DE2823169A1 - Tinting black polyacrylonitrile spinning compsns. - by addn. of blue or violet cationic or basic dyes which are resistant to migration - Google Patents

Abstract

The black shade of acrylonitrile (co)polymers is improved by addn. of cationic and basic dyes with migration factor (M) of is not >20, combination coefficient (I) 2.5 and cation wt. 310, which are blue or violet in colour. Neutral or bluish-black shades are obtd. Although soluble in the solns., so that no blocking or wear of spinning nozzles occurs, very little bleeding-out takes place in the coagulation, stretching or wash baths. Very high dye yields are obtd., with constant and uniform shade and without fading. Changes in shade are easily affected, and contamination of regenerate by dye decompsn. prods. avoided. Increased cost of regenerating baths to remove extracted dye is eliminated.

Description

Process for the leveling of blackened by means of carbon black

Polymers and copolymers of acrylonitrile, especially when spinning from the spinning mass It has long been known to use polymers and copolymers of acrylonitrile to dye black in the spinning mass using soot and then this spinning mass to spin black threads and fibers. Carbon blacks that are used for this are, for example, in Ullmanns Encyklopadie der technischen Chemie, 3rd edition (1963), Volume 14, pages 793-810, in particular pages 803 ff. Depending on The black colorations thus obtained show one more of the carbon black quality used or less gray, brown or yellow cast. Neutral or bluish black tones cannot be achieved with carbon black alone. So it is desirable to remove the soot or the material colored black with it by adding blue or violet ones Nuance colorants. Known methods of shading blackened with carbon black Polymers and copolymers of acrylonitrile, especially in spin dyeing, however, have disadvantages. So is the subsequent IYuancierunO (black fining) of threads and fibers of polymers and mixed polymers of acrylonitrile according to the Production of the threads because of the subsequent additional work process from technical of little interest, as these materials are obtained by mass spinning and the technically easier z to use Blackening in the crowd is preferred. However, the nuance of the polymers in the spinning mass is through The addition of color pigments is associated with considerable disadvantages, since it is used from pigments for spinning to threads and fibers a very good pigment finish to achieve an even, very fine and qualitatively constant grain size is required; Such a pigment finish is associated with a lot of effort. Furthermore, the use of pigments in spinning has an increased mechanical effect Wear and tear on the spinnerets, which in turn leads to nozzle clogging and titer inaccuracies of the threads or even to the complete failure of individual threads. Further Increased matting effects can occur due to color pigments, furthermore the mechanical properties of the threads are changed unfavorably.

When shading polymers and copolymers colored black with carbon black of the acrylonitrile in the spinning mass by means of dyes soluble in the spinning mass hitherto the disadvantage that such dyes when spinning and passing through the Coagulation, stretching and washing baths from n threads and fibers bleed out, causing changes in the nuance and difficulties in the work-up by distillation the solvent leads. Also the well-known process of blackening polymers and copolymers of acrylonitrile in the spinning mass by means of spinning mass-soluble ones black azine dyes of the nigrosine and indulin series have significant disadvantages afflicted; so these dyes fix insufficiently in the polymer and bleed when spinning the dope, in particular according to the wet spinning procedures in the coagulation bath to a very great extent, so that it is only suitable for the dry spinning process Have found use.

The present invention now provides a method for shading of polymers colored black with carbon black and copolymers of acrylonitrile, especially in mass spinning for the production of black-coated threads and Fibers, found that these disadvantages do not have these disadvantages or only to a very minor extent. With the present invention it was found that you can get the black fining of polymers colored black with carbon black and copolymers of acrylonitrile are advantageous can be done in the way if the polymer mass is cationic or basic, Dyes soluble in the spinning mass of polymers or copolymers of acrylonitrile adds, which have the property to fix strongly and quickly in the polymer.

These dyes color the coagulation, stretching and washing baths the mass spinning does not or only imperceptibly, although it is in water and solvents, which are used in the spinning dope in spinning processes, or in their aqueous Mixtures such as those used in the working baths are soluble.

The present invention thus relates to the use of blue and purple cationic or basic dyes for shading with carbon black black-colored polymers and copolymers of acrylonitrile, in particular of Threads and fibers made from polymers and copolymers of acrylonitrile in mass spinning, these spinning pulp-soluble cationic and basic dyes characterized by this are that they have a migration factor M of 20 or less than 20, a combination indicator K of less than 2.5 and a cation weight (KG) of greater than 310, preferably greater than 380, in particular greater than 480. The present invention therefore also relates to a process for blackening (shading) of with soot black-colored polymers and copolymers of acrylonitrile, especially in Spinning out of the spider mane, which is characterized by the fact that one is the i'arbstolle or? lisciiun: en this dye is used in the spinning mass and this spinning mass, optionally subsequently, into threads or fibers in the usual way Process of dry spinning or wet spinning.

Violet dyes mean dyes from red-violet to blue-violet Understand color. Blue paraffins also have a more or less strong greenish tinge blue dyes. This principle of color and shade selection for black finishing is known.

The migration factor M gives the migration behavior and affinity ability a dye on or to the fiber; it can be according to the definition below and determination have values between zero and 100. A lower value means for the method according to the invention has a strong fixation, a high value a weak one Fixation of the dye in the polymer. It is determined as follows: One stains first a polyacrylonitrile fiber material (yarn) in 1/1 standard depth according to the exhaust process from an aqueous bath in a liquor ratio of 1:30; the bath contains, based on the weight of the fiber used, 0.3 ffi of the dye, 1% of a 60 wt Acetic acid, 2 ffi sodium acetate (crystalline), 10% anhydrous sodium sulfate and 0.3 % of an action product «n about 2.5 moles of ethylene oxide to 1 mole of stearylamine as a migration aid. The fiber material is in this dye bath for 60 minutes 98-100 ° C moved; the coloration obtained in this way has a depth of color F = 100.

Part of this colored fiber material is then treated with the same part of an undyed (original) polyacrylonitrile fiber material under the same conditions given above in the aqueous, but no dye containing bath, the dye from the already dyed fiber material with F = 100% on the undyed accompanying fiber material depending on its migration behavior draws up more or less strongly. The original color now has after the migration test a lower color depth, which is referred to here as FM, the Dyed accompanying tissue now has a color depth F, from both is determined the Migration factor M by the following equation: FW M = ---- . 100 FM FM Nature and meaning of the combination index K and its determination are in the journal "J.Soc. Dyers Col." Volume 88 (1972), pages 220-222. For the method according to the invention, a low value of K means a fast one Fixation, a high value of K results in slow fixation of the dye in the polymer.

Those blue and blue that can be used according to the invention for blackening violet cationic or basic dye with the mentioned indicators, the fix strongly and quickly in the polymer, the most diverse classes of dyes can belong, in particular to the class of the cationic monoazo dyes, the cationic Disazo dyes, the cationic or basic methine, lactam, anthraquinone, Phthalocyanine and triphenylmethane dyes.

A large number of these dyes which can be used according to the invention are known and can analogously known synthesis processes for these dyes, which the Pachmann are common, such as by azo coupling, oxidative coupling, condensation reactions, Quaternization reactions.

The invention is particularly advantageous when used of such blue or purple cationic or basic dyes that have a Migration factor of 20 and less than 20, a combination index K of 2 and less than 2 and a cation weight greater than 710, especially a migration factor of 10 and less than 10, a combination index of less than 2 and a cation weight greater than 380, in particular greater than 480.

The decisive factor here, however, is the selection of the key figures M and K.

The dyes used for blackening with the above Key figures are in the spinning mass to about 10 to 35 wt .-%, based on the amount on the soot used in the spinning mass. It can be assumed here that that for the black coloration of the polymer in the spinning mass usually 0.5 to 3 Carbon black by weight, based on the polymer, can be used; this is how you "color" the polymer for the production of threads and fibers to be spun from it with a coarse titer by means of about 0.5 to 2% by weight of carbon black, based on the polymer, during manufacture of filaments and fibers of fine denier with 2 to 3 weight carbon black. In the invention Process one uses an amount of dye especially for black finishing 10 to 20% by weight, based on the carbon black, when using carbon black with a large grain size, which means in particular carbon black with an average particle size of 30 to 50 m / u and the dye is used in an amount by weight of about 20-35% by weight, based on the carbon black, when using a carbon black with fine grain size, including in particular a carbon black with an average particle size of 10 to 30 m / u is understood.

The ones used in bulk spinning to color the polymer black Carbon blacks generally have an average particle size of 10 to 50 m / u, preferably from 10 to 30 m / u, as well as a surface determined by Brunnauer, Emmet and Teller (so-called BET surface area; see Ullmanns Encyclopadie loc. cit., p. 808) from 50 to 800 m2 / g, preferably from 2 80 to 500 m2 / g.

The dyes used according to the invention show because of their strength and rapid fixation on (in) the polymer only an extremely minor one Bleeding into the working baths of the spirin process. To assess the high quality of the method according to the invention can be used as a feature of the degree of bleeding (A) refer to this in the form of the percentage of paraffin present in the relevant Coagulation, stretching and washing baths bleeds, in relation to expresses the dye originally contained in the spinning mass. The degree the bleeding is easy after the spin dyeing process via the measurement of the absorbance to determine the baths mentioned in the absorption maximum of the dye used. In the method according to the invention, the degree of dye bleeding into the Coagulation, drawing and washing baths of the wet spinning process each no more than 1 %, in particular at most 0.3% in the coagulation and stretching baths and at most 0.2% in the washing baths, in the drawing and washing baths of the dry spinning process in each case a maximum of 0.5 k, in particular a maximum of 0.2% in the stretching baths and a maximum of 0.1% in the washing baths, based on the amount of dye used.

The barely noticeable bleeding of the dyes which can be used according to the invention in the coagulation, stretching and washing baths leads to a very high color yield, to a very high maximum color depth of the spun threads, to more perfect Nuance constancy with dye mixtures and completely constant depths of color (no "fading"). The very little bleeding still allows time and cost saving Change of shades without large areas in between, avoids contamination of the regrind by decomposition products of the dyes and largely includes an increased Effort to regenerate the baths compared to spinning undyed ones Pädens out.

The cationic dyes which can be used in the present invention have the above The indicators mentioned can have one or more, such as 2 or 3, cationic groups contain, these cationic groups being identical to or different from one another could be. Cationic groups are, for example, quaternary ammonium groups, such as for example a trialkylammonium group with lower alkyl radicals, which optionally can be substituted, furthermore with an N, N-dialkyl-N-aryl-ammonium group optionally substituted never- their alkyl radicals, an N, N-dialkyl-N-aralkyl-ammonium group with lower, optionally substituted alkyl groups and an N-monoalkyl-N-aryl-N-aralkyl-ammonium group with a lower, optionally substituted alkyl group; these ammonium groups can be used directly or via an optionally with heteroatoms and / or small groups of atoms linked aliphatic radical to the aromatic part of the chromophoric system be bound, such as a benzene or naphthalene nucleus.

Cationic groups of the dyes which can be used according to the invention are furthermore lower dialkylhydrazonium groups and cyclammonium radicals, preferably aromatic character, especially mesomeric 5- or 6-membered cationic rings, the other heteroatoms, such as oxygen, sulfur and / or nitrogen atoms, may contain.

The Cylammoniumreste can be part of the chromophoric system or to an aromatic carbocyclic radical, such as a benzene nucleus or naphthalene nucleus, be bound directly or be condensed to this. Cyclammonium reeds and their Derivatives are, for example, pyridir, ium, pyrazolium, imidazolium, triazolium, Tetrazolium, oxazolium, thiazolium, oxdiazolium, thiadiazolium, quinolinium, Indazolium, benzimidazolium, benzisothiazolium, benzthiazolium, arylguanazolium or benzoxazolium radicals, these radicals in the heterocycles being preferred by lower, optionally substituted alkyl radicals, by aralkyl, aryl and / or Cycloalkyl radicals can be substituted and in the aromatic carbocyclic Dividing by cationic ones, such as those mentioned above, by basic ones and / or nonionic groups can be substituted; basic groups are for example primary, secondary or tertiary amino groups, hydrazino or amidino groups, furthermore heterocyclic, nitrogen-containing rings, such as the pyridine, imidazole, Morpholine, piperidine or piperazine ring, and non-ionic groups, such as for example Halogen atoms, such as chlorine or bromine atoms, lower, optionally substituted alkyl groups, lower alkoxy groups, the nitro group, the sulfamoyl or carbamoyl group, a sulfamoyl or carbamoyl group substituted by lower alkyl, phenyl and / or benzyl, lower alkylsulfone and lower alkanoylamino group, the benzoylamino group, the Trifluoromethyl and cyano groups.

In the foregoing and in the following: The indication down! 'Means that the alkyl or alkylene radical contained in this group or this radical from 1 - Consists of 4 carbon atoms; the phrase "optionally substituted alkyl" means that the Alkyl by one or two, preferably one substituent from the group hydroxy, Acetyloxy, lower alkoxy, cyano, lower carbalkoxy, such as carbomethoxy and carbethoxy, Chlorine, phenyl and carbamoyl can be substituted, the phenyl still by Halogen, such as chlorine, bromine or fluorine, lower alkyl, lower alkoxy, nitro, acetylamino, Sulfamoyl and / or carbamoyl can be substituted and the carbamoyl still by lower alkyl, a phenyl group or a benzyl radical mono- or disubstituted can be, where the substituted alkyl radical, for example, a ß-hydroxyethyl, ß-cyanoethyl, ß-acetoxy-ethyl, V-hydroxyprcpyl, B-methoxyethyl, benzyl or Is phenethyl group; the term "aryl" means an aryl radical, in particular a phenyl or naphthyl radical, which is still by the above-mentioned basic, cationic or non-ionic groups can be substituted; non-ionic substituents, of which can preferably contain 1 to 3 in the aryl radical, are special halogen, such as chlorine or bromine, lower alkyl such as methyl or ethyl, lower alkoxy such as Methoxy, ethoxy or propoxy, nitro, lower alkyl sulfone and trifluoromethyl; the Specification aralkyl "means a lower alkyl radical which is substituted by an aryl radical is, where the aryl radical has the abovementioned meaning; the aryl radical is preferred in the "Aralkyl" is a phenyl radical which is made up of 1 or 2 substituents the group lower alkyl, lower alkoxy and chlorine may be substituted; the "Cycloalkyl" is a cycloalkyl radical of 4-12 carbon atoms, such as the cyclopentyl or cyclohexyl radical, which is also replaced by 1 - 3 lower alkyl groups, such as methyl groups, can be substituted.

Lower alkyl groups (alkyl radicals) are in particular the methyl and Ethyl group, lower alkoxy groups, especially the methoxy and ethoxy groups. Aralkyl radicals are in particular the benzyl and phenethyl groups. As quaternary ammonium groups are preferred the trimethylammonium group, the triethylammonium group, the dimethylethylammonium group, the benzyl-dimethyl-ammonium group and the phenyl-dimethylammonium group should be mentioned.

Lower, substituted alkyl radicals connected to the alkyl radical on a nitrogen atom are bonded, are preferably alkyl groups of 1-4 carbon atoms, which are represented by a hydroxy, lower alkoxy, cyano or phenyl groups are substituted, such as, for example ß-hydroxyethyl, B-cyanoethyl, ß-methoxyethyl, the benzyl or phenethyl group.

The cationic dyes used in the present invention contain as anion X (preferably the anion of a strong inorganic or organic Acid, such as sulfuric acid or its (lower alkyl) half-ester (= lower alcohol sulfate), hydrochloric acid, phosphoric acid, perchloric acid, tetrafluoroboric acid, hydrofluoric acid, Acetic acid, chloroacetic acid, trichloroacetic acid, formic acid, oxalic acid, lactic acid, Propionic acid or malonic acid.

The dyes can also be used as chlorides in the form of their double salts present with zinc chloride. The type of anion is important for the colouristic properties of the dyes used according to the invention are irrelevant insofar as they are colorless Anions and so far the ratio of the cation weight to the anion weight is 2.5 or greater than 2.5; at this low weight Due to the proportion of the anion, colorations with particularly high color strength are achieved. About that In addition, it is useful to choose the type of anion so that the invention The dye to be used is obtained in a pure form, free of inorganic salts can be according to a mode of operation that the skilled person based on his knowledge and is familiar to his experience.

In particular, X () means the equivalent of the sulphate, phosphate, oxalate or tetrachlorozincate anion or the chloride, bromide, tetrafluoroborate, rhodanide, Acetate, monochloroacetate, trichloroacetate, trichlorozincate anion or the alkosulfate anion with a lower alkyl group, such as the methosulfate or ethosulfate anion.

Such dyes are of the dyes which can be used according to the invention emphasize, whose cationic charge is delocalized, what by different mesomeric boundary structures can be expressed in terms of formulas.

Of the blue and violet cationic or basic dyes which can be used in accordance with the invention for blackening and having the aforementioned key figures, dyes with the general formulas (1) to (10) can preferably be emphasized: In these formulas: D (+) is the thiazolium, triazolium, thiodiazolium, isothiodiazolium, isothiazolium, pyridinium, benzthiazolium, benzisothiazolium, indazolium or quinolinium radical which is in the cyclammonium groups and in those optionally fused to them aromatic carbocyclic radicals, as described at the beginning, can be substituted, Ar is the p-phenylene or 1,4-naphthylene radical, which is substituted by substituents, preferably 1 or 2 substituents, from the group of lower alkyl, lower alkoxy, chlorine, bromine and lower alkanoylamino can be substituted, CuPc represents the copper phthalocyanine radical, which can optionally be substituted by chlorine or phenyl, and n is an integer or fractional number from 1 to, R is a hydrogen atom, a lower alkyl group, the benzyl or phenethyl group, R1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a chlorine or bromine atom, R2 is a lower alkyl group, R3 is a lower A. Alkyl group, the benzyl or phenethyl radical, R4 is a hydrogen atom, a lower alkyl group or a phenyl radical which can have 1 or 2, identical or different substituents of the formula radical R1, the above-mentioned formula radicals R, R1, R2, R3 and R4 can be identical or different from one another, R 'is a hydrogen atom, a lower alkyl group, the phenyl, benzyl or phenethyl radical, A is an alkylene radical of 1-8 carbon atoms, preferably 1-4 carbon atoms Atoms, which by 1 or 2 bridge members from the group of the formulas -O-, and can be interrupted, or a phenylene radical, Q (+) is a quaternary ammonium or a cyclammonium group of the type mentioned at the beginning, in particular an imidazolium or pyridinium group of the type mentioned, and is the equivalent of an anion, where those in the above formulas optionally D (+), Ar and R 'formulas occurring twice can each be identical to or different from one another, preferably identical.

Of the above azo dyes of the formulas (1), (2) and (3), the blue and violet cationic dyes of the formulas (11) to (17) are particularly preferred: In this formula, R, R1, R2, R3, R4 and X (-) have the meanings given for formulas (1) to (10); the other formula radicals mean: R1 has the meaning of R1 or is a phenyl radical, A is a lower alkylene radical, a phenylene radical or a radical of the formula - (CH2) mO- (CH2) m- or is a radical of the formula (CH2) m (CH2) m or the formula R. in which m is an integer from 1 to 4.

The cationic or basic that can be used according to the invention ting Dyes with the above-mentioned indicators have good solubility in the known, solvents used for spinning polymers and copolymers of acrylonitrile, such as in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and in aqueous sodium thiocyanate solutions. The solubility (L) of the dyes in Dimethylformamide, the most widely used solvent in spin dyeing, is at 200C more than 5 wt. 5 &, preferably more than 10 wt. 917.

The invention, i.e. blackening of the polymer or mixed polymer made of acrylonitrile, in particular of threads or fibers made from it during mass spinning, can also be used with particular advantage using two or more carry out the dyes which can be used according to the invention for blackening.

In addition to the polymers of acrylonitrile, there are also substrates to be spun Copolymers of acrylonitrile with other vinyl compounds, such as vinylidenecyanide, Vinylchlo, ld, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl pyridine, Vinylimidazole, vinylpyrrolidone, vinylethanol, acrylic or methacrylic acid, acrylic or Methacrylic acid esters, acrylic or methacrylic acid amides into consideration, these copolymers contain at least 50% by weight, preferably at least 85% by weight, of acrylonitrile. the Polymers of acrylonitrile or its copolymers are preferably acid-modified; they contain acidic groups that act as end groups, such as sulfo or sulfato groups, introduced into the polymer by means of a catalyst or as containing acidic groups Comonomers, such as styrene-4-sulfonic acid, vinyl, allyl or methallyl sulfonic acid, were polymerized.

The cationic or basic dyes which can be used according to the invention can be used directly or after preparing a stock solution with the one to dissolve the polymer used th solvents, such as dimethylformamide, dimethylacetamide, Dimethyl sulfoxide, ethylene carbonate or its mixtures with water or aqueous Sodium rhodanide solutions to be added to the spinning solution. After homogenization the spinning solution can be prepared by a known wet spinning process or dry spinning process to be spun. In the wet spinning process, a coagulation bath which in addition to the solvent used to dissolve the polymer still about 70 contains up to 70% by weight, preferably 40 to 60% by weight, of water, spun in; after this In a coagulation bath, the threads spun in this way go through a stretching bath, which is still contains about 30 to 85 wt .-%, preferably 40 to 85 wt .-% water, and then a washing bath that is still over 70 wt .-%, preferably over 80 wt .-%, or completely consists of water. If one proceeds according to a known dry spinning procedure, so is preferably used as a solvent dimethylformamide, in which the After passing through the hot-air spinning shaft, threads enter a drawing bath, which in addition to dimethylformamide still contains about 70 to 95% by weight, preferably 80 to 95% by weight, of water, and then Go through a wash bath, which in addition to dimethylformamide to over 80 wt., preferably consists of over 90% by weight of water.

The dyes which can be used according to the invention and have the characteristic numbers mentioned but can also be particularly advantageous in the form of "preparations" in the spinning mass solution be introduced. For this purpose, analogous to known methods, are used with these dyes intensely colored polymer materials as carrier material according to the procedures of mass coloring. These polymer materials as a carrier material be with the dyes for example either after. the so-called "breading process" or by coloring a polymer powder, granulate or threads from an aqueous, aqueous organic or organic dyebath that can be used according to the invention Contains dyes, or by dissolving the polymer in one suitable Solvent, such as dimethylformamide, with subsequent precipitation of the so colored Polymers by mixing with or pouring into water in medium to strong Colored shades. The so-called breading process is one example so before that you get the polymer in the form of granules or in the form of chips first with one of the cationic or basic dyes which can be used according to the invention or a powder or granular dye preparation of this dye mixed and this mixture heated so that the dye thermally into the polymer penetrates.

The "preparations" obtainable by the above well-known methods, those from the polymer and the cationic dye which can be used according to the invention exist, can then be added to the spinning mass solution in a well-dosed form. In this way it is little because of what is required for blackening Dye content of the black-embellished goods possible, which were used for black-embellishment To dose dyes particularly precisely.

Polymer materials that are used as carrier materials for these "preparations" can serve include polymeric materials that are in the solvents commonly used are used when spinning polymers or copolymers of acrylonitrile, such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and aqueous sodium thiocyanate solution, are readily soluble and are very much used in the case of the used low concentrations, based on the polymer to be spun, with the polymer or mixed polymer of acrylonitrile and its properties are well tolerated Don `t change. Such polymers are known from the literature; used advantageously However, the polymer or a copolymer of acrylonitrile is used as the carrier material self.

With the use according to the invention of the dyes with the aforementioned Key figures you get a with soot deep black colored polymer mass with the desired neutral and bluish shade or those made from it Filaments and fibers. Furthermore, the black-embellished material has lien through the strong fixation of the cationic or basic used according to the invention Dyestuffs with the mentioned key figures in the polymer material have excellent wet fastness properties, such as water, wash and perspiration fastness and one, especially in the case of black dyeing very important, excellent color fastness. All that can be used according to the invention Dyes can be combined with each other in any way, which is why they are used in a wide variety of ways Adjustment of nuances is possible. The imperceptible bleeding that can be used according to the invention Dyes in the coagulation 5 stretching and washing baths lead to a very high "Color yield in the beautified material, to a perfect nuance constancy of the Blackening, especially when using mixtures of the invention usable dyes, and does not interfere with the spinning process in any way.

The use of two or more of those which can be used according to the invention Dyes in combination with one another make it possible to produce colorations with completely constant nuances of the spun threads with precisely adjusted intermediate nuances of black fining to obtain. Due to the very low bleeding of the different, in combination Dyes used according to the invention are obtained regardless of the constitution and regardless of the current state of regeneration and water content of the coagulation, Stretching and washing baths the desired completely nanosized threads.

The following examples serve to illustrate the invention. The parts and percentages given therein are parts and percentages by weight, unless otherwise noted. Parts by volume are related to parts by weight how liters to kilograms.

The values A represent percentages of the bleeding tion the dyes used from the spun threads in the coagulation baths (AK), in the stretching baths (A5) and in the washing baths (Aw), calculated on the basis of the amount of thread spun, amount of dye used. The examples also give the key figures of the dyes used according to the invention, as well as the migration factor M, the combination index K and the cation weight KG the ratio V of the cation weight to the anion weight of the dyes and the solubility L of the dye in them Solvent used to dissolve the polymer in each example became.

Example 1: To 100 parts of a 28% solution of a polymer composed of 94% acrylonitrile, 5% methyl acrylate and 1% sodium methallylsulfonate in dimethylformamide, 0.42 part of a channel carbon black with an average particle diameter 2 of 13 my and a surface area ( BET> of 460 m / g and 0.12 parts of the dye of the formula given. The spinning mass is homogenized on a conventional agitator and heated to 80.degree. Then threads with a titer of 12 dtex are spun in the customary manner using the wet spinning process, a coagulation bath of 50 ° C each consisting of 50% by volume of dimethylformamide and water, followed by a stretching bath of 80 ° C of 30% by volume of dimethylformamide and 70% by volume. Water and finally a washing bath of 90 - 950C hot water is used.

The coagulation, stretching and washing baths are only very minor bled. The degree of bleeding from the spun, dyed threads into the baths was determined as follows: 1 kg of the colored spinning solution described above was at a rate of 8 g / min in 20 liters of the above-mentioned coagulation bath spun, then drawn in 12 l of the above-mentioned drawing bath and then washed in 32 1 of the above-mentioned wash bath, these baths during the spinning process neither regenerated nor replenished. After the spinning process was finished a sample was taken from all baths, for which the extinctions in the Absorption maximums of the dye were measured. By comparing the measured values with a calibration curve of the dye used and the conversion to the bath volumes could the amount of bleeding in the individual baths dye can be determined as follows: The coagulation bath contained 1.19 mg of dye, the stretching bath contained 0.16 mg of dye, the wash bath contained 0.11 mg of dye.

The following were therefore found for the bleeding in the individual baths percentage values: AK = 0.10% AS = 0.05% AW = below 0.01%.

The dye used for blackening has the following characteristics: M = 2, K = 1-2, KG = 492, V = 3, L = over 10%.

There are threads of brilliant and deeper, bluish black Get color that is extremely good for water, sea water, washing, sweat and have over-dyeing fastness properties as well as very good lightfastness.

Example 2: To 100 parts of a 28% solution of a polymer composed of 85% acrylonitrile, 3% vinyl chloride and 2% sodium methallylsulphonate in dimethylacetamide, 0.7 parts of a channel black with an average particle diameter of 29 mpt and 2 a surface ( BET) of 100 m / g and 0.1 part of the dye of the formula given. After the spinning mass has been homogenized at 400C, the spinning is carried out to a titer of 3.3 dtex, with a coaulation bath of 500C consisting of 60 vol % By volume of water and a wash bath of 80-90 ° C. made of 5% by volume of dimethylacetamide and 95% by volume of water is used.

The threads obtained have a deep blue-tinged black color and excellent Authenticity properties.

The dye used has the following key figures and properties: AK = 0.05% AS = 0.04% AW = less than 0.01% M = 4, K = 1-2, KG = 620, V = 2.9, L = over 10%.

Examples 3 - 7: The procedure is as described in Example 2, replaced however, in the dye used there, described by one of the following table Dye, threads of a deep bluish black color are likewise obtained with excellent fastness properties.

The bleeding values of the dyes used in the working baths and the key figures for these dyes in Examples 3-7 are listed in the table according to the dye formulas.

E.g. dye E.g. dye E.g. AK (%) As (%) AW (%) MK KG VL over ...

3 0.07 0.04 0.01 9 1 333 4.6 10% 4 0.08 0.05 0.03 5 1 367 5.2 10% 5 0.09 0.06 0.03 9 2 370 5 , 2 10% 6 0.07 0.05 0.02 6 1 353 5.0 10% 7 0.06 0.04 0.01 5 1 409 5.8 10% Example 8: 400 parts of a 29% solution of a polymer of 85% acrylonitrile, 14% vinyl acetate and 1% sodium styrene-4-sulfonic acid in dimethylformamide at 800C are mixed with part of a furnace carbon black with an average particle diameter of 25 µm and a surface area of 95 m2 / g and 0, 2 parts of the dye of the formula in which CuPc represents the remainder of the copper phthalocyanine, and 0.1 part of the dye of the formula stirred. After the spinning mass has been homogenized, threads with a titer of 10 dtex are spun therefrom in the conventional manner using the dry spinning process using an air temperature of 230-2500C in the spinning shaft.

The threads are then drawn in water at 70-80C and washed.

There are threads of a deep black color with excellent Get wet fastness properties. The working baths are barely noticeably bled.

The ones used for the fining and nuance of the black threads Dyes have the following characteristics CuPc dye: M = 6, K = 1-2, KG = 1116, V = 4.4, L = over 5%; Triphenylmethane dye: M = 4, K = 1, KG = 558, V = 15.9, L = over 5%.

Example 9: The procedure is as described in Example 8, but the two dyes used there are replaced by 0.3 parts of the Dye of the formula (+) O N-CH2-CH2-N (CH3) 3 (-) loI $ Cl CH3 this also gives a deep black coloration with excellent wet fastness properties.

The dye used has the following characteristics and properties: AS = 0.15% AW = 0.05% M = 16, K = 1-2, KG = 414, V = 11.8, L = over 5%.

Example 10: If the procedure is as described in Example 1, but instead of the dye used there, a dye of the formula is used in the same amount which does not have the characteristic numbers required according to the present invention, one also obtains threads with slightly blue nuances, which, however, bleed these baths blue-violet to a large extent when they pass through the coagulation, stretching and washing baths.

The dye used has the following characteristics and staining properties: AK = 6.5% AS = 4.2% AW = 1.8% M = 42, K = 3, KG = 275, V = 2.8, L = over 10%.

This example demonstrates that a method for spin dyeing under Blackening or nuance only with the selection and use of dyes, which follow the criteria (indicators) of this invention, carried out advantageously can be. When using dyes that are not included in the scope of the invention Procedure fall, there are no satisfactory results, and the work-up The wheels are associated with difficulties due to their dye content.

Claims (2)

Claims: 1. Use of blue and purple cationic or basic dyes for blackening polymers colored black with carbon black and copolymers of acrylonitrile, characterized in that these are cationic and basic dyes have a migration factor M of 20 or less than 20, a Combination index K of less than 2.5 and a cation weight of greater than 310 own. 2. Process for shading polymers colored black with carbon black and copolymers of acrylonitrile, especially in bulk spinning by means of blue or purple dyes, characterized in that such dyes blue or purple cationic or basic dyes, each represented by a Migration factor M of 20 or less than 20, a combination, key figure K of less than 2.5 and a cation weight greater than 910 are marked, used in the spinning mass and possibly this spinning mass into threads ouer fibers spun.