DE1494081C - Triphendioxazines for mass coloring of polymers - Google Patents

Description

A T Cf T \ J «-» X

The present invention relates to the use of finely dispersed 2,6 or! SJ-Diamino ^ .lO-dichlorotriphendioxazines of formula I.

NH

in which the Behzölkefne; Ä ™. and vB by halogen; * · low molecular weight alkyl, alkoxy or alkylsulfohyl groups; or) aralkoxy groups are also employed can be ^ if necessary- to be creamed. with 'a & carrier' serving organic macromolecular '~ Küristr substances that can be film-forming, as pigments for the mass coloring of natural,. or synthetic Polymers.

The two benzene nuclei marked by A and B can be used as Halogenätpnie Jrisbesoridere ChJQr or Brpnval low molecular weight ^; Alkyl groups e.g. B. methyl, ethyl, ri-propyl, isopropyl, butyl and amyl groups, as low molecular weight alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy and butoxy groups, as aralkoxy groups z. B. benzyloxy and Chlorbenzyloxygruppen and finally _d as niederinolekuläre i \ lkyisulforiyigflippen eg Κϊβ | .. ^ thyl-sulforiyl-;. Üriy Äthylsulforiylgruppen contain. ^

In preferred 2,6- or ST-Diariiinp- ^, lO ^ chloro-tripheridioxazines which can be used according to the invention, the benzolke A and B Mti "jeGirier ortho-continuation" to the primary aryanine groups by halogen, preferably, preferably chlorine or bromine ,. or a low molecular weight .35 kular alkyl, alkoxy or alkylsulfonyl group with preferably a maximum of 3 carbon atoms. A particularly) valuable and therefore preferred group of substances that can be used according to the invention are the 2, Ö-t) iaminp-9, | Ö-dichlorj: triphendipxazine, whose. ^ Benzp
3.77 position idurchι. Halogeri ^, a _; jiiedermplekuiare. _; ..-, alkyl- or, .jiirie ^^ NiederrnoiekuiaVe 'Älkoxy'group ¹ ^ further substituted: sirid.: ".'. '. ·'." vv ΐ; .-; ^ ^:

Compounds of,, general formula I obtained -4.5 z. B. ^ duith Reduk ^ ipf ^ eheftts'sprechenderi Di- ^! i ^{:. !} nitroyerbiridun £ eri. ^ Mänökänrii ^, ie /: R for example in an inert prgahischeri solvent. ·. ,. ■■. with catalytically excited ^ hydrogen or weak _; > sour ι. Mediüm _; mittej, Sii * ^^ j eri _by; Be c h ₄ am, p>_{5o; ";} Run salts of sulfurous acid hydrör i A, .Other manufacturers' ■] lungsajt is, in the hydrolysis, the acylamino groups vjnjBistacylaminp-v-for example, bis-acetyl .Agent with...""or alkaline- -amino / odef '; iis-beiizoyjani ^ ^

Urii as strong as possible. obtain and extensive * pigments, raw .müssenidie often ^one ieinzerteilte still in one; Be brought into shape. Average particle sizes from 0.1 to 1 micron give the best results: '- ■ "

This Feinzteilurig causes z. B. by precipitation from a solution, best by dissolving the pigment in concentrated sulfuric acid or its monohydrate at low temperature and then pouring it into water, if necessary with ⁶ S addition of a little alkali for the purpose of faster hydrolysis of the sulfate. Mari can also achieve fine division by grinding in the presence of grinding aids such as salts of inorganic or organic acids. It is often advantageous to add inert organic solvents in small amounts as further grinding aids. "

As, polymers pigmented according to the invention can be, natural, refined and come

z. B. rubber, natural and paraffins and for example 'Celluloseather ,, Cellulose esters, paper and cellulose regene- ·; xratijisehc.iech ^ pigmeritierenr. ■■■ ',.

^v "When ^ synthetic polymers DIE come by polymerization, polycondensation and / or poly-, addition plastics available in question, including in particular the ^ - ^ filmbildendeni plastics, ie in the first Lirjie '^ the so-called" thermoplastics ^ ..

From the group of polymers are pigmentable according to the invention: for example polyethylene, polypropylene, polystyrene, _i polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylonitrile, polyacrylic acid esters and polymethacrylic acid esters. From the group of Polycondensateiiurid, -. Polyadded products can be, for example, the condensate products of phenols, amines and amides with formaldehyde, and also polyamides and polyurethanes, then above all polyesters - namely, spiyphlj saturated ones; such as B. alkyd resins, as well as unsaturated ones, such as: z..B., Maieinatharze. ^ And finally the ^^ under the name "Epoxydharze" known polyaddition or Pplykondensatiprisproxlukte of; Epjchlprhyiclrinxmit; Pigmenting polyalcohols; n or polyphenols according to the invention1. The same applies to 'aüchlfuröemische from it as well as for co-condensates and co-polymers to z. B. for plastics that are made on the basis of butadiene.

The incorporation of the 2,6- or 3,7-diamino-9,10-dichloro-triphendioxazine pigments in the natural or synthetic polymers takes place according to the known Methods. For coloring ybni regenerated cellulose and von Cellulpsee.steni ^ are that according to the invention .yerwen "dbarenl \ -i ^^ ta

triphendioxazine is expediently added to the spinning masses. Polyamides and polyesters can also be used in the molten state, for example as spinning gauges, with the 2.6 or 3 _? 7Tpiamino-9,10-dichloro- ^: iripheridipxazinen.! Be colored ..:. _; · '; · '.> ■ <■. ^1v : Mey can also incorporate finely divided 2,6- or 3; 7-diamino-9,10-dichloro-triphehdipxaziri into a prepolymer or pre-polymerizate. and from pigmented semi-finished products according to the usual processes: finished products ^; manufacture / > ; ^{; :} S ί I; -v

The amount of pigment to be chosen is directed after. the. desired color strength of the end product ^^ and is -jrri general 0.05 to 6i; Ge ■, chtsprpzente, fAezpgeji ^ aluf, that too; pigmentifciende

^ MateriäY.1; iK; i; ^. V ^ fe '^ vV> i ^^ v ^{: κ} :: v. The uerfiridungsgemäß ν _o-pigmented natural fe _r synthetic polymers are distinguished by a very good Hitzebeständigkeit'sowie by good wet rubbing, oil, solvent and sublimation fastness and in particular by good to very good / light 'migration and Uberlackierechtheit: from. The colorations are very strong and brilliant.

. These good fastness properties according to the prevailing Invention bluish red to blue pigmented Polymers allow processing according to known methods, for example by calendering, pressing, Extrusion, painting, casting or injection molding.

* s T UU 1

Film-forming polymers pigmented blue according to the invention are also valuable for paints and varnishes also in printing pastes, e.g. B. for paper and textile printing and finally as raw materials for Paints and inks.

Triphendioxazinverbindungen.mit free primary amino groups are so far only from the Belgian Patents 568 112 and 570 725 as intermediates for the production of substituted benzoylamino-triphendioxazines become known. It It was therefore surprising that the 2,6- or 3,7-diamino-9,10-dichloro-triphendioxazines which can be used according to the invention are found suitable for dyeing natural or synthetic polymers because for their As is well known, staining is only possible with permanent compounds. It is particularly noteworthy that that the polymers colored according to the invention are also without the influence of alkalis and acids resist any noticeable change in shade.

In comparison with the dioxazine pigment known from British patent specification 831 243, the Condensation product of 2 moles of 3-amino-N-ethylcarbazole and 1 mole of tetrachlorobenzoquinone, and the from American patent specification 2,843,498 2,6-diphenyl-9J0-dichloΓ-triphendioxazine pigment have the similar 2,6-diamino-3,7-diethoxy-9,10-dichloro- or 2,6-Diamono-3,7i9,10ttetra'chloΓ-triphendous! oxazine Surprisingly, a better migration resistance in polyvinyl chloride films. ': V

In the following ¹ examples, parts are parts by weight. The temperatures are given in degrees Celsius.

Example

40 parts of finely divided 2,6-diamino-3,7-diethoxy-9,10-dichloro-triphendioxazine, 360 parts of alumina hydrate, 600 parts of medium viscosity linseed oil varnish and 2 parts of cobalt linoleate are applied on a three-roll mill grated mixed. A graphic paint is obtained which has fine blue prints of considerable color strength and excellent solvent, oil, acid, alkali and Lightfastness results /

Prints of some green-blue shade and of similar good fastness properties are obtained; if you have lόParts of 2,6-diamine-p-3,7-dimethoxy-9,10-dichloΓ-triphendioxazine and of a redder pale hue, if you have 10 parts of 2,6-piamino; 3 ^
.triphendioxazin ^ yerwe'n ^

The: - yöxgeriarintetf '^^ pjamirio-P.ip ^ dichlorrtfiphehdioxazine can duYch V ^ r ^ ifung ^ the ■ corresponding' 2,6-pibenzoyI- or 2,64piäcetyllaminor 9, lÖ-dichlör-tripheridiox $ ziriem ^
Felsäüre ^ oh; 80 to \ l00% content and discharge of the solutions in a lot of water. The fine division of the dry 'powder' takes place by grinding in the presence of anhydrous calcium chloride or sodium sulfate in a vibrating mill and then washing out the grinding substrates with water.

B e i s ρ i e 1 2

15 parts of collodion wool containing 35% butanol, 15 parts of one modified with castor oil Phthalate resin, 15 parts of a 79%> gen butanolic Solution of a urea lacquer resin, 20 parts of butyl acetate, 10 parts of glycol monoethyl ether, 20 parts of toluene and 5 parts of alcohol are processed into a varnish. This is then finely divided with 2 parts 2.6 - diamino - 3.7 - diisopropoxy - 9.10 - dichloro triphendioxazine and 2 parts of titanium dioxide (rutile) pigmented and ground. After spraying z. B. on cardboard and drying this varnish you get a blue coating of very good light and light fastness to overpainting. Reddish-tinged blue colorations are obtained from 2,6-diamino-3,7-dimethyl or diethyl ^ lO-dichloro-triphendioxazine.

The aforementioned 2,6-diamino-9,10-dichloro-triphendioxazines can by saponifying the corresponding 2,6 - Dibenzoylamino - 9,10-dichloro - triphendioxazine can be produced using 96% sulfuric acid.

Be i s ρ i c I 3

To 100 parts of a stoving enamel made from 58.5 parts of a 60% solution of a coconut alkyd resin in xylene, 23 parts of a 65% solution of a melamine lacquer resin in butanol, 17 parts of xylene and 1.5 parts of butanol, 1 part of finely divided 2,6-diamino-9,10-dichloro-triphendioxazine is added and 5 parts of titanium dioxide. The mixture is ground in a ball mill for 48 hours and injected the varnish pigmented in this way on a cleaned metal surface. Receives after baking at 120 ' one has a blue coloration of good lightfastness and fastness to varnish.

If the 2,6-diamino is replaced by the 3,7-diamino-9, 10-dichloro-triphendioxazine, similar blue dyeings with similar fastness properties are obtained in this way.

The 2,6- or SJ-Diamino ^ lO-dichloro-triphendioxazines can be obtained by reducing the corresponding yellow ^; Nitrötriphendioxazine can be produced using sodium hyposulfite.

Example 4

A finely ground paste of 50 parts Polyvinylchloridpulyer (emulsion), 32 parts of dioctyl phthalate, 1 part of dibutyltin dilaurate, 0.25 part of a stabilizer based on phosphate, 6Teilen chalk powder, '10, 75 parts Lackbenziri and 2.5 parts of a finely ground 40 ° / _o aqueous dough of 2,6-diamino-3,7,9,10-tetrachloro-tripheridioxazine in dioctyl phthalate is irt ^! a layer of 0.2 mm thickness applied to cotton fabric. The coated fabric is then heated to 160 ° for 3 minutes, whereupon a "further application of 0.3 mm thickness takes place and again; 3" minutes is heated to 160 ° is wet fast.

Very similarly colored artificial leather is obtained if one uses the 2,6-diamino-3,7,9, Iό-tetΓachlor- through 2,6-diamino-3,7-dibromo-9,10-dichloro-triphendioxazine replaced. Both aminotriphendioxazines can be obtained by saponifying the corresponding benzoylaminotriphendioxazines be made in 86% sulfuric acid.

Example 5

0.2 part of finely divided 2,6-diamino-1,5,9,10-tetrachloro-triphendioxazine and 100 parts of polystyrene granulate are mixed and processed on the mixing roll mill at 130 ° until the color appears homogeneous. The mass is then pressed between chrome-plated plates at 150 ° to form plates The violet-blue The coloring of the plates is very lightfast. Man

The pigmentation can also take place on the mixing mill in the extruder. It is also possible to add the homogeneously pigmented mass granulate and deform in the injection molding machine. · ■. '· ■■ · ■■■

The 2,6-diamino-1,5,9,10-tetrachloro-triphendioxazine can by saponification of the corresponding 2,6 - dibenzoylamino - 9,10 - dichloro - triphendioxazins. which is formed by ring closure of the dianil from chloranil and 2 molecules of 4-benzoylamino-3-chloroaniline, getting produced.

Be i s ρ i e 1 6

A rubber mixture made from 40 parts of Hevea Latex CrSpe. 24.5 parts of barium sulfate. 24.8 parts Chalk. 5.22 Share Lithopone. 4.0 parts zinc oxide. 0.2 parts paraffin. 0.7 parts sulfur. 0.18 parts Vulcanizing agent (Vulkacite P). 0.4 parts of an anti-aging agent, 1 part of finely divided copper phthalocyanine and 1 part of refined 2,6-diamino-3,7-dimethyl-9,10-dichloro-triphdioxazine is processed in the usual way on the mixing mill and then in the press for 10 minutes at 140 vulcanized. You get a good lightfast, migrationfast, reddish blue color.

Example 7

25 parts of Zo-DiaminoOJ-dimethyl ^ .lO-dichlorotriphendioxazine are mixed with 5000 parts of polyhexamethylene adipamide and in the usual way fused under a nitrogen atmosphere at about 285. After spinning the thick viscous ones obtained in this way The mass becomes blue fibers, the color of which is light and wet fast. get that if appropriate stretched and / or puckered and shrink-set.

Example .8

: 50 parts by ^ grinding with anhydrous calcium chloride finely divided ii.ö-diamino-SJÄlO-tctrachlortriphendioxazin with 12.5 parts of the sodium salt of the condensation product. of naphthalene-2-sulfonic acid with formaldehyde. 0.5 parts of sodium hydroxide and 2 * 00 parts of water in a ball mill ground for 72 hours. 5 parts of this dough are 2000 parts of a sodium xanthogate solution, made from 180 parts of cellulose. 180 parts ; Sodium hydroxide. 64O parts of carbon disulfide and 100 parts water. ,, added and the suspension by stirring ·, homogenized. After 12 hours cm > o When under vacuum, the viscose is spun in the usual way, desulphurized, washed out, and removed and dried. Pure blue fibers are obtained, the color of which is good lightfast and wetfast.

- "" ^ VY '---. ^; - Example 9 ■ '''^

, .40 parts fine / granted Z-o-Diamino-i ^ -dimethyisulfonyl-y.lO-dichloro ^ triphcndioxa / ia will be like in the case

25th

10

35 game 1 indicated mixed with alumina hydrate and linseed oil varnish and rubbed. A graphic ink is obtained which gives violet prints of high color strength and lightfastness.

The 2,6-diamino-3,7-dimethylsulfonyl-9,10-dichloro-triphendioxazine is obtained by reducing the corresponding yellow-brown nitro compound using sodium hyposulfite.

Prints of similarly good fastness properties are obtained if 2,6-diamino-3,7-diethylsulfonyl-9,10-dichloro-triphendioxazine is used used.

Example 10

0.5 part 1,5.3,7,9,10-HeXaChIOr- ^ o-diamino-triphendioxazine and 4.5 parts of titanium dioxide are mixed with 40 parts of an alkyd melamine lacquer, which is 50% Contains solid. Ground in a rod mill for 24 hours. The varnish obtained is in a thin layer applied to aluminum foil and baked at 120 ° for one hour. You get one violet paint with excellent light and varnish fastness.

In the above example, if the 0.5 parts 1.5.3.7.9,10 - hexachloro - 2,6 - diamino - triphendioxazine are replaced by an equivalent amount of 1,5,3,7-tetramethoxy-Zo-diamino ^ 10-dichloro-triphendioxazine or by an equivalent amount of l, 5,3,7-Telramethyl-2,6-diamino ^ .lO-dichloro-triphendioxazine, in this way, with otherwise the same procedure, violet-blue colorants with similar fastness properties are obtained.

The aminodioxazines used in this example are obtained by condensation of 3,5-dichloro-, 3,5-dimethoxy- or 3,5-dimethyl- 1,4 -diaminobenzene with chloranil. Ring closure in the presence of benzoyl chloride. Treatment with concentrated sulfuric acid and salt grinding of the raw pigments obtained.

Claims (1)

Claim: '. Use of finely dispersed 2.6 or 3.7 di amino ^ .lO-dichloro-iriphendioxazines of the form NH, wherein the benzene nuclei Λ and B by Halogci low molecular weight alkyl. Alkoxy or alk \. sulfonyl groups. or aralkoxy groups while may be substituted, optionally together with organic macromol serving as a carrier kularcn plastics that could be film-forming as pigments for mass coloring of. natural or synthetic polymers.