DE2061512A1 - Disubstd diamino anthraquinones - for blue or turquoise dyeing of water swellable cellulosics - Google Patents

Abstract

Blue or turquoise non-vattable dye for H2O-swellable cellulosic fibres opt. mixed with synthetic fibres, are of formula:- where both R's are jointly where X is benzyl, cyclohexyl or 6-20C alkyl, or both are the same selected from alpha-naphthylthio or phenylthio opt. substd. with 1-3 of F, Cl, Br, NO2, R1, R2, OR1, OR2, COOR1, CON(R1)2, CONR2R2, NHCOR1, NHCOR2, SO2R1, SO2R2, SO2N(R1)2, or SO2NR1R2 where R1 is 1-8C alkyl, the radicals contng. a max. of 12 alkyl C atoms, and R2 is phenyl opt. substd. with 1-2 of 1-4C alkyl, 1-4C alkoxy, NO2 or Cl. The uniformly dyed fibres are fast to washing, dry-cleaning and cracking, and have a reflectance colour value (S') of >=2 after one thorough scour in aq. detergent at 90-100 degrees C. and one thorough scour in perchloroethylene at 50 degrees C.

Description

Evenly colored blue or turquoise, water-swellable cellulose fibers or mixtures thereof with synthetic fibers The invention relates to dyed, cellulose fibers which are swellable in water and mixtures thereof with synthetic fibers.

Synthetic fibers, e.g. Fibers made of polyesters, polyamides or cellulose acetate, can be colored with the most diverse disperse dyes known to be have very low to moderately high solubilities in water.

Natural fibers, such as cellulose fibers that swell in water, especially cotton, are colored according to processes and dyes which are usually significant differ from the processes and dyes used for synthetic fibers be used. The previously customary processes for dyeing water-swellable Cellulosic fabrics are carried out as follows: (1) A water-insoluble one High molecular weight dye is used in either the starting material to be colored by converting two smaller molecules, as in the production of an azo dye by a coupling reaction, or by a chemical reaction that produces a makes soluble dye-forming agents insoluble, as in Ku'-pen and stain dyeing.

(2) Leave a ready-made, water-soluble dye that has an affinity for the cellulosic fabric, according to a method in which the Solubility of the dye in the aqueous solution is reduced from an aqueous one Apply the liquor to the goods to be dyed, as is the case with direct dyes.

(3) A dye with a substi «Ut; th, the one with the cellulose or reacts with a modified cellulose, can consist of an aqueous or non-aqueous Liquor can be drawn onto the goods to be dyed under such conditions, that the dye is chemically bound to the material to be dyed, as is the case with the fiber reactive dye L is seen.

(4) Water-insoluble pigments are attached to the cellulose with the help of Bound polymers, as in pigment printing.

(5) A water-insoluble dye is used in finely divided fors the production of cellulose is stored in the same as it is sometimes during spinning of Reyon happens.

Neither of these known methods can be applied to water swellable cellulose fibers by directly pouring in an already finished, to dye non-reactive 'water-insoluble dye, as such dyes have hardly any natural affinity or absorption capacity for cellulose fabrics.

The above processes in which dyes are in the dyed material even be generated after a dye former on or in the cellulosic fibers has been deposited are shown in U.S. Patents 596,692 and 2,069,215 and in British Patent 1,071,074. A method of dyeing of cellulose fibers with already finished, water-soluble dyes is in journal of the Society of I) yers and Colouristan, hand 73 (1957), page 23.

The above methods have a number of disadvantages, since they are cumbersome to siren are unable to cover a wide area of different parbs to produce, and the dyed cellulose fibers an inadequate Fastness to washing with aqueous washing solutions and / or dry cleaning with organic solvents.

The use of dyes of low water solubility for Dyeing of cotton is described in British patent specification 1,112,279. In this process, dye, water and urea or a structurally related one are used Compound applied to the starting material, whereupon this is heated. With this one In the process, dye utilization is often inadequate and it can be undesirable basic degradation products from urea or its related compounds form.

Further difficulties arise with the previously known dyeing processes in the case of mixtures of water-swellable cellulosic materials and synthetics. In general, cumbersome two-step processes are required in which the individual components of the mixture in different process stages with different Dyes to be colored. This can lead to mutual rub-off, and very large amounts of paraffin are usually required, each component undesirably the coloring effect of the interferes with other components. If there is mutual staining, the dye must have the property to be washed off by the fiber component on which he dyed But Even under the most favorable conditions, matching shades can be found two fiber components of the mixture can only be achieved with difficulty, the inconvenience the two-step process for dyeing mixed textiles also results from the Difference in working conditions between conventional dyeing methods for cellulosic fabrics and for synthetics. In contrast to the procedures mentioned above The conventional methods are based on dyeing cellulose fibers which are swellable in water for dyeing synthetics on the solution of water-insoluble dyes in the synthetic material.

The coloring of mixtures of cellulose and synthetics after a Two step process is described in U.S. Patent 3,313,590. Analogous to the coloration of such mixtures and in confirmation of the difference mentioned above describes between swellable cellulose substances and non-swellable cellulose acetate U.S. Patent 3,153,563 describes a two-step process in which the cellulose acetate is dyed with a water-insoluble dye without staining the cellulose, whereupon the latter is colored in an independent process step.

The swellability of cotton fibers and other similar cellulose materials in water has long been known. The swelling takes place on contact with water usually quick, but is eased by wetting agents and heat. The swollen Fibers are bigger and more flexible, have a lower strength and are too otherwise changes in their physical and mechanical properties. As a result Their open structure is swollen cellulosic fabrics from water-soluble compounds permeated with low molecular weight and react with the same. Valko and Limdi report in "Textile Research Journal, Volume 32 (1962) Pages 331-337 that cotton in water, which is both high-boiling, water-soluble, non-reactive compounds of limited molecular weight as well Contains crosslinking agent, swells. That, water can be maintained while maintaining remove the swelling, whereupon the crosslinking can be carried out. The writers propose to apply this procedure to not only water-soluble, reactive Substances (crosslinking agents), but also other reactive substances that.

insoluble in water, in the high-boiling, water-soluble, not reactive compound, however, are soluble to introduce into cotton. A similar The method is described in U.S. Patent 2,339,913. First you let the cellulose fibers swell in water, then the water is displaced by a mixture from methanol and benzene and finally from benzene, the swelling being preserved remain. Then the cellulose-reactive compound (the crosslinking agent) added in the form of a solution in benzene and carried out the crosslinking.

The subject of the German patent ..... (patent application P 18 11 796. 9-43) is a process for dyeing cellulosic fabrics or mixtures thereof with plastics using glycols or glycol derivatives that have a certain solubility in water and a boiling point above 1200 at atmospheric pressure C, as a dye solvent, which is characterized in that a water-swellable cellulose material or at least this component of a mixture thereof is colored with plastic by mixing the cellulose material or the mixture with (1) water in sufficient quantity at the same time or in any order, to allow the cellulose to swell, (2) a dye, the saturated solution of which in boiling 0.1 molar aqueous sodium carbonate solution at the length of the maximum absorption does not have an extinction above about 30 if the extinction is diluted 10 times the boiling saturated solution with triethylene glycol dimethyl ether, measure the absorption of the dilute solution and calculation of the extinction of the saturated boiling solution is determined according to Beer's law, in sufficient amounts to color the cellulose fabric, and (3) a solvent which optionally contains a solubilizer for the dye, treated in sufficient amounts to maintain swelling of the cellulosic fabric when the water is removed, the solvent (a) being at least 2.5% by weight soluble in water at 250 ° C, (b) boiling at atmospheric pressure above 1500 ° C, (c) at a temperature in the range from about 0 to 2250 ° C. is a solvent for the dye and (d) the general formula where n has the value 0 or t, m means a positive integer, x means the number of unsaturated valences in JL, Ä means ROCH2CHORCX2-, -CH2CHORCH2-, -CH26HCH2-, -CH2C (CH20R) 3 ( -cH2) 2c (cH2OR) 2, (-CH2) 3CCH20R,. (- CH2) 4C, -CH2 (CHORO) yCH20Rw -CH2 (CHORO) yCH2- or -CH2 (CHORO) yz (-CH) zCH2- has, where y has the value 2, 3 or 4 and z has the value 0, 1, 2, 3 or 4, but is not greater than y, R is a hydrogen atom, a C1 8-alkyl radical, is a C715 aralkyl or alkaryl radical or the interpretation: R2C-, R2S02- or R20C- 1t " 0 0 and R1 has the meaning -OH, -oR2, -SR2, -NHR², -NR² (C1-8- Alkyl), -NR (C7 ~ 15-aralkyl or alkaryl), 2 -0S02R, -OCOR2, -NE (phenyl or ,. .. 0 0 -NH (naphthyl), where R2 denotes a G1 8-alkyl group, a C5-10-cyloalkyl group, a C715-aralkyl or alkaryl group, a C6-aryl group, a C1o-aryl group or the furfuryl group, with the wet addition, that in any process step the interior of the swollen cellulose fabric is brought into contact with a solution of the dye in an aqueous solvent or in a solvent, with any dyeing process of plastics present in a mixture with cellulose fibers in a manner known per se with heating to a temperature not exceeding about 2250 a is made.

According to particular embodiments of the process mentioned, the Solution generated inside and / or outside of the swollen cellulose fabric, and according to another modification the dissolution of the dye in the aqueous one is achieved or anhydrous dye solvent with the aid of heat, by reducing the Amount ratio of water to dye solvent or by adding a Solubilizer. Further embodiments of the method of the cited patent are dyeing at elevated temperatures and dyeing mixtures of cellulose fabrics and synthetics such as polyamides or polyesters with the same dye. at In such a process, the cellulose fabric is dyed as described above, and the synthetics are either simultaneous with it or in one colored independent of the process stage.

In the process of the patent mentioned, conventional vat and disperse dyes are used; most are such dyes however, unsatisfactory for technical purposes. Preserves with vat dyes you usually only get a superficial staining because they are in the ones mentioned Patent-recommended solvents are not soluble enough and do not penetrate the fiber. Such surface staining can easily be done by washing with aqueous detergents or wash with dry cleaning agents. The conventional disperse dyes on the other hand, they can penetrate the fiber, but are so in hot alkali soluble in that they are washed out when washing with aqueous detergents.

The invention is based on the object of uniformly colored fibers, namely, water-swellable cellulose fibers and mixtures thereof with synthetic ones Fibers. The fibers according to the invention are uniform blue or turquoise colored fibers that are fast to washing, dry cleaning and Exhibit Abrussen. Another object of the invention is to produce uniformly colored To provide fibers that are essentially water-insoluble, not vettable anthraquinone dyes are colored.

The invention relates to uniformly blue or turquoise colored, water-swellable cellulose fibers or mixtures of the same with synthetic fibers, which are distinguished by their fastness to washing, dry cleaning and peeling and after one thorough washing in an aqueous detergent solution at 90 to 1000 C and one thorough washing in perchlorethylene at 500 C have a reflection color value (S ') of at least about 2, characterized in that the dye in the fibers is a non-viable anthraquinone dye of the general formula is, in which the two radicals R together have the meaning where X is a benzyl, cyclohexyl or C6 to C20 alkyl radical, or both radicals R are the same and a-naphthylthio radicals or phenylthio radicals which are unsubstituted or substituted by 1 to 3 substituents are, the substituents having the composition F, Cl, Br, NO2, R1, R2, OR1, OR2, C02R1, CON (R1) 2, 00NR1R2, NHCOR?> NHCOR2, S02R1, S02R2, S02N (R1) 2 or SO2NR1R2, where R1 can have a Ci to C8 alkyl radical the stipulation means that all radicals R1 together may not have more than 12 carbon atoms, and R2 denotes a phenyl radical which is unsubstituted or substituted by 1 or 2 C1 to C4 alkyl groups, C to C4 alkoxy groups, N02 groups or chlorine atoms.

The essentially water-insoluble, non-viable ones described above Dyes which are used according to the invention to produce the colored fibers, can be prepared by processes known per se.

Blue 1,4-diamino-2,3-bis (phenylthio) anthraquinone dyes can be prepared by adding 1,4-diamino-2,3-dichloroanthraquinone with 2 moles of a substituted thiophenol in an organic solvent such as pyridine or Dimethylformamide, condensed, using an alkali, such as sodium hydroxide solution, for neutralization the resulting acid is used. In many cases, the implementation is very quick; The more electronegative the Are substituents of the thiophene ring, the more difficult the reaction is. Trichlorothiophenol works with 1,4-diamino-2,3-dichloroanthraquinone, for example a bis-condensation; but it takes several days (at room temperature) to the reaction is complete.

Examples of thiophenols which are used for the preparation of according to the invention Usable blue dyes are given in Table I.

Table 1 Thiophenol Trichlorothiophenol o-, m- or p-thiocresol 2,4-dichloro-3-thiocresol thioxylenols 4,6-dichloro-3-thiotresol 4-n-octylthiophenol p-fluorothiophenol o-methoxythiophenol m- (methylsulfonyl) -thiophenol p-octyloxythiophenol p- (methylsulfonyl) thiophenol p-phenoxythiophenol o- or p-nitrothiophenol m-bromothiophenol p-phenylthiophenol p-chlorothiophenol 2-mercaptobenzoic acid-2-bromo-4-tert. butylthiophenol isopropyl ester 3-mercaptobenzoic acid 4-bromo-2-isopropylthiophenol cyclohexyl ester 2-methyl-4-tert-butylphenol, 4-mercaptobenzoic acid ethylthiophenol methyl ester 4-mercaptobenzoic acid 4-chloro-2-thiocresol n-octyl ester 5-chloro-2-methoxythiophenol 4-mercaptobutyranilide 6-methoxy-3-thiocresol 4-tert-butyl-4'-mercapto-4-chloro-2, 5-dimethylthiophenol benzoic anilide 2, 6-dichlorothiophenol 4-bromo-3-thiocresol 2,5-dichlorothiophenol'-naphthalenethiol 4-methoxy-3-thiocresol 3-mercaptobenzoic acid 2-methoxy-4-thiocresol 2-mercapto-5-chlorobenzoic acid.

The dyes produced from the thiophenol can be prepared according to known methods Convert process into sulfonamides by sulfonation and amination. Carbonamides can be prepared by carboxylated thiophenols for condensation used and then aminated in a conventional manner.

Turquoise 1,4-diaminoanthraquinone-N-substituted 2,3-dicarboxiinide dyes can be prepared by adding 1,4-diaminoanthraquinone 2,) - dicarboximide at 100 Reacts up to 2000 C in a suitable organic solvent with an amine, The solvent used, for example, is ethylene glycol monoethyl ether, mixtures of nitrobenzene and isopropanol, mixtures of o-dichlorobenzene and methanol or an excess of the amine itself can use. If the solvent mixture has a low boiling point Contains alcohols, the reaction is conveniently carried out in an autoclave to to achieve the desired reaction temperature as described in the United States patent 2,628,963.

Examples of amines that interact with 1,4-diaminoanthraquinone-2,3-dicarboximide can be converted to turquoise dyes which can be used according to the invention Benzylamine, n-hexylamine, cyclohexylamine, n-octylamine, tert. Octylamine, n-iodecylamine and n-octadecylamine.

According to the method of the patent mentioned with the above dyes Dyeable cellulosic fabrics include all forms of cellulose that are exposed to it become bigger and more flexible with water. Suitable fabrics are natural fibers and purified Wood pulp and regenerated cellulose in fiber and film form. Cotton fibers can be dyed in any form in which they are usually found in textiles, as well as after the treatments that are traditionally applied to them prepare for coloring. Can be used cotton in any way may have been treated in such a way that its swelling capacity when heated with water not is noticeably diminished, raw or washed cotton and cotton that is mercerized or otherwise preshrunk. Regenerated cellulose fibers, the one have a sufficiently open structure so that they swell in water and from the Dye solvents can also be dyed, e.g. copper ammonia silk. Viscose rayon usually has a structure that swells more heavily and slightly longer exposure times to dye, water and dye solvent at lower ones Temperatures may require. To make dyeing easier, such Textiles are pretreated with 10 percent aqueous alkali lye, or dyeing can be done in the presence of wetting agents, preferably non-ionic wetting agents, be performed. Mixtures of cotton and rayon fibers can be dyed and the method is also applicable to purified wood pulp and paper. not The process is applicable to cellulose acetate because it is not the required one Has swelling capacity in water.

To the synthetics, which are colored with the parbstoffees mentioned above include polyesters, polyamides, cellulose ethers and esters and copolymers and mixtures of these synthetics with other components that do the job To make synthetics easier to color or give them other desirable properties to give, synthetics can be mixed with the dyes by conventional methods, e.g. using the thermosol process or aqueous dyeing processes.

The dyes can be prepared according to that described in the above-mentioned patent Process on water-swellable cellulose substances or mixtures of the same with synthetics let rise. The dyes are particularly suitable for dyeing mixtures made of cotton and polyester or polyamide fabrics, such as mixtures of 65 to 80 ß Polyethylene terephthalate and 20 bis 35 o / o cotton. In such When mixed, the synthetics are colored under conventional process conditions. The above-mentioned dyes for coloring both components of a mixture can be used, the washability plays a role in the choice of dyes does not matter, since the difficulty of mutual staining (which is a washout requires), which in the known, working with two different types of dyes Procedure frequently occurring has been kept to a minimum.

The dyes used according to the invention dye the substrate directly, i.e. they do not require oxidation, reduction, hydrolysis or any other chemical Modification to develop color or authenticity. The colorations are excellent Authenticity against demolition, washing and rough cleaning.

When dyeing cellulosic fabrics by the method of the above Patents can use water, dye, and sarcinol solvent in any arbitrary Order to be applied to the material to be stained, provided only the water and the sarcinol solvent in any process either before or at the same time as the actual Coloring are present at the same time. The preferred method of dyeing fabrics of cellulose fibers or mixtures of cellulose and synthetic fibers consists of the textile fabric with a mixture of one or more paraffin, water and to soak the dye solvent in a conventional dye liquor and then squeeze to remove excess liquid or fabric to be printed with a solvent-based printing ink and. then by heating to bring so much water to evaporate that the dye goes into solution, whereupon the fabric is dyed0 You can only make so little water evaporate that the dye does not go into solution, and then pressure and heat to act bring the dye into solution without further evaporation of water see below bring. Printing inks can be produced by known methods, e.g.

by grinding the paraffin in the presence of a dispersant or surfactants.

A dye liquor can be produced by diluting the printing ink with water or can be made with an aqueous solvent.

Adding a solvent to the printing ink before adding water adds, the dye can be precipitated, which is why this procedure usually avoided. In addition to a dye solvent, the parb liquors can also be used and a dispersant contain other additives. Used as such additives one often uses means of preventing migration such as purified vegetable resins and Wetting agents, for example ionic and non-ionic surface-active agents, such as ethylene oxide condensation products, hydrocarbon sulfonates and long chain Alcohol sulfates.

The dye liquors can also contain other dyes than those described above contain; for example, dyes can be direct or reactive with the fiber Dyes for cotton or for polyamides may be present in order to achieve color gradations achieve.

According to the preferred dyeing process, an aqueous dye dispersion is left and the organic solvent from a single pad bath onto the fabric act. The pad bath usually has a water content of 70 to 95 percent by weight and a solvent content of 5 to 30 percent by weight. The padded textile is heated to 180 to 2250 C for 30 to 180 seconds. Usually enough for cotton temperatures of 1500 C. The dyed textile fabric is generally in one aqueous bath and, if necessary, rewashed in perchlorethylene to achieve the full Ensure removal of surface staining.

The reflection color value (S), which is defined in British patent specification 1,056,358, is expediently used as a quantitative measure of the color shades that are obtainable on the Paser after rewashing. The reflection color value is given by the equation s = (L + IVI + To '), in which L, M and N are used instead of the known colorimetric standard values Xi, Y and Z of the CIE (Commission Internationale d'Eclairage). if (where RA = reflection characteristic of the wavelength, = = radiation function of the radiation source and x, y and z = CIE distribution coefficients which characterize a certain parbe), then (where Ko = dye concentration and where R # has the above meaning and r = residual surface reflectivity of the completely black colored substrate).

The sum (L + M + N) in terms of equation (ii) is for a given Dye is a constant and is independent of the concentration of the dye on the substrate. To obtain values for (L + M + N) that correspond to the hue depth of the colored Are proportional to the textile fabric, the concentration term K is from the equation (ii) eliminated; as it is desirable to use numbers in the range from 0 to 25 to obtain, the values of the sum (L + M + N) have been further modified by that they have been divided by 100. This new sum included in the present Description used and by S ' is shown, is entitled the value S defined in British patent specification 1,056,358 in the by the Equation Ko S '= 100 x S given relationship, where Ko has the above meaning.

A reflection color value (S ') of 2 represents a bright but still valuable one Parbton, that is, a coloration and not just a slight discoloration or Staining of the fibers. It has been found that you can get such hue depths on cotton can easily be obtained with the above dyes, and by increasing the Dye concentration in the pad bath can easily be achieved with depths of color, which correspond to ten times this value.

The dyes used according to the invention cannot be used on cotton can be applied as vat dyes. In other words: they cannot be reduce to a water-soluble form that has affinity for aqueous solution Cotton, and then make it insoluble in the cotton fibers by oxidation.

In the following examples, the typical manufacturing process for To explain the dyes used according to the invention, the parts relate to Weight quantities.

Example 1 Condensation of 1,4-diamino-2,3-dichloroanthraquinone with p-tert ~ ~ butylthiophenol A mixture of 13.8 parts of 1,4-diamino-2,3-dichloroanthraquinone, 55 parts of dimethylformamide and 30 parts of p-tert-butylthiophenol are heated to 700.degree. Then 36 parts of 30 percent sodium hydroxide solution are added and the mixture is stirred for 20 minutes. After stirring for 1 hour at 70 ° C., 50 parts of ethanol are added and the mixture is filtered the product. The wet filter cake is thoroughly with ethanol, then washed with water and again with ethanol and dried. Thin layer chromatography on polyester plates coated with silica gel (using a mixture from 19 parts of benzene and 1 part of acetonitrile as eluent) results in a predominant one blue component contaminated with a trace of a purple component, which is probably the monocondensation product, the visible spectrum of the Dye (in a mixture of 4 parts of dimethylacetamide and 1 part of water) shows Absorption maxima of comparable height at 595 and 635 mW, which results in that the dye 1, 4-diamino-2, 3- (bis-p-tert-butylphenylthio) -anthraquinone is.

When using cotton with this dye following the procedure of the examples 12 and 13, you get level blue shades.

B e i 5 p i e 1 e 2 to 9 Other dyes are made according to the process of Example 1, but with the thiophenols given in Table II. The structure of the dyes corresponds to that of the dye according to the example 1, but with the changes due to the various thiophenols. All dyes produce blue shades of good washing fastness on cotton, if they are used for dyeing according to Examples 12 and 13.

T a b e 1 1 e II Example thiophenol 2 m-thiocresol mixed thioxylenols 4 p-bromothiophenol 5 trichlorothiophenol 6 "-naphthalenethiol 7 4-mercaptobenzoic acid methyl ester Table I1 (continued) Example Thiophenol 8 3-Mercaptobenzoic acid cyclohexyl ester 9 2-methyl-4-tert. butylthiophenol 6 B e i s p 1 e 1 10 Conversion of n-octylamine with 1,4-diaminoanthraquinone-2,3-dicarboximide A slurry of 50 parts 1,4 - Diaminoanthraquinone-2,3-dicarboximide in 400 parts of n-octylamine is 20 hours heated to 100 to 1100 ° C. with stirring and under nitrogen. Then the reaction mixture cooled from the outside to room temperature and diluted with 800 parts of isopropanol. The product is filtered off and successively with isopropanol and with 2N hydrochloric acid and washed with water and then dried. The dry filter cake (5 parts; Yield 81.) shows on thin layer chromatography using a mixture from 96 parts of chlorobenzene, 2 parts of pyridine and 2 parts of acetone as eluent a single blue ribbon. Analysis: Calculated for C24H2504N3 C = 68.9% O; H = 5.9 ; N = 10.1%; found C = 68.7%; H = 6.0; N = 10.0%.

The dye has a melting point of 200 to 2020 C and a special extinction coefficient of 36.8 l / g / cm at 676 m. Based on the above Analysis is 1,4-diaminoanthraquinone-N-n-octyl-2,3-dicarboximide. Following the procedures of Examples 12 and 13, this product dyes cotton turquoise Tints.

Instead of the n-octylamine, one can use the method described above use other alkylamines with 6 to 20 carbon atoms to make turquoise dyes to obtain that can be used to produce the dyed fibers according to the invention suitable.

B e i s n i e 11 Reaction of benzylamine with 1,4-diaminoanthraquinone-2,3-dic arboximid A mixture of 90 parts of 1,4-diaminoanthraquinone-2,3-dicarboximide, 140 Parts of benzylamine, 650 parts of o-dichlorobenzene and 400 parts of methanol are used for 4 hours heated to 165 to 1700 ° C. in a steel autoclave with stirring. After milling on The product is 1,4-diaminoanthraquinone-N-benzyl-2,3-dicarboximide at room temperature filtered off and washed with ethanol until the washing liquids are almost colorless are. The product melts at 2900 C. Analysis: Calculated for 023111 504N3 N = 10.56 ; found N = 10.27.

Following the procedures of Examples 12 and 13, cotton is made with this Dye colored in turquoise tints.

The following examples illustrate the dyeing or printing of cellulosic fabrics and of mixed textiles made of cellulose and polyesters with the dyes described above.

B e i s p i e 1 12 dyeing a mixed textile made of 65 0 polyethylene terephthalate and 35% cotton (a) A pad bath is made up of the following ingredients produced: blue dye paste (15% active ingredient) according to Example 1. . . . . . . . . . . . . . . . 50 g of purified vegetable resin as a thickener. . . . . . . 20th g methoxypolyethylene glycol (molecular weight 350). . . . . . . . . . . . . 100 g made up to 1 1 with water.

A continuous length of 65 g polyethylene terephthalate fabric and 35% cotton is used in this bathroom up to a recording of 60, based on the fiber weight, padded and then at a speed of 1.8 m / min. between two 1000 W infrared lamps (Fostoria-Fannon, Inc .; infrared heater Model 6624) passed through the opposite sides of the fabric irradiate from a distance of 7.6 cm. he becomes continuously advancing textile fabric then with a residence time of 1 minute through a convection oven at 80 to 1000 C. and then with a dwell time of 1.7 minutes through an oven at 200 up to 2100 C. The hot, dry fabric is cooled to room temperature and rinsed 1 minute in succession in the following baths: in water from 20 to 300 C, in water from 90 to 950 C, in water from 90 to 95 ° C, the 1 ffi of an ether alcohol sulfate as a cleaning agent, in water from 90 to 950 C and in water from 20 to 30 ° C. The fabric is dried and then 5 minutes at 500 C in perchlorethylene washed. The fabric is now in a satisfactory mixed fabric color the cotton and polyester fibers are evenly dyed.

(b) One works according to experiment (a), but using the following Heating process: The padded fabric is padded at a speed from 1.8 m / min. passed between an aggregate of infrared lamps, wherein one 1000 W lamp each (Postoria-Pannon, Inch; infrared heater model 6624) one each of the two sides of the fabric irradiated vertically from a distance of 7.6 cm. Then it will be the damp textile fabric over a series of four rotating drums with smooth Surface, the temperature of which increases gradually from 1000.0 to 1500 C. The average contact time on each drum is 18 seconds. Then will the fabric is continuously passed through an oven at 2100 C, where the total residence time is 90 seconds.

The same procedures are - 100 percent mercerized Cotton clothing fabric used, with the exception that the pad bath t50 g of nethoxy polyethylene glycol (Molecular weight 350) per liter and the post-heating temperature to 1800 C is decreased. After that in this way with regard to the solvent concentration and the post-heating temperature modified procedure of Example 12 (a) a sample of cotton clothing fabric in a deep, evenly blue shade colored. After washing in the aqueous detergent and then Washing for 5 minutes in perchlorethylene at 500 ° C., as described above, shows the dyed fabric has a reflection color value of 7.77> -if you get the blue dye of Example 1 in the above process by the dye according to Example 10 replaced, a sample of cotton clothing fabric turns out to be as described above Wash with detergent and perchlorethylene colored as deep turquoise and has a reflection color value of 5.8.

EXAMPLE 1 13 Printing on 100 percent cotton fabric A Cotton fabric is padded with an aqueous solution up to an absorption of 70%, which contains 200 g of polyethylene glycol (molecular weight 600) per liter. The pounded Tissue is heated to 1600 a for 5 minutes to cause the water to evaporate. Then the fabric is coated with a printing paste consisting of the following ingredients printed with a pattern: blue paste (15% active ingredient) according to example 3. . . . . 0 0. . 10 g purified natural resin ether as a thickener. . . . . . . 60 g of water . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 g That Printed fabric is heated to 1800 C for 100 seconds and at 900 C for 5 minutes Water, which contains an ither alcohol sulfate as a cleaning agent, washed, then dried, washed in tetrachlorethylene at 500 ° C. for 5 minutes and dried again. The printed areas are strongly colored.

Following a procedure similar to that of Example 13 will be Mixed fabric of polyester and cotton printed with the heating temperature is increased to 2000 C. The authenticity of these prints is the same as that the coloring generated according to Example 12 with the same dyes.

Claims (3)

P a t e n t a n s p r u c h e ~ 1. Evenly blue or turquoise colored, water-swellable cellulose fibers or mixtures of the same with synthetic fibers, which are characterized by their fastness to washing, dry cleaning and rubbing and after one thorough washing with an aqueous detergent solution at 90 to 1000 s and after one thorough washing in perchlorethylene have a reflection color value (St) of at least 2 at 500 C, characterized in that the dye in the fibers is a non-connectable anthraquinone dye of the general formula is, in which the two radicals R together have the meaning where X is a benzyl, cyclohexyl or C6 to C20 alkyl radical, or both radicals R are the same and a-naphthylthio radicals or phenylthio radicals that are unsubstituted or substituted by 1 to 3 substituents are, the substituents having the composition F, Cl , Br, NO2, R1, R2, OR1, OR2, C02R1, CON (R1) 2, CONR1R2, NIICOR1, NHCOR2, S02R2, SO2R2 'S02N (R1) 2 or S02NR1R2, where R1 is a C1 to C8 alkyl radical the stipulation means that all radicals R1 together may not have more than 12 carbon atoms, and R2 denotes a phenyl radical which is unsubstituted or substituted by 1 or 2 Ci to C4 alkyl groups, C1 to C4 alkoxy groups, NO2 groups or chlorine atoms. 2. Fibers according to claim 1, characterized in that they are made of cotton exist. 3. Fibers according to claim 1, characterized in that they consist of one Consists of a mixture of cotton and polyester fibers.