CH624425A5 - Process for the preparation of new chromiferous dyes - Google Patents

Description

The present invention relates to a process for the preparation of new complex chromiferous dyes 1/2.

Synthetic polyamides have a high melting point and their fusion is accompanied by a strong reducing effect. Few organic dyes have sufficient stability to envisage their use for coloring or dyeing in the spinning mass of synthetic polyamides. On the other hand, in the current state of knowledge, it is not possible to extrapolate the dyeing results obtained by conventional dyeing to the results obtained by coloring in the mass of these polyamides.

The process for the preparation of chromium complex dyes corresponding, in acid form, to formula I, is characterized in claim 1 above.

As substituents of radical A, mention may, for example, be made of chlorine or bromine atoms and alkyl groups,

alkoxy, acylamino, sulfo, nitro or sulfamoyl optionally substituted for nitrogen by one or two alkyl groups. The alkyl, alkoxy and acylamino groups contain no more than 8 carbon atoms. The term “acylamino group” means the alkylcarbonylamino groups (such as acetylamino) and arylcarbonylamino groups (such as benzoylamino).

The monoazo compounds II can be prepared in a manner known per se by coupling the diazo derivative of an o-amino-phenol or -naphthol HO-A-NH2, preferably chosen from the following compounds: chloro-4 or -5 amino -2 phenol, 4,6-dichloro-2 amino-phenol, 4-methyl-2-amino-phenol, 4,6-dimethyl-2,5-amino 65 phenol, 4-methyl-5-sulfo-2 amino-phenol, 4-chloro-sulfo-6 2-amino phenol, 4-acetylamino 2-amino phenol, 1-amino-4-sulfo naph-tol-2, with a naphthol B-OH such as, for example, oc-naphthol, ß-naphthol, naphthol-1 sulfonic acid 4 or 5, naphthol-2 acid

3

624,425

sulfonic-6, chloro (or bromo) -6 naphthol-2, 2,6-dihydroxy naphthalene.

The 1/1 chromium complexes of the monoazo compounds of formula II can be obtained by the action of a chromium III salt in slight excess, in an aqueous medium or in an organic solvent, at a temperature between 100 and 150 °. vs. In some cases, the 1/1 chromium complex can also be prepared from the corresponding o-alkoxy, o'-hydroxy-monoazo compound, the alkoxy group ortho to the azo bond being dealkylated during metallization according to the methods classics. This is the case, for example, when the o-amino-phenol HO-A-NH2 is replaced by an o-alkoxy-aniline such as, for example, the amino hydroquinone dimethyl ether.

The monoazoic compounds III can be prepared in a manner known per se by coupling the diazo derivative of anthranilic acid or a mono- or disubstituted derivative thereof such as, for example, 5-chloro anthranilic acid, dichloro-3,5 anthranilic acid, acetylamino-5 anthranilic acid and 5-sulfo anthranilic acid, with 5-amino-3-methyl-1-phenyl pyrazole or a derivative thereof substituted on the phenyl radical by a chlorine atom or a methyl, ethyl, sulfo or nitro group.

The complexes in their acid form or more simply in the form of alkali or alkaline-earth metal salts or of protonated ethanola mines such as, for example, the sodium, potassium, ammonium, calcium or magnesium,

lead to full-bodied black or brown undertones. They can be applied to polyamide and wool fibers by conventional dyeing in a weak acid bath.

Most of the complexes and more frequently those which do not carry nitro groups prove to be particularly advantageous for the coloring in the melt of synthetic polyamides such as nylons 6, 6-6 and 11 which are most commonly used to obtain yarns. or textile filaments, as well as horsehair, sheets or molded or extruded articles. The colors obtained are thermally very stable and do not give rise to any sublimation. The other solidities, particularly in wet and light proofs, are excellent.

For bulk coloring, the powder dyes can be mixed beforehand with the polyamide (granules or powder), then homogenize the mixture in a screw extruder at a temperature 10 to 15 ° C higher than that of the polymer melt. At the outlet of the extruder, the mixture can either be cooled and then granulated and stored as such in a hopper supplying spinning melters, or maintained in the molten form and introduced directly by means of metering pumps into the spinning melters.

The new dyes have a high solubility rate (greater than 1% and sometimes even greater than 3%) in polyamides which allows them to be used for coloring at very high intensities, even very fine threads, such as for example filaments of polyamide 6-6 of two decitex dyed with 2% dye, without any of the incidents commonly encountered during spinning occurring with dyes which are too insoluble or with pigments occurring. These incidents are most often manifested by blockage of the filters protecting the very fine orifices of the dies or by frequent ruptures of the filaments, mainly during drawing operations.

It is also possible, in particular in the case of polyamide 6, to dye in an aqueous medium on polymer granules before their transformation into fibers. This operation is carried out under the usual conditions for dyeing the polyamides in an acid medium, in a short bath, preferably with a bath ratio of between 2 and 6. After dyeing, the dyed polyamide is dried and then extruded under the usual conditions.

The following examples, in which the parts and percentages are by weight, illustrate the invention without limiting it.

Example 1:

In 1500 parts of demineralized water, 80 parts of the 1/1 chromium complex derived from the monoazoic of formula:

DH

ho3s n

G

N = N

and containing exactly 5.2 parts of complexed chromium III, as well as 120 parts of paste of the monoazoic of formula:

CD0H

o

N = N

(V)

corresponding to 31.2 parts of pure monoazo. 25 parts of monoethanolamine or 40 parts of diethanolamine or 60 parts of triethanolamine are added to the well-stirred suspension and the mixture is heated to 95-100 ° C. A black solution of the mixed chromium complex 1 is rapidly formed / 2, which is precipitated, after cooling, by the addition of 300 parts of sodium chloride. After filtration and drying, 30 98 parts of a black powder, very soluble in water, which dyes wool and nylon fibers in an aqueous bath at pH 3 to 6 and which is thermally colored, are finally obtained. very stable in solution in molten polyamides.

35 Example 2:

The procedure is as in Example 1, but replacing the 31.2 parts of monoazoic of formula V by 34.5 parts of monoazoic phenyl-1 methyl-3 (2-carboxy-chloro-4 phenylazo) -4 amino-5 pyrazole . A mixed complex of a 4Q black shade more red than that of the complex of Example 1 is obtained.

Example 3:

The procedure is as in Example 1, but replacing the 31.2 parts of monoazoic of formula V with 38 parts of the monoazoic phenyl-1 methyl-3 (2-carboxy-dichloro-4,6 pheny-45 lazo) -4 amino -5 pyrazole. A mixed complex of a dark green shade is obtained.

Example 4:

The procedure is as in Example 1, but replacing the 50 31.2 parts of monoazoic of formula V by 36 parts of monoazoic phenyl-1 methyl-3 (acetylamino-4 carboxy-2 pheny-lazo) -4 amino-5 pyrazole. A mixed complex of a black shade more red than that of the complex of Example 1 is obtained.

55 Example 5:

The procedure is as in Example 1, but replacing the 31.2 parts of monoazoic of formula V by 32.5 parts of the monoazo p.tolyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole. A mixed complex is obtained with a black mass identical to that of the complex of Example 1.

Table I below brings together other examples of mixed complexes according to the invention of dark shade, most of which have excellent thermal stability in coloring in the bulk of the polyamides. These complexes are prepared as in Example 1 by reacting in equimolar proportions the 1/1 chromium complex of the monoazo mentioned in the second column and the monoazo mentioned in the third column.

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4

Table I

Example

Monoazoic used as a 1/1 chromium complex

Monoazoic of formula (III)

Shade

6

Hydroxy-1 acid (5-chloro-2-hydroxyphenyl-azo) -2 naphthalenesulfonic-5

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Purplish black

7

Hydroxy-1 acid (5-chloro-2-hydroxyphenyl-azo) -2 naphthalenesulfonic-5

Phenyl-1 methyl-3 (acetylamino-4 carboxy-2 phenylazo) -4 amino-5 pyrazole

Purplish brown

8

Hydroxy-1 acid (3,5-dichloro-2-hydroxyphenylazo) -2 naphthalenesulfonic-5

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Purplish black

9

Hydroxy-1 acid (4-chloro-2,5 dimethoxy-phenylazo) -2 naphthalenesulfonic-5 (demethylating chromium plating)

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Reddish black

10

Hydroxy-1 acid (4-chloro-2,5 dimethoxy-phenylazo) -2 naphthalenesulfonic-5 (demethylating chromium plating)

Phenyl-1 methyl-3 (2-carboxy-4,6-dichloro phenylazo) -4 amino-5 pyrazole

Reddish black

11

Hydroxy-1 acid (4-chloro-2,5 dimethoxy-phenylazo) -2 naphthalenesulfonic-5 (demethylating chromium plating)

p-tolyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Reddish black

12

Hydroxy-1 acid (5-methyl-2-methoxy-4-benzoylamino-phenylazo) -2 5-naphthalenesulfonic (demethylating chromium plating)

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Black-brown

13

Hydroxy-1 acid (2-hydroxy-sulfamoyl-4 phenylazo) -2 naphthalenesulfonic-5

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Black

14

Hydroxy-1 acid (2-hydroxy-4 nitro-phenyl-azo) -2 naphthalenesulfonic-5

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Gray green

Example 15:

Into an autoclave containing 1000 parts of demineralized water, 120 parts of paste of the monoazo dye obtained by coupling 13.7 parts diazo of anthranilic acid with 17.5 parts of 3-phenyl-3-amino-5-pyrazole are introduced. in an acidic aqueous medium, buffered with sodium acetate. 35 parts of sodium carbonate and 95 parts of a 1/1 chromium complex containing 5.5 parts of chromium in complex bond with the dye of formula:

(VI)

and prepared by demethylating chromium plating, with a slight excess of basic chromium sulphate in aqueous solution in an autoclave at 140 ° C. for 6 h, of monoazoic acid (2,5-dimethoxyphenylazo) -1 hydroxy-2 naphthalene-sulfonic 6.

The well-stirred mixture is brought to 130 ° C. in 1 hour, then rapidly cooled to 80 ° C. The mixed complex formed is then precipitated from the black solution by the addition of sodium chloride. It dyes wool and nylon fibers in a tight black shade, with good general solidities. In the dry state, it dissolves easily in molten polyamides in which it has good thermal stability up to 280 ° C.

Example 16:

The procedure is as in Example 15, but replacing the anthranilic acid with an equimolar amount of 5-chloro anthranilic acid. A mixed black-brown complex is obtained, which can also be used in bulk coloring of polyamides.

Example 17:

The procedure is as in Example 15, but replacing the anthranilic acid with 3,5-dichloro-anthranilic acid. The mixed complex 35 obtained in gray-green shade can also be used in bulk coloring of polyamides.

Table II below collates other examples of mixed complexes according to the invention of dark shade suitable for the bulk coloring of polyamides and prepared by reacting in equimolar proportions the 1/1 chromium complex of the monoazo mentioned in the second column of the table and the monoazo mentioned in the third column, in an aqueous medium at a temperature between 80 and 130 ° C. while maintaining the pH at a value between 7 and 12 by means of etha-45 nolamine or an aqueous solution of sodium hydroxide or carbonate or ammonia.

(Table at the top of the next page)

Example 29:

By chromium plating in ethylene glycol using chromic chloride as described in French patent No. 1083983, of the monoazo compound of formula:

N =

(VII)

65

we actually get the 1/1 chromium complex of the monoazoic formula:

5

Table II

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Example Monoazoic used in the form of Monoazoic of formula (III) Complex shade 1/1

18

Acid (2,5-chloro-2,5-dimethoxyphenylazo) -1 hydroxy-2-naphthalenesulfonic-6 (demethylating chromium plating)

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Black

19

Acid (4-chloro-2,5-dimethoxyphenylazo) -1 hydroxy-2-naphthalenesulfonic-6 (demethylating chromium plating)

Phenyl-1 methyl-3 (carboxy-2 chloro-4 phenylazo) -4 amino-5 pyrazole

Purplish black

20

Acid (2,5-chloro-2,5-dimethoxyphenylazo) -1 hydroxy-2-naphthalenesulfonic-6 (demethylating chromium plating)

Phenyl-1 methyl-3 (2-carboxy-4,6-dichloro phenylazo) -4 amino-5 pyrazole

Gray green

21

Acid (2,5-chloro-2,5-dimethoxyphenylazo) -1 hydroxy-2-naphthalenesulfonic-6 (demethylating chromium plating)

Phenyl-1 methyl-3 (acetylamino-4 carboxy-2 phenylazo) -4 amino-5 pyrazole

Reddish black

22

Acid (4-chloro-2,5-dimethoxyphenylazo) -1 hydroxy-2-naphthalenesulfonic-6 (demethylating chromium plating)

Phenyl-1 methyl-3 (carboxy-2 sulfo-4 phenylazo) -4 amino-5 pyrazole

Black

23

Acid (5-chloro-2-hydroxyphenylazo) -l 2-hydroxy-naphthalenesulfonic-6

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Purplish black

24

Acid (5-chloro-2-hydroxy-3-sulfo phenyl-azo) -l 2-hydroxy-naphthalenesulfonic-6

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Purplish brown

25

[1-hydroxy-naphthyl- (2) -azo] -l 2-hydroxy-naphthalenesulfonic-4 acid

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Dark grey

26

[1-hydroxy-naphthyl- (2) -azo] -l hydroxy-2 naphthalenesulfonic-4 acid

Phenyl-1 methyl-3 (carboxy-2 chloro-4 phenylazo) -4 amino-5 pyrazole

Black

27

Acid (5-chloro-2-hydroxyphenylazo) -2 hydroxy-1-naphthalenesulfonic-4

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Purple brown

28

Acid (2,5-dimethoxyphenylazo) -2 hydroxy-1

Naphthalenesulfonic-4

(demethylating chrome plating)

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole

Classic black of wool and nylon in an aqueous medium, gray or black shades of good general strength. It is also soluble and has excellent thermal stability in molten polyamides.

Table III below brings together other examples of mixed complexes according to the invention, appreciable for the coloring in the mass of synthetic polyamides, prepared by reacting in equimolar proportions the 1/1 chromium complex of the monoazoic indicated in the second column and the monoazoic of formula III indicated in the third column.

(Table at the top of the next page)

Application A:

3 parts of one of the black dyes from the preceding examples are impastoed in 8 parts of demineralized water at 40 ° C. The mixture is introduced into a dyeing apparatus capable of operating under pressure and containing 1000 parts of demineralized water brought to pH 5 by addition of acetic acid. 300 parts of polyamide 6 are then added in the form of small granules of approximately 2 mm on a side, then the temperature is raised to approximately 130 ° C. in the space of 30 minutes and this temperature is maintained for 1 h with stirring. . The granules dyed black are then washed with demineralized water and then dried. They are then introduced into a spinning apparatus where the molten mixture is subjected to constant pressure on a melting grid at 290 ° C. before passing over a filter bed based on washed and grilled river sand whose grains have a dimension of the order of 0.3 mm, then through a die having 7 orifices 0.23 mm in diameter. The device is adjusted so that after a subsequent stretch

(VIII)

JLUJ

Cl

OCH

3

20 parts of this complex are reacted, in the form of a paste containing 0.52 parts of chromium, with 3 parts of the monoazoic phenyl-1 methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole in 100 parts of ethylene glycol added with 2 parts of monoé-thanolamine. The condensation leading to the mixed complex is completed in less than an hour between 80 and 120 ° C. The precipitate, formed by diluting the organic solution in 300 parts of salt water is filtered, rinsed with pure water and dried. A black powder is obtained which, in the dispersed state, has a good affinity for nylon fibers according to the conventional methods of dyeing in an aqueous medium. This powder, well soluble and thermally stable in polyamides melted up to 280 ° C, also makes it possible to obtain fibers and articles whose polymer has been colored in the mass before extrusion or spinning.

Example 30:

The procedure is as in Example 29, but replacing the 3 parts of 1-phenyl-methyl-3 (2-carboxyphenylazo) -4 amino-5 pyrazole by 4 parts of 1-phenyl-methyl-3 (2-carboxy-sulfo- 4 pheny-lazo) -4 amino-5 pyrazole. In the same way, a water-soluble monosulfonated mixed complex is obtained, which gives

45

624,425

6

Table III

Example Chromium complex 1/1 derived from:

Monoazoic of formula (III)

Shade

31 Bromo-6 (2,5-dimethoxyphenylazo) -l hydroxy-2 naphthalene (demethylating chromium plating)

32 Bromo-6 (2,5-dimethoxy phenylazo) -1 hydroxy-naphthalene (demethylating chromium plating)

33 (3,5-Dichloro-2 hydroxy-phenylazo) -1 dihydroxy-2,6 naphthalene

34 (3,5-Dichloro-2-hydroxyphenylazo) -l 2,6-dihydroxy naphthalene

35 Hydroxy-1 acid (2-hydroxy-5-nitro-phenyl-azo) -2 5-naphthalenesulfonic

36 Bromo-6 (2-hydroxy-4-sulfo-5-methyl-phenylazo) -l 2-hydroxy-naphthalene

37 (2-Hydroxy-naphthyl-1 azo) -l 2-hydroxy-naphthalenesulfonic-4 acid

38 Acid (2-hydroxy-1-naphthyl-azo) -l 2-hydroxy-6-nitro-4-naphthalene sulfonic

Phenyl-1 methyl-3 (carboxy-2 phenylazo) -4 Black amino-5 pyrazole

Phenyl-1 methyl-3 (carboxy-2 sulfo-4 Black phenylazo) -4 amino-5 pyrazole

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 Gray-green 5-amino pyrazole

Phenyl-1 methyl-3 (carboxy-2 sulfo-4 Gray-green phenylazo) -4 amino-5 pyrazole

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 Brown amino-5 pyrazole

Phenyl-1 methyl-3 (2-carboxyphenylazo) -4 Brown amino-5 pyrazole

Phenyl-1 methyl-3 (acetylamino-4 Reddish black 2-carboxyphenylazo) -4 amino-5

pyrazole

Phenyl-1 methyl-3 (carboxy-2 phenylazo) -4 Black amino-5 pyrazole of coefficient 4, the 7 filaments each have a titer of 17 decitex. Polyamide 6 filaments are thus colored in a very solid black shade.

Application B:

One of the sulfonated dyes described in the previous examples is purified by dissolving in hot water, filtering and reprecipitation by adding a sodium, potassium, magnesium or calcium salt. After wringing, drying and grinding, 1.5 parts of the fine powder obtained is mixed for 1 hour in a cylindrical container rotating on its axis with 100 parts of polyamide 6-6 in the form of granules. The mixture is then introduced into a screw extruder, the die of which is brought to 285 ° C. On leaving the extruder, the mixture is cooled and then transformed into grains of approximately 2 mm on a side. By then operating under the conditions of the previous example, these grains can be transformed into filaments of black, brown or dark green shade, very solid in light, heat and wet proofs.

Application C:

A paste is prepared containing 35% of the dye from Example 26 and 65% of a polyethylene glycol (Emkapol 400 for example). This paste constitutes a masterbatch which is preheated and injected continuously by gear metering pumps in an extruder where it is mixed with molten polyamide 6 so as to maintain a rate of 1.5% of dye. The colored solution is redistributed by gear pumps, regulating the titer of the filaments, towards melters and filters leading to a die. The yarns obtained have a full-bodied black coloring having excellent general solidity.

35

R

Claims (2)

624,425 2 1. Process for the preparation of chromiferous complex dyes corresponding, in acid form, to formula (I): © (I) in which A represents an o-phenylene or o-naphthylene radical which can carry one or two substituents, B represents an o-naphthylene radical which can carry one or two substituents, Xi represents a hydrogen or chlorine atom, X2 represents a hydrogen or chlorine atom or an acetylamino, sulfo or nitro group, and X3 represents a hydrogen or chlorine atom or a methyl, ethyl, sulfo or nitro group, the molecule being able to carry up to two sulfo groups and being free from sul-fone group, characterized in that it consists in reacting in an alkaline medium the chromium complex 1/1 of a compound o, o'-dihydroxy-monoa-zoic of formula (II): 25 -NOT _/ HO - A N = N - B OH (II) with an equivalent or slightly lower molar proportion of an o-carboxy o'-amino-monoazo compound of formula (III): CODH / (ili) NOT 35 the symbols A, B, Xi, X2 and X3 having the same meanings as above, and, optionally, neutralizing the complex with salts of alkali or alkaline earth metals or protonated ethanolamines. 2. Method according to claim 1, in which the optional substituent (s) of the radical A are chosen from chlorine or bromine atoms and alkyl, alkoxy, acylamino groups, sulfo, nitro or sulfamoyl optionally substituted for nitrogen by one or two alkyl groups. 3. The method of claim 1, wherein the substituent or substituents of the radical B are chlorine or bromine atoms and / or sulfo or hydroxy groups. 4. Complex chromiferous dyes of formula (I), obtained by the process according to claim 1 in acid or neutral form. 50 marked out.