours, or repeated (at least twice) recrystallization of the pure, dried α- modification from 2-methoxy- or 2-ethoxyethanol.

The δ crystal form of the new dye is created by a preferably several hours, z. B. one to four hours treatment of the aqueous suspension of any crystal form at about 130 ° in an autoclave, it may be advantageous to inoculate the suspension before this heat treatment. Here too, the treatment is preferably carried out in the presence of a surfactant.

The following table shows the X-ray diagrams (according to Guinier / De Wolff, recorded with Cu-K _{α 1} radiation) of the α , β , γ and δ crystal modification.

The new dye of formula I, when processed into a dye preparation in a known manner, excellently draws on fibers or threads or materials made therefrom from fully or semisynthetic, hydrophobic, high molecular weight organic substances, in particular those from linear, aromatic polyesters, cellulose 2½- and cellulose triacetates, but also made of synthetic polyamides, and gives brilliant, greenish-yellow colorations with excellent fastness properties. The good light, wash, sublimation and rub fastness are particularly worth mentioning. Only dyeing preparations containing the γ and / or δ modification are suitable for dyeing at temperatures above 100 ° C. However, these preparations can also contain small amounts (up to a maximum of 10%) of the α and / or β modification.

In the German patent application 27 27 421 is the dye of the formula 1-n-butyl-3-cyano-4-methyl-5- (4'-phenylethoxycarbonyl- phenylazo) -6-hydroxy-pyridon-2 and in the US PS 41 40 684 the dye of the formula 1-methoxypropyl-3-cyan 4-methyl-5 (4'-benzyloxy-carbonylphenylazo) -6-hydroxypyridone- 2 described. DE-OS 19 17 278 also contains disperse dyes with a 1-n-butyl-3-cyano-4-methyl-6-hydroxypyridone 2 coupling component described. Towards the two Comparative tests were carried out on the first-mentioned dyes, which prove that the dye according to the invention an improved pH stability or a superior winding speed having. From the results of these comparative tests no legal claims are derived.

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

Example 1 (Clutch under normal conditions)

17.7 parts of benzyl p-aminobenzoate (100%) in 70 parts of glacial acetic acid solved at 50 °, with 20 parts conc. Hydrochloric acid, 40 parts ice and another 20 parts conc. Hydrochloric acid added. At 4-6 ° the fine Crystal suspension then quickly with 22 parts of a 4N sodium nitrite solution transferred. The mixture is stirred at 10-12 ° for 10 minutes, then with Ice cooled to 0-5 °, freed of excess nitrite with amidosulfonic acid, filtered and used for coupling.

A solution of 16.2 parts of 1-n-butyl-3-cyano-6-hydroxy-4-methylpyridone-2 in 200 parts of water at pH 5-7 and 0-5 ° is stirred for about 1 Hour with the diazo solution, the pH being maintained by adding sodium hydroxide solution and the temperature by adding ice. Finally, there is a very small excess of diazo. The mixture is left to stir overnight, during which the suspension warms to room temperature and the excess diazo disappears. The dye is obtained in very good yield and purity by filtering, washing out and drying (at 60 ° in vacuo). It is in the unstable α crystal form.

Example 2 (Conversion to the thermostable γ crystal form)

10 grams of the dye obtained according to Example 1, used in the form of the dried material or as a moist press cake, are mixed with water to give a thin paste. Then 1 gram of a surface-active substance (eg sodium dinaphthylmethane disulfonic acid) is added, the pH is adjusted to 3 with HCl and the mixture is heated to 85-95 ° for 2 hours. After filtering, washing and drying, the dye is obtained in the γ -crystal modification with the lines characteristic of this shape in the X-ray diffraction diagram.

Instead of the isolated dye, you can also use the uncoupled dye suspension subject unfiltered to the heat treatment described above, in a particularly economical manner the dye into the stable form is transferred.

The desired crystal shape is also created by repeatedly redissolving the raw, dried dye (according to Example 1) from 4 times the amount boiling methyl or ethyl glycol.

Example 3 (Conversion to the thermostable δ crystal form)

10 parts of the dye obtained according to Example 1, used in the form of the dried material or as a moist press cake, are mixed with water to give a thin paste. Then 1 part of a surface-active substance (for example sodium dinaphthylmethane disulfonic acid) is added and the mixture is heated in an autoclave at 130-132 ° for two hours. After cooling, filtering, washing and drying, the dye is obtained in the stable δ modification with the lines characteristic of this form in the X-ray diffraction diagram.

Instead of the isolated dye, you can also use the uncoupled dye suspension subject unfiltered to the heat treatment described above, in a particularly economical manner the dye into the stable form is transferred.

Example 4

The one obtained according to Example 2 or 3, in a color-stable crystal form the present dye is ground using sand in the presence of dispersants, e.g. B. lignin sulfonates, and subsequent atomization in one ultradisperse dye preparation with an average particle size of 1 µ and one Coupage ratio of 3: 10 transferred.

10.0 parts of the ultra-disperse dye preparation are mixed with 1000 parts of water and dispersed, and the circulating liquor (13,000 parts, still containing 30 parts of ammonium sulfate and 0.3 part of formic acid as a buffer mixture) at 60 ° added. The pre-cleaned and pressed cheese (1000 PE yarn on a plastic sleeve) is then inserted and the autoclave is closed and heated from 60 to 130 ° in 35 minutes. After 15 minutes at 130 ° is cooled to 80 °, the exhausted liquor is drained and the colored one Wash the coil thoroughly with cold water. Then it swings and dried in a drying cabinet.

You get a deep (approx. ² / ₁ standard depth), perfectly level, pure coloring of greenish-yellow shade, free of filtering, with excellent Wet and rub fastness. The dye liquor is practically colorless, the dyeing equipment shows no deposits and can be used immediately for the next staining be used.

Example 5

7 parts of the dye obtained in Example 1 are mixed with 4 parts sodium dinaphthylmethane disulfonic acid, 4 parts sodium cetyl sulfate and 5 parts of sodium sulfate (anhydrous) in a ball mill for 48 hours  ground.

1 part of the dye preparation thus obtained is made into a paste with a little water and a 12 part sodium sulforicinoleate (degree of sulfonation 80%) and 8 parts of anhydrous ammonium sulfate in 4000 parts of water-containing Dye bath added. The bath is adjusted to pH 5 with formic acid. 100 parts of cleaned polyester fiber material are then added at room temperature in the bath, heated to 98 ° in the course of 30 minutes (at At 60 °, 12 parts of ortho-phenylphenol are added to the carrier) and dyes 2 hours at this temperature. The greenish-yellow color obtained is removed from the bath, rinsed, soaped, rinsed again and dried. The fastness of this coloring corresponds to that of the coloring according to example 4.

Claims (7)

1. The disperse dye of the formula I 2. The γ- crystal modification of the disperse dye of the formula I according to claim 1, characterized by characteristic lines in the X-ray diagram (Cu-K _{α 1} radiation) at grid spacings of 11.5 (weak), 10.6 (weak), 8.0 (weak), 7.5 (weak), 5.48 (medium), 5.43 (medium), 4.8 (weak), 4.62 (weak), 4.45 (weak), 3.4 ( strong), 3.18 (medium), 2.94 (weak) and 2.9 (weak) Ångström. 3. The δ crystal modification of the disperse dye of the formula I, according to claim 1, characterized by characteristic lines in the X-ray diagram (Cu-K _{α 1} radiation) at grid spacings of 14.1 (medium), 8.2 (medium), 7.8 (medium), 7.2 (weak), 5.08 (weak), 3.69 (medium), 3.48 (weak), 3.4 (medium), 3.19 (weak) and 3 , 1 (weak) Ångström. 4. A process for the preparation of the disperse dye of the formula I, according to Claim 1, characterized in that diazotized para- Benzyl aminobenzoate with 1-n-butyl-3-cyano-4-methyl-6-hydroxypyridone 2 couples. 5. A process for the preparation of the γ crystal modification of the disperse dye of the formula I, according to claim 1, characterized in that the crystal slurry obtained after the coupling in aqueous, adjusted to pH 2 to 4 suspension, at temperatures between 80 ° and 100 ° C. heated. 6. A process for the preparation of the δ- crystal modification of the disperse dye of the formula I, according to claim 1, characterized in that the α -, β - or γ -crystalline form of the disperse dye is heated in an aqueous medium and under pressure at temperatures around 130 ° C. 7. Use of the γ - and / or δ crystal form of the dye of formula I, according to claim 2 or 3, for dyeing or printing fibers or threads or materials made therefrom from fully or semi-synthetic, hydrophobic, high molecular weight organic substances.