DE1278644B - Process for the production of pigment dyes - Google Patents

Description

Process for the preparation of pigment dyes The invention relates to the preparation of new dyes of the general formula in the Me zinc, manganese, nickel or cadmium, A an optionally still substituents, but not water-solubilizing substituents, containing divalent aromatic radical, which the molecular part completed to a benzene or naphthalene ring, and the radicals R 1 and R 2 are hydrogen atoms or substituents which do not make water soluble.

These dyes are suitable because of their insolubility in water and organic solvents and their very good fastness properties as pigment dyes.

The new dyes are obtained by adding 1,2,4,5-tetraaminobenzene derivatives of the general formula according to methods known per se with aromatic formyl compounds of the general formula to azines of the general formula reacted, where in the formulas II, III and IV A and the radicals R and R2 have the abovementioned meaning, and the hydroxyl groups are metallized in a manner known per se with agents that donate zinc, manganese, nickel or cadmium.

Contain 1,2,4,5-tetraaminobenzene derivatives of the general formula 1I in the 3- and or or 6-position hydrogen atoms or those which do not make them water-soluble Substituents such as chlorine atoms, methyl groups or nitrile groups. As examples are named: 1,2,4,5-tetraamino-3-methylbenzene, 1,2,4,5-tetraamino-3-cyanobenzene, 1,2,4,5-tetraamino-3-chlorobenzene and 1,2,4,5-tetraamino-3,6-dimethylbenzene. The aromatic formyl compounds of the general formula IH are derivatives of benzene or naphthalene. You can optionally other substituents which do not make water soluble, such as halogen atoms, low molecular weight alkyl or alkoxy groups, carbonamide groups, sulfonamide groups, Contain nitrile groups, nitro groups or arylazo groups. For example, be called: 2-hydroxy naphthaldehyde, 5-bromo- or chlorosalicylaldehyde, 3,5-dibromo- or -dichlorosalicylaldehyde, 5-phenylazosalicylaldehyde, 5- (4- or 3'-chloro) -phenylazosalicylaldehyde, 5- (4'- or 3'-nitro) -phenylazo-salicylaldehyde, 2-hydroxynaphthaldehyde-3, 1-formyl-2 = hydroxy - 3 - naphthoic anilide, 2 - hydroxy 6-bromonaphthaldehyde, 2-hydroxy-3,6-dibromonaphthaldehyde, 2-hydroxy-5-nitronaphthaldehyde, 1-hydroxy-2-formyl-4-chloronaphthalene and 2-hydroxy S-ffimethylsulfonamide-napkthaldehyde.

The low molecular weight alkyl or alkoxy groups in the compounds of the general formula III are preferably those having 1 to 4 carbon atoms. The carbonamide groups of these compounds can in turn by halogen atoms or be substituted by alkyl, aryl or nitro groups.

The metal salts of weak acids, e.g. B. the acetates, formates or carbonates. Mixtures of these salts can also contain various of the metals mentioned, e.g. B. for the production of; Use intermediate tones.

For the preparation of the novel dyes 4 mol is heated at # ise a formyl compound of the general formula HI with 1 mole of a Tetraaminobem "the aHgemnemen formula 1I in the presence of mannten zinc, manganese, nickel or cadmium cmes releasing agent in an organic 1 äS1 obtained in this Umsetztmg, the stand auerh in Gehwart a uence of Verder formula IQ amMhrm UBt, ummittelbar you neam FarbsAls L; äsmng9Onttel are hierrr z _t B:... can Fonmamid, dimethylformamide, N Me-Düe1tean, ButlyrobadtonundGlykolmonomethyl an Sder Te @ heaaminobenzole one AUU & the Salzre. e.g. diel hydrochlorides, using. 4 IM ie it zwe & diel conversion Silw in thee nurse he% amount e zmugeh. the metal m can in added d, the pigments without night portion, a portion 5 mm fic = 3 to entthaiöm. The gel e®ale Hrr the meta-carbonates mentioned_ One can, however, for the production of the new dyes also proceed in such a way that the reaction of 4 moles of formyl compound of the general formula III with 1 M ol 1,2,4,5-tetraaminobenzene of the general formula 11 carried out in the solvents mentioned in the absence of the metal donating agents. This gives the azines of the general formula IV, not yet described, which are then metallized by treatment with the metal donating agents. When producing the new dyes, it is advisable to keep atmospheric oxygen away in order to avoid a reduction in yield. However, the new dyes themselves are no longer sensitive.

The new pigments can be used in doughs, flush pastes, Preparations, printing inks, glue paints, binder paints and varnish paints of all kinds. The Pigments can be incorporated into synthetic or natural macromolecular substances such as polyvinyl chloride, polystyrene, polyamide, polyethylene, polypropylene, polyester, Phenoplasts, aminoplasts and gums. The pigments can also be used for bulk coloring of fibers made from acetyl cellulose, polyacrylonitrile, polyester, polyurethane and polyvinyl chloride use. They are also suitable for bulk coloring paper or for dyeing inorganic substances, e.g. B. cement.

In these substances, the new pigments are characterized by a large Color strength and through high solvent fastness, light fastness and temperature stability the end.

The pigment dyes known from the USA: Patent Specification 2,877,252 are produced by the pigment dyes which can be produced by the claimed process surpassed by a considerably greater color strength and brilliance.

The parts given in the examples are parts by weight. Example 1 172 parts of 2-hydroxynaphthaldehyde and 70 parts of 1,2,4,5-tetraaminobenzene hydrochloride are stirred in 1700 parts of formamide at room temperature. The oxygen in the air is displaced by introducing nitrogen. 120 parts of anhydrous sodium acetate are then added and the mixture is heated at 60 ° C. for 1 hour, at 0 ° C. for 2 hours and at 120 ° C. for 4 hours. The residue is then filtered off with suction while hot, with hot formamide; Ethanol and finally washed with water and dried. 170 parts of the bluish-tinged red azine of the formula are obtained 100 parts of this azine are heated in 1000 parts of formamide with 50 parts of zinc acetate for 2 hours at 90.degree. C. and for 5 hours at 120.degree. The residue is filtered off with suction, washed with hot formamide and hot ethanol and dried. This gives 98 parts of a red-violet pigment of the formula 20 parts of this pigment are rubbed in the usual way with lemo oil on a three-roll mill. The printing ink produced in this way gives prints of excellent color strength, lightfastness and brilliance when processed in letterpress and offset printing.

With a nitrocellulose solution containing 10 parts of nitrocellulose (alcohol-soluble, low viscosity), 5 teas of dibutyl phthalate, 80 parts of ethyl alcohol-ethyl glycol 9 : 1 , 3 parts of the pigment are rubbed in the usual way. This gives a strong red-violet gravure ink, the position is for manufacturers is not expiring printing in excellent fastness properties. By making appropriate changes, printing pastes such. B. for textile printing, screen printing, etc. can be obtained.

A mixture of 70 parts of pyvinyl chloride, 30 parts of dibutyl phthalate and 1 part of titanium dioxide is colored with 0.5 part of the pigment in the usual way. A red-violet colored mass is obtained from which z. B. films and profiles can be produced. The dyeing is characterized by excellent plasticity fastness and light fastness .

1 part of polystyrene granulate is mixed with 0.03 part of the pigment in a mixing drum. The mixture is then homogenized by a dye screw heated to 180 ° C. The strand emerging from the nozzle is shredded on the Schoeidemaschme. After spraying is obtained on the Spritrgußmaschine blaustichigtotgef`arbte moldings with excellent Echtheitefl.

In an analogous manner also polyethylene can and - polyamide will inked - Example 2 110 parts Salicylaldeäyd and 70 parts of 1,2,4,5-Tetraaminobenzolhydrochloorid be in 7i00 parts formamide under Stickosphäre with 120 parts of anhydrous Natriumaoetat 1 hour at -80 ° C and 3 hours 110®C erhita- is filtered off and, after washing with water and 86 parts of Atbanol orangd'arbmm AAEM the formula The mixture is heated under nitrogen 100 parts of this azine in 1000 parts of formamide with 100 parts Tu.kactat 3 hours at 110C. The residue is filtered off and washed with cold formamide and cold ethanol. One .erhält 96 pieces of analog zinc complex compound as an orange powder.

Example 3 172 parts of 2-hydroxynaphthaldehyde, 70 parts of 1,2,4,5-tetaaminobetzol hydrochloride and 2400 parts of dimethylformamide are added in a nitrogen atmosphere after adding 200 parts of butylamine and 185 parts of anhydrous zinc acetate for 1 hour at room temperature, 2 hours at 80'OC and 3 Stirred at 110 ° C for <hours. The residue is filtered off with suction while hot, washed with hot dimethylformamide, ethanol and water. This gives 168 parts of red-violet pigment described in Example. 1

Example 4 The procedure described in Example 1, which produced it, however, in place of 50 parts of zinc acetate, the angqi in the following table used> erasn parts metal acetate, one obtains the corresponding manganese, cadmium and nickel endalternden pigments in the anenn in the Tabdk amount and color. K Tale TC & color cks * UBWCUI a) Manganaoew .. 50 99 Violet b) Cadmium acetate 65 99 violet c) Nickdacxtat . . _ 5D 100 purple Example 5 Proceed as in tim example, 3 anpegbea, where but one at S1kk Sam 172 talm 2-hydroxy naphthous carbohydrates specified in the faiperdm table the necessary parts Aklehydi can be Spra; hmde Pigmdaf in the specified in the table quantity and color. Parts parts color of the Aldehyde Aldehyde Pigment Pigments a) Cl \ CH = O 156 110 red / OH b) Br "\ H = O 300 186 red / OH Br c) CI \ H = O 190 114 red / OH C1 CH = O d) / \ OH 251 244 violet Br \ / CH = O e) / \ 0 H 279 211 red fOz CH3-N-CH3 CH = O / \ OH 291 218 purple C-NH / \ 11 O CH = O g) / \ 0 H 2 1 7 172 red NOZ CH = O h) / - \ N = N / - \ OH 226 184 orange-red EXAMPLE 6 The procedure described in Example 3 is repeated, except that instead of 70 parts of 1,2,4,5-tetraaminobenzene hydrochloride, the parts of the amine salt given in the table below are used. this gives the corresponding pigments in the amount and color indicated in the table. Share parts Amine salt amine salt pigment paint CH3 HZN \ NHZ a) 4 HCl 74 164 red-violet HZN / NHZ CN H2 N \ NHZ b) 4 HC1 77 160 red-violet H ZN / NHZ C1 H2N \ NHZ 4 HCI 81 152 red-violet H ZN / NHZ These pigments and the pigments obtainable according to Examples 2 to 5 can be used as indicated in Example 1. This gives dyeings with appropriate fastness properties.

Example 7 A suspension of 40 parts of 1,3-dinitro-4,6-diaminobenzene is hydrogenated in 500 parts of ethanol after the addition of Raney nickel under normal pressure, the Temperature rises to around 60 ° C. The hydrogen uptake is after 2 to 3 hours completed. The suspension is suctioned off. The residue that the hydrogenation 1,2,4,5-tetraaminobenzene formed and containing Raney nickel is 1000 parts Washed out 30 weight percent acetic acid.

138 parts are immediately added to the filtrate under a nitrogen atmosphere 2-hydroxynaphthaldehyde in 500 parts of glacial acetic acid. It is refluxed for 3 hours, The residue is filtered off with suction at about 50 ° C. and the residue is washed with acetic acid and Ethanol. 141 parts of the azine described in Example 1 are obtained, the already small one Contains proportions of the corresponding nickel complex compound.

15 parts of the azine thus prepared are in 300 parts of monomethyl glycol ether refluxed with 11 parts of nickel acetate for 3 hours. 17.5 is obtained Parts of the pigment described in Example 4, c), which is characterized by excellent Pigment properties.

Claims (1)

Claim: Process for the production of pigment dyes of the general formula in the Me zinc, manganese, nickel or cadmium, A an optionally still substituents, but not water-solubilizing substituents, containing divalent aromatic radical, which the molecular part completed to form a benzene or naphthalene ring, and the radicals R 1 and R 2 are hydrogen atoms or substituents which do not make water soluble. mean, thereby marked -z eichnet that 1,2,4,5-tetraaminobenzene derivatives of the general formula according to methods known per se with aromatic formyl compounds of the general formula to azines of the general formula converts, where in the formulas II, III and IV A and the radicals Ri and R2 have the abovementioned meaning, and the hydroxyl group is metallized in a manner known per se with agents that donate zinc, manganese, nickel or cadmium. Documents considered: '. U.S. Patent No. 2,877,252. An explanatory staining chart was laid out in the publication of the application.