DE3021555A1 - PYRIDON DISPERSION DYES - Google Patents

Description

- 3 - Case 150-4319

Pyridone dispersion dye

The invention relates to the disperse dye of the formula I

CIiCN

H ₅ C ₆ -CH ₂ -O-CU - (ÖV N = N - ^) = O (I),

r \

^{0H (CH} 2 ^} 3 ~ ^CH 3

which can exist in four crystal modifications, of which two (ot, ß) than dyeing conditions than 100 ⁰ C and two unstable (Cg, 0) are referred to know in all the dyeing conditions as stable.

In general, disperse dyes are mainly used according to the so-called "Exhaust process" applied. Thereby the substrate to be colored becomes treated in a dye liquor at temperatures between approx. those in addition to dispersants, inorganic or organic salts and / or organic acids (for setting the optimum pH value) Contains finely divided dye, which is sparingly soluble in water. Unstable dyes store in such a dye liquor when increasing the Temperature their crystal modification around, with the dispersion, with the formation of relatively large crystals, which are poorly usable for dyeing are collapsing.

The result of such a "coloring" is weaker and / or uneven colored substrate with superficial deposits of non-fixed dye, which in addition to mostly reduced light, washing, sweat and ■ Reibor'hthpi t means an economic loss.

The two, designated as α- and ß-modification unstable when coloring about 100 ⁰ C crystal forms of the dye of the formula I are formed: the a modification in the conventional preparation according to the invention by known methods by coupling diazotized para-Aiainobenzoesäurebenzylester with LN butyl-S-cyano ^ -methyl-S-hydroxypyridone-Z, preferably in aqueous solution, at pH 3-6 and 0-1O ⁰ C, the .beta.-form can be dried by recrystallizing the α-modification of 2-ethoxyethanol obtained .

030064/0621

- 4 - Case 150-4319

Of the four existing crystal modifications of the dye according to the invention, the § -form is the most stable. All crystal modifications are finally converted into aiej ^ crystal modification by means of a heat treatment.

Suitable methods for producing the ^ modification are heating the crystal slurry obtained after the coupling for one to five hours, in aqueous suspension adjusted to a pH between 2 and 4, to 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 P crystal form of the new dye is created by a preferably several hours, e.g. one to four hours, treatment of the aqueous suspension of any desired crystal form at approx. 130 ° in an autoclave, whereby it can 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 radiation) of the α-, β-, Tf- and?

αΐ w

cation specified.

030064/0621

_ R -

Case 150-4319

α modification

Lin.No. there)* *
I. 1 16.8 VW 2 14.0 W. 3 11.5 VW 4th 10.0 m 5 8.0 VW 6th 7.55 VW 7th 7.0 W. 8th 6.8 W. 9 5.99 VW 10 5.8 VW 11 5.7 VW 12th 5.4 VW 13th 5.35 VW 14th 4.75 VW 15th 4.35 vw d 16 4.2 VW 17th 4.0 VW 18th 3.95 VW 19th 3.85 VW 20th 3.48 S. 21st 3.38 m 22nd 3.29 m 23 3.19 VW 24 3.09 VW 25th 2.25 VW

-Mo di f ik a ti on

S-

modification

Lin.No.

d (A) I.

Lin.No.

O Ä

there)

* d (A) = grid spacing, I = intensities: s = strong, m = medium, w = weak, vw = very weak, (v) wd = (very) weak, diffuse.

1 2 3 4 5 6 7 8 9

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29

16.5 VW 11.5 W. 10.6 W. 8.4 VW 8.0 W. 7.5 W. 5.65 VW 5.48 m 5.43 m 4.99 VW 4.8 W. 4.62 W. 4.45 W. 4.21 VW 4.13 VW 4.09 VW 3.92 VW 3.63 VW 3.55 VW 3.4 S. 3.18 m 2.94 W. 2.9 W. 2.78 VW 2.73 VW 2.48 VW 2.23 VW 2.18 VW 1,873 wd

1 14.1 m there) I. 2 11.5 VW 8.6 wd 3 10.3 VW 8.0 vwd 4th 8.2 El 7.4 wd 5 7.8 m 5.6 wd 6th 7.2 W. 4.5 W. 7th 5.08 W. 4.3 vwd 8th 4.9 VW 3.9 vwd 9 4.5 VW 3.6 vwd 10 4.25 VW 3.38 vwd 11 3.69 m 3.15 vwd 12th '3.48 W. 2.6 vwd 13th 3.4 m 14th 3.19 W. 15th 3.14 VW 16 3.1 W. β modification Lin.No. 1 2 3 4th 5 6th 7th 8th 9 10 11

030064/0621

- 6 - Case 150-4319

The new dye of the formula I, when processed in a known manner into a dye preparation, is excellent on fibers or threads or materials made therefrom made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances, especially those made from linear, aromatic polyesters, cellulose ?. 1/2 and cellulose triacetates, but also from synthetic polyamides, and produces brilliant, greenish-yellow dyeings with excellent fastness properties. The good fastness to light, washing, sublimation and rub should be mentioned in particular. Only dyeing preparations are suitable for dyeing at temperatures above 100 ⁰ C, which the * $ -, and / or fr * modification. However, these preparations can also contain small amounts (up to a maximum of 10%) of the α- and / or ß-modification.

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

Example 1 (coupling under normal conditions)

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

A solution of 16.2 parts of 1-n-butyl-3-cyano-6-hydroxj'-4-methylpyridon-2 in 200 parts of water at pH 5-7 and 0-5 ° with thorough stirring in the course The diazo solution is added for about 1 hour, the pH being maintained by adding sodium hydroxide solution and the temperature by adding ice will. At the end there is a very small excess of diazo. One lets Stir overnight, during which the suspension warms to room temperature and the excess of diazo disappears. By filtering, washing out and drying (at 60 ° in vacuo), the dye is obtained in very good yield and purity. It is in the unstable a-crystal form.

030064/0621

- 7 - Case 150-4319

Example 2 (conversion into the thermostable Qf 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 form a thin paste. Then 1 gram of a surfactant (eg sodium dinaphthylmethanedisulphonic 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 ^c q crystal modification with the lines characteristic of this form in the X-ray diffraction diagram.

Instead of the isolated dye, the uncoupled dye suspension can also be subjected, unfiltered, to the heat treatment described above, the dye being converted into the stable form ¹ in a particularly economical way.

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

Example 3 (conversion to the thermostable y-crystal form)

10 parts of the dye obtained according to Example 1, in the form of the dried Materials or used as a moist press cake are mixed with water to form a thin paste. Then 1 part of a surface-active Substance (e.g. sodium dinaphthylmethanedisulfonic acid) was added and the mixture was heated to 130-132 ° in the autoclave for two hours. After cooling down, Filtering, washing and drying gives the dye in the stable ^ -Modification with the lines characteristic of this form in the X-ray diffraction diagram.

030064/0621

- 8 - Case 150-4319

Instead of the isolated dye, it is also possible to use the uncoupled dye suspension unfiltered subject to the heat treatment described above, whereby in a particularly economical way the dye in the stable form is convicted.

example

The dye obtained according to Example 2 or 3, present in a color-stable crystal form is converted by means of a sand milling in the presence of dispersants such as lignin sulfonates, and subsequent atomization into a ultradisperses dyeing preparation of the average particle size l ^ fi and a Coupageverhältnis 3:10.

10.0 parts of the ultradisperse dyeing preparation are mixed with 1000 parts of water and dispersed, and the circulating liquor (13,000 parts, containing 30 parts of ammonium sulfate and 0.3 parts of formic acid as a buffer mixture) at 60 ° added. The pre-cleaned and pressed cheese (1000 parts PE thread on a plastic tube) is then inserted and the staining autoclave is closed and heated from 60 ° to 130 ° in 35 minutes. After 15 minutes at 130 °, the mixture is cooled to 80 °, the drawn-out liquor is drained off and the colored liquor Coil washed thoroughly with cold water. Then it is swung down and dried in the drying cabinet.

2
The result is a deep (approx. I γ standard depth), perfectly level, pure coloration with a greenish-yellow shade, free from filtering off, with excellent wet and rub fastness properties. The dye liquor is practically colorless, the dyeing apparatus shows no deposits and can be used immediately for the next dyeing.

B is ρ ie 1

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

030064/0621

9 Case _J. ^^^ - i _{XJ> (L} _ _ _

ground.

1 part of the resulting dye preparation is made into a paste with a little water and a 12 parts of sodium sulforicinoleate (degree of sulfonation 80%) and 8 parts of anhydrous ammonium sulfate in a dyebath containing 4000 parts of water were added. The bath is adjusted to pH5 with formic acid. 100 parts of cleaned polyester fiber material are then added to the bath at room temperature and heated to 98 ° (at At 60 °, 12 parts of ortho-phenylphenol, the carrier, are added) and colors

2 hours at this temperature. The greenish yellow coloration obtained is taken out of the bath, rinsed, soaped, rinsed again and dried. The fastness properties of this dyeing correspond to those of the dyeing according to example 4.

Q30Q6A / 0621

ORIGINAL INSPECTED

Claims (9)

SANDOZ-PATENT-GMBH Case 150-4319 L ö r r a c h FYRIDON - DISPERSION DYE Claims !., j The disperse dye of the formula I. H_C -CH -0-C OH 2. The ^ 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 radiation) with 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) angstroms. 3. The Λ 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 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) angstroms. 030064/0621 - 2 - Case 150-4319 4. Process for the preparation of the disperse dye of the formula I according to Claim 1, characterized in that diazotized para-aminobenzoic acid bezyl ester with l-n-butyl-3-cyano-4-methyl-6-hydroxypyridon-2 clutch. 5. A process for the preparation of crystal modification jj of the disperse dyes of the formula I according to claim 1, characterized in that the crystal slurry obtained after the coupling in aqueous, to pH 2 to 4 adjusted suspension to temperatures of between 80 ° and 100 ⁰ C. heated. 6. Process for the preparation of the ^ y crystal modification of the disperse dye of the formula I, according to claim 1, characterized in that the α, β or ^ crystal form of the disperse dye is heated ^{to temperatures around 130 ° C. in an aqueous medium and under pressure} . 7. Use of the 'Jf and / or ^ crystal form of the dye of the formula I, according to claim 2 or 3, for dyeing or printing fibers or threads or materials made therefrom made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances. 8. The articles dyed with the dye of the formula I. 9. dye preparation which contains a disperse dye of the formula I according to claim 1 in the ¹ J and / or J modification. 030064/0621