DD151953A5 - Pyridone DISPERSION DYE - Google Patents

Abstract

The invention relates to a process for the preparation of a novel disperse dye for dyeing or Bedruecken fibers or Faeden or materials made therefrom fully or semisynthetic, hydrophobic, high molecular weight organic Stoffe.Ziel the invention is the provision of a hydrolysis-stable yellow disperse dye. According to the invention, a disperse dye of the formula I is prepared by coupling diazotized para-aminobenzoic benzoate with 1-n-butyl-3-cyano-4-methyl-6-hydroxy-pyridone-2. Upon heating, the dye of formula I becomes stable gamma-crystalline modification with characteristic lines in the Roentgend diagram (Cu-K & ind alpha 1! Radiation) at lattice 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 (low) strong), 3.18 (medium), 2.94 (weak) and 2.9 (weak) Angstroem, or into its stable delta-crystal modification with characteristic lines in the Roentgen diagram (Cu & ind alpha1! radiation) at lattice 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) fear troop, rearranged.

Description

Berlin, 3. 11. 80 AP C 09 B / 221 831

Method for manufacturing np; a Dispe rs ions rbs f a _n t f it of

'ι ^Ί

A nwe ndu ngsgebiet the invention

The invention relates to a process for the preparation of novel disperse dyes for dyeing or printing fibers or filaments or materials made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances.

C harak teristik of the known technical solutions

Disperse dyes are generally applied mainly by the so-called "exhaust method" Here, the substrate to be dyed is treated at temperatures between about 70 and 130 ⁰ C in a dyeing liquor, in addition to dispersants, inorganic or organic salts and / or organic acids (for adjustment of the optimum pH) contains the dye which is sparingly soluble in water in very finely divided form. "In such a dyeing liquor, unstable dyes convert their crystal modification as the temperature is raised, forming the dispersion with the formation of relatively large crystals which are poorly useful for dyeing , collapses.

The result of such a "staining" is a weakly and / or unevenly stained substrate with surface deposits of unfixed dye, which in addition to mostly reduced light, washing, welding and similar fastnesses means an economic loss "

In particular, yellow disperse dyes are very common

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- 2

susceptible to hydrolysis »They easily decompose when exposed to high temperatures * Such a dye has become known, for example, from DE-AS 1 901 711«

The aim of the invention is to provide a hydrolysis-stable yellow disperse dye «

Darleguncj of essence of invention

The invention has for its object to find a compound which is suitable as a yellow disperse dye and which is resistant to hydrolysis, as well as to provide a method for ih rer production.

According to the invention, a disperse dye of the formula I

which can exist in four crystal modifications, of which two (o £, β) are unstable under staining conditions and two (Z _{i (} f) can be said to be stable,

Both as oi ~ ß-modification and designated Oer under dyeing unstable crystal forms of the dye of formula I are formed; the modification in the usual

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According to the invention, preparation by known methods by coupling diazotized p-aminobenzoic acid benzyl ester with ln-butyl-3-cyano-4-methyl-6-hydroxypyridone, preferably in aqueous solution, at pH = 3 to 6 and 0 to 10 ⁰ C, the ß- Form can be obtained by recrystallizing the dried c6 modification from 2-ethoxyethanol.

Among the four existing crystal modifications of the dye of the present invention, the T-form is the most durable. All crystal modifications are finally converted to the crystal modification by heat treatment.

Suitable methods for preparing the Y modification are heating the crystal slurry obtained after 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 brought to pH = 3 and heated in the presence of a surfactant at temperatures ^ between 90 and 95 ⁰ C for about * 2 hours or repeated (at least two times) recrystallization of the pure, dried ^ modification of 2-mothoxy or 2-ethoxyethanol,

The <f-crystal form of the new dye is formed by a preferably several hours, z, B, one to four hours treatment of the aqueous suspension of any crystal form at about 130C in an autoclave, where it may be advantageous to the suspension prior to this heat treatment to inoculate,.

In the following table the X-ray diagrams (after Guinier / De Wolff, taken with Cu-K-radiation) are the

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, β, If and σ crystal modification.

© 6 Modification

-Modification

Modification

Lin. No. 0xd (A) I ^x Lin. No * there)* I ^X Lin _e no. O y d (A) ^X I ^X ß-modification d (X) I ^X 1 16.8 VVV 1 16.5 VW 1 14.1 m LIn ₀ 8.6 wd 2 14.0 2 11.5 W 2 11.5, VW 1 8.0 vwd 3 11.5 WV 3 10.6 W 3 10 * 3 VW 2 7.4 wd 4 10.0 m 4 8.4 VW 4 8.2 m 3 5.5 wd 5 8.0 VVV 5 8.0 W 5 7.8 m 4 6 7.55 VVV 6 , 7.5 W 6 7.2 W 7 7.0 VV 7 5.65 VVV 7 5.08 W 8th 6.8 W 8th 5.48 m 8th 4.9 VVV 9 5.99 VW 9 5.43 m 9 4.5 VW 10 5.8 VW 10 4.99 VW 10 4.25 VW 3.1 5.7 VVV 11 4.8 Vi? 11 3.69 .1" 12 5.4 VW 12 4.62 W 12 3.48 W 13 5.35 VW 13 4.45 VV 13 3.4 m 14 4.75 VW 14 4.21 VW 14 3.19 W 15 4.35 vw d 15 4 <13 VW 15 3.14 VW 16 4.2 VW 16 4.09 VW 16 3a W 17 4.0 VW 17 3.92 VW 18 2.9 3.95 3.85 VW VW 18 19 3.63 3 55 VW VW 20 3.48 S 20 3.4 8th 21 3.38 m 21 3.18 m 22 3.29 m • 22 2.94 W 23 3.19 VW 23 · 2.9 W

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5 -

24 3 , 09 VW > S strong, 24 2.78 VW 5 4.5 • W 25 2 25 VW η medium, 25 2.73 VW 6 4.3 vwd terabstsnd sz weak, 26 2.48 VW 7 3.9 vwd I o intensities: ta 27 2.23 VW 8th 3.6 vwd S 28 2.18 VW 9 3.38 vwd m 29 1,873 wd 10 3.15 vwd W 11 2.6 vwd ^xd (X). Git VW very weak,

(v) wd a (very) weak, diffuse »

The ο - or α- modification according to the invention of the novel dyestuff of the formula I and also mixtures of these two modifications, when processed in a known manner to a dyeing preparation, excel on fibers or filaments or materials made thereof from fully or semi-synthetic, hydrophobic , high molecular weight organic substances, in particular those of linear, aromatic polyesters, cellulose 2 1/2 and cellulose triacetates, but also of synthetic polyamides, and give brilliant, greenish-yellow colorations with excellent fastness properties. , Washing, sublimation and rubbing fastness.

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The invention is explained in more detail below with reference to some examples

In the following examples, parts mean parts by weight,

(Coupling under normal conditions)

17.7 parts of p-aminobenzoic acid benzyl ester (100 %) are dissolved in 70 parts of glacial acetic acid at 50 ⁰ C, with 20 parts of conc. Hydrochloric acid, 40 parts of ice and 20 parts of concentrated again "hydrochloric acid" At 4 to 6 C ⁰ is then added to the fine crystal suspension rapidly with 22 parts of a 4n ~ Natrlumnitritlösung. The mixture is stirred for 10 minutes at 10 to 12 ⁰ C, then cooled with ice to 0 to 5 ⁰ C, freed of excess nitrite with sulfamic 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 to 7 and

0 to 5 ⁰ C is added with good stirring in the course of ca «

The diazole solution is added for 1 hour, the pH being maintained by addition of sodium hydroxide solution and the temperature by addition of ice. "Finally, there is a very small excess of diazo. The mixture is left to stir overnight, during which the suspension is warmed to room temperature and Oer Diazoübers.schuß disappears. Filtration, washing and drying (at 60 ^° C. in vacuo) give the dye in very good yield and purity. It is present in the unstable <-crystal form. "

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(Transformation into the thermostable.

10 grams of the dye obtained according to Example 1, in the form of the dried material or used as a moist presscake, are stirred with water to a thin slurry. Then 1 gram of a surfactant (eg. B _e dinaphthylmethandisulfonsaures sodium) was added, the pH adjusted to 3 with HCl and the mixture heated for 2 hours at 85 to 95 ⁰ C. After filtration, washing and drying, the dye is obtained in the γ-crystal modification with the lines characteristic of this form in the X-ray diffraction diagram.

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

The desired crystal form is also produced by repeated reprecipitation of the crude, dried dye (of Example 1) from the 4-fold amount of boiling methyl or Ethylglykols.

Example 3 (Conversion to the thermostable c / crystal form)

10 parts of the dye obtained according to Example 1, used in the form of the dried material or as a moist P _r Esskuchen be mixed with water to a · thin paste "Then, 1 part of a surfactant (eg. B.. Dinaphthylmethandisulfonsaures sodium) was added and the mixture is heated in an autoclave at 130 to 132 ⁰ C for two hours. After cooling, filtration, washing and drying

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one obtains the dye in the stable cf-Modifikstion with the characteristic of this form lines in the X-ray diffraction diagram.

Instead of the isolated dye, it is also possible to subject the disengaged dye suspension unfiltered to the above-described heat treatment, the dye being converted into stable form in a particularly economical manner »

The obtained according to Example 2 or 3 and present in a dye-stable crystal form dye is by means of a Sandmahlung in the presence of dispersants, for. B _e lignosulfonates, and subsequent atomization into an ultradisperses dyeing preparation of average particle size < 1 l, u and a Coupageverhältnis of 3 j IO transferred

10.0 parts of the ultradispersen Därbepräparates are dispersed with 1000 parts of water and the circulating liquor (13 000 parts, containing 30 parts of ammonium sulfate and 0.3 parts of formic acid as a buffer mixture) added at 60 ⁰ C "The pre-cleaned and pressed cheese (1000 parts PE yarn on plastic sleeve) is then introduced, the dye autoclave sealed and heated in 35 minutes from 60 to 130 ⁰ C After 15 minutes at 130 ⁰ C is cooled to 80 ° C, drained drained liquor and the dyed coil with cold water thoroughly washed "and then dried and dried in a drying oven"

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This gives a deep (approx. / 1 standard depth), perfectly level and pure coloration of greenish-yellow shade, free from filtration and with excellent wet and rubbing fastness. "The dyeing liquor is practically colorless, the dyeing machine shows no deposits and can be used immediately for dia next staining can be used.

Claims (2)

3. 11 "80 AP C 09 B / 221 831 57 667 12 - 10 - Erfinduη μ s pleasant setti rυ ch 1, Process for the preparation of a disperse dye of the formula I. H-Cr-CH ₉ -O-COYOV "NN- / W 0 (I), 5 6 2 OH characterized in that diazotized para-aminobenzoic acid benzyl ester is coupled with 1-n-butyl-3-cyano-4-methyl-6-hydroxy-pyridone-2. 2 * Method of Making the ο Crystal Modification de; Disperse dye of formula I, according to item 1 with characteristic lines in the X-ray diagram (Cu K ^ ₁ radiation) at lattice 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, characterized in that the crystal slurry obtained after the coupling in aqueous , adjusted to pH = 2 to 4, suspension, heated to temperatures between 80 and 100 ⁰ C. » 3 * Process for the preparation of ο -Crystal modification of the Oispersionsfarbstoffes of formula I ₍ according to point 1 3. 11 ·. 80 AP C 09 B / 221 831 57 667 12 11 - with characterxstic lines in the X-ray diagram (Cu-K ₀ J.. radiation) at lattice 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) Angström, characterized by the fact that the <& -, ß- or ^ crystal form of the disperse dye in an aqueous medium and heated to temperatures around 130 ⁰ C under pressure »