DE950188C - Use of the condensation products of halobenzanthrones as pigment dyes - Google Patents

Description

Use of the condensation products of halogen benzanthrones as Pigment It is known from German Patent 212 471 that at the condensation of halobenzanthrones containing halogen in the benzene ring with I-Aminoanthraquinone imide-like condensation products are formed, which are known as I-N- (Benzanthronyl) -aminoanthraquinones can be designated. These condensation products serve as intermediates for the production of vat dyes; so far they have no other in practice Use found.

This is probably due to this; because it uses dyes as pigments - deliver cloudy and unsightly colors.

The surprising observation has now been made that this I-N- (benzanthronyl) -aminoanthraquinones are valuable pigment dyes after suitable preparation, which are generally characterized by great color strength and very good fastness properties distinguish. Suitable I-N- (Benzanthronyl) -aminoanthraquinones for this purpose come especially the condensation products of halobenzanthrones, which contain a halogen atom have in the benzene ring and are optionally further substituted with aminoanthraquinones, which have one or more amino groups in the a-position and still may carry further substituents or fused rings, into consideration. Own the aminoanthraquinones several a-amino groups, so can also several benzanthronyl radicals are introduced into the anthraquinone molecules.

The conversion of the condensation products into pigment dyes can in various ways., For example by fine grinding in suitable Mills, where appropriate milling aids such as inorganic salts, organic carboxylic acids or their alkali or alkaline earth salts, etc., are added. Become the meal helpers removed after grinding by dissolving with water or diluted acids, whereupon dispersants can be added to the pigments obtained in this way: A very useful method of converting the condensation products into the desired ones finely divided state consists in their dissolution in cold concentrated sulfuric acid and then pouring the sulfuric acid solution into cold, warm or hot water Water that is in vigorous motion, optionally with the addition of suitable water Dispersants. After filtering off and washing neutral, the obtained Pigment dyes by further treatment on roller mills or other means for processing machines that can be used with pigments, if necessary with the addition of distribution agents, Convert into ready-to-trade pastes. The properly processed pigment dyes can of course also be obtained as a powder, for example by Drying a treated dye paste in a spray dryer.

The pigment pastes or powders obtained in this way can be used for coloring Papers in bulk, for printing on textiles, for dyeing synthetic fibers in the spinning mass, etc. find use. Their colors are clear and valuable shades.

The following examples illustrate the invention; included the parts mean parts by weight, the percentages mean percentages by weight, and the temperatures are given in degrees Celsius.

Example I 200 parts of I-N- (Bz-I'-benzanthronyl) -aminoanthraquinone (obtained by condensation of 1 mole of Bz-I-bromobenzanthrone with 1 mole of I-aminoanthraquinone) are dissolved in 1200 parts of sulfuric acid monohydrate with cooling and thorough stirring. The sulfuric acid. The solution is then fine-tuned into 8,000 to 10,000 parts Water of 10 to 75 °, which is moved very quickly, poured in. The unusual one The pigment is stirred for a while, then filtered and washed until neutral. The filter cake is in a suitable apparatus, for example in a roller mill, optionally with the addition of a dispersant, such as dinaphthylmethanedisulfonic acid, processed into a uniform pigment paste. The paste provides strong, purple-red-brown Spin dyeings, cotton prints and paper dyeings in the bulk that spread through very good light and chlorine fastness.

The filter cake can after suitable processing in the spray dryer can also be converted into a pigment powder.

Example 2 20 parts of I-N- (Bz-I'-benzanthronyl) -amino-6,7-dichloroanthraquinone (produced by condensation of 1 mole of Bz-I-bromobenzanthrone with 1 mole of I-amino-6, 7-dichloroanthraquinone) with cooling in 140 parts of sulfuric acid from 94 to 100% dissolved. The sulfuric acid solution is then poured into 2000 parts of water 70 to 75 °, which is moved very quickly, and the suspension obtained is still stirring some time. The precipitated pigment is according to that described in Example 1 Process worked up. It gives strong, real, violet-brown viscose spin dyes and prints on cotton.

Example 3 30 parts of 1-N- (Bz-1'-benzanthronyl) -amino-5-aminoanthraquinone (obtained by condensation of 1 mole of Bz-I-bromobenzanthrone with 1 mole of I, 5-diaminoanthraquinone) are dissolved in 6 to 8 times the amount of sulfuric acid from 95 to 100% with cooling, whereupon the sulfuric acid solution in 1500 parts of water, which is in rapid motion is located, is poured. The pigment dye worked up in the usual way there are very real corduroy spun dyeings in viscose or acetate silk as well as corresponding ones Prints on textiles or paper dyeings in bulk.

Is used in place of the I-N- (Bz-I'-benzanthronyl) -amino-5-aminoanthraquinone the I-N- (Bz-I'-benzanthronyl) -arnino-8-aminoanthraquinone, one obtains an in pigment shifted to the shade of violet.

The table below lists further benzanthronylaminoanthraquinones which can be processed into pigment dyes according to the procedure of the preceding examples. Nuance of N- (Benzanthronyl) -aminoanthraquinone viscose- spin dyeing IN- (Bz-I '-benzanthronyl) -amino- 5-N-benzoylaminoanthraquinone. . Chocolate- Brown -N- (BZ-I'-b enzanthronyl) -amino- 2-methylanthraquinone. . . . . . . . . . Brown IN- (Bz-I '-benzanthronyl) -amino- 4-methoxyanthraquinone ................ purple-gray IN- (Bz-I '-benzanthronyl) -amino- 4-oxyanthraquinone ................. red-gray IN- (Bz-I '-benzanthronyl) -amino- 4, 8-dioxy-5-aminoanthraquinone navy blue IN- (Bz-I '-benzanthronyl) -amino- 4-N- (2 ", 5" -dichlorophenyl) - aminoanthraquinone ................. ~ reddish gray Example 4 30 parts of 1,5-di-N # N- (Bz-1'-benzanthronvl) -aminoanthraquinone (obtained by condensation of 2 moles of Bz-1-bromobenzanthrone with 1 mole of 1,5-diaminoanthraquinone) are 6 times the amount Dissolved sulfuric acid monohydrate with cooling and stirred the solution into 2000 parts of water at 70 °, which is in vigorous motion. The precipitated pigment is worked up in the usual way. He dyes artificial silk or paper in the mass in very real and strong purple-brown tones.

If, instead of the 1,5-di-N N- (Bz-1'-benzanthronyl) -aminoanthraquinone, other di-N- (Bz-1'-benzanthronyl) -aminoanthraquinones are used, similar pigment dyes are obtained. Tue-N. N- (Bz-L'-benzanthronyi) - shade of the Viscose- aniinoantkrachinon spirit coloring Technical mixture of I, 5- and I, 8-Di-N N- (Bz-I'-benz- anthronyl) -amino-2-methyl- anthraquinone. Brown 1,5-Di-N # N- (Bz-1'-benzanthronyl) - amino-4, 8-dioxyanthraquinone blue-gray 1,8-Di-N # N- (Bz-1'-benzanthronyl) - aminoanthraquinone. . . Purple gray Example 5 25 parts of IN- (Bz-I '-benzanthronyl) -aminoanthraquinone, 12 parts of a water-soluble dispersant and 100 parts of water are ground in a ball mill until a particle size of I u and below is reached. The pigment paste obtained can be used as such, or it is processed into a pigment powder in an atomization dryer.

Example 6 30 parts of 2-methyl-4-N (Bz-1'-benzanthronyl) -amino-1,9-C-carbethoxyanthrapyridone (produced by condensation of 1 mole of Bz-I-bromobenzanthrone with 1 mole of 2-methyl-4-amino-I, 9-C-carbäthoxyanthrapyridon) are 95--100% in 180 parts of sulfuric acid dissolved under cooling. The solution is stirred into 2000 parts of water in the customary manner and the pigment worked up; he delivers in spun-dyed artificial silk, in textile printing etc. Corinthian shades with excellent fastness properties.

Example 7 30 parts of 4-N- (Bz-1'-benzanthronyl) -amino-2, I-N -benzanthraquinone acridone (produced by condensation of 1 mole of Bz-I-bromobenzanthrone with 1 mole of 4-amino-2, I-N-benzanthraquinone acridone) are dissolved in 170 parts of sulfuric acid at 98 ° lo and then rapidly moving water in 1700 parts, which has a temperature of 70 up to 80 °.

The precipitated pigment is worked up in the usual way and gives very real brown-violet spin dyeings.

Example 8 20 parts of I-N- (6'-bromo-bz-I '-benzanthronyl) -aminoanthraquinone (produced by condensation of 1 mole of 6-Bz-I-dibromobenzanthrone with 1 mole of I-aminoanthraquinone) are dissolved in 140 parts of sulfuric acid monohydrate with cooling. The solution will be in a known manner in 1500 parts of water from 20 to 300, which is in rapid motion is, poured and the precipitated pigment worked up in the usual way. It gives real, corinth-colored spin dyeing in artificial silk.

Similar pigment dyes are obtained from I-N- (6'-bromo-bz-1'-benzanthronyl) -amino-6, 7-dichloroanthraquinone (produced by condensation of 1 mol 6 - Bz -1 - dibromobenzanthrone with I mol of 1-amino-6, 7-dichloroanthraquinone) or I-N- (6'-bromo-bz-1'-benzanthronyl) -amino-5-animoanthraquinone (produced by condensation of 1 mole of 6-Bz-I-dibromobenzanthrone with 1 mole of I, 5-diaminoanthraquinone).

Example g A medium-deep paper coloring is achieved in such a way that one 2 parts of a ro% aqueous paste of the according to Example 1, 1st paragraph, obtained Pigment dye in the Hollander to a mixture of 100 parts of bleached sulfite cellulose adding in 2000 parts of water.

The colored paper pulp is then - for the purpose - more vegetable Sizing and simultaneous fixation of the pigment on the paper fibers - with 40 parts of a 2.5% rosin resin soap milk and then with 40 parts of a 5% aluminum sulfate solution are added.

In the same or similar way paper pulp is also used with the dyes the remaining examples colored.

Example 10 Another important application of the pigment dyes described consists - as mentioned several times above - in the dyeing of synthetic fibers in the spinning mass. The principle of spin dyeing viscose rayon consists in that ripened viscose solutions colored by stirring in the dye pigments and then be spun with the spinning machine.

100 parts of a 20% strength aqueous paste of that obtainable according to Example 1 Pigment are 22500 parts of an aqueous, approximately g0 /, strength viscose solution added in the agitator. The dyed spinning mass is then stirred for 15 minutes, then vented and subjected to the usual spinning and desulfurization processes.

The dyes in the remaining examples are used in a similar manner for dyeing spinning masses.

Example II A dough consisting of 100 parts of a 20% strength aqueous Paste of the pigment dye which can be prepared according to Example 6, 400 parts of tragacanth 3%, 400 parts len of a 50% aqueous egg albumin solution and 100 Parts of a non-ionic wetting agent are printed onto a textile fiber fabric. The print is dried and then attenuated for 112 hours at 100 to 101 °.

In the pressure approach, all of the above-mentioned dye can be used other products described in Examples I to 8 and / or instead of the Traganths and egg albums usually used for fixing pigments on the fiber binders used, for example those based on synthetic resin, are used As a dispersant, such as that used for converting the I-N- (Benzanthronyl) -aminoanthraquinones Used in pigment dough or powder, serve in addition to the already dinaphthylmethanedisulfonic acid mentioned, for example, also include alkyl polyglycol ethers with 20 to 25 ethenoxy groups such as cetyl, stearyl or oleyl polyglycol ethers, alkylphenyl polyglycol ethers, such as Dodecylphenylp olyglykoläther, then alkylarylsulfonates, such as alkylbenzenesulfonates and alkylnaphthalene sulfonates, sulfonated oils, fatty acid condensation products, higher molecular weight alkyl sulfates and alkyl sulfonates and many others.

Claims (1)

PATENT CLAIM: Use of the finely divided form Condensation products of halobenzanthrones, which contain a halogen atom in the benzene ring have and are optionally further substituted with aminoanthraquinones, which have one or more amino groups in the a-position and other substituents or can carry fused rings, as pigment dyes for dyeing paper in the mass and of synthetic fibers in the spinning mass as well as for printing textiles.