FR2473052A1 - Anionic water insol. dyes, easily dispersible in cold water - in the form of a salt of a cationic water soluble condensn. prod. of a guanidinium salt and formaldehyde - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS ANIONIC DYES INSOLUBLE IN WATER BUT EASILY DISPERSABLE IN COLD IN AQUEOUS MEDIUM. THESE COLORANTS ARE CHARACTERIZED IN THAT THEY ARE AT LEAST PARTLY IN THE STATE OF SALTS OF A WATER-SOLUBLE CATIONIC RESIN RESULTING FROM THE CONDENSATION OF FORMALDEHYDE WITH A GUANIDINIUM SALT. THE DYES ACCORDING TO THE INVENTION WHICH ARE VERY EASY TO PIPE IN WATER AND IN PRINTING BATHS, ALLOW THE REALIZATION ON FABRICS OF SOLID COLORS WITHOUT PICOTS.

Description

 The present invention relates to anionic dyes insoluble in water, but easily dispersible in an aqueous medium. In the following description and claims, the term "dyes" includes optical brighteners.

Many anionic dyes generally in the form of alkali or alkaline-earth metal salts are more or less soluble in water and have the drawback of wetting slowly and of forming lumps when mixed with cold water. or in aqueous baths containing in advance the other ingredients necessary for the intended application of dyeing or printing.

Some anionic dyes also have a tendency, after partial solubilization, to reform large crystalline particles in the case of concentrated dye baths or printing pots, as well as during drying on the support before vaporization in the case of the impression.

 There is also a tendency for many anionic dyes which are very soluble in hot water to form a gel when the solution cools, a gel which can also appear during the formation of cold dye baths and printing pastes containing these dyes.

 This lack of stability of the aqueous solutions or suspensions of anionic dyes frequently leads to the appearance, on the material to be colored, of small intense spots (spikes) due to the crystallized or gelatinous agglomerates which a violent stirring does not always manage to disperse.

 Now, it has just been unexpectedly found that it can present the anionic dyes in the form of fine particles which are insoluble in water, but which are easily dispersed and cold in water and in dye baths and pastes. printing without giving rise to recrystallization, gelation or re-agglomeration, when these dyes are at least partially in the state of salts of a water-soluble cationic resin resulting from the condensation of formaldehyde with a guanidinium salt.

 The new anionic dyes according to the invention can be obtained by subjecting an aqueous suspension or solution of an anionic dye salt at least partially soluble in liteau, for example an alkali or alkaline earth metal salt, to the action of '' an aqueous solution of a cationic resin resulting from the condensation of formaldehyde with a guanidinium salt such as carbonate, bicarbonate, chloride, sulfate or nitrate, in the proportion of 0.5 to 5 moles of formaldehyde per mole of guanidine and 0.1 to 3 moles of guanidine per anionic molar equivalent of dye.

 The anionic dyes which can be thus treated are first of all dyes which carry at least one acid group such as the sulfonic, phosphonic or carboxylic acid group, and can belong to the most diverse chemical classes, for example to the phthalocyanine series, nitro dyes, dyes of di- or triphenylmethane, oxazine, thiazine, dioxazine, xanthene, and especially to the series of anthraquinone and azorque dyes, in particular to the series of monoazo, disazoric dyes or Polyazos.Can also be treated according to the process of the invention dyes lacking an acid functional group, but which are metallized in the form of complexes of anionic character, such as for example the complexes 1/2 of chromium or cobalt of the dyes o-carboxy-o'-hydroxy or o, o'-dihy droxyazoSques.

The cationic resins derived from guanidine and formaldehyde to be used to precipitate the anionic dyes according to the technique of the invention can be prepared according to known methods, for example those described in U.S. Patents Nos. 2,668,808, 2,631,920 and 2,736,749. However, the preferred method, because it is simple and well suited to the industrial treatment of dyes, consists in heating between 50 and 900C the mixture of a guanidinium salt such as carbonate, bicarbonate, chloride, sulfate or nitrate, with an aqueous solution of formaldehyde in an amount of 0.5 to 5 moles, preferably 0.8 to 2 moles of formaldehyde per mole of guanidine, the pH of the reaction mixture being maintained between 4 and 12, preferably between 7 and 10, by optional addition of a small amount of an acid, a base or a salt such as hydrochloric, sulfuric or acetic acids, ammonium chloride, ammonia, carbonate sodium, sodium and potassium hydroxides.

 The concentration of the aqueous solution of cationic resin in guanidinium equivalents can vary from 0.1 to 6 moles per liter, depending on the volumes and viscosities compatible with the apparatus and the physical form of the dyes used. These can in fact be treated in the form of dilute solutions or suspensions, such as the raw production formations, the dye concentration of which is of the order of 0.1 to 1 mole per liter in an aqueous medium, or to the state of pasta, of sufficient fluidity to allow homogeneous stirring, and the dry extract of which generally varies from 5 to 30% of dry matter per kilo of dough.

 The reaction of the dye with the resin solution requires approximately one hour of stirring at room temperature or a quarter of an hour at around 800C, but these times can be extended for several hours if necessary.

The pH of the mixture can be between 4 and 11, but it is preferably maintained between 6 and 10. The evolution of the precipitation of the dye in its new form can be followed qualitatively by observation on paper of keys of the reaction mass. We thus appreciate the minimum quantity of resin to be used to obtain a satisfactory precipitation for filtration and subsequent application. Note that the precipitation of the dye in its new form is favored by a reaction medium more concentrated in dye and resin, but low in other salts such as those of sodium, potassium, ammonium, and a fortiori those of alkaline-earth metals and heavy metals, which tend to strongly insolubilize the dyes without however conferring on them the advantages of dry grinding easy which leads to greater particle fineness and to more homogeneous suspensions during subsequent application.

 The best proportion corresponds to the stoichiometry of a mole of guanidine condensed with a mole of formaldehyde, for an anionic equivalent of dye used. However, a sufficient improvement in the physical form of the dye is sometimes obtained with a proportion ten times less of resin. Nevertheless, to accelerate the formation of the salt and facilitate its precipitation, one can optionally use an excess of guanidinium equivalents per anionic charge of dye.

After the treatment according to the invention, filtration is generally very easy. If the suspension is pasty and contains little water, it is also possible to dry it directly, without filtering it, in the trays of an oven, or better by instant vaporization in the hot gas stream of an atomizer.

 The dry cake can be easily ground using known techniques and the powder obtained, although very fine, does not give rise during handling to the flying dust encountered with untreated dyes. A type setting can then be carried out with the usual cutting agents such as chloride, sulphate and sodium or potassium phosphates, sugar, maltodextrin, lignosulfonates and other dispersants. These cutting agents can also be introduced before drying, especially in the case of atomization.

The fineness of the powders obtained, which can be estimated by touch, for example between two glass slides, or after introduction into a printing paste by examination (fluidity, absence of lumps) of the latter between two glass plates , allows to appreciate the quality of the treatment.

 The dye powders thus obtained are very easy to paste in water or in preconstituted printing baths, at high concentrations of up to 100 g / l, and allow the production on fabrics of uniform coloring and devoid of dots by dyeing. with a scarf or by roller printing or with a flat or rotating frame, both in full-bodied shades and in cuts of the parent color.

 Certain dyes normally unsuitable for application according to the "space-dyeing", "knit deknit" processes, or in jet or nozzle printing systems, or else according to any cold dyeing process, because of their tendency to gel in the dye bath and to clog the pipes of the devices, become usable according to these techniques after having been transformed in accordance with the present invention.

 In addition, in order for the suspensions of these insolubilized dyes to behave like true solutions which do not pass through the filter, it is always possible to subject them to further grinding in a liquid medium, using sand or small beads and / or dispersants, treatment analogous to the conventional dispersion of insoluble nonionic dyes of the "dispersed" class.

 Thanks to the treatment process according to the present invention, it is also possible to obtain anionic dyes free of mineral salts and other water-soluble impurities originating from their method of manufacture.

For this, a simple washing with cold purified water of the precipitate obtained is sufficient, washing which also eliminates any excess of the cationic resin used. This purification is particularly appreciable for anionic dyes intended for the coloring in the melt of synthetic polyamides, the shades obtained are more vivid and the frequent clogging of the dies by particles of salts insoluble in the molten polyamide can thus also be avoided.

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

contenant 830 parties de colorant pur pour environ 4500 parties de pâte, on verse progressivement sous agitation 500 parties d'une solution aqueuse de résine, préalablement préparée par chauffage à 800C pendant une demi-heure de 180 parties de carbonate de guanidinium, 200 parties d'une solution aqueuse à 30 % de formaldéhyde et 120 parties d'eau.EXAMPLE 1
In an aqueous paste, warmed to around 500C, chromium complex 1/2 red dye of formula

containing 830 parts of pure dye for approximately 4500 parts of paste, gradually poured with stirring 500 parts of an aqueous solution of resin, previously prepared by heating at 800C for half an hour of 180 parts of guanidinium carbonate, 200 parts of '' a 30% aqueous solution of formaldehyde and 120 parts of water.

 At first, the mixture tends to thicken, then it becomes more fluid, while touches on filter paper show around the precipitate a halo less and less colored.

After one hour of brewing, the dye can be easily filtered and the cake (or directly the unfiltered pgte) is dried in an oven at 90 ° C, 900 ° C, then transformed into a fine powder in a hammer or pin mill. This powder can then be brought to the type by homogenization with a cutting agent-such as sodium chloride or sugar, in an amount ranging from 10% to 50% by weight of the crude dye.

 By dusting the powder thus obtained in an aqueous printing bath containing 3 to 5% of urea or thiourea, 0 to 5% of a solvent such as 2-ethoxyethanol or thiodiglycol, 0.1 to 5% (by dry weight) of a thickener such as a guar derivative or an industrial gum, 1 & 3 1 of ammonium sulphate or acetic or formic acid, and O at 0.5% of a wetting agent, after vigorous stirring at room temperature, a mother color can be obtained which may contain up to 5% dye. Unlike an analogous color produced with the dye not treated with the resin (i.e. isolated in the form of sodium, ammonium, guanidinium or calcium salt), this mother color and its cuts obtained by dilution with a white solution (that is to say without dye) of the same composition lead on polyamide and wool fabrics to solid red or pink prints without dots.

 Furthermore, the pure dye powder of the present example gives thermally stable solutions in the molten polyamides; it can be injected in the form of a masterbatch, consisting 2/3 of a liquid polymer such as a polyethylene glycol or a polyamide of low molecular weight, in an extruder containing polyamide 6 melted at 2800C. The colored solution, stable for more than an hour and which may contain up to 2% of dye, is redistributed by pumps controlling the titer of the filaments towards the melters and filters leading to the die, without causing the frequent clogging observed with the same dye precipitated as sodium salt.

 By operating as in Example 1 with the anionic dyes mentioned below, they are insolubilized in a form easily dispersible in cold water.

EXAMPLE Anionic dye
2 Mixed chromium 1/2 complex of mono compounds
azo and (b) below:
(a) 4-hydroxy acid (5-hydroxy-3-methylphenyl-1
pyrazolyl-4 azo) -3 nitro-5 benzenesulfonic
(b) Dinitro-4,6 (2-hydroxy-5-methoxyphenylazo) -2
phenol.

3 Chromium 1/2 complex of monoazot compounds
(a) and (b) below
(a) (2-hydroxy-5-nitro-phenylazo) -l naphthol-2
(b) (2-hydroxy-4-nitro-phenylazo) -1 naphthol-2.

4 Dihydroxy acid 1 ', 2 azo-1,2'naphthalenedisulfonic
4.8 'and its chromium complexes 1/1 and 1/2.

5 Hydroxy-2 acid (hydroxy-5 methyl-3 phenyl-1
pyrazolyl-4 azo) -3 5-nitro benzenesulfonic acid and its
1/1 and 1/2 chromium complexes.

6 Hydroxy-2 acid (2-hydroxy-naphthyl-1 azo) -1 nitro-6
Naphthalenesulfonic-4 and its chromium complexes
1/1 and 1/2.

7 Hydroxy-2 acid (hydroxy-5 methyl-3 phenyl-1
pyrazolyl-4 azo) -1 naphthalenesulfonic-4 and its
1/1 and 1/2 chromium complexes.

8 Acid [5-hydroxy-3-methyl (p-sulfophenyl) -1 pyra
4-zolyl azo] -2 benzoic and its chromium complexes
1/1 and 1/2.

9 Acid (5-chloro-2-hydroxyphenylazo) -2 dihydroxy-1,8
naphthalenedisulfonic-3,6 (chromable dye
during application).

10 Acid (1,5-dihydroxy-2 naphthyl-azo) -3 hydroxy-4
benzenesulfonic (dye chromatable during
application).

12 Acide 0(o-chlorophénylazo)-4 hydroxy-5 méthyl-3
pyrazolyl-1-]-4 dichloro-2 , 5 benzènesulfonique.11 Chromatable dye from the triphenylmethane series
of formula

12 Acid 0 (o-chlorophenylazo) -4 5-hydroxy-3-methyl
pyrazolyl-1 -] - 4-dichloro-2, 5 benzenesulfonic.

13 Acid [(N-ethyl N-phenyl sulfamoyl-3 methyl-4
phenylazo) -4 hydroxy-5 methyl-3 pyrazoïyî-ÎJ-4
2,5-dichloro benzenesulfonic.

14 p- (2-Hydroxy-naphthyl-1 azo) benzenesulfonic acid.

15 Anilino-2 acid (2,4-dinitro anilino) -5 benzene
sulfonic.

16 2-Hydroxy acid 4-emesyloxyphenylazo) -4 'biphé
nylyl-4 azo] -l naphthalenedisulfonic-6.8.

17 Amino-1 hydroxy-8 acid [(2-hydroxy-o-toluidino-4
phenylazo) -4 'biphenylyl-4 azo] -2 phenylazo-7
naphthalenedisulfonic-3,6.

19 Colorant acide xanthénique de formule

20 Colorant acide xanthénique de formule :

21 Colorant acide de la série triphénylméthane de formule

22 Colorant acide anthraquinonique de formule

23 Colorant acide anthraquinonique de formule

24 Acide amino-l dioxo-9,10 dihydro-9,10 (triméthyl
2,4,6 anilino)-4 anthracènesulfonique-2.18 Acid heterocyclic dye of formula:

19 Xanthenic acid dye of formula

20 Xanthenic acid dye of formula:

21 Acid dye of the triphenylmethane series of formula

22 Anthraquinonic acid dye of formula

23 Anthraquinonic acid dye of formula

24 Amino-l dioxo-9,10 dihydro-9,10 (trimethyl
2,4,6 anilino) -4 anthracenesulfonic-2.

25 Mono- and disulfonated copper phthalocyanine.

27 Colorant nitrosé acide, complexe de fer de
formule

28 Acide benzoylamino-6 hydroxy-1 (p-sulfophényl
azo-4 phénylazo)-2 naphtalènesulfonique-3.26 Acid nitrose dye, iron complex
formula

27 Acid nitrose dye, iron complex
formula

28 Benzoylamino-6 hydroxy-1 acid (p-sulfophenyl
4-azo phenylazo) -2 naphthalenesulfonic-3.

29 Amino-1r acid (2,4-diamino phenylazo) -4 'biphenylyl
-4 azoJ-2 hydroxy-8 phenylazo-7 naphthalenedisulfo
pic-3.6.

31 Colorant direct mixte azoSque anthraquinonique de
formula

32 Colorant direct trisazoïque cuivrable à l'applica
tion de formule

33 Colorant direct disazoîque, complexe de cuivre de formule:

34 Colorant direct trisazoSque, complexe de cuivre
de formule

35 Acide bis [bis[ss-hydroxyéthyl)amino-4 méthylamino-6
triazinyl-2 amino7-4,4' stilbènedisulfonique-2,2'
(agent de blanchiment optique). 30 Trisazorque direct dye of formula

31 Azo anthraquinone mixed direct dye
formula

32 Direct coloring trisazoic copper-coated with applica
tion of formula

33 Disazo direct dye, copper complex of formula:

34 TrisazoSque direct dye, copper complex
of formula

35 Bis [bis [ss-hydroxyethyl) -4-amino-methylamino-6 acid
triazinyl-2 amino7-4,4 'stilbenedisulfonic-2,2'
(optical bleaching agent).

Claims (7)

1. Anionic dyes insoluble in water, but easily dispersible in cold water, characterized in that they are at least partially in the form of salts of a water-soluble cationic resin resulting from the condensation of formaldehyde with a salt of guanidinium. 2. Dyes according to claim 1 characterized in that the cationic resin results from the condensation of formaldehyde with a guanidinium salt in the proportion of 0.5 to 5 moles, preferably 0.8 to 2 moles, of formaldehyde per mole guanidine. 3. A method of manufacturing a dye according to claim 1 or 2, characterized in that a suspension or an aqueous solution of an anionic dye salt at least partially soluble in water is subjected to the action of an aqueous solution of a cationic resin resulting from the condensation of formaldehyde with a guanidinium salt in the proportion of 0.1 to 3 moles of guanidine per anionic molar equivalent of dye. 4. Method according to claim 3, characterized in that the aqueous solution of cationic resin is itself prepared by heating between 50 and 900C of the mixture of a guanidinium salt z with an aqueous solution of formaldehyde in an amount of 0.5 to 5 moles, preferably 0.8 to 2 moles, of formaldehyde per mole of guanidine, the pH of the mixture possibly being maintained between 4 and 12, preferably between 7 and 10. 5. Method according to claim 3 or 4, characterized in that one uses a mole of guanidine condensed with one mole of formaldehyde per anionic molar equivalent of dye. 6. Application of the anionic dyes according to claim 1 or 2 to the coloring of textile materials comprising natural or synthetic polyamide fibers and / or cellulosic fibers. 7. Textile materials comprising natural or synthetic polyamide fibers and / or cellulosic fibers, colored using a dye according to claim 1 or 2.