Process for dyeing cellulose fibers with water-insoluble azo dyestuffs produced on the fiber
This invention relates to a process for dyeing cellulose fibers with water-insoluble azo dyestuffs produced on the fiber. 
     British Pat. No. 1,422,995 relates to a process for the single-bath dyeing of cellulose fibers using water-insoluble azo dyestuffs produced on the fiber, wherein the textile material is treated at a temperature within the range of from room temperature to a moderately elevated temperature with an aqueous bath containing, besides an alkaline agent, sodium nitrite and an anionic dispersing agent, the solution or dispersion of at least one azoic coupling component and at least one non-diazotized primary aromatic amine in a water miscible organic solvent or solubilizer and, after adsorption of the coupling component, diazotation of the amine and formation of the dyestuff are brought about at room temperature by adding an acid or acid salts to the bath. 
     This process has the drawback that some amine dispersions become unstable, especially on standing for a prolonged period of time, that special care is required for preparing the dispersions and that selected dispersing agents and additional solvent must be used. 
     It is also known to print and dye textile webs of cellulose fibers according to the so-called ice-color technique using developing dyes. In this process, water-insoluble azo dyes are produced on the fiber. In general, the textile material is first impregnated with the alkaline solution of the coupling component and, optionally after drying, the material is treated with the acid bath or printing paste of the diazo component, whereby the water-insoluble azo dyestuff is formed on the fiber. The material is then rinsed, soaped and dried. This mode of operation necessitates an additional process, i.e. the impregnation. Moreover, some of the diazonium salts have marginal stability so that the shade may vary from end to end in continuous dyeing. 
     Numerous proposals have been made to overcome these disadvantages. It is possible, for example, to use the diazonium component in the form of the anti-diazotates or diazoamino compounds, the preparation of which is rather expensive. In other processes free amines are used, for example in those of German Pat. Nos. 638,878, 644,070, 661,496 and 729,846, which amines are applied to the fiber in the presence of alkali metal salts of coupling components and sodium nitrite and are diazotized by an acid passage. Azo coupling is then brought about by drying or exposing to air. This mode of operation is complicated and little reproducible. 
     It has also been proposed to print the material with dispersed amines and alkaline solutions of coupling components and sodium nitrite and to develop the dyestuff by acid steaming. However, when the printing pastes are allowed to stand for a prolonged period of time, the lack of stability of the dispersed amines causes some difficulties and the preparation of dispersions is not very easy. In general, the process must be carried out very cautiously with selected dispersing agents or additional solvents have to be used. 
     It has now been found that the aforesaid difficulties do not arise or at least that they are distinctly reduced when in such a process primary amines are used carrying a carboxylic acid ester or amide group. 
     It is, therefore, the object of the present invention to provide a process for dyeing or printing cellulose fibers with azo dyestuffs produced on the fiber by treating the material with aqueous baths or printing pastes containing an azoic coupling component, the solution or dispersion of a diazotizable primary aromatic amine, an alkaline agent and sodium nitrite and subjecting the material to a subsequent acid treatment, which comprises using an amine containing a carboxylic acid ester or amide group. 
     To produce the dyeings by the process of the invention the coupling components known from ice-color techniques can be used. In the case of exhaust processes they preferably have a substantive character for the fiber material. 
     Compounds of this type couple in a position adjacent to a hydroxy group and do not contain solubilizing groups. There are especially mentioned aryl amides of aromatic or heterocyclic o-hydroxy-carboxylic acids or of acyl acetic acids and other aromatic or heterocyclic hydroxy compounds containing in a heterocyclic ring a keto-methylene group which is enolized or capable of being enolized. Substances of this type are, for example, aryl amides of 2,3-hydroxy-naphthoic acid, of 2-hydroxyanthracene-3-carboxylic acid, of 4-hydroxydiphenyl-3-carboxylic acid, of 2-hydroxycarbazol-3-carboxylic acid, of 3-hydroxydiphenylene oxide-2-carboxylic acid, of 3-hydroxy-diphenylene sulfide-2-carboxylic acid, of acetoacetic acid, or of benzoylacetic acid. There are further suited, inter alia, hydroxybenzenes, polyhydroxy-benzenes, hydroxy-naphthalenes and pyrazolones which may be substituted by nonionic radicals. 
     Suitable coupling components in printing and padding processes are preferably low or medium substantive aryl amides of aceto-acetic acid, of 2-hydroxy-naphthalene-3-carboxylic acid or of heterocyclic o-hydroxy-carboxylic acids, for example 5-chloro-2-acetoacetylamino-1,4-diethoxybenzene, 4,4&#39;-bis(acetoacetylamino)-3,3&#39;-dimethyl-diphenyl, 2-acetoacetylamino-6-ethoxybenzthiazole, 2-hydroxy-naphthalene-3-carboxylic acid phenylamide, the derivatives thereof substituted in the phenylamide radical by lower alkyl or lower alkoxy groups or chlorine atoms, such as 2-hydroxy-naphthalene-3-carboxylic acid-(2&#39;-methoxyphenyl-1&#39;)-amide, 2-hydroxy-naphthalene-3-carboxylic acid-(2&#39;-methoxy-phenyl-1&#39;)-amide, 2-hydroxy-naphthalene-3-carboxylic acid-(3&#39;-chloro-6&#39;-methoxy-phenyl-1&#39;)-amide and 2-hydroxy-carboazole-3-carboxylic acid-(4&#39;-chlorophenyl-1&#39;)-amide. 
     All non-diazotized primary aromatic amines containing at least one carboxylic acid amide or ester group and forming water-insoluble mono-, dis- or poly-azo dyestuffs with the aforesaid coupling components can be used, including heterocyclic amines besides the carbocyclic amines. Thus, practically all diazotizable primary aromatic amines can be used provided that they contain at least one carboxylic caid amide or ester group and do not contain any group rendering soluble in wter the azo dyestuff formed. 
     There are mentioned in the first place amines of the formula ##STR1## in which R represents a group of the formula 
     
         -- G -- CO -- O -- R&#39;; -- G -- O -- CO -- R&#39;; -- G -- CO -- NR&#39;R&#34; or -- G -- NR&#34; -- CO -- R&#39; 
    
     in which G stands for a group of the formula 
     
         -- (C.sub.x H.sub.2x) --, --CH═CH -- or --N ═N -- Y -- 
    
     x being zero or an integer in the range of from 1 to 3, 
     Y represents phenylene or the group &gt;CH -- Ac in which Ac stands for acetyl or benzoyl, 
     R&#39; represents hydrogen or preferably an aliphatic or aromatic radical, 
     R&#34; represents hydrogen or an aliphatic or aromatic radical, R&#34; and R&#39; possibly being linked with each other to form a ring, 
     X represents identical or different non-solubilizing substituents or is defined as R, and 
     n stands for zero or an integer in the range of from 1 to 3. 
     Suitable substituents X at the nucleus are nitro, lower alkyl or lower alkoxy radicals, phenoxy, lower alkylsulfone, trifluoromethyl, or nitrile groups and/or halogen atoms, preferably chlorine atoms. 
     In view of their low price and easy accessibility, there are preferred aromatic amines containing ester groups and corresponding to the formulae ##STR2## in which R&#39;&#34; represents alkyl, aralkyl, aryl or hetaryl which may be substituted and the alkyl radicals preferably have from 1 to 4 carbon atoms; especially suitable are the methyl, trifluoromethyl or ethyl group. The preferred aralkyl radical is a substituted or unsubstituted benzyl radical while as aryl radical the phenyl radical is preferred which may be substituted, for example by halogen, preferably chlorine, nitro, methyl or methoxy radicals. Suitable hetaryl radicals are preferably the radicals of N-containing heterocyclic compounds. 
     Especially good results are obtained with compounds of formula II in which R&#39;&#34; represents methyl or ethyl, for example 2-chloro-4-amino-benzoic acid methyl ester, 3,5-dichloro-2-amino-benzoic acid methyl ester, 5-nitro-2-amino-benzoic acid ethyl ester, 3-nitro-4-amino-benzoic acid ethyl ester, 4-aminobenzoic acid methyl ester, 4-amino-benzoic acid ethyl ester, 3-amino-4-chloro-benzoic acid methyl ester, 3-amino-benzoic acid methyl ester, 3-amino-4-chloro-benzoic acid ethyl ester, 3-amino-6-chlorobenzoic acid methyl ester, or 3-amino-6-chlorobenzoic acid ethyl ester. Additional suitable compounds are amino-cinnamic acid esters, for example 3-amino-cinnamic acid methyl ester, 4-amino-cinnamic acid methyl ester, 3-aminocinnamic acid ethyl ester and 4-amino-cinnamic acid ethyl ester, as well as derivatives of said esters substituted in the benzene nucleus, 5-amino-isophthalic acid dimethyl ester, or 4-aminobenzoic acid n-propyl ester. 
     Preferred amide compounds are those of the formulae ##STR3## in which R&#34;&#34; represents hydrogen or has the same meaning as R&#39;&#34;, and R&#39;&#34; and R&#34;&#34; may be linked to each other to form a ring. In the case of formula III b, the radicals R&#34;&#34; are identical or different, preferably one radical R&#34;&#34; being hydrogen and the other one a possibly substituted phenyl radical. 
     Especially suitable compounds of formula III a are, for example, 1-methyl-2-amino-4-chloro-5-benzoylaminobenzene, 1-amino-3-methyl-4-benzoylamino-6-methoxybenzene, 1-methoxy-2-benzoyl-amino-4-chloro-5-aminobenzene, 1-amino-4-benzoylamino-2,5-diethoxybenzene, 1-amino-4-benzoylamino-2,5-dimethoxybenzene and 6-amino-4-benzoylamino-1,3-xylene and suitable compounds of formula III b are 3-amino-benzoic acid amide, 4-amino-benzoic acid amide, 3-amino-4-methoxy-benzoic acid amide, 3-methoxy-4-amino-benzoic acid amide, 3-amino-benzoic acid methylamide, 4-amino-benzoic acid anilide, 3-amino-benzoic acid anilide, 3-amino-benzoic acid-2&#39;-chloroanilide, 4-chloro-3-amino-benzoic acid anilide, 5-nitro-2-amino-benzoic acid anilide, 3-amino-4-methoxy-benzoic acid anilide, 3-amino-4-methoxy-benzoic acid-3&#39;-chloro-2&#39;-methyl anilide, 6-amino-2-benzoylamino-1,4-dimethyl-benzene, 4-amino-1-(4-nitro-benzoylamino)-benzene, 4-amino-2-benzoylamino-toluene, 6-amino-3-(N-ethylbenzoylamino)-toluene, 2-amino-4-acetamino-toluene, 2-amino-4-formylamino-toluene or compounds of the formulae ##STR4## or derivatives thereof, for example the compound of the formula ##STR5## and analogous compounds. 
     Additional suitable compounds are 4-aminocinnamic acid amide and 4-aminocinnamic acid anilide. 
     For the dispersion of the amine there are used preferably, if necessary, anionic agents, for example alkyl sulfonates, alkylaryl sulfonates, aryl sulfonates, lignin sulfonates, sulfonated cresol-formaldehyde resins, formaldehyde-naphthalene-sulfonic acid condensation products, taurines and acylamino-sulfonic acids, especially the sodium salt of 2,2&#39;-dinaphthyl-methane-6,6&#39;-disulfonic acid or a mixture of oleylmethyl taurine and lignin sulfate. 
     Alternatively, non ionic agents can be used, optionally in admixture with anionic agents. Suitable non ionic agents are, for example, alkyl polyglycol ethers, alkylaryl polyglycol ethers, aryl polyglycol ethers, acyl polyglycol ethers and oxalkylated fatty amines. 
     The process according to the invention is used to dye known cellulosic fibers such as native fibers, for example flax, hemp, linen, or cotton, or regenerated fibers, for example viscose staple fibers, spun rayon and modal fibers (polynosic type). The cellulosic fibers can be used as such or in admixture with other fibers, for example polyester fibers. 
     As far as the process of the invention is carried out as exhaust process, the conditions set forth in British Pat. No. 1,422,995 are applied. Instead of the anionic dispersing agents mentioned in the aforesaid patent, in the present process other dispersing agents as indicated above can be used. Moreover, with the use of some of the amines, the dyestuff components can be dissolved separately, the amine being simply dissolved in water. 
     As compared with the process disclosed in the above British patent, the process of the present invention has the following advantages: 
     1. The dispersions or solutions have a higher stability. 
     2. The dispersing agents need no specific activity so that a greater number of substances can be used, for example non ionic dispersing agents. 
     3. The dyeing baths can be prepared with less precision so that the process becomes safer. 
     4. In some cases solvents for the amine need not be used. 
     When the process of the invention is carried out as jigpadding or slop padding process, the liquors can be prepared in known manner by dissolving the coupling components, in the manner usual in ice-color techniques, and dissolving or dispersing the amine and combining the solutions or solution and dispersion, preferably while adding a solvent and/or dispersing agent to the amine. Alternatively, the individual component can be jointly dissolved or dispersed. 
     The fibrous material is impregnated in known manner with the aqueous liquor containing the amine, the coupling component, an alkaline agent and sodium nitrite, for example by padding, nip-padding, spraying or dipping, or by applying in foam form. 
     As far as the process of the invention is carried out as printing process, the printing pastes are applied in usual manner. The material is then dried or immediately treated with acid, for example by acid steaming, padding, nip-padding, spraying, dipping, or foaming. 
     It proved advantageous to pass the material through air, or to heat or to steam it after printing. For developing, the usual inorganic and organic acids are used. 
     The after-treatment is effected by rinsing and soaping under the conditions used for the ice-color techniques. To bring up to shade a reactive dye may be added to the acid aqueous developing bath and, after complete coupling to form the azo dyestuff, optionally after intermediate drying, the reactive dye can be fixed by a treatment with an alkaline agent with subsequent heating or allowing to dwell for some time. 
     It is surprising that the amines used in the present process yield colorations which have a high fastness to wet processing as the hydrophilic carboxylic ester or amide group would rather point to a distinctly reduced fastness to wet processing. Moreover, it could have been expected that the diazotization would cause alterations of the amide or ester group resulting in non uniform shifting of the shade and useless results. Such changes of shade have, however, not been observed. 
     The numbers of the Colour Index indicated in the examples to characterize the dyestuffs were taken from the 2nd Edition 1956, the supplemental volume of 1963 and the 3rd Edition 1971. 
    
    
     The following examples illustrate the invention, the parts and percentages being by weight unless stated otherwise. 
     EXAMPLE 1 
     Cotton cross-wound bobbins were prepared for the dyeing process by boiling and bleaching. Next, the bobbins were treated at a goods-to-liquor ratio of 1:20 for 45 minutes at 30° C in a bath prepared as follows: 
     
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0.62 g/l                                                                  
       of 3-amino-benzoic acid ethyl ester were dis-                      
       solved in water and added, while stirring, to-                     
       gether with a solution obtained by cold dissolu-                   
       tion of                                                            
1.15 g/l                                                                  
       of Azoic Coupling Component 9 (C.I. No. 37,620)                    
       in                                                                 
6 ml/l of ethanol,                                                        
1.5 ml/l                                                                  
       of 32.5 % sodium hydroxide solution (38° Be) and            
3 ml/l of water of 50° C,                                          
       to an aqueous bath of 30° C having the following            
       composition:                                                       
6 ml/l of 32.5 % sodium hydroxide solution (38° Be),               
3 g/l  of sodium 2,2&#39;-dinaphthylmethane-6,6&#39;-disulfonate,                 
1 g/l  of sodium nitrite and                                              
20 g/l of sodium chloride.                                                
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     After 30 minutes the liquor was pumped back into the preparing vessel and admixed with 
     
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1.8 ml/l  of 32.1 % hydrochloric acid (20° Be) and                 
2 ml/l    of 60 % acetic acid.                                            
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     With the liquor obtained the textile material was treated for 30 minutes at 25° to 30° C. 
     After rinsing with cold and hot water, the material was treated with 
     
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1    g/l     of oleylmethyl taurine,                                      
1    g/l     of anhydrous sodium carbonate and                            
1    g/l     of sodium tripolyphosphate,                                  
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     at 60° C and at boiling temperature, each time for 15 minutes, rinsed again and finished. 
     A greenish yellow coloration was obtained. 
     EXAMPLE 2 
     Knitted cotton fabric ready for dyeing was treated in a jet dyeing apparatus for 30 minutes at a goods-to-liquor ratio of 1:10 in an aqueous bath prepared as follows: 
     
         ______________________________________                                    
0.74 g/l                                                                  
       of 6-chloro-3-amino-benzoic acid ethyl ester were                  
       dissolved in water and added to a mixture of                       
1.15 g/l                                                                  
       of Azoic Coupling Component 28 (C.I. No. 37,541),                  
       dissolved in                                                       
6 ml/l of ethanol,                                                        
1.5 ml/l                                                                  
       of 32.5 % sodium hydroxide solution (38° Be) and            
3 ml/l of water of 50° C.                                          
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     The solution obtained was added to an aqueous bath of 30° C having the following composition: 
     
         ______________________________________                                    
6 ml/l of 32.5 % sodium hydroxide solution,                               
3 g/l  of sodium 2,2&#39;-dinaphthylmethane-6,6&#39;-disulfonate,                 
2 g/l  of crystalline sodium nitrite,                                     
20 g/l of sodium chloride and                                             
4 g/l  of crystalline disodium phosphate.                                 
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     After a treating time of 30 minutes, 
     
         ______________________________________                                    
7.5 ml/l                                                                  
       of 32.1 % hydrochloric acid (20° Be) and                    
0.75 ml/l                                                                 
       of 60 % acetic acid                                                
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     were metered into the circulating bath and the material was treated at a pH of about 5.9 for 30 minutes at 25° to 30° C. 
     The after-treatment was carried out as described in Example 1. A bright scarlet coloration having a high brillancy was obtained. 
     EXAMPLE 3 
     The fabric was dyed under the conditions specified in Example 2 in a bath prepared as follows: 
     
         ______________________________________                                    
0.56 g/l                                                                  
       of 4-amino-cinnamic acid ethyl ester was dis-                      
       persed in water with                                               
0.56 g/l                                                                  
       of a dispersing agent (according to Fiat Final                     
       Report 1013) and the dispersion obtained was - added to a solution 
       obtained by cold dissolu-                                          
       tion of                                                            
1.15 g/l                                                                  
       of Azoic Coupling Component 9 (C.I. No. 37,620).                   
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     The dispersiion obtained was added, while stirring, to an aqueous bath of 30° C having the composition specified in Example 2. The material was dyed and after-treated under the conditions of Example 2. 
     A full golden yellow coloration was obtained. 
     In the following table are summarized further combinations of dye-forming components, the amount thereof to be used and the colorations obtained on cellulose fibers under the conditions set forth above. 
     
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Example                                                                   
     Coupling Component         amine                shade                
__________________________________________________________________________
4    1.15 g/l Azoic Coupl. Component 9 C.I.No 37 620                      
                                0.5 g/l 4-amino-benzoic acid methyl       
                                ester                yellow               
5    1.15 g/l Azoic Coupl. Component 9 C.I.No. 37 620                     
                                0.7 g/l 4-chloro-2-amino-benzoic          
                                acid methyl ester    yellow               
6    1.15 g/l Azoic Coupl. Component 28 C.I.No. 37 541                    
                                1.14 g/1 4-nitro-2-amino-benzoic acid     
                                ethyl ester          orange               
7    1.15 g/l Azoic Coupl. Component 8 C.I.No. 37 525                     
                                1 g/l 4-amino-benzoic acid ethyl          
                                ester                red                  
8    1.15 g/l Azoic Coupl. Component 12 C.I.No. 37 550                    
                                0.9 g/l 3-amino-benzoic acid ethyl        
                                ester                scarlet              
9    1.15 g/l Azoic Coupl. Component 32 C.I.No. 37 580                    
                                1.1 g/l 5-bromo-2-amino-benzoic acid      
                                methyl ester         red                  
10   1.15 g/l Azoic Coupl. Component 4 C.I.No. 37 560                     
                                1.1 g/l 4-chloro-3-amino-benzoic          
                                acid methyl ester    red                  
11   1.15 g/l Azoic Coupl. Component 32 C.I.No. 37 580                    
                                0.9 g/l 4-amino-cinnamic acid methyl      
                                ester                bordeaux             
__________________________________________________________________________
 
    
     EXAMPLE 12 
     
         ______________________________________                                    
20 g/l of Azoic Coupling Component 12 (C.I. No. 37,550)                   
       were dissolved in                                                  
30 ml/l                                                                   
       of ethanol,                                                        
10 ml/l                                                                   
       of 32.5 % sodium hydroxide solution (38° Be)                
       and                                                                
25 ml/l                                                                   
       of water of 50 to 60° C.                                    
9.2 g/l                                                                   
       of 3-aminobenzoic acid ethyl ester were dissolv-                   
       ed in water of 50° C and the solution was added             
       to the solution of the coupling component addi-                    
       tionally containing                                                
1 g/l  of lignin sulfonate.                                               
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     The solution obtained was added, while stirring, to a padding liquor containing 
     
         ______________________________________                                    
20 ml/l                                                                   
       of 32.5 % sodium hydroxide solution (38° Be) and            
20 g/l of sodium nitrite.                                                 
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     Bleached and mercerized cotton fabric was treated with the padding liquor at a liquor pickup of 60 to 70 % and dried. 
     After drying, the material was steamed for 30 seconds in overheated steam of 130° C containing formic acid and acetic acid. Next, the material was treated in usual manner by rinsing with cold and hot water, soaping at boiling temperature and rinsing with hot and cold water. 
     After drying, a clear and brilliant red coloration was obtained. 
     Alternatively, the coloration can be developed by passing the material through an acid bath with subsequent air passage, drying or steaming. 
     EXAMPLE 13 
     
         ______________________________________                                    
20 g/kg                                                                   
       of Azoic Coupling Component 20 (C.I. No. 37,530;                   
       in the following: &#34;naphtholate&#34;)                                   
       were dissolved with                                                
40 ml/kg                                                                  
       of ethanol,                                                        
30 g/kg                                                                   
       of β,β-dihydroxy-diethyl sulfide and                     
13 ml/kg                                                                  
       of 32.5 % sodium hydroxide solution (38° Be)                
       by adding                                                          
50 ml/kg                                                                  
       of water of 60 to 70° C,                                    
12 g/l of 6-chloro-3-amino-benzoic acid ethyl ester                       
       were dissolved in water and the solution added                     
       to the naphtholate solution.                                       
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     400 Parts of a 6 % aqueous thickening of a locust bean flour ether, diluted with 300 parts of water, were successively blended with the naphtholate solution, the amine solution and a solution of 20 g/kg of sodium nitrite dissolved in 40 ml of water. 
     Bleached and mercerized cotton fabric was printed with the printing paste so obtained and dried. The print was then subjected for 20 seconds to the action of superheated steam of 130° C containing formic acid and acetic acid. Finally, the fabric was after-treated in usual manner. A dark red print was obtained. 
     EXAMPLE 14 
     
         ______________________________________                                    
20 g/l of Azoic Coupling Component 24 (C.I. No. 37,540;                   
       in the following: &#34;naphtholate&#34;)                                   
       were dissolved with                                                
30 ml  of ethanol,                                                        
20 ml  of 32.5 % sodium hydroxide solution (38° Be) and            
40 ml  of water.                                                          
13 g/l of 4-amino-cinnamic acid ethyl ester were dis-                     
       persed with water/ethylene glycol and                              
1.5 g/l                                                                   
       of the compound of the formula                                     
 ##STR6##                                                                 
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     and 20 g/l of sodium nitrite were added. 
     The amine dispersion obtained was stirred into the naphtholate bath and made up to 1 liter. 
     Mercerized and bleached cotton fabric was impregnated with this padding liquor and dried. A mixture of hydrochloric acid and acetic acid was applied as a foam onto the dried material which was then steamed and after-treated. Alternatively, the material can be treated with a somewhat higher acid concentration, rolled up and allowed to dwell at room temperature for some time. A very dark claret shade (bordeaux) was obtained. 
     EXAMPLE 15 
     
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1) 20 g/l                                                                 
       of Azoic Coupling Component 13 (C.I. No. 37,595)                   
       were dissolved in                                                  
  10 ml                                                                   
       of ethanol and                                                     
  20 ml                                                                   
       of water of 40° C.                                          
2) 8 g/l                                                                  
       of 4-aminobenzoic acid methyl ester were dissolv-                  
       ed in hot water and                                                
  0.5 g/l                                                                 
       of a dispersing agent on the basis of lignin-                      
       sulfonic acid was added.                                           
3) 10 g/l                                                                 
       of sodium nitrite were dissolved in 30 ml of hot                   
       water.                                                             
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     The 3 solutions were successively stirred into water of 90° C containing 
     
         ______________________________________                                    
0.5 g/l                                                                   
       of dispersing agent on the basis of lignin sul-                    
       fonate and                                                         
5 g/l  of a condensation product of naphthalene sul-                      
       tonate with formaldehyde and adjusted to 1 liter.                  
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     A cotton warp or a cotton fabric were padded at a liquor pickup of 60 to 70% and dried. 
     Development was brought about by cross padding with 
     
         ______________________________________                                    
40 ml/l  of 60 % acetic acid and                                          
10 g/l   of sodium acetate with subsequent drying.                        
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     When a cotton warp is used it may be sized in the acid bath. 
     After having carried out the usual after-treatment (in the case of the cotton warp the after-treatment only being effected after weaving with white weft yarn) a black shade was obtained. 
     The following table summarized further combinations of dyestuff-forming components, the amounts to be used and the shades obtained on cellulose fibers. 
     
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Example                                                                   
      Coupling Component         primary aromatic amine                   
                                                       shade              
__________________________________________________________________________
16    40 g/l Azoic Coupl.Component 9, C.I.No. 37 620                      
                                 25.8 g/l 3-amino-benzoic acid methyl     
                                 ester                 yellow             
17    20 g/l Azoic Coupl.Component 5, C.I.No. 37 610                      
                                 37.8 g/l 4-amino-benzoic acid            
                                                       golden             
                                 ester                 yellow             
18    40 g/l Azoic Coupl. Component 9, C.I.No. 37 620                     
                                 34.1 g/l 6-chloro-3-amino-benzoic        
                                                       oldd               
                                 ethyl ester           gold               
19    20 g/l Azoic Coupl.Component 5, C.I.No. 37 610                      
                                 8.4 g/l 4-amino-cinnamic acid            
                                                       golden             
                                 ester                 orange             
20    20 g/l Azoic Coupl.Component 18, C.I.No. 37 520                     
                                 9.2 g/l 3-amino-benzoic acid ethyl       
                                 ester                 orange             
21    20 g/l Azoic Coupl.Component 28, C.I.No. 37 541                     
                                 13.7 g/l 4-nitro-2-amino-benzoic acid    
                                 ethyl ester           orange             
22    20 g/l Azoic coupl.Component 8, C.I.No. 37 525                      
                                 13.7 g/l 4-chloro-2-amino-benzoic acid   
                                 methyl ester          scarlet            
23    20 g/l Azoic Coupl.Component 4, C.I.No. 37 560                      
                                 14.4 g/l 4-nitro-2-amino-benzoic acid    
                                 ethyl ester           red                
24    20 g/l Azoic Coupl.Component 34, C.I.No. 37 531                     
                                 12.6 g/l 4-chloro-3-amino-benzoic acid   
                                 methyl ester          red                
25    20 g/l Azoic Coupl.Component 12, C.I.No. 37 550                     
                                 8.0 g/l 4-amino-benzoic acid             
                                                       darkyl             
                                 ester                 red                
26    20 g/l Azoic Coupl.Component 8, C.I.No. 37 525                      
                                 15.2 g/l 4-amino-benzoic acid            
                                                       darkl              
                                 ester                 red                
27    20 g/l Azoic Coupl.Component 32, C.I.No. 37 580                     
                                 10.7 g/l 4-amino-cinnamic acid ethyl     
                                 ester                 bordeaux           
28    20 g/l Azoic Coupl.Component 15, C.I.No. 37 600                     
                                 12.4 g/l 5-bromo-2-amino-benzoic         
                                 acid methyl ester     brown              
29    40 g/l Azoic Coupl.Component 16, C.I.No. 37 605                     
                                 12.1 g/l 5-chloro-2-amino-benzoic        
                                                       blackish           
                                 methyl ester          brown              
30    80 g/l Azoic Coupl.Component 13, C.I.No. 37 595                     
                                 24.8 g/l 2-chloro-4-amino-benzoic acid   
                                 ethyl ester           black              
31    60 g/l Azoic Coupl.Component 107, C.I.No. -                         
                                 21.6 g/l 4-nitro-2-amino-benzoic         
                                                       very dark          
                                 ethyl ester           grey               
32    60 g/l Azoic Coupl.Component 107, C.I.No. -                         
                                 19.2 g/l 4-chloro-2-amino-benzoic        
                                                       dark reddish       
                                 methyl ester          brown              
__________________________________________________________________________
 
    
     EXAMPLE 33 
     After purification in usual manner by boiling, cotton crosswound bobbins were treated for 45 minutes at 30° C at a goods-to-liquor ratio of 1:20 in a bath prepared as follows: 
     
         ______________________________________                                    
0.82 g/l                                                                  
       of 2-chloro-4-amino-acetanilide, which is sub-                     
       stantially soluble in water, was stirred up and                    
       fully dissolved with                                               
1.15 g/l                                                                  
       of Azoic Coupling Component 32 (C.I. No. 37,580),                  
6 ml/l of ethanol,                                                        
1.5 ml/l                                                                  
       of 32.5 &amp; sodium % solution (38° Be) and                    
3 ml/l of water of 50° C                                           
______________________________________                                    
 
    
     and the solution obtained was introduced, while stirring, into an aqueous bath of 30° C of the following composition: 
     
         ______________________________________                                    
6 ml/l of 32.5 % sodium hydroxide solution (38° Be),               
3 g/l  of sodium 2,2&#39;-dinaphthylmethane-6,6&#39;-disulfonate,                 
20 g/l of sodium chloride and                                             
1 g/l  of sodium nitrite.                                                 
______________________________________                                    
 
    
     A limpid dark brown solution was obtained. 
     After 45 minutes, the bath was recycled by pumping into the preparing vessel and in said vessel it was admixed with 
     
         ______________________________________                                    
2.5 ml/l                                                                  
       of 32.1 % hydrochloric acid (20° Be) and                    
1.5 ml/l                                                                  
       of 60 % acetic acid.                                               
______________________________________                                    
 
    
     The textile material was treated in this bath for 30 minutes at 25° to 30° C. Next, it was rinsed with hot and cold water, treated with a solution of 
     
         ______________________________________                                    
1 g/l  of oleylmethyl taurine,                                            
1 g/l  of anhydrous sodium carbonate and                                  
1 g/l  of sodium tripolyphosphate                                         
______________________________________                                    
 
    
     for 45 minutes each at 60° C and at boiling temperature, and rinsed with hot and cold water. A deep dark red coloration was obtained. 
     EXAMPLE 34 
     Boiled and bleached knitted cotton fabric was treated in a jet dyeing apparatus for 30 minutes at a goods-to-liquor ratio of 1:10 with an aqueous liquor prepared as follows: 
     
         ______________________________________                                    
0.81 g/l                                                                  
       of 4-amino-benzoic acid methyl amide dissolved                     
       in water were dissolved with                                       
1.15 g/l                                                                  
       of Azoic Coupling Component 28 (C.I. No. 37, 341),                 
6 ml/l of ethanol,                                                        
1.5 ml/l                                                                  
       of 32.5 % sodium hydroxide solution (38° Be) and            
50 ml/l                                                                   
       of water of 40° C                                           
______________________________________                                    
 
    
     and the solution was introduced, while stirring, into an aqueous bath of 30° C containing 
     
         ______________________________________                                    
6 ml/l of 32.5 % sodium hydroxide solution (38° Be),               
3 g/l  of sodium 252&#39;-dinaphthylmethane-6,6&#39;-disulfon-                    
       ate,                                                               
2 g/l  of crystalline sodium nitrite and                                  
20 g/l of sodium chloride.                                                
______________________________________                                    
 
    
     After a treatment time of 30 minutes 
     
         ______________________________________                                    
3.5 ml/l                                                                  
       of 32.1 % hydrochloric acid (° Be) and                      
2 ml/l of 60 % acetic acid                                                
______________________________________                                    
 
    
     were added by means of an additional pump, the pH of the bath was adjusted to about pH 5.9 and the fabric was treated for a further 20 minutes at about 25 to 30° C. 
     After rinsing with cold and hot water, the fabric was treated with 
     
         ______________________________________                                    
1    g/l     of oleylmethyl taurine,                                      
1    g/l     of anhydrous sodium carbonate and                            
1    g/l     of sodium tripolyphosphate,                                  
______________________________________                                    
 
    
     each time for 10 minutes at 60° C and at boiling temperature, rinsed again and finished. 
     A dark brilliant scarlet coloration having an excellent fastness to light was obtained. 
     In the following table are summarized further combinations of dyestuff-forming components to be used under the conditions of Examples 33 and 34, the amounts thereof and the shades produced on cellulose fibers. 
     
         __________________________________________________________________________
Example                                                                   
     Coupling Component         primary aromatic amine                    
                                                    shade                 
__________________________________________________________________________
35   1.15 g/l Azoic Coupl.Component 9, C.I.No. 37 620                     
                                0.82 g/l 3-amino-4-methoxy-benzoic        
                                acid anilide        yellow                
36   1.15 g/l Azoic Coupl.Component 4, C.I.No. 37 560                     
                                0.8 g/l 3-amino-benzoic acid              
                                                    orange                
37   1.15 g/l Azoic Coupl.Component 28, C.I.No. 37 541                    
                                1.2 g/l 3-amino-benzoic acid              
                                                    scarlet               
38   1.15 g/l Azoic Coupl.Component 12, C.I.No. 37 550                    
                                0.8 g/l 3-amino-benzoic acid methyl       
                                amide               red                   
39   1.15 g/l Azoic Coupl.Component 12, C.I.No. 37 550                    
                                0.8 g/l 3-amino-4-methoxy-benzoic         
                                acid 3-chloro-2&#39;-methyl                   
                                                    redlide               
40   1.15 g/l Azoic Coupl.Component 32, C.I.No. 37 580                    
                                1.16 g/l 1-methyl-2-amino-4-chloro-       
                                5-benzoylaminobenzene                     
                                                    bordeaux              
41   1.15 g/l Azoic Coupl.Component 4, C.I.No. 37 560                     
                                1.78 g/l 1-amino-4-benzoylamino-          
                                                    navy                  
                                2,5-diethoxybenzene blue                  
42   1.15 g/l Azoic Coupl.Component 15, C.I.No. 37 600                    
                                0.76 g/l 6-amino-4-benzoylamino-          
                                1,3-xylene                                
__________________________________________________________________________
 
    
     EXAMPLE 43 
     
         ______________________________________                                    
20g/l  of Azoic Coupling Component 4 (C.I. No. 37,560)                    
       were dissolved with                                                
30 ml/l                                                                   
       of ethanol,                                                        
10 ml/l                                                                   
       of 32.5 % sodium hydroxide solution (38° Be) and            
25 ml/l                                                                   
       of water of 50 to 60° C.                                    
9 g/l  of 4-aminobenzoic acid methyl amide were dissolv-                  
       ed in water of 50° C and                                    
1 g/l  of lignin sulfate were added.                                      
______________________________________                                    
 
    
     Both solutions were added, while stirring, to a padding liquor containing 
     
         ______________________________________                                    
20 ml/l                                                                   
       of 32.5 % sodium hydroxide solution (38° Be) and            
20 g/l of sodium nitrite.                                                 
______________________________________                                    
 
    
     Bleached and mercerized cotton fabric was treated with the padding liquor obtained at a liquor pickup of 60 to 70% and dried. 
     After drying, the fabric was steamed for 30 seconds with superheated steam of 130° C containing formic acid and acetic acid. The fabric was then after-treated in usual manner by rinsing with cold and hot water, soaping at boiling temperature, and rinsing again with hot and cold water. After drying, a clear and brilliant red coloration having good wet fastness and very good fastness to light was obtained. Alternatively, the dyestuff can be developed by an acid passage with subsequent air passage, drying or steaming. 
     EXAMPLE 44 
     
         ______________________________________                                    
20 g/kg                                                                   
       of Azoic Coupling Component 8 (C.I. No. 37,525;                    
       in the following: &#34;naphtholate&#34;)                                   
       were dissolved with                                                
40 ml/kg                                                                  
       of ethanol,                                                        
30 g/kg                                                                   
       of β,β-dihydroxydiethyl sulfide,                         
13 ml/kg                                                                  
       of 32.5 % sodium hydroxide solution (38° Be) and            
50 ml/kg                                                                  
       of water of 60 to 70° C                                     
10 g/l of 2-chloro-4-amino-acetanilide were dissolved                     
       in water containing                                                
2 g/l  of caster oil fatty acid polyglycol ether.                         
______________________________________                                    
 
    
     First, the naphtholate solution, then the amine solution and finally a solution of 20 parts of sodium nitrite in 40 parts of water were stirred into 400 parts of a 6% aqueous thickening of locust bean flour ether, diluted with 300 parts of water. 
     Bleached and mercerized cotton fabric was printed with the printing paste so obtained and dried. The fabric was then treated for 20 seconds with superheated steam of 130° C containing formic acid and acetic acid and further treated in usual manner. 
     A red print having good fastness properties was obtained. 
     EXAMPLE 45 
     
         ______________________________________                                    
20 g/l of Azoic Coupling Component 11 /C.I. No. 37,535;                   
       in the following: &#34;naphtholate&#34;)                                   
       were dissolved with                                                
30 ml  of ethanol,                                                        
20 ml  of 32.5 % sodium hydroxide solution and                            
40 ml  of water.                                                          
13.6 g/l                                                                  
       of 3-amino-benzoic acid anilide and                                
1.5 g/l                                                                   
       of the compound of formula                                         
 ##STR7##                                                                 
were dispersed in a water/ethylene glycol mixture and                     
20 g/l of sodium nitrite were added.                                      
______________________________________                                    
 
    
     The amine dispersion was introduced, while stirring, into the naphtholate bath and the whole was made up to 1 liter. 
     Mercerized and bleached cotton fabric was impregnated with the padding liquor obtained and dried. A mixture of hydrochloric acid and acetic acid was foamed onto the dried fabric, the fabric was steamed and further treated. Alternatively, a somewhat higher acid concentration can be used, whereupon the fabric is rolled up and allowed to dwell for some time at room temperature. 
     A brilliant scarlet coloration having excellent fastness to light and wet processing is obtained. 
     EXAMPLE 46 
     
         ______________________________________                                    
1)  20 g/l  of Azoic Coupling Component 18 (C.I. No. 37,560)              
            were dissolved with                                           
    10 ml/l of 32.5 % sodium hydroxide solution (38° Be),          
    10 ml/l of ethanol and                                                
    20 ml/l of water of 40° C.                                     
2)  15 g/l  of 1-amino-4-benzoylamino-2,5-diethoxybenzene                 
            were dispersed with                                           
    2 g/l   of a dispersing agent on the basis of lignin                  
            sulfonic acid                                                 
            in approximately 100 ml of water.                             
3)  10 g/l  of sodium nitrite were dissolved in 30 ml/l of                
            hot water.                                                    
______________________________________                                    
 
    
     The three solutions were successively stirred into water of 90° C containing 5 g/l of a condensation product of naphthalene sulfonate with formaldehyde. 
     A cotton warp or cotton fabric was padded at a liquor pickup of 60 to 70% and dried. 
     The dyestuff was developed by cross padding with 40 ml/l of 60% acetic acid and 10 g/l of sodium acetate with subsequent drying. 
     When a cotton warp is used it can also be sized in an acid bath. 
     After the usual after-treatment (in the case of the warp yarn only after weaving with a white weft yarn), a dark blue coloration was obtained 
     In the following table are summarized further combinations of dyestuff-forming components to be used under the aforesaid conditions, the amounts thereof and the shades obtainable on cellulose fibers. 
     
         __________________________________________________________________________
Example                                                                   
     Coupling Component        primary aromatic amine                     
                                                     shade                
__________________________________________________________________________
47   20 g/l Azoic Coupl.Component 5, C.I.No. 37 610                       
                               8.6 g/1 3-amino-benzoic acid               
                                                     golden               
                                                     yellow               
48   20 g/l Azoic Coupl.Component 9, C.I.No. 37 620                       
                               10.0 g/l 3-amino-benzoic acid methyl       
                               amide                 yellow               
49   20 g/l Azoic Coupl.Component 18, C.I.No. 37 520                      
                               13.6 g/l 3-amino-benzoic acid              
                                                     orangee              
50   20 g/l Azoic Coupl.Component 20, C.I.No. 37 530                      
                               8.6 g/l 3-amino-benzoic acid               
                                                     reddish              
                                                     orange               
51   20 g/l Azoic Coupl.Component 18, C.I.No. 37 520                      
                               13 g/l 3-amino-benzoic acid-n-             
                                                     reddish              
                               butyl amide           orange               
52   20 g/l Azoic Coupl.Component 28, C.I.No. 37 541                      
                               14.5 g/l 2-chloro-4-amino-acetanilide      
                                                     scarlet              
53   20 g/l Azoic Coupl.Component 24, C.I.No. 37 540                      
                               12.6 g/l 3-amino-4-methoxy-benzoic         
                               acid amide            red                  
54   20 g/l Azoic Coupl.Component 11, C.I.No. 37 535                      
                               9 g/l 4-amino-benzoic acid                 
                                                     covered              
                                                     red                  
55   20 g/l Azoic Coupl.Component 34, C.I.No. 37 531                      
                               13 g/l 3-amino-4-methoxy-benzoic           
                                                     bright               
                               acid anilide          red                  
56   20 g/l Azoic Coupl.Component 20, C.I.No. 37 530                      
                               14.6 g/l 3-amino-4-methoxy-benzoic acid    
                               3&#39;-chloro-2&#39;-methyl anilide                
                                                     red                  
57   20 g/l Azoic Coupl.Compoonent 4, C.I.No. 37 560                      
                               14.6 G/l 3-amino-4-methoxy-benzoic acid    
                               3&#39;-chloro-2&#39;-methyl anilide                
                                                     bordeaux             
58   20 g/l Azoic Coupl.Component 12, C.I.No. 37 550                      
                               14.5 g/l 2-chloro-4-aminoacetanilide       
                                                     currant              
                                                     red                  
59   20 g/l Azoic Coupl.Component 2, C.I.No. 37 505                       
                               19 g/l 1-amino-3-methyl-4-benzoylamino-    
                               6-methoxybenzene      violet               
60   20 g/l Azoic Coupl.Component 15, C.I.No. 37 600                      
                               13.6 g/l 3-amino-benzoic acid              
                                                     brownde              
61   20 g/l Azoic Coupl.Component 16, C.I.No. 37 605                      
                               13 g/l 3-amino-4-methoxy-benzoic           
                                                     blackish             
                               acid anilide          brown                
62   20 g/l Azoic Coupl.Component 13, C.I.No. 37 595                      
                               10.9 g/l 4-amino-benzoic acid methyl-      
                               amide                 black                
63   20 g/lAzoic Coupl.Component 18, C.I.No. 37 520                       
                               21 g/l 1-amino-4-benzoylamino-2,5-         
                               dimethoxy-benzene     blue                 
__________________________________________________________________________